Foam products and their manufacturing

Abstract

There is a need to provide materials that reduce the burden on the environment, in particular insulating materials that have good insulating properties but have little impact on the environment. [Solution] A foam product comprising an expanded foam having cells defined therein and a blowing agent retained within the cells, wherein at least 5% by weight of the foam is formed from at least one component from a renewable source.

Description

[Technical field]

[0001] The present invention relates to a foam product, particularly a thermal insulation foam and its preparation. In particular, the present invention relates to a foam product with a low environmental impact and good thermal insulation performance. The present invention also relates to a highly sustainable closed-cell thermal insulation foam product. The present invention further relates to a phenolic foam product based on the condensation of a phenolic structure with an aldehyde, a composition for forming the sustainable thermal insulation foam, and the use of the sustainable foam. [Background technology]

[0002] The Paris Agreement, ratified in 2016, agreed on the long-term goal of limiting the global temperature increase this century to well below 2 degrees Celsius above pre-industrial levels to avoid dangerous climate change, and to pursue efforts to further limit the temperature increase to 1.5 degrees Celsius. Actions are needed to achieve these goals, and buildings are one area where significant improvements can be made.

[0003] According to the United Nations Environment Programme, buildings and their construction together account for 36% of the world's energy use and 39% of energy-related carbon dioxide emissions each year. According to the US Energy Information Administration, residential and commercial buildings account for 40% of energy consumption. And in the EU, nearly 40% of final energy consumption and 36% of greenhouse gas emissions come from homes, offices, shops and other buildings. Improving the energy performance of the building stock is therefore crucial to limiting global warming.

[0004] The use of insulation materials, such as closed-cell foam insulation materials, such as closed-cell foam products, plays an important role in the goal of reducing energy consumption in buildings. Closed-cell foam insulation materials, such as polyisocyanurate (PIR), polyurethane (PUR), extruded polystyrene (XPS), and phenolic or phenol-formaldehyde (PF) foams, provide improved insulation performance at comparable insulation thicknesses compared to more traditional insulation materials, such as man-made mineral fiber (MMMF) insulation materials (such as refractory ceramic fiber (RCF), fiberglass, glass wool, rock wool, slag wool, glass filament, etc.) and expanded polystyrene (EPS).

[0005] Closed-cell foam insulation materials offer a solution to reduce energy consumption in the renovation of existing buildings. In many cases, the space available for insulation is limited by the existing structure. The use of closed-cell PF insulation (low thermal conductivity PF: λ=0.018W / mk) can reduce heat loss by almost half compared to the same thickness of traditional insulation (high thermal conductivity MMMF: λ=0.038W / mk).

[0006] Although high-performance insulation materials, such as vacuum insulation panels, nanoparticle insulation, and aerogel insulation, offer even higher insulation performance than closed-cell insulation materials, their price-performance ratio makes them unattractive from a commercial point of view. In the case of vacuum insulation panels, a further disadvantage is the inability to mold the product as needed at the building site. Summary of the Invention [Problem to be solved by the invention]

[0007] In spite of the above situation, there is a need to provide materials that reduce the environmental load, in particular to provide insulating materials that have good insulating performance but have a low impact on the environment. [Means for solving the problem]

[0008] If existing buildings can be renovated without the need for major changes to their structure, this not only reduces the energy footprint but also reduces the consumption of materials used to rebuild the building. 50% of all raw materials are used for construction purposes. Upgrading the existing building stock to net-zero energy consumption levels would significantly accelerate energy savings in an environmentally friendly way.

[0009] The invention is based on the use of closed cell foam insulation, which has a very positive impact on the energy consumption of buildings.

[0010] According to the present invention there is provided a foam product as claimed herein.

[0011] The present invention relates to a foam product comprising an expanded foam having cells defined therein and a blowing agent held within said cells, wherein at least 5% by weight of said foam is formed from at least one component from renewable sources, and optionally wherein the foam product has an average thermal conductivity of less than or equal to 0.025 W / mK over a 25-year service life, as measured according to standards EN 12667 or EN 12939.

[0012] The at least one component from a renewable source may also form at least 5% by weight of the foamable composition from which the foam product is made. In general, the amount provided for the at least one component from a renewable source may also apply to the amount in the foamable composition from which the foam product is made.

[0013] A renewable source is a natural resource that can replenish itself for a limited time, which may be a few years or up to decades, but preferably within a few months.

[0014] Additionally or alternatively, the present invention relates to a foam product comprising an expanded foam having cells defined therein and a blowing agent held within said cells, wherein at least 5% by weight of said foam is formed from at least one component from renewable sources, and optionally wherein said foam product has an average thermal conductivity of less than or equal to 0.026 W / mK over a 50-year service life, as measured according to standards EN 12667 or EN 12939.

[0015] Additionally or alternatively, the present invention relates to a foam product comprising an expanded foam having cells defined therein and a blowing agent held within said cells, wherein at least 5% by weight of said foam is formed from at least one component from renewable sources, and optionally wherein the foam product has an average thermal conductivity of less than or equal to 0.025 W / mK over a 25-year service life, as measured according to standards EN 13166 and / or EN 14314.

[0016] Additionally or alternatively, the present invention relates to a foam product comprising an expanded foam having cells defined therein and a blowing agent held within said cells, wherein at least 5% by weight of said foam is formed from at least one component from renewable sources, and optionally wherein said foam product has an average thermal conductivity of less than or equal to 0.026 W / mK over a 50-year service life, as measured according to standards EN 13166 and / or EN 14314.

[0017] Additionally or alternatively, the present invention may relate to a foam product comprising an expanded foam having cells defined therein and a blowing agent held within the cells, wherein the foam is formed from at least one component from renewable sources, and wherein the foam has a total GWP (Global Warming Potential) for the Cradle-to-gate stages (A1-A3) of less than 1.0 kg-CO2eq / kg (measured according to standard EN16783:2017).

[0018] Additionally or alternatively, the present invention may relate to a foam product comprising an expanded foam having cells defined therein and a blowing agent held within said cells, the foam product comprising cardanol as a plasticizer, rosin, or a polyol derived from polyethylene terephthalate; polyurethane; and / or polyisocyanurate; or combinations thereof. Polyols are compounds containing at least two hydroxyl functional groups, aliphatic OH and / or aromatic OH.

[0019] Additionally or alternatively, the present invention may relate to a foam product comprising an expanded foam having cells defined therein and a blowing agent held within the cells, wherein at least 5% by weight of the foam is formed from at least one component from renewable sources, the at least one component comprising technical lignin derived from paper and pulp processing. For example, the technical lignin derived from paper and pulp processing may be kraft lignin, soda lignin, or lignosulfonate.

[0020] Additionally or alternatively, the present invention may relate to a foam product comprising an expanded foam having cells defined therein and a blowing agent retained within the cells, wherein at least 5% by weight of the foam is formed from at least one component from a renewable source, the at least one component comprising soda lignin.

[0021] Additionally or alternatively, the present invention may relate to a foam product comprising an expanded foam having cells defined therein and a blowing agent retained within the cells, wherein at least 5% by weight of the foam is formed from at least one component from a renewable source, and the at least one component comprises an organosolv lignin.

[0022] Additionally or alternatively, the present invention may relate to a foam product comprising an expanded foam having cells defined therein and a blowing agent retained within the cells, wherein at least 5% by weight of the foam is formed from at least one component from a renewable source, the at least one component comprising depolymerised lignin.

[0023] Additionally or alternatively, the present invention may relate to a foam product comprising an expanded foam having cells defined therein and a blowing agent retained within the cells, wherein at least 5% by weight of the foam is formed from at least one component from a renewable source, the at least one component comprising sulfonated lignin and / or phenolized lignin.

[0024] Additionally or alternatively, the at least one component comprises sulfonated kraft lignin.

[0025] The weight percent of sulfur in the sulfonated kraft lignin may be at least 2% by weight of the kraft lignin.

[0026] The sulfonated kraft lignin may have a weight average molecular weight (Mw) of 2,000 to 23,000 Daltons (Da).

[0027] The at least one component from a renewable source may include phenolized lignin. Without wishing to be bound by theory, the phenolized lignin may increase the reactivity of lignin during the manufacture of foam products. The phenolized lignin may include pyrolytic lignin, technical lignin derived from paper and / or pulp processes, soda lignin, organosolv lignin, depolymerised lignin, kraft lignin, or combinations thereof. When the at least one component from a renewable source includes phenolized lignin, the foam may be a phenolic foam.

[0028] The at least one component from a renewable source can include pyrolytic lignin.

[0029] Additionally or alternatively, the invention may relate to a foam product comprising an expanded foam having cells defined therein and a blowing agent retained within the cells, wherein the foam is formed from a reaction of a phenolic material with formaldehyde, and wherein at least 10% by weight of the formaldehyde used is bioformaldehyde, such as at least 20% by weight, for example at least 30% by weight, such as at least 40% by weight, desirably at least 50% by weight.

[0030] The bioformaldehyde can be produced from biomethanol. Optionally, the biomethanol is produced by fermentation of biowaste. The biomethanol can be produced from synthetic gas, for example, synthetic gas obtained by gasification of biowaste, such as forestry waste.

[0031] Additionally or alternatively, the invention may relate to a foam product comprising an expanded foam having cells defined therein and a blowing agent retained within the cells, the foam being formed from a reaction with phenol, wherein at least 10% by weight of the phenol is formed from biophenol, such as at least 15% by weight, such as at least 20% by weight, such as at least 25% by weight. The biophenol may be produced from biobenzene. The biophenol may be produced from biobenzene, optionally using pyrolysis of biowaste such as wood waste and wood-based materials including by-products of wood processing such as paper. The biobenzene may be made from tall oil.

[0032] It is understood that all of the components described above as components of the foam products of the present invention can be combined in any combination to form the foam products of the present invention.

[0033] Suitably, at least 7% by weight of the foam is formed from at least one component from renewable sources, such as at least 10% by weight, for example at least 15% by weight, desirably at least 20% by weight, optionally at least 25% by weight, for example at least 30% by weight.

[0034] Desirably, at least 70% of the blowing agents (based on the total weight of the blowing agents) have a gas phase thermal conductivity of 12 mW / mk or less, e.g., 11.8 mW / mk at 25° C. Suitable blowing agents are set out in the table of Figure 6, which may be used individually or in any suitable combination.

[0035] Optionally, the weight of the at least one component from a renewable source includes carbon, measured according to standard EN16640:2017, and is C 14 It is based on measurements.

[0036] The foam has a C content of more than 3% as measured according to standard EN16640:2017. 14Carbon content, e.g., greater than 3.5%, greater than 4%, greater than 5%, greater than 6%, greater than 7%, greater than 8%, greater than 9%, greater than 10%, greater than 30%, or greater than 50% C 14 Has a carbon content of more than 3% C measured according to standard EN16640:2017 14 Carbon content, e.g., greater than 3.5%, greater than 4%, greater than 5%, greater than 6%, greater than 7%, greater than 8%, greater than 9%, greater than 10%, greater than 30%, or greater than 50% C 14 The foam having a carbon content may be a phenolic foam.

[0037] Desirably, for all foam products of the invention, the average thermal conductivity of the foam product over a 25-year service life is less than or equal to 0.025 W / mK, measured according to standard EN 16783:2017; and / or the foam product has a 50-year average thermal conductivity of less than or equal to 0.026 W / mK, measured according to standard EN 16783:2017; and / or the total global warming potential of the foam product is equal to or less than 1.7 kg-CO2eq / kg, such as equal to or less than 1.5 kg-CO2eq / kg, such as equal to or less than -0.5 kg-CO2eq / kg, measured according to standard EN16783:2017; and / or the biogenic global warming potential of the foam product is equal to or less than -0.2 kg-CO2eq / kg, e.g. equal to or less than -0.4 kg-CO2eq / kg, measured according to standard EN16783:2017; and / or The foam-forming components in the foam product have a renewable primary energy supply equal to or less than 0.7 MJ / kg as measured according to standard EN16783:2017.

[0038] The biogenic global warming potential (GWP-biogenic) according to the standard EN15804+A2 describes the GWP from the removal of CO2 from all sources, except primary forests, to biomass as the transfer of carbon sequestered by living biomass from nature to the product system declared as GWP-biogenic. GWP-biogenic also describes the GWP from the transfer of biogenic carbon from the previous product system to the product system under study. The fossil global warming potential (GWP-fossil) according to the standard EN15804+A2 describes the GWP from the emission and removal of greenhouse gases to any medium resulting from the oxidation or reduction of fossil fuels or substances containing fossil carbon by their transformation or decomposition (e.g. combustion, incineration, landfill, etc.). GWP-fossil also describes the GWP from GHG emissions, e.g. from peat and "calcination", and GHG removal, e.g. from the carbonation of cement-based materials and lime.

[0039] The foam products according to the invention desirably exhibit a fire resistance in the single flame source test as defined in standard EN ISO 11925-2 with a flame height of <100 mm.

[0040] The foam product according to the invention has a closed cell content, measured according to standard EN ISO 4590, of at least 90%, such as at least 92%, for example at least 94%, optionally at least 95%.

[0041] The foam product according to the present invention desirably has a friability of less than 20% as measured by standard ASTM C421-08(2014).

[0042] The foam product according to the invention desirably has a compressive strength, measured according to standard EN826:2013, of 100 kPa or more.

[0043] The foam product according to the invention has a compressive strength of 10 kg / m2 as measured according to standard EN1602:2013. 3 ~125kg / m 3 density, for example, about 15 kg / m 3to about 100 kg / m 3 , preferably about 15 kg / m 3 to about 60 kg / m 3 , preferably about 20 kg / m 3 to about 35 kg / m 3 has a density of

[0044] The foam product of the present invention may be a phenolic foam product.

[0045] The foam products of the present invention may be polyisocyanurate (PIR) foam products, polyurethane (PUR) foam products, extruded polystyrene (XPS) foam products, or expanded polystyrene (EPS) foam products. Such foam products desirably include a lignin component as described herein.

[0046] The present invention also relates to the use of lignin as a color-imparting additive in a foam product comprising a foam having cells defined therein and a blowing agent retained within the cells, and / or the use of lignin as a color-stabilizing additive in a foam product comprising a foam having cells defined therein and a blowing agent retained within the cells.

[0047] The present invention also relates to a method for the preparation of long-lasting thermosetting foams with excellent thermal, mechanical and fire properties based on the use of natural polyphenols, in particular sulfonated lignin and / or phenolated lignin, and the use of formaldehyde produced from bio-methanol. The process includes a) preparing a prepolymer by condensing a mixture of fossil phenol monomers and at least one natural polyphenol, the at least one natural polyphenol being at least 20% by weight based on the total phenolic compound mixture, with formaldehyde in a ratio of 1:1.5 to 1:2.5, using 0.15 to 5% by weight of an alkaline catalyst, at a reaction temperature of 50°C to 100°C, b) adding one or more surfactants / emulsifiers and their mixtures at 2 to 10% by weight, c) adding one or more plasticizing additives (plasticizers) and their mixtures at 2 to 10% by weight, d) adding one or more nucleating agents and their mixtures at 0.1 to 2% by weight, e) adding one or more blowing agents and their mixtures at 1 to 10% by weight, f) adding 10 to 20% by weight of a curing agent, and g) a curing phase. All weight percentages (wt%) are relative to the total raw material input.

[0048] To assess the overall contribution of insulation materials to the environment, the entire life cycle of the product must be considered. The Environmental Product Declaration (EPD) according to standard EN16783:2017 defines rules for a specific product category for insulation products based on the rules for construction products established in standard EN15804:2012+A2:2019. These rules are therefore a measure of the impact of insulation products on the environment. The EPD according to EN15804:2012+A2:2019 must also comply with the requirements of ISO14044:2006+A1:2018, an international standard for life cycle assessment (LCA), and ISO 14025:2010 and ISO 21930:2017, international standards dealing with EPDs for construction products. These three standards, together with the more detailed requirements of EN15804:2012+A2:2019 / EN16783:2017 in terms of precise application of the LCA Life Cycle Assessment principles, make it possible to compare results for different insulation product types.

[0049] The EPD provides life cycle impact assessment (LCA) data for a product in a series of modules covering the different life cycle stages described in Figure 1.

[0050] The product phase (cradle to gate), modules A1-A3, are the most relevant phases to quantify the impact of renewable content on insulation products. Phases A4-A5 relate to the building construction process. The in-use phase (B1-B7) is not relevant for insulation. The end-of-life phase (C1-C4) and supplementary module D relate to the building demolition / insulation recycling.

[0051] The output parameters of the EPD can be divided into four different categories: core environmental impact indicators (Table 1), indicators showing resource use (Table 2), environmental information describing waste categories and output streams, and additional environmental impact indicators. [Table 1] Table 1: Core Environmental Impact Indicators in EN15804:2012+A2:2019

[0052] The indicator GWP-total expresses the total potential contribution to global warming in kg-CO2 per functional unit, also known as the declared unit.

[0053] In the range of modules A1-A3, an increase in the amount of renewable raw materials leads to a decrease in the GWP-total due to the amount of carbon embedded in said raw materials. [Table 2] Table 2: Resource use indicators in EN15804:2012+A2:2019

[0054] The indicator PERM quantifies the renewable primary energy resources used as feedstock, and PENRM quantifies the non-renewable primary energy resources used as feedstock. PERT and PENRT are the sum of primary energy from primary energy resources and primary energy resources used as feedstock. If the amount of renewable raw materials increases compared to the amount of non-renewable raw materials, the indicator PERM will increase and PENRM will decrease.

[0055] Both conventional PIR closed cell foam insulation and PF closed cell foam insulation are produced from raw materials that are mostly of fossil origin, and therefore the embedded CO2 and PERNT, expressed as contributions to GWP, are relatively high.

[0056] Renewable insulation materials derived from agricultural or forestry sources have a relatively low environmental impact during production compared to fossil-derived materials. It should be noted that the term "renewable" is used specifically in reference to the embedded energy and embedded carbon of these materials. Examples of renewable insulation materials are: [Table 3] Table 3: Thermal conductivity of renewable insulation materials

[0057] All of these materials have a relatively high thermal conductivity (λ), which means that to obtain sufficient thermal insulation performance, a relatively thick layer of the insulating material must be applied.

[0058] The thermal conductivity (lambda value) of closed cell foam insulation materials is significantly lower than these renewable insulation materials. Thinner insulation means less material is needed for insulation. This must be taken into account when comparing EPDs since functional units should be based on insulation performance rather than product weight or volume. [Table 4] Table 4: Typical thermal conductivities of closed cell foam insulation materials

[0059] The importance of insulation performance to the total GHG (greenhouse gas) footprint can be demonstrated with a concrete sandwich panel. As the insulation layer becomes thicker, the concrete inner and outer walls also need to be thicker to maintain the structural strength. For example, if the insulation layer increases from 12 cm to 18 cm, the concrete needs to be increased by approximately 10 mm. The total GWP of the concrete is 246 kg-CO2eq / kg. An increase of 10 mm increases the GWP of the building by 24.6 kg-CO2eq / kg, which is more than the total GWP of the insulation product.

[0060] Environmental product declarations according to EN 16783:2017 can be published by trade associations or producers (Table 5). [Table 5] Table 5: EPD results for several closed cell foam products

[0061] Comparing EPDs is not always easy. Functional units vary from insulation product to insulation product. From Table 5 we can see that Kooltherm phenolic insulation foam has a lower total GWP (8.4 kg-CO2-eq) compared to Recticel (11.4 kg-CO2-eq), Unilin (14.6 kg-CO2-eq) and the value claimed by the German trade association (11.2 kg-CO2-eq). Also, insulation performance can differ. For example, a PUR / PIR product with thermal conductivity of 0.022 W / mK and a thickness of 110 mm will have the same insulation performance as a PF foam with thermal conductivity of 0.020 W / mK and a thickness of 100 mm.

[0062] The indicator of renewable primary energy resources (PERM) used as raw materials for all foam products in Table 5 is less than 5 MJ for all products. This very low contribution is a result of the facer's contribution (block foams do not have a facer). The contribution of the foam can be neglected. The use of non-renewable primary energy resources (PENRM) used as raw materials for facer products is the lowest for Unilin products with 116 MJ. This is almost equal to Kooltherm foam, which has a value of 116 MJ. Considering the thermal insulation performance, Kooltherm products would be 10% better.

[0063] Comparing the EPDs of the two phenolic foams in Table 5, it is clear that the Kooltherm product has a significantly lower GWP environmental impact compared to the Safe R product. This difference is partially due to density differences. The zero value of PENRM for the Safe R product is presumed to be incorrect since it is technically not feasible.

[0064] The HFO-foamed Jackson XPS product with lambda value of 0.025 requires a 25% thicker insulation layer compared to the Kooltherm product. Assuming a linear increase in GWP as a function of thickness, the GWP is 19.5 kg-CO2 equivalent (15.6*0.025 / 0.020), more than twice as high.

[0065] Pentane-foamed XPS (FPX) has a lower GWP (11.3 kg-CO2 equivalent), but a higher λ. Assuming a λ of 0.035 W / mK, a 75% thicker insulation layer is required. Linearly interpolated, this implies a GWP of 19.8 kg-CO2 equivalent. In other words, the blowing agent has a limited effect on the EPD power data, but when the insulation performance is taken into account, XPS has a higher CO2 footprint in both cases.

[0066] The PENRM index for pentane and HFO foamed Jackon products is 145MJ and 154MJ at 80mm thickness respectively, which is higher than PIR / PUR and PF foams.

[0067] The environmental performance of PIR / PUR, PF and XPS insulation materials can be improved by increasing the renewable content of these products and by recycling the materials at the end of life stage. Creating circular business models is complicated by the fact that insulation materials often have a life cycle of more than 50 years. This relatively long product life makes it difficult to ensure recycling. Another complicating factor is contamination as a result of the demolition of buildings. For this reason, a 50 / 50 rule is often envisaged, where 50% can be recycled and the other 50% is either landfilled or incinerated in waste incinerators. In cases where the renewable content in a product is relatively high, the energy contribution of the renewable materials can be classified as green energy.

[0068] Phenolic foams are used in a wide variety of applications due to their excellent combination of thermal insulation and fire protection properties. Both the thermal insulation and / or fire protection properties of the product may be the main reason for selecting this insulation material. Examples of such applications include cavity wall applications, pipe insulation and internal wall applications. Suitable insulation foams meet the requirements of EN13166:2012+A2:2016 and EN14314:2015.

[0069] In cavity wall construction, the insulation board is installed against the internal wall. In most cases, the insulation board is fixed by screwing wall ties into the insulation. In a second step, the external wall is attached. In traditional cavity walls, a small air gap is maintained between the insulation board and the external wall to prevent moisture from entering the insulation from the external wall. Reflective foil facers (emissivity) combined with an air gap (e.g. 15mm or more) can also be used to improve the insulation performance. The advantage of a high-performance insulation material is that it minimizes the wall thickness. However, if renewable insulation materials are used, the environmental footprint of the building will be optimized. A material that combines both aspects would be the desired solution for this application.

[0070] Pipe insulation is used to limit energy losses in heating, ventilation and air conditioning systems (HVAC). The material is manufactured online in cylindrical form or cut into pipe sections from blocks. The inner diameter of the insulation product is dimensioned to closely fit the outer diameter of the pipe that transports the cooling / heating medium. The thickness of the insulation depends on the insulation requirements at the installation site. The outer surface of the foam can be provided with aluminum foil, which acts as a vapor barrier and prevents the accumulation of moisture inside the structure. When renovating buildings, space is often limited, so optimizing the insulation and environmental performance is essential.

[0071] Internal wall insulation is applied on the inside of a structure. This application is often used when renovating existing buildings, where the structure does not allow the application of insulation on the outside of the building. Since interior space in buildings is scarce, optimal insulation performance is often selected in combination with minimum thickness. The poor insulation performance of renewable insulation materials makes these products less preferred for this application.

[0072] Phenolic foams are produced by expanding and curing a foamable composition prepared by mixing a phenolic resin, a surfactant, a blowing agent and a catalyst. Other additives such as formaldehyde scavengers such as urea, plasticizers, flame retardants, neutralizing agents or pigments can be optionally mixed into the uncured phenolic resin.

[0073] Phenolic resole resins are used in the manufacture of phenolic foams. They are condensation polymers of phenol and formaldehyde and are produced under aqueous basic conditions with excess formaldehyde, generally at high temperatures. Generally, phenolic resins used in the manufacture of phenolic foams are viscous liquids with a water concentration of about 1-25% by weight. They have methylol groups as reactive substituents for condensation polymerization reactions. Crosslinked phenolic foams can be formed by heating and curing a mixture of phenolic resin, blowing agent, surfactant and acid catalyst. When an acid catalyst is added to a chemical mixture consisting of phenolic resin, blowing agent and surfactant, an exothermic reaction occurs between the methylol and phenolic groups, forming methylene bridges between the phenol rings. The methylene bridges crosslink the phenolic polymer chains and generate water of condensation polymerization. The chemical and physical properties of the resole resin composition, the amount and nature of the acid curing catalyst, the blowing agent and the surfactant present in the foaming reactant greatly affect the ability to control the exothermic reaction and form closed-cell foams.

[0074] The amount of water in the foam-forming reactants, and particularly the amount of water in the resin, can affect the amount and type of acid catalyst required to drive the reaction to completion.

[0075] Blowing agents with low thermal conductivity are used to form insulating foams. Since the gas volume of the foam can occupy up to about 95% of the foam's volume, the amount and nature of the blowing agent trapped in the foam has a significant effect on the insulating performance of the foam. A closed cell content of 90% or more is generally required to form insulating foams. One of the main determinants of the insulating performance of a foam is the ability of the foam's cells to retain the low thermal conductivity blowing agent.

[0076] The insulating properties of phenolic foam depend on the retention of the blowing agent, which has low thermal conductivity, in the closed cell structure formed during the formation of the phenolic foam. The key properties of phenolic foam are the foam cell size, which is preferably in the micrometer range, and the foam cells, which are uniformly distributed to provide a closed cell structure that enhances the insulating properties of the phenolic foam product through retention of the blowing agent.

[0077] Surfactants are commonly used in phenolic resin foamable compositions to promote the formation of cells that are more structurally stable and thus reduce the loss of blowing agent from the resulting foam over time. Surfactants can also aid in the emulsification of the blowing agent within the phenolic foam resin.

[0078] EPD is calculated for a 50 year lifespan. For this reason, aged thermal conductivity is of fundamental importance. The product standards for phenolic foam (EN13166:2012+A2:2016 and EN14314:2015) specify how to declare the lambda value for a 25 year lifespan. EPFA (European Phenolic Foam Association) publishes information that the performance of phenolic foam is maintained even after 50 years.

[0079] Bio-based products / materials are materials whose raw materials are entirely or partly derived from biomass. In this respect, the term "bio" is used in this specification to distinguish them from fossil resources. In particular, the present invention uses the term bio to refer to materials that are direct products from biomass or by-products from biomass. For example, by-products from papermaking are of interest. Papermaking involves the processing of wood (biomass). Desirably, the (renewable) content, e.g. the organic content, should be greater than 30% by weight.

[0080] The majority of raw materials used in the production of phenolic foams are based on fossil resources. The present invention relates to a foam product that combines excellent thermal and fire performance with renewable content. For example, at least 7% by weight of the foam body is formed from at least one component from renewable sources, for example at least 10%, for example at least 15%, desirably at least 20%, optionally at least 25%, for example at least 30%. The renewable content can be achieved by introducing bio-based formaldehyde (bioformaldehyde) to replace fossil-based formaldehyde. Furthermore, fossil-based phenol can be replaced with bio-based phenol and / or lignin, or a combination thereof.

[0081] The type of lignin used is very important since the addition of lignin generally results in the loss of desirable foam product properties, such as low thermal conductivity.

[0082] In the case of laminates, improvements can be achieved by using facers that are mainly made from renewable materials. In this invention, the term laminate is used for foam products that are generally produced in a laminator, for example between two belts. Typically, they are formed as continuous profiles (desired thickness and width) and cut to the desired length as formed. Generally, they are formed between an upper and a lower facer. When cut to discrete lengths, they are often called foam boards. Block foams are produced as large blocks and cut to the final desired shape after curing. In the case of block foams, an optional facer can be attached, for example to be attached to the product later.

[0083] The Global Warming Potential in the Environmental Product Declaration of the inventive foam products such as Phenolic / Lignin / Bioformaldehyde Foam Products for life stages A1-A3 (cradle to gate) is relatively low compared to conventional closed cell insulation materials. The resource utilization indicators for use in stages A1-A3 are significantly improved. The PERM indicator increases with decreasing PENRM values.

[0084] A high renewable content will have a positive impact on the environmental footprint. Insulation products have a relatively long service life, often more than 50 years. This means that the carbon is absorbed in the product over a very long period of time. This is important because biomass turnover is an important aspect, especially for slow-turnover biomass (e.g. forests). When using wood to generate energy, the released CO2 is captured by growing plants after spending some time in the atmosphere. During this period, the atmospheric CO2 has a warming effect. As a result of this time scale, it can be said that in the case of energy generation from wood, the net negative emission effect is not immediate, but is only achieved once the carbon is fixed back into the biomass.

[0085] If the insulation product is burned after the demolition of a building, for example in a cement kiln, the natural resource has the ability to regenerate before the product reaches its end-of-life stage. Even when using very slow turnover biomass, renewable resources have had the opportunity to regenerate. Therefore, high turnover biomass is preferred.

[0086] The GWP (Global Warming Potential) of foams such as PF foam depends on the contribution of different components in the product. Since phenol-formaldehyde resin is the main component of the foam-forming composition, it contributes more than 60% of the total product.

[0087] The density of foams, such as phenolic foam, also influences the GWP rating of phenolic foam products in EPDs. Figure 2 shows that the GWP decreases proportionally to the density of the product.

[0088] To eliminate the effect of density, the functional unit is 1 kg of insulation material. The graph in Figure 3 shows that the embodied energy of closed cell insulation and EPS is significantly higher than the other insulation materials on the graph.

[0089] The technical challenge is that in many cases, substitution of fossil-based raw materials results in a loss of performance or a commercially unviable product. The main challenge is to maintain insulation performance below the lambda of conventional renewable materials. Also, good fire performance is essential. These problems are solved by the present invention.

[0090] According to the present invention, the biomass is a mixture of phenols (optionally one or more of bio-based phenols (biophenols)); lignin; bio-based urea; bio-formaldehyde resins (optionally in combination with fossil raw materials); Foaming agent, Acid catalyst, Surfactants, and Optionally, other additives A phenolic / lignin / bio-based formaldehyde (bioformaldehyde) foam product is provided, the foam product being formed from a composition consisting of: The resin may include bio-formaldehyde produced from bio-methanol and / or bio-phenol, which may be produced from bio-based benzene, and the phenol may be partially or completely replaced with lignin.

[0091] The resulting product has a renewable content of at least 7% by weight of the foam formed from at least one component from a renewable source, such as at least 10%, such as at least 15%, desirably at least 20%, optionally at least 25%, such as at least 30%. By combining said bio-based components, the renewable content can be increased to at least 30%, 40%, or even at least 50% (all by weight). In the case of laminates such as phenolic foam boards, by proper selection of facers, the renewable content can even be increased to 70% by weight or more.

[0092] The renewable foam product-forming compositions of the present invention may include a phenolic and aldehyde resin having a molar ratio of phenolic groups to aldehyde groups in the range of about 1:1.5 to about 1:2.5, such as about 1:1.6 to about 1:2.4, including about 1:1.7 to about 1:1.2.3, such as about 1:1.8 to about 1:2.2.

[0093] The preferred aldehyde is formaldehyde produced from biomethanol. Biomethanol can be produced by fermentation or gasification of biomass. The maximum level of crops grown for energy production is limited to 75% by weight. At high levels of energy grown crops, the impact of fertilizer on the LCA of biomethanol will be negative.

[0094] Lignin is the most abundant source of naturally occurring phenolic substances, typically constituting 15-30% by weight of plant biomass. Unfortunately, lignin is in the form of a complex and intractable polymer embedded in the strong cell walls of plants. Thus, integrating this renewable resource into the chemical industry is a challenging task. A wide variety of lignins exist, each with its own unique properties depending on the type of biomass, the lignin isolation process, and downstream processing. There are two main groups of lignins: paper pulp lignins, which are recovered from the wastewater of the paper pulp process, and bio-refined lignins, which are the result of refining processes that treat biomass. An overview of the various lignins is provided herein.

[0095] Kraft lignin - The pulp and paper industry is the largest sector that handles lignin. By far the dominant chemical pulping process is kraft pulping, which produces over 90% of chemical pulp. In the kraft pulping process, (hemi)cellulose is separated from lignin in the so-called "white liquor". Kraft lignin can be recovered from black liquor waste streams. Depending on the industrial scale, different techniques are employed to separate the kraft lignin: simple acid precipitation and more advanced processes such as LignoBoost and LignoForce technologies.

[0096] Lignosulfonates - derived from sulfite pulp. Although the sulfite process is less commercially important than kraft pulp when considering the total world pulp production, lignosulfonates account for the largest amount of lignin traded worldwide. Lignosulfonates can also be obtained via sulfonation of isolated kraft lignin, for example by Ingevity (USA). In this way, the degree of sulfonation of the lignin can be adjusted independently of the pulp process.

[0097] Soda lignin - The third pulping method is named soda pulping. This process can be considered as a kraft pulping method without the use of sulfur-containing chemicals. The resulting soda lignin does not contain sulfur, but the absence of sulfide ions during the pulping step makes the process less efficient.

[0098] Hydrolyzed lignin - Cellulosic bioethanol is generally targeted via hydrolysis of the carbohydrate fraction of biomass, followed by enzymatic fermentation of the released sugars. The lignin fraction is recovered as a water-insoluble residue. These so-called "hydrolyzed lignins" are generally characterized by low purity and a high content of residual carbohydrates.

[0099] Organosolv Lignin - The raw biomass is treated with organic solvents, optionally containing water and / or catalytic amounts of acid / base. This treatment is carried out at elevated temperatures (100-210 °C) which results in solvolysis and extraction of the lignin. The lignin-containing liquid is then separated from the carbohydrate-rich pulp. Lignin can be isolated as a solid powder by solvent evaporation and / or precipitation in water.

[0100] Biomass solubilized lignin - produced through complete solubilization of biomass in a liquid medium, followed by selective precipitation of the main components of the biomass.

[0101] Depolymerized lignin - The pulping and biorefining processes mentioned above result in lignin polymers, often in powder form. There is growing interest in depolymerization of lignin in order to improve its value. Many depolymerization methods have been proposed, which can be classified by terms such as acid-catalyzed depolymerization, base-catalyzed depolymerization, oxidative depolymerization, reductive depolymerization, and thermal depolymerization. Depolymerized lignin consists of lignin oligomers, which have a lower average molecular weight compared to the parent material. Furthermore, depolymerized lignin can contain lignin monomers. The amount and structure of the monomers are highly dependent on the depolymerization technique and the feedstock.

[0102] Resin compositions such as phenolic resin compositions for forming foam products of the present invention may have a water content of about 4% to about 20% by weight, preferably about 5% to about 19% by weight, and preferably about 8% to about 19% by weight, based on the total weight of the phenolic resin, before curing the foam formed by the composition. The water content is measured by dissolving the resin in anhydrous methanol (manufactured by Honeywell Speciality Chemicals) in the range of 25% to 75% by weight. The water content of the resin, such as the phenolic resin, is calculated from the water content measured by this method. The apparatus used for the measurement was a Metrohm 870 KF Titrino Plus. Hydranal Composite 5 manufactured by Honeywell Speciality Chemicals was used as the Karl Fischer reagent for the water content measurement, and Hydranal Methanol Rapid manufactured by Honeywell Speciality Chemicals was used for the Karl Fischer titration. The titer of the Karl Fischer reagent was measured using Hydranal® Water Standard 10.0 manufactured by Honeywell Speciality Chemicals, Inc. The measured water content was determined by the KFT IPol method, and the titer of the Karl Fischer reagent was determined by the Titer IPol method set in the above-mentioned instrument.

[0103] Resins such as phenolic resins may have a viscosity of about 1,500 to about 200,000 cPs, preferably 1,500 to 100,000 cPs, preferably 1,500 to 50,000 cPs, preferably 1,500 to 25,000 cPs at 25° C. (cPs is centipoise). The viscosity of the resins employed in the manufacture of the foam products of the present invention can be determined by methods known to those skilled in the art, for example, using a Brookfield viscometer (Model DV-II+Pro) equipped with a temperature controlled water bath, maintaining the sample temperature at 25° C., spindle number SC4-29 rotating at 20 rpm or an appropriate rotational speed, while maintaining a torque in the mid-range that is acceptable for the viscosity measurement accuracy for the spindle type or appropriate test temperature.

[0104] The phenolic resin may have a low free formaldehyde content of about 0.1% to about 3.0% by weight of the phenolic resin, preferably about 0.1% to about 0.5% by weight of the phenolic resin, preferably about 0.1% to about 0.3% by weight of the total resin, as measured by potentiometric titration using the hydroxylamine hydrochloride method according to ISO 11402: 2004. A free formaldehyde content of about 0.1% to about 0.5% by weight of the total resin is desirable.

[0105] In one embodiment, the phenolic foam includes an organic modifier for co-acting with the phenolic resin. The modifier may include 1 to 10 parts by weight of a compound having an amino group per 100 parts by weight of the phenolic resin. In some cases, the compound containing at least one amino group is selected from urea, dicyandiamide, and melamine.

[0106] Surfactants affect the foam structure and are therefore used to provide stability to the foam cells. Surfactants act as surface active agents by lowering the surface tension of the phenolic resin liquid phase and by providing an interface between the highly polar phenolic resin and the relatively less polar blowing agent. The formation of closed cells is driven by the internal pressure due to the expansion of the blowing agent and countered by the surface tension of the phenolic resin liquid phase.

[0107] Preferably, the composition for forming the foam product of the present invention comprises a surfactant in an amount of from about 0.5 to about 10 parts by weight per 100 parts by weight of phenolic resin, preferably the surfactant may be present in an amount of from about 1 to about 8 parts by weight, such as from 2 to 6 parts by weight, for example from 3 to 5 parts by weight, per 100 parts by weight of phenolic resin.

[0108] The surfactant may be a castor oil-ethylene oxide adduct, for example, more than 20 moles and less than 80 moles of ethylene oxide are added per mole of castor oil. The surfactant may include a polysiloxane, where the polysiloxane has a molecular weight of about 10,000 to about 30,000 g / mol. The surfactant may be a combination such as a blend of the castor oil-ethylene adduct and the polysiloxane described above.

[0109] The composition from which the foam products of the present invention, such as the phenolic foam products of the present invention, are formed preferably includes a blowing agent.

[0110] The blowing agent may include C1-C7 hydrocarbons. C1-C7 hydrocarbons are advantageous as blowing agents because they have low thermal conductivity, can be used to form stable closed-cell foams with excellent thermal insulation performance, have low environmental impact, and are relatively low cost.

[0111] The blowing agent may comprise a C1-C7 hydrocarbon, the C1-C7 hydrocarbon comprising at least one of butane, pentane, hexane, heptane and isomers thereof. Preferably, the butane is isobutane or cyclobutane. Preferably, the pentane is isopentane or cyclopentane.

[0112] The blowing agent may be composed of a C2-C5 halogenated hydrocarbon, for example, the blowing agent may be composed of a chlorinated aliphatic hydrocarbon, for example, the blowing agent may be composed of a chlorinated aliphatic saturated or unsaturated hydrocarbon. Preferably, the chlorinated aliphatic hydrocarbon having 2-5 carbon atoms has 1-4 chlorine atoms. Preferably, the chlorinated aliphatic hydrocarbon having 2-5 carbon atoms is selected from the group consisting of dichloroethane, 1,2-dichloroethylene, n-propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, 1,1-dichloroethylene, trichloroethylene, and chloroethylene.

[0113] The blowing agent may include a halogenated hydroolefin. For example, the blowing agent may include a halogenated hydroolefin selected from the group consisting of hydrofluoroolefins and hydrochlorofluoroolefins. Halogenated hydroolefins are advantageous as blowing agents because they have low global warming potential and excellent heat insulating properties.

[0114] The blowing agent may be composed of a combination of the C1 to C7 hydrocarbon and the halogenated hydroolefin.

[0115] The blowing agent is selected from the group consisting of 1-chloro-3,3,3-trifluoropropene, 1-chloro-2,3,3,3-tetrafluoro-1-propene, 1,3,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,3,3-pentafluoro-2-propene, and combinations thereof.

[0116] The blowing agent may include 1-chloro-3,3,3-trifluoropropene, preferably trans-1-chloro-3,3,3-trifluoropropene or cis 1-chloro-3,3,3-trifluoropropene or a combination thereof, preferably trans-1-chloro-3,3,3-trifluoropropene.

[0117] The blowing agent can include trans-1,1,1,4,4,4-hexafluoro-2-butene, cis-1,1,1,4,4,4-hexafluoro-2-butene, cis-1-chloro-3,3,3-trifluoro-1-propene, cis-1-chloro-2,3,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene, 1,3,3,3-tetrafluoro-2-propene, 1,1,1,3,3-pentafluoro-1-propene, trans-1,2-dichloroethylene, or methyl formate, or a combination thereof.

[0118] The blowing agent may be comprised of a C1-C7 hydrocarbon selected from butane, pentane, hexane, heptane, and at least one of their isomers. The blowing agent may be comprised of an alkyl halide such as isopropyl chloride.

[0119] The blowing agents may include hydrocarbons as well as halogenated hydroolefins.

[0120] The blowing agent of the composition from which the foam product of the present invention is formed may comprise from 20% to 80% C1 to C7 hydrocarbons, based on the total weight of the blowing agent of said composition.

[0121] The blowing agent of the composition from which the foam product of the present invention is formed may comprise from 20% to 80% halogenated hydroolefin, based on the total weight of the blowing agent of the composition.

[0122] The blowing agent may comprise about 30% to about 50% by weight of 1-chloro-3,3,3-trifluoropropene and about 50% to about 70% by weight of C1 to C7 hydrocarbons, based on the total weight of the blowing agent.

[0123] Suitably, in compositions from which foam products of the invention are formed, such as phenolic foams optionally containing lignin, the blowing agent may be present in an amount of 1 to 20 parts by weight per 100 parts by weight of phenolic resin. Preferably, in compositions for forming foam products of the invention, the blowing agent is present in an amount of 5 to 15 parts by weight per 100 parts by weight of phenolic resin, such as 8 to 10 parts by weight of blowing agent per 100 parts by weight of phenolic resin.

[0124] The composition from which the foam products of the present invention are formed may include an acid catalyst, where the acid catalyst may be an organic acid or an inorganic acid or a combination thereof.

[0125] The acid catalyst may consist of an inorganic acid, such as sulfuric acid or phosphoric acid, or an organic acid, such as benzenesulfonic acid, xylenesulfonic acid, paratoluenesulfonic acid, naphtholsulfonic acid, phenolsulfonic acid, or the like, or a combination thereof.

[0126] The acid catalyst may be present in an amount of from about 1 to about 20 parts by weight of acid catalyst per 100 parts by weight of phenolic resin, preferably from 5 to 15 parts by weight of acid catalyst per 100 parts by weight of phenolic resin, and preferably from 8 to 10 parts by weight of acid catalyst per 100 parts by weight of phenolic resin.

[0127] In addition to the above, the foam may contain other additives such as plasticizers, inorganic additives, nucleating agents, microspheres, flame retardants, pigments, neutralizing agents, and the like.

[0128] The resulting product has a total GWP from cradle to gate (A1-A3) of less than 2.0 (<1.5;<1.0;<0,75;<0,5) kg-CO2-eq / kg of foam, calculated according to EN16783:2017, which defines specific product type criteria for insulation products based on the rules for all building products laid down in the standard EN 15804:2012+A2:2019.

[0129] PENRM will be reduced to below 27.5MJ / kg and PERM will be increased to above 1.5MJ / kg.

[0130] Advantageously, foam products such as the phenolic / lignin / bioformaldehyde foams of the present invention have a closed cell content of greater than 90%, preferably greater than 95%.

[0131] For laminated foam products such as phenolic foam boards, the declared thermal conductivity measured according to EN 13166:2012+A2:2016 (Method 2, Annex C) after aging at 70°C for 14 days, then at 110°C for 14 days, and conditioning to stable weight at 23°C / 50% RH to simulate average thermal performance after 25 years of application is less than 0.025 W / m·K, such as less than 0.022 W / m·K, such as less than 0.020 W / m·K, such as less than 0.018 W / m·K. To simulate performance after 50 years of application, the accelerated ageing at 110°C was extended to 4 weeks. Alternatively, the standard allows for aging at 70°C for 25 weeks, followed by conditioning at 23°C and 50% RH, thereby simulating the average value after 25 years of application (RH being relative humidity in this application).

[0132] For block foam products such as bio-phenol / lignin / bio-formaldehyde foam, the aged thermal conductivity measured according to EN14314:2015 (thermal aging B4, Annex B) after 25 weeks accelerated aging at 70°C and conditioning to stable weight at 23°C / 50%RH is less than 0.025 W / m·K, such as less than 0.022 W / m·K, such as less than 0.020 W / m·K, such as less than 0.018 W / m·K. 50 year thermal performance is simulated by aging for 50 weeks at 70°C followed by conditioning to stable weight.

[0133] The combination of excellent insulation performance and a low environmental footprint offers significant advantages over existing insulation products.

[0134] The foam products of the invention, such as the phenolic / lignin / bioformaldehyde foams of the invention, can have a pH of about 3 to about 7 as measured by EN 13468:2001(e). Foam products of the invention, such as the phenolic / lignin / bioformaldehyde foam products, having a pH in the range of about 3 to about 5 are beneficial because they are less likely to cause corrosion of metal surfaces in contact with the phenolic foam. Foam products with a pH below 3 can cause corrosion of metal surfaces.

[0135] The foam products of the present invention, such as the phenolic / lignin / formaldehyde (and / or combinations thereof) bio-based foam products of the present invention, have a foam density of about 10 kg / m2 as measured according to ASTM D1622-14. 3 to about 150 kg / m 3 of density, preferably about 15 kg / m 3 to about 60 kg / m 3 , preferably about 20 kg / m 3 to about 35 kg / m 3 It can have a density of about 10 kg / m 3 to about 100 kg / m 3 Foam densities in the range of m are lower density foams. 3This is advantageous because it contains a higher amount of blowing agent per unit area, which is desirable since the blowing agent has a large effect on the thermal insulating performance of the foam product.

[0136] The foam products of the present invention, such as the phenolic / lignin / formaldehyde (and / or combinations thereof) bio-based foam products of the present invention, can have a compressive strength of about 80 kPa to about 250 kPa, preferably about 100 kPa to about 175 kPa, as measured by EN826: 2013. A compressive strength of about 80 kPa to about 220 kPa is desirable because strong foams such as phenolic foams are resistant to compression damage when used as building insulation.

[0137] The foam products of the present invention, such as the phenolic / lignin / formaldehyde (and / or combinations thereof) bio-based foam products of the present invention, can have a friability of about 10% to about 50%, preferably about 10% to about 40%, as measured by ASTM C421-88. Low friability is desirable because foams such as phenolic foams are less prone to have surface dust and / or to fracture under stress.

[0138] The foam products of the present invention, such as phenolic / lignin / formaldehyde bio-based foam products, preferably have a foam density of 1 kg / m according to EN1609:2013. 3 and a water vapor transmission rate (μ) of 20 to 500 in accordance with EN12086:2013.

[0139] Block foams are generally produced without a facer. Laminated foam products, such as foam boards, are generally produced with a facer (also called a facing). The facing may be comprised of at least one of fiberglass nonwovens, spunbond nonwovens, aluminum foil, bonded nonwovens, metal sheets, metal foils, plywood, hemp, flax, kenaf, jute, calcium silicate boards, gypsum boards, kraft or other paper products, cork, and wood boards. Generally, the facings are applied to the top and / or bottom surfaces of the foam product as the foam product is formed. Generally, the same facings are used on these opposing surfaces of the foam product, although different facings may of course be employed.

[0140] To increase the renewable content of the product, preferred facer materials have a high renewable content, such as cellulose, hemp, flax, kenaf, and jute fibers.

[0141] The foam products of the present invention, such as the phenolic / lignin / bioformaldehyde foams of the present invention, can be used as insulation for buildings, facilities, and transportation. Examples of building insulation include flat roofs, pitched roofs, cavity walls, floors, interior walls, ETICS (Exterior Thermal Insulation Composite Systems), and weatherproof facades. Examples of utilities include heating systems, ventilation systems, and air conditioning systems (HVAC), and process equipment. Examples of transportation applications include refrigerated / freezer trucks and shipping containers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0142] The present invention relates to a foam product, for example based on phenol / lignin / bioformaldehyde resin, where at least 7% by weight of the foam, such as at least 10%, for example at least 15%, desirably at least 20%, optionally at least 25%, for example at least 30%, is formed from at least one component from renewable sources, which are non-fossil origin raw materials. The foam product of the present invention comprises the use of recycled, bio-based and mineral materials.

[0143] Phenolic resin-based foams are used as thermal insulation in construction and technical applications. These foams are produced based on water-based resols that are processed into foamed materials using surfactants, blowing agents and curing compounds in a continuous (and discontinuous) foaming process.

[0144] The actual manufacturing process of resole resins for thermal insulation foams consists of condensing phenolic compounds and formaldehyde in a ratio of 1.0:1.5 to 1.0:2.5 at elevated temperatures ranging from 50 to 100 °C with an alkaline catalyst ranging from 0.15 to 5.0% by weight, calculated on the total amount of phenol and formaldehyde. The condensation is stopped at the required viscosity ranging from 1500 to 50,000 mPa·s at 25 °C by neutralizing the mixture with an acid. In the final step, the water content of the final resin can be adjusted to the required level ranging from 5 to 20% by weight, either by adding water or by removing the water by distillation under vacuum.

[0145] The first monomer in the condensation polymerization reaction to produce phenolic resins is formaldehyde. It is produced from methanol. The Formox and Silver processes are used to convert methanol to formaldehyde on an industrial scale. In the Formox process, methanol is directly oxidized with air over a metal oxide catalyst at a temperature of 470 °C. 2CH3OH+O2 → 2CH2O+2H2O Excess heat is removed with an oil-transfer medium. The product gas is cooled and absorbed in water to obtain a 37% aqueous formaldehyde solution, the concentration of which can be increased by distillation.

[0146] The first step in the Silver process is the dehydrogenation of methanol: 2CH3OH → 2CH2O+2H2 Secondary combustion of hydrogen occurs: H2+(1 / 2)O2→ H2O The reaction takes place in air over a crystalline silver catalyst. The reaction is carried out at elevated pressure and at temperatures of 650-700 °C. A controlled amount of water is fed to the reaction. A 40-50% aqueous formaldehyde solution is obtained, concentrated, and purified by distillation.

[0147] Typically, for every kg of bioformaldehyde produced, approximately 1.04 kg of biomethanol is consumed. Electricity consumption is 0.15 kWh / kg. CO2 emissions are 0.11 kg-CO2 / kg of formaldehyde produced along with the generation of 2.3 kg of steam.

[0148] Approximately 80% of methanol (MeOH) is produced from natural gas. Approximately 17% of global methanol production is coal-based. A smaller percentage of methanol is produced from petroleum. Of the 75 million tons of methanol produced annually, 40% is consumed for energy uses (fuel).

[0149] Methanol can also be produced from alternative feedstocks, including biomass, waste and by-products from various sectors, such as biogas, wastewater, solid waste, glycerin (glycerol) from biodiesel production and black liquor from the pulp and paper industry.

[0150] Biomethanol (BioMeOH) from renewable resources and processes is chemically identical to fossil fuel-derived methanol, but can produce significantly reduced greenhouse gas emissions throughout its lifecycle. In this patent application, the term "Biomethanol" is used for both methanol produced from renewable resources and methanol produced from captured CO2.

[0151] FIG. 4 shows an outline of the synthesis pathway for biomethanol.

[0152] Bio-methanol production plant configurations / processes can be divided into several main types. The first process type is used to produce bio-methanol from biogas (which has some similarity to methanol production from natural gas). The second process type is a gasification to syngas process, which shows similarities to coal-based methanol production via gasification. The third process type uses wastewater streams from the kraft paper process. The fourth process produces bio-methanol from CO2 using renewable energy. Besides these processes, there are also hybrid and low-carbon methanol processes.

[0153] Biomethanol production from biogas has some similarities to methanol production from natural gas. Several types of substrates can be used for biogas production, such as biowaste, sewage sludge, liquid manure, co-fermentation of liquid manure and biowaste, grass, crops grown for energy production such as corn / grain, etc. (In this application, the term substrate as used in this context refers to the raw material / feedstock from which the components used in the present invention are derived).

[0154] The feedstock for fermentation is pretreated (shredding and size separation). The feedstock is mixed with process water and already fermented feedstock in a mixer. Through a heat exchanger, the mixture is pumped into the fermenter. The fermentation process is based on anaerobic thermophilic dry fermentation at 35-50 °C. The residence time in the fermenter is about 14 days. Biogas is generated during fermentation. The sludge from the fermenter is dewatered and the sludge can be used as fertilizer. The water can be used for agriculture. Typically, a water content of 0.1 Nm per kg of feedstock is required. 3 It is estimated that biogas will be produced.

[0155] Surprisingly, the biogas substrates used for the production of formaldehyde have a significant impact on the resulting LCA of formalin (formaldehyde is dissolved in water). Biogas derived from the digestion of crops grown for energy production has the highest scores for most presented non-biogenic emissions and land occupation. In most cases, it is the supply chain of crops grown for energy generation that dominates the emissions scores. This is a consequence of the fact that these input substrates are not modeled as by-products but as raw materials with assigned loads in the production of chemical substrates. Furthermore, the resulting process wastewater and subsequent water treatment dominate or contribute significantly to the SO2 and Biological Oxygen Demand (BOD) emissions of biogas. Emissions of organic water pollutants are measured by BOD, which refers to the amount of oxygen that will be consumed by bacteria in the water as they break down the waste.

[0156] For input substrates such as raw sewage sludge, fertiliser and pasture, all environmental burdens are allocated to other products and services, so that raw material inputs have the characteristic of having zero environmental burden.

[0157] Compared to natural gas, raw biogas is a heavy gas, containing non-flammable CO2 and water vapor. Table 6 below shows a typical composition of biogas: [Table 6] Table 6: Biogas composition

[0158] It is essential to remove H2S (hydrogen sulfide), CO2 and water. Biogas upgrading is carried out by Pressure Swing Adsorption technology (PSA). The raw biogas is first compressed and then led to the H2S removal reactor. H2S removal is based on the principle of decomposing H2S molecules on the surface of activated carbon at temperatures between 60 and 90°C. 2H2S+O2 → 2H2O+(1 / 4)S8 The sulfur is then adsorbed on the surface of the activated carbon. As a result, the H2S content in the biogas is reduced to 5 mg / Nm 3 The life of the removal adsorbent is about one year. In the subsequent conditioning system, the temperature of the biogas is reduced to about 20-30°C, and a dew point of about 3-5°C is obtained by low-temperature drying. This drying serves to protect the following components from corrosion:

[0159] The dry biogas, almost free of H2S, is then led to a four-bed pressure swing adsorption (PSA) plant for methane purification. Each adsorber in this plant operates in a four-stage cycle: adsorption, depressurization, regeneration, depressurization. The adsorber is fully regenerated by venting, so no replacement of the adsorbent is required.

[0160] 1m 3 To produce biomethane, typically 1.5 m 3 of biogas will be consumed.

[0161] The main processes for converting methane (CH4) to methanol are desulfurization, steam reforming, water-gas shift, pressure swing adsorption, methanol synthesis and purification. The first process step is desulfurization. This is followed by steam catalytic cracking (reforming) of biomethane. In this step, methane is first converted by steam into hydrogen (H2) and carbon monoxide (CO): CH4+H2O ←→ CO+3H2

[0162] In a simultaneous exothermic water-gas shift reaction, carbon monoxide and moisture are converted to carbon dioxide and hydrogen: CO+H2O ←→ CO2+H2

[0163] Pressure swing adsorption can be used, for example, to adjust the stoichiometry of the synthesis gas (H2 / CO ratio). Depending on the synthesis conditions (including reactor temperature, pressure, amount and type of catalyst), the process usually aims for a (H2-CO2):(CO+CO2) ratio of about 2:1. The synthesis gas thus produced is purified, compressed and converted to methanol by a catalyst. The catalytic system used for methanol synthesis is usually a mixture of copper, zinc oxide, alumina and magnesia. Recent advances have also brought the possibility of new catalysts made of carbon, nitrogen and platinum. The residue of the reaction is transferred to the product side by the temperature and high pressure. To produce 1 kg of methanol, it is typically necessary to consume 0.68 kg of methane. Commercial quantities of biomethanol produced from biogas are produced by commercial producers, such as BioMCN, New Fuel and Nordic green.

[0164] The main steps in the synthesis gas process are gasification, gas purification by reforming of higher molecular weight hydrocarbons, water-gas removal, hydrogenation and / or CO2 removal, and methanol synthesis and purification. The process has similarities to the production of methanol from coal. Pretreatment of the feedstock may be required, for example chipping or drying of woody biomass, or purification of liquid feedstock.

[0165] In the first step, the feedstock is gasified to synthesis gas (syngas), which is a mixture of primarily carbon monoxide (CO) and hydrogen (H2). This synthesis gas also contains CO2, moisture (H2O) and other hydrocarbons. The composition of the synthesis gas depends on many factors, including: 1.Gasification technology (fixed bed, fluidized bed, entrained flow, atmospheric or pressurized reactor, oxygen or air blown, direct or indirect heating of the gasification reaction) 2. Selection of various operating parameters: steam / biomass (S / B) ratio, equivalence ratio (oxygen ratio in the feed), temperature, and pressure. 3. Feedstock composition (ultimate chemical analysis, moisture content, etc.).

[0166] The use of limited amounts of oxygen during heating of the feedstock (i.e. above 700°C) improves the production of CO and H2 and reduces the amount of unwanted CO2 and H2O. However, when using air as the oxygen source, the increased gas flow rate through the equipment leads to higher investment costs. On the other hand, using pure oxygen is quite expensive and the energy consumption required for the process negatively affects the LCA of the resulting bio-methanol.

[0167] After gasification, impurities and contaminants are removed, and the gas goes through a conditioning process to obtain an optimal composition for methanol synthesis. The aim is to produce a synthesis gas with at least twice as many H2 molecules as CO molecules. The initial composition of the synthesis gas depends on the carbon source and the gasification method. The concentrations of CO and H2 can be varied in several ways. Firstly, raw synthesis gas can contain small amounts of methane and other light hydrocarbons with a high energy content. These are reformed to CO and H2, for example by high temperature catalytic steam reforming or autothermal reforming (ATR).

[0168] Second, the initial hydrogen concentration in the synthesis gas is usually too low for optimal methanol synthesis. To reduce the proportion of CO and increase the proportion of H2, the water gas shift reaction (WGSR) can be used to convert CO and H2O to CO2 and H2. CO2 can also be removed directly, for example by using chemical absorption with amines.

[0169] Gasification of 1 kg of mixed wood chips (dry material) in a typical fixed bed gasifier produces a net energy yield of 1.922 Nm 3 (net Nm 3 ) of synthesis gas is produced (273K, 1 atm). 3 is the standard m 3 ) The overall efficiency of the process is about 50%. The total CO2 emissions of a typical fixed-bed gasifier are 3 This amounts to 0.374kg-CO2 per unit.

[0170] A typical fluidized bed gasifier produces 1.545 Nm 3 (Standard m 3 ) of synthesis gas. The overall efficiency of the process is slightly higher, at about 53%. In the case of a fluidized bed gasifier, direct CO2 emissions are about 1 Nm 3 Therefore, from the viewpoint of LCA, the fluidized bed furnace is preferable.

[0171] Hydrogen can be produced separately and added to the synthesis gas. Industrial hydrogen is produced by steam reforming of methane or by electrolysis of water. Electrolysis is usually expensive, but can offer important synergies if the oxygen produced during electrolysis is used for partial oxidation in the gasification step, replacing the need for air or the need for oxygen production from air separation. However, from an environmental point of view, electrolysis only makes sense if renewable electricity is available. In many cases this is not the case, so the GWP contribution in the LCA of biomethanol is negatively affected.

[0172] After conditioning, the synthesis gas is converted to methanol by a catalytic process based on copper oxide, zinc oxide, or chromium oxide catalysts. Distillation is used to remove the water evolved during the methanol synthesis.

[0173] The technology used to produce methanol from biomass is relatively well known due to its similarity to the long-applied coal gasification technology. Technically, any carbon source can be converted into syngas. The main categories of feedstocks are municipal solid waste (MSW), agricultural waste, forestry waste / residues, black liquor from pulp processing, glycerin from biodiesel production, and bagasse (crushed sugarcane fiber from bioethanol production).

[0174] 7.13 Nm to produce 1 kg of bio-methanol 3of syngas needs to be generated. Direct CO2 emissions from the conversion of syngas to biomethanol are typically 2.76 kg-CO2 per kg of methanol.

[0175] According to (Althaus 2004), the overall heat demand for methanol synthesis from natural gas is 7.7-10.5 MJ / kg methanol. In the syngas-to-methanol process, the additional heat required in the syngas-to-methanol process brings the overall heat demand to about 9.5 MJ / kg methanol. This means that both processes are somewhat competitive in terms of energy efficiency.

[0176] Commercial quantities of biomethanol from gasification are produced, for example, by Enerkem.

[0177] Biomethanol can also be produced from waste products of the Kraft process for making paper. In sulfate pulping, wood chips are treated with chemicals (NaOH / NA2S) to separate the wood into its components: cellulose and hemicellulose (pulp) and lignin. Methanol is produced when the wood reacts with the chemicals.

[0178] After processing / cooking, chemicals, lignin, and other residues are washed from the pulp. This becomes black liquor, whose water content is reduced by evaporation. What remains is a condensate of methanol, turpentine, and sulfur compounds.

[0179] The condensate is washed for reuse in the mill, and then raw methanol, a mixture of combustible residues, is produced. Raw methanol can be burned to produce heat and energy, but it can also be used, for example, to produce formaldehyde. This energy can also be used to obtain commercial-grade bio-methanol. Approximately 10 kg of methanol can be produced per tonne of pulp.

[0180] Commercial grade methanol derived from the Kraft process is available, for example, from Sodra.

[0181] Besides bio-methanol from renewable sources, methanol can also be produced from captured CO2. CO2 can be captured from the atmosphere and from industrial exhaust streams. Power plants, steel mills, cement plants, and even volcanic activity produce CO2 that can be used as a source to produce methanol.

[0182] A key element of this technology is the presence of renewable energy. This renewable energy can be from any source (e.g., solar, wind, hydroelectric, geothermal). This energy is used to produce hydrogen from the electrolysis of water. By mixing CO2 and H2, a synthesis gas suitable for the production of biomethanol or e-methanol can be produced. (In the context of this invention, e-methanol is used to refer to methanol produced by a process that includes an electrolysis step, see for example FIG. 4).

[0183] Commercial quantities of e-methanol are produced, for example, by Carbon Recycling International.

[0184] Besides bio-methanol, hybrid and so-called low-carbon methanol are also commercially available. An example of this technology is the injection of sequestered CO2, for example from industrial facilities, into a conventional methanol synthesis route. This process significantly improves environmental performance. Another example is the extraction of CO2 from flue gases and reinjecting it into the methanol production, reducing GHG emissions and water consumption.

[0185] Commercial quantities of these grades are available from, for example, Methanex and QAFAC.

[0186] Most of the available biomethanol is used as fuel or for other energy uses. Renewable fuels significantly reduce greenhouse gas emissions. This includes reducing CO2 by 50-95% and NO xThese include reducing emissions by up to 80% and removing sulfur oxides and particulate matter.

[0187] Biomethanol from biogas is readily available on a commercial scale. Also biomethanol from gasification of woody biomass is available in large quantities. The availability of other sources, e.g. e-methanol, is low. When investigating the contribution of the different methanol production pathways, some surprising results were obtained: Biomethanol from mixed biogas increases the fossil GWP (1.07 kg-CO2eq / kg). The reason for this high value is that manure (from livestock) constitutes a significant part of the substrate. The GWP is not related to CO2, but to methane and N2O emissions (mainly from the digestion process).

[0188] In the case of crops grown for biogas production (e.g. rapeseed - vegetable oil), the contribution of the fertilizers used to grow the crop has a large impact on the fossil GWP. When more than 50% of the biomass is obtained from the waste stream, the GWP-fossil of the resulting biomethanol is comparable to fossil methanol.

[0189] However, by optimizing the chemical substrate for biogas fermentation, the contribution of fossil fuels can be reduced to approximately the same level as fossil methanol (0.6 kg-CO2eq / kg). Agricultural waste from the cultivation of food crops is of particular interest since all CO2 emissions are allocated to the food produced.

[0190] Even more surprising, the syngas route has a lower GHG footprint despite being relatively less efficient (around 50%), which could contribute to the feedstock of waste wood chips. [Table 7] Table 7: GWP of bioethanol

[0191] The GWP of methanol contributes more than 95% of the GWP of the formaldehyde produced.

[0192] The GWP-fossil can be improved if biogas from agricultural waste or pasture is used as substrate for digestion. Biomethanol from biogas is less favorable than biomethanol from gasification of biomass to syngas. Fixed-bed and fluidized-bed gasifiers have negligible GWP. The high GHG emissions of digestion are mainly a result of the production of chemical substrates and the treatment of biogas to increase methane levels.

[0193] To significantly improve the environmental footprint of novel insulation foams, the preferred option is to use bio-methanol, which has a lower fossil GWP than conventional methanol. In the final product (cradle to gate), a 10-20% reduction in total GWP can be achieved, from approximately 2.0 kg-CO2eq / kg to less than 1.7 kg-CO2eq / kg insulation foam. In substrates optimized for biogas digestion or syngas, 1.5 kg-CO2eq / kg can be achieved.

[0194] Phenol, the second monomer in the condensation, is produced from petrochemical precursors, mainly using cumene-based technologies. To produce phenol, fossil benzene and propylene are converted to cumene, which is subsequently converted to acetone, alpha-methylstyrene (AMS), and phenol. The main sources of fossil benzene are petroleum and natural gas. The fossil-GWP-total of conventional phenol is 1.79 kg-CO2eq / kg (CEFIC, European Chemical Industry Council, formerly known as Conseil Europeen des Federations de l'Industrie Chimique in France).

[0195] Several first generation bio-refineries are producing bio-benzene. Bio-based benzene can be produced from (animal) fats, fatty acid residues, edible oils and vegetable oils (palm, soybean, rapeseed).

[0196] Commercial quantities of biobenzene are available from, for example, Total (France), Versalis (Italy), INEOS (Germany) and Neste (Finland).

[0197] The schematic below shows a potential chemical pathway for producing biobenzene from bio-waste such as lignin. [ka]

[0198] As with biomethanol, the raw material is very important to minimize the environmental impact of the insulation product. Palm oil (or other vegetable oils) is a very common raw material for the production of biobenzene. However, the preferred route is to produce biobenzene from syngas, where wood or biowaste is used as substrate. More specifically, waste from the paper and pulp industry (tall oil, etc.). These biobenzene grades allow a significant reduction in the total GWP of the resulting product: [Table 8] Table 8: Impact of biobased phenols on GWP-total

[0199] By replacing 25% of the fossil phenol with biophenol, the total GWP of the phenolic insulation foam can be reduced to 1.7 kg-CO2eq / kg foam or less. At 50% replacement, the GWP is about 1.5 kg-CO2eq / kg foam. At 100% replacement, the total GWP of the foam can be reduced to 1.0 kg-CO2eq / kg foam or less.

[0200] The carbon footprint of the phenolic resin manufacturing process is mainly due to the raw materials used. The total carbon footprint for the production of 1 kg of resin is 0.072 g-CO2eq. See Table 9 below. [Table 9]

[0201] This is the result of an exothermic chemical reaction and does not require significant heating. Water is removed from the reaction by vacuum distillation. The energy consumed is actually used to cool the reaction mixture under vacuum reflux to a condenser in the reaction vessel.

[0202] To further reduce the GWP of the product, (bio)phenols can be replaced with natural, bio-based and therefore sustainable polyphenols found in nature, such as lignin, tannin, rosin, ...

[0203] Lignin is a high molecular weight aromatic structure found in plants that acts as a binder for (hemi)cellulose fibres. This lignin can be recovered from vegetation or biowaste by various techniques.

[0204] Lignin can be divided into sulfur-containing and sulfur-free lignins. The main classifications of lignins are shown diagrammatically in Figure 5.

[0205] The structure, composition and functionality of lignin depend on the origin of the feedstock (lignocellulosic) and the extraction and purification processes. Lignins extracted from waste streams of paper and pulp manufacturing are kraft lignin, soda lignin and lignosulfonates, depending on the pulping process. The pulping process focuses on the production of high quality cellulose pulp.

[0206] Biorefineries that convert biomass into biofuels also generate waste streams that contain lignins. These lignins are often referred to as organosolv lignins.

[0207] Other processes, such as biorefining processes, can also extract lignin directly from biomass, called hydrolyzed lignin. Such processes focus on the co-production of lignin, cellulose, and (fermentable) sugars.

[0208] The most common wood chemical pulping process today is the kraft pulping process, in which sodium sulfite is used under alkaline conditions. This process results in solubilized sulfur-containing lignin (1-3%), which is recovered from the black liquor. In 2020, several companies, e.g. LignoBoost, LignoForce, etc., produce kraft lignin using various separation processes.

[0209] The sulfite process is also widely applied in the production of pulp. In this process, an aqueous solution of sulfur dioxide forming H2SO3 is used at various pH values. Lignin from this process contains sulfonate groups (sulfonate groups are 3-8% by weight of the lignin). Most lignosulfonates are water soluble, thus making these lignins different from other types of lignins in terms of water solubility.

[0210] In the soda pulping process, sodium hydroxide is used instead of sodium sulfide to dissolve lignin from lignocellulosic materials such as annual fiber crops like flax, straw, and wood. The soda lignin is recovered by alternative recovery processes through acid precipitation, maturation processes, and filtration, resulting in sulfur-free lignin.

[0211] The organosolv pulping and / or fractionation process uses organic solvents (such as ethanol) to avoid the production of sulfur-containing by-products. Organosolv pulping or fractionation allows the production of both high quality cellulose and high quality lignin. The water-insoluble organosolv lignin is cleaner and contains a higher percentage of lignin than other extraction methods.

[0212] Biorefining processes consist of several different techniques, such as steam explosion and acid hydrolysis. The steam explosion process is used for fractionation of lignocellulose to produce cellulose, fermentable sugars and lignin. Woody biomass is pretreated with high-temperature and high-pressure steam, followed by rapid pressure release. The fiber network is broken down and liberated fibers and bundles are formed. In this process, the acid hydrolyzed lignin is extracted from the cellulose, mainly by solvents. As a result, the liberated lignin by steam explosion contains less carbohydrates and less wood-extracted impurities. Acid processes use acids, with or without steam, and are often applied to fractionate different types of biomass, for example agricultural wastes and tree species. All lignins are crude grade and can be used as is, but often require further fractionation, depolymerization, and chemical modification. Kraft lignin and lignosulfonates are widely used for industrial applications. [Table 10] Table 10: Examples of available lignin types

[0213] Lignins useful in the present invention can be utilized to replace at least 20% by weight of phenol in the synthesis of phenolic resins used in the manufacture of closed-cell phenolic insulation foams. Useful lignins can have one or more of the following characteristics: (i) their high purity, e.g., low carbohydrate, ash, S, ... content, (ii) their relatively narrow molecular weight distribution range, since they are a mixture of oligomers, and (iii) their sufficient number of chemical functional groups, resulting in favorable reactivity towards aldehydes.

[0214] These issues will affect the resin synthesis process since their water solubility will be different compared to phenolic monomers. Furthermore, the use of these resins may result in foams with reduced polymer strength. As a result, the foams will have poor mechanical properties, high friability and open cells, which means poor thermal insulation performance.

[0215] Further process modifications consisting of purification, fractionation, depolymerization, chemical modification, and combinations of these techniques are required to make lignin suitable for use in phenolic insulation foam applications.

[0216] Lignin can be refined to remove residual carbohydrates and to reduce the sulfur and / or ash content that would function as fillers in the final foam.

[0217] Lignin can be fractionated into narrow molecular weight ranges which will improve the homogeneity of the lignin.

[0218] Lignin can be depolymerized by cutting the polymer into smaller molecular weight fractions. Base- and acid-catalyzed depolymerization, enzymatic depolymerization and thermal (pyrolytic) depolymerization are some of the methods that can be used.

[0219] Lignin can be functionalized, a chemical modification that increases its reactivity in foam production, for example through techniques such as phenolization, methylation, glyoxalation, demethylation, and sulfonation.

[0220] Another object of the present invention is to use sulfonated kraft lignin to at least partially replace fossil-based materials, such as fossil-based phenols, in the synthesis of phenolic resins, such as resole phenolic resins, further increasing the bio-based content of the final insulation foam. [Table 10a] Table 10a: Examples of (commercially available) lignin types (and their sources)

[0221] Sulfonation of Kraft lignin is a separate process. The sulfonation step consists of a chemical reaction of lignin with sulfuric acid, resulting in the presence of sulfonic acid functional groups in the lignin structure. Kraft lignin is blended with 95-98% sulfuric acid. The chemical reaction is controlled by keeping the temperature in the range of 25-40°C. After sulfonation, the sulfonic acid functional groups are neutralized to alkali salts (e.g. potassium, sodium). The lignin is recovered by precipitation and washed with water to remove excess acid. The sulfonation process can be modified to obtain lignins with different degrees of sulfonation, expressed as the number of moles of sulfonic acid groups per 1000 unit weight of lignin. Schematically, it is represented as follows: Lignin +H2SO4 → Lignin-SO2-OH (sulfonation) Lignin-SO2-OH → Lignin-SO2-O-Na+ (neutralized with alkali)

[0222] Sulfonated kraft lignin is commercially available in industrial quantities and is supplied to the market by Ingevity.

[0223] It is a further object of the present invention to use phenolized kraft lignin to at least partially replace fossil-derived phenol in the synthesis of resins such as resole resins, further increasing the bio-based content of the final insulation foam.

[0224] The phenolization of kraft lignin is carried out in a separate process, although in practice there are two options: the one-stage process (OSP) or the two-stage process (TSP). The phenolization step consists of a chemical reaction of phenol with lignin under acidic conditions, increasing the amount of aromatic phenolic functional groups in the lignin. A schematic diagram of phenolized lignin is shown below: [ka]

[0225] The two-stage phenolization process consists of combining lignin with phenol and reacting at high temperature in the presence of an acid catalyst. The phenolized lignin is then recovered as a solid material by precipitation and purified by final washing or neutralization as required. The resulting phenolized lignin is used as a co-reactant with phenol in the synthesis of phenolic resins.

[0226] The one-step phenolization is carried out prior to resin synthesis, but both phenolization and resin synthesis can be performed in two consecutive steps in the same reactor. A portion of the required phenol is blended with lignin and heated under acidic conditions to initiate phenolization of the lignin. To stop further reaction, the acid catalyst is neutralized. An alkaline catalyst and water are then added to the remaining phenol. A condensation polymerization reaction is initiated by gradually adding formaldehyde. The reaction is stopped at the target viscosity by cooling and neutralizing with acid. This method omits purification and isolation of the phenolized lignin prior to resin synthesis.

[0227] A further objective of the present invention is to use pyrolytic lignin to partially replace fossil-derived phenols in the synthesis of resins such as Lysol resins, further increasing the bio-based content of the final insulation foam.The pyrolysis of biomass produces pyrolytic oil that can be fractionated into pyrolytic lignin and pyrolytic sugars.

[0228] A fast pyrolysis process is known in which organic matter is heated to 450-600 °C in an oxygen-free environment for a short period of time. Under these conditions, organic vapors, pyrolysis gases, and charcoal are produced. The vapors are condensed into bio-oil, typically with a yield of 60-75 wt.%.

[0229] The fast pyrolysis process is based on a rotating cone reactor, where biomass particles are fed near the bottom of the pyrolysis reactor together with an excess flow of hot carrier material, such as sand, where they are pyrolyzed. The steam produced passes through several cyclones before entering a condenser, where the steam is quenched by recycled oil. To significantly improve the environmental footprint of this novel insulation foam, the preferred option is to use biomethanol, which has a lower fossil GWP than traditional methanol. For the final product (cradle to gate), the total GWP can be reduced by 10-20%, from about 2.0 kg-CO2eq / kg to less than 1.7 kg-CO2eq / kg insulation foam. With optimal substrates for biogas digestion and / or syngas, even values ​​of 1.5 kg-CO2eq / kg can be achieved. The pyrolysis reactor is integrated into a circulating sand system. The system consists of a fluidized bed char combustor, a pyrolysis reactor and a riser that feeds a so-called "down-comer" that returns sand from the char combustor to the pyrolysis reactor. In this concept, char is combusted with air to provide the heat required for the pyrolysis process. Oil is the main product and the non-condensable pyrolysis gases are burned and can be utilized, for example, to generate additional steam. The excess heat can be used to dry the feedstock.

[0230] Due to the presence of large amounts of oxygen-containing components, the oil is polar and does not mix easily with hydrocarbons. Decomposition products from the biomass components include organic acids (such as formic and acetic acid) that lower the pH of the oil, typically to 2.9, and reduce its density to 1,170 kg / m 3 (hydrophilic) bio-oil, with a lower heating value of about 16 MJ / kg, has a typical moisture content of 15-35 w% and a kinematic viscosity of 1.3 cSt (40°C). Typical wood-derived pyrolysis oil contains 46 w% carbon, 7 w% hydrogen, <0.01 w% nitrogen, and 47 w% oxygen.

[0231] Pyrolysis oil is a mixture of decomposition components derived from the pyrolysis of the three basic components of biomass: cellulose, hemicellulose and lignin. Pyrolysis is a good pretreatment to facilitate the fractionation of biomass. After pyrolysis, the oil can be easily fractionated into three product streams: pyrolytic lignin (derived from lignin), pyrolytic sugars (derived from cellulose), and an aqueous phase containing small organic components such as acetic acid (mainly derived from hemicellulose).

[0232] Typical yields are 20-30 wt% pyrolytic lignin with a moisture content of about 10-11 wt%. The pyrolytic lignin obtained in this process is a highly viscous liquid. The pyrolytic sugars and small organic species can then be extracted from the remaining bio-oil obtained after pyrolytic lignin separation. Acetic acid can be produced from the aqueous phase by an extraction process followed by simple distillation.

[0233] Another unexpected benefit of the addition of lignin is the color change of the product. Phenolic foam is light pink in color after production. During the life of the product, the material turns brown in color. This color change is caused by oxidation, which has a darkening effect. This discoloration process is accelerated when the product is exposed to light (UV). This tendency to discolor is undesirable as the insulation product may visually look different, even though it retains its insulating properties.

[0234] The color can be changed to a yellowish color by modification with urea or alternative nitrogen-containing materials that can react into the matrix. Alternatively, colorants can be added to the phenolic foam. For example, a commonly used colorant is carbon black. Other colorants can also be used, but the selection is limited because many colorants interfere with the foam's cell formation, resulting in open cells and loss of thermal performance over time.

[0235] The use of lignin results in a stable light brown product with less color variation, which is color stable and allows the product to be distinguished from alternative conventional closed cell phenolic foam materials.

[0236] The greenhouse gas (GHG) emissions associated with the production of resin from bio-phenol and / or lignin and / or bio-methanol are estimated to be 0.0468 kg-CO2eq / kg resin, which is comparable to the production of fossil-based resins. The electricity consumed during this production is estimated to be 0.33 kWh / kg resin.

[0237] The impact of sequestered CO2 in the feedstock significantly contributes to the total GWP of the final product from cradle to gate (A1-A3), necessitating a shift to bio-based feedstocks to achieve significant GWP reductions.

[0238] A further object of the present invention is to use bio-based and / or recycled polyurethane foam based plasticizing additives to replace fossil-derived additives in foam processing formulations, further increasing the sustainable content of the final insulation foam.

[0239] Bio-based polyols can be produced from a variety of sources. They can be produced from bio-based phthalic anhydride, phthalic acid and terephthalic acid. Also high renewable content vegetable, rapeseed oil and epoxidized soy polyols are options, for example. Finally, e-polyols based on captured CO2 could also be an option to reduce GWP.

[0240] Using a glycolysis process, ground polyurethane foam waste is recycled for conversion with glycols and catalysts / additives into liquid polyols. The result of this process is that no further purification steps need to be used. These polyols act as plasticizers and can be used in foam formulations to form the foam products of the present invention.

[0241] The foam's chemical formulation has a relatively low plasticizer content and therefore a limited contribution to the total GWP. Nevertheless, this type of technology can be used to generate further reductions in GWP.

[0242] A further objective of this invention is to use blowing agents such as cyclopentane recovered from refrigeration applications to replace fossil-based grades in foam processing formulations, further increasing the sustainable content of the final insulation foam product.

[0243] The addition of solids to the foam, such as neutralizing agents, can affect the GWP value of the EPD. These solids are generally inert in the formulation and the maximum amount of solids is generally limited to 10 w% and often even less than 5 w% so that the overall impact on the GWP of the foam product's EPD is relatively limited.

[0244] Possible examples of bio-based neutralizing agents are seashells and / or eggshells. These types of materials contain sequestered CO2, for example in the form of CaCO3 / MgCO3 / Na2CO3 / .... The particulate form allows for dispersion in the foam-forming composition.

[0245] Flame retardants such as triethyl phosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCCP) or red phosphorus have a high GWP compared to other components and can have a large impact. For example, red phosphorus has a total GWP of 13.3 kg-CO2eq / kg.

[0246] By combining bioformaldehyde with phenolized and / or sulfonated kraft lignin and / or pyrolyzed lignin and / or biophenols in the resole resin synthesis process and processing the resole resin in the foam formulation with optional addition of surfactants / emulsifiers and / or recycled plasticizing additives and / or recycled blowing agents and / or mineral acids, it is possible to obtain insulation foams with a non-fossil content of more than 7% that almost completely match the thermal and mechanical performance of fossil phenolic insulation foams. In such products, at least 7% by weight of the foam is formed from at least one component from a renewable source, such as at least 10%, for example at least 15%, desirably at least 20%, optionally at least 25%, for example at least 30%.

[0247] A chemical formulation consisting of bioformaldehyde, phenolized lignin and / or sulfonated kraft lignin, and / or pyrolyzed lignin, and biophenols can be used to produce resol phenolic resins for foam insulation products. The final foam formulation will also contain surfactants / emulsifiers, plasticizing additives, (recycled) blowing agents, and acid catalysts, creating an insulation foam with a non-fossil content of more than 7% measured according to standard EN16640:2017, which matches the thermal and mechanical performance of almost completely fossil phenolic insulation foams.

[0248] More importantly, the achievable cradle-to-gate (A1-A3) GWPs are below 2kg-CO2eq / kg, 1kg-CO2eq / kg, 0.5kg-CO2eq / kg, and even 0.3kg-CO2eq / kg. The biobased content (or bio-attribution) can be increased up to 30-70%, respectively. Example type

[0249] The present invention is directed to two different types of foaming processes: the phenolic resin procedure followed by foaming process type A can be used to produce both discontinuous block foams and continuous foam laminates; process type B can be used to formulate continuous laminate foams. Working Example Section A

[0250] Examples A1 to A4

[0251] Comparative example Comp-A1

[0252] Commercially available fossil methanol produced from fossil methane with a GWP-fossil of 0.64 kg-CO2eq / kg was used to produce resole-type phenolic resin. The methanol was converted to an aqueous formalin solution by passing air through the heated methanol. The vapor mixture was introduced over a platinum-asbestos catalyst (300°C) to form a mixture of water (52%), formaldehyde (40%) and methanol (8%). Methanol was removed from the mixture by fractionation to obtain a formalin solution. The final purity of the formalin solution was 49 w% (storage at 50°C).

[0253] We used fossil phenol with a purity of 99%, produced from fossil benzene by the cumene process, and with a GWP-fossil of 1.79 kg-CO2eq / kg. Resin synthesis Comp-A1

[0254] A laboratory reactor is loaded with 659 g of fossil-based phenol (>99% purity), 68 g of water, and 26 g of 40% aqueous solution of potassium hydroxide (KOH). The mixture is brought to a temperature of about 60 °C. Over a period of 1-2 h, 647 g of 49 w% fossil-based formalin solution is gradually added while increasing the reaction temperature to about 80 °C. After the addition of the formalin, about 300 g of water is removed by vacuum distillation over a period of 1 h while maintaining the temperature at 55-80 °C. The resin viscosity is then measured every 15 min until the target viscosity (2,000 ± 500 mPa·s @ 25 °C) is reached. It is then neutralized with 1.6 g of 85% formic acid and cooled to room temperature.

[0255] Final resin properties: [Table 11] Table 11: Specifications of Resin Comp-A1

[0256] The GWP-total of the resulting resin is 1.5 kg-CO2eq / kg based on the Gabi-database (version: GaBi ts 9.2 Gabi ts 9.2 (Service Pack 39)). The Gabi-database contains raw material profiles that hold the environmental impact of the transformation of one substance to another. Using the Eco invent database, which is used in some countries, the GWP-total is 2.2 kg-CO2eq / kg. The Gabi-database is used because the profiles are generally up to date. Resin synthesis Comp-A2

[0257] It is identical to Comp-A1, except that the fossil-based formalin was replaced with bio-formalin produced from bio-methanol. The GWP-fossil of bio-methanol was approximately 1.07 kg-CO2eq / kg as a result of the substrate being market-mix biogas. In this application, the term "market-mix" biogas refers to commercially sold biogas (usually produced for fuel use) and includes a number of biogases from different sources. The GWP of such "market-mix" biogas is listed in Table 7 above. This market-mix biogas includes those produced from various sources (which may include sources other than those listed in Table 7), including the use of specially grown crops and fertilizers, which negatively impact the GWP. The GWP-Biogenic is approximately -1.38 kg-CO2eq / kg. The GWP-total of bio-methanol from market-mix biogas is -0.31 kg-CO2eq / kg. Resin Synthesis A1

[0258] It is identical to Comp-A1, except that the fossil-based formalin was replaced by bioformalin produced from biomethanol. The GWP-fossil of biomethanol was about 0.6 kg-CO2eq / kg, since the source was biogas. Biogas was produced by fermentation of biowaste (50% of the substrate in this case consisted of road grass). The GWP-total of biomethanol is -0.8 kg-CO2eq / kg (based on the GWP-biogenic of -1.38 kg-CO2eq / kg of biomethanol). Resin A1 has a GWP-fossil of 1,55 kg-CO2eq / kg, a GWP-biogenic of -0,44 kg-CO2eq / kg, a GWP-luluc of 0,03 kg-CO2eq / kg and a GWP-total of 1.14 kg-CO2eq / kg. Resin synthesis A2

[0259] It is the same as Comp-A1, except that fossil formalin was replaced with bioformalin produced from biomethanol derived from synthetic gas. The synthetic gas was produced by wood gasification, and the GWP-fossil was 0.3 kg-CO2eq / kg. The GWP-total of the biomethanol was -1.1 kg-CO2eq / kg (GWP-biogenic of biomethanol was -1.38 kg-CO2eq / kg). The GWP-fossil of Resin A2 was 1.45 kg-CO2eq / kg, the GWP-biogenic was -0.44 kg-CO2eq / kg, the GWP-luluc was 0.03 kg-CO2eq / kg, and the GWP-total was 1.04 kg-CO2eq / kg. Resin Synthetic A3

[0260] It is identical to Comp-A1, except that fossil phenol is replaced by biophenol produced from bio-naphtha. The source of bio-naphtha is tall oil (bioresistance from the paper and pulp industry). The GWP-fossil of biophenol is 1.79 kg-CO2eq / kg. The GWP-total of the resulting phenolic resole resin is -1.13 kg-CO2eq / kg (GWP-biogenic of biophenol is -2.81 kg-CO2eq). The GWP-fossil of resin A3 is 1.48 kg-CO2eq / kg, GWP-biogenic is -1.87 kg-CO2eq / kg, GWP-luluc is 0.03 kg-CO2eq / kg and GWP-total is -0.36 kg-CO2eq / kg. Resin synthesis A4

[0261] It is the same as Comp-A1, except that the fossil formalin was replaced by bioformalin produced from biomethanol. Biomethanol was produced from synthetic gas produced by wood gasification, and had a GWP-fossil of 0.3 kg-CO2eq / kg. The fossil phenol was replaced by biophenol produced from bionaphtha. The source of the bionaphtha was tall oil (bioresidue from the paper and pulp industry). The GWP-fossil of biophenol is 1.79 kg-CO2eq / kg. The GWP-total of the resulting phenolic resin is -1.57 kg-CO2eq. The GWP-biogenic of this resin is (based on -1.38 kg-CO2eq / kg of biomethanol and -2.81 kg-CO2eq / kg of biophenol). The GWP-fossil of Resin A4 is 1.39 kg-CO2eq / kg, the GWP-biogenic is -2.32 kg-CO2eq / kg, the GWP-luluc is 0.03 kg-CO2eq / kg, and the GWP-total is -0.90 kg-CO2eq / kg. Foaming Process A1

[0262] Load 368 g of Resin A1 into an empty beaker, add 16 g of surfactant (ethoxylated castor oil) with ethylene oxide degree 10-80 and 16 g of plasticizer (dimethyl phthalate) and mix uniformly (blend). Add 0.96 g of nucleating agent (perfluoro compound) and 22 g of blowing agent (mixture of cyclopentane and isopentane in ratio 70 / 30 wt%) and make a homogeneous blend. Hold this chemical blend at 20°C for 1-2 hours. Add 60 g of acid catalyst (mixture of 62.5 wt% sulfuric acid (50% solution) and 37.5 wt% phosphoric acid (85% solution)) to the phenol resole blend. Mix until a homogeneous mixture is formed and pour the reacting chemical mixture into a wooden mold (simulating a typical block foaming process) preheated to 70°C. Close the wooden mold and place in a preheated oven at 70°C for a minimum of 4 hours.

[0263] The foam is demolded. The foam is left to dry at ambient room conditions for one week to achieve a stable moisture content. Samples are then cut out and the foam properties are measured. Comparative Examples Comp-A1 and Comp-A2 and Examples A1 to A4:

[0264] Comparative foam samples Comp-A1 and Comp-A2 were made with resins made according to the methods of Resin Comp-A1 and Resin Comp-A2, respectively. The foams were made using Foaming Method A1. Foam Examples A1-A4 were made with resins made according to the methods of Resins A1-A4. The foams were made using Foaming Method A1.

[0265] The properties of these samples were measured and the results are shown in Table 12: [Table 12] Table 12: Properties of foam samples Comp-A1 to A4

[0266] The foam properties are not affected by the use of bio-based materials. However, a surprising finding is that only bio-waste produces GWP-total values ​​that are comparable to or smaller than the GWP-fossil values, and that the negative contribution of the GWP-biogenic in the final product (cradle-to-gate) actually results in a decrease in the GWP-total value: [Table 13] Table 13: Global warming potential of foam samples Comp-A1 to A4

[0267] The GWP-total of the foam includes a GWP-luluc of 0.1 kg-CO2eq / kg (GWP-luluc means Global Warming Potential (land use only) - see Table 1 above). For phenol and formaldehyde the GWP-luluc is less than 0.1 kg-CO2eq / kg. As bio-waste is used the land use is relatively low.

[0268] A combination of partial replacement of fossil phenol with biophenol and / or replacement of fossil formaldehyde with bioformaldehyde, or a combination thereof, can be used to achieve the desired total GWP of the product. The footprint is minimized by complete replacement with both biophenol and bioformaldehyde.

[0269] Global warming potential values ​​were determined using the Gabi database (version: Gabi ts 9.2 Gabi ts 9.2 (Service Packs 39)). Gabi ts 9.2 contains standardized profiles for phenol, formaldehyde and other substances in the formulation. From these profiles, the GWP-value of the resin was determined by using the data standard (RER) of the phenolic resin production. This result was then used to determine the value of the insulation foam. The calculations were performed with the software package Envision Web (version 5.0.0.82332bc) from the company Sphera Solutions GmbH.

[0270] The biocarbon content is calculated from the molecular weight of the ingredients and the molecular weight of carbon. For the final product, the dry core density is used to eliminate the influence of residual water in the product. The biocarbon content of 3% in Comp-A1 comes from ethoxylated castor oil and is determined by C14 measurement according to standard EN16640:2017.

[0271] Besides the Global Warming Potential, for insulation products there is the renewable primary energy resources used as raw materials (PERM; calculated according to standard EN16783:2017). The PERM is increased by including biophenol and bioformaldehyde in the formulation: [Table 14] Table 14: Global warming potential of foam samples Comp-A1 to A4

[0272] By including bioformaldehyde and / or biophenol, or a combination thereof, the PERM can be increased. In Example A4, the PERM is further increased to a value greater than that of the non-renewable raw material (PENRM). This is beneficial because it indicates that the depletion of fossil raw materials is significantly reduced. Section B Examples B1 to B4 Resin synthesis Comp-B1

[0273] A reaction vessel was charged with 500g ± 10g of fossil phenol, 10-40g of water, and 0.7-1.1g of 50% potassium hydroxide at 50°C. The temperature was raised to 70-76°C, and 650g ± 10g of 49% fossil formalin solution was added slowly over 1-2 hours to dissipate the heat of reaction exotherm. To cool the mixture, about 300g of water was removed by distillation under reduced pressure over 1 hour. The temperature was then raised to the range of 82-85°C and maintained in the range of 82-85°C until the viscosity of the resin reached 7,500mPa·s ± 1,500mPa·s. Cooling was commenced while 3g of 90% formic acid was added to neutralize the pH. When the temperature had dropped below 60°C, the following were added sequentially: 20-60g of polyester polyol plasticizer (preferably 25g), and 30-60g of urea (preferably 35g). Once the urea is dissolved, 20-60 g of ethoxylated castor oil (surfactant; preferably 30 g) is mixed at 30-40° C. The resulting phenolic resin comp-B1 contained 10-13 wt % moisture, less than 4 wt % free phenol, and less than 1 wt % free formaldehyde.

[0274] Resin synthesis Comp-B2 It is the same as Comp-B1, except that fossil formalin was replaced with bioformalin produced from biomethanol. The GWP-fossil value of biomethanol was about 1.07 kg-CO2eq / kg because the substrate was market mix biogas. The GWP-biogenic was about -1.38 kg-CO2eq / kg. The GWP-total of the biomethanol was -0.3 kg-CO2eq.

[0275] Resin synthesis B1 Same as Comp-B1, except that fossil formalin was replaced by bioformalin produced from biomethanol. The GWP-fossil of biomethanol was about 0.6 kg-CO2eq / kg as a result of the feedstock being biogas, but in this case the substrate for the biogas was biowaste (grass). The GWP-total of said biomethanol is -0.8 kg-CO2eq / kg (based on the GWP-biogenic of biomethanol being -1.38 kg-CO2eq / kg). The GWP-fossil of Resin B1 is 1.55 kg-CO2eq / kg, the GWP-biogenic is -0.44 kg-CO2eq / kg, the GWP-luluc is 0.03 kg-CO2eq / kg, and the GWP-total is -1.14 kg-CO2eq / kg.

[0276] Resin synthesis B2 It is the same as Comp-B1, except that fossil formalin is replaced with bioformalin to produce biomethanol from syngas. The syngas is produced by wood gasification, and has a GWP-fossil of 0.3 kg-CO2eq / kg. The biomethanol has a GWP-total of -1.1 kg-CO2eq / kg (based on the biomethanol's GWP-biogenic of -1.38 kg-CO2eq / kg). Resin B2 has a GWP-fossil of 1.45 kg-CO2eq / kg, a GWP-biogenic of -0.44 kg-CO2eq / kg, a GWP-luluc of 0.03 kg-CO2eq / kg, and a GWP-total of -1.04 kg-CO2eq / kg.

[0277] Resin Synthesis B3 It is the same as Comp-B1, except that the fossil phenol is replaced by biophenol produced from bio naphtha. The source of the bio naphtha is tall oil (bioresidue from the paper and pulp industry). The GWP-fossil of the biophenol is 1.79 kg-CO2eq / kg. The GWP-total of the resulting resin is -1.13 kg-CO2eq / kg (based on the GWP-biogenic of the biophenol being -2.81 kg-CO2eq). Resin B3 has a GWP-fossil of 1.48 kg-CO2eq / kg, a GWP-biogenic of -1.87 kg-CO2eq / kg, a GWP-luluc of 0.03 kg-CO2eq / kg, and a GWP-total of -0.36 kg-CO2eq / kg. Resin synthesis B4

[0278] Same as Comp-B1, except that fossil formalin was replaced by bioformalin produced from biomethanol. The biomethanol was produced from synthetic gas produced by wood gasification, and had a GWP-fossil of 0.3 kg-CO2eq / kg. The fossil phenol was replaced by biophenol produced from bionaphtha. The source of the bionaphtha was tall oil (bioresidue from the paper and pulp industry). The GWP-fossil of the biophenol was 1.7 kg-CO2eq / kg. Resin B4 had a GWP-fossil of 1.39 kg-CO2eq / kg, a GWP-biogenic of -2.32 kg-CO2eq / kg, a GWP-luluc of 0.03 kg-CO2eq / kg, and a GWP-total of -0.90 kg-CO2eq / kg. Foaming process B1

[0279] To 110±2 pbw (pbw=parts by weight) of resin B1 at 15°C-19°C, 10±1 pbw of isopropyl chloride / isopentane (iPC:iP) blowing agent (weight ratio 80 / 20) was added while mixing at 300±100 rpm at 1-3°C. Using a high speed mixer, 20±1 pbw of toluenesulfonic acid:xylenesulfonic acid catalyst in a weight ratio of 2:1 is quickly mixed into the resin blend at 8-15°C. High speed mixing at 1000-4000 rpm is used to achieve intimate mixing, thereby producing a foamable composition. The foamable resin composition is then discharged into a mold and foamed at a desired foam thickness, e.g., 20-200 mm, at a desired flow rate, e.g., 35 kg / m 3 The cured foam was removed from the mold and placed in an oven at 80-100°C for at least 8 hours. The foam was then left at room temperature for one week before being cut into samples for physical property measurements. Comparative Examples Comp-B1 and Comp-B2 and Examples B1 to B4:

[0280] Comparative foam samples Comp-B1 and Comp-B2 were made with resins made using the methods of Resin Comp-B1 and Resin Comp-B2. The foams were made using Foaming Process B1. Foam Examples B1-B4 were made with resins made according to the methods of Resins B1-B4. The foams were made using Foaming Process B1.

[0281] The properties of these foam samples were measured and the results are shown in Table 15: [Table 15] Table 15: Properties of foam samples Comp-B1, Comp-B2 and B1-B4

[0282] Again, foam properties are not affected when bio-based formalin and / or bio-based phenol are used. Also, thermal performance remains stable as a function of time, with the value after 4 weeks at 110°C being indicative of a 50 year average insulation value. The product standard allows for two sets of conditions for accelerated aging of the product (accelerated aging at 70°C and 110°C). The results are assumed to be equivalent in both cases. The impact on global warming potential is summarized in Table 16. [Table 16] Table 16: Global warming potential of foam samples Comp-B1 to B4

[0283] The GWP-total of foam includes a GWP-luluc of 0.1 kg-CO2eq / kg. The GWP-luluc of phenol and formaldehyde resins is less than 0.1 kg-CO2eq / kg (0.03).

[0284] The desired GWP of a product can be achieved by partial replacement of phenol with biophenol and / or formaldehyde with bioformaldehyde, or a combination thereof, however the footprint is minimized by complete replacement with both biophenol and bioformaldehyde.

[0285] Bio-based carbon content is calculated from the molecular weight of the ingredients and the molecular weight of carbon. In the case of bio-formaldehyde, the wt% of formaldehyde in the final product is divided by the molecular weight of formaldehyde (30.0 g / mol). Multiply the result by the molecular weight (12.0 g / mol) to get the bio-based carbon content. Divide this number by the total weight and multiply by 100% to get the bio-based carbon content.

[0286] For the final product, the dry core density is used, eliminating the influence of water. The bio-carbon content of 2% in Comp-B1 is the result of ethoxylated castor oil and is determined by C14 measurement according to the standard EN16640:2017 (Bio-based products - Bio-based carbon content - Determination of the bio-based carbon content using the radiocarbon method). This standard specifies the method for determining the bio-based carbon content in a product based on the 14C content measurement. This European standard also specifies two test methods used to measure the 14C content, from which the bio-based carbon content is calculated: - Method A: Liquid Scintillation Counter (LSC); - Method B: Accelerator Mass Spectroscopy (AMS). The bio-based carbon content is expressed by a fraction of the sample mass or as a fraction of the total carbon content. This calculation method is applicable to any product containing carbon, including biocomposites (products that are composites of resins and natural fiber reinforcements).

[0287] Besides the global warming potential, the renewable primary energy resources obtained from the raw materials used in insulation products (calculated according to standard EN 16783:2017) are increased by including biophenols and bioformaldehyde in the foam formulation: [Table 17] Table 17: Global warming potential of foam samples Comp-B1 to B4

[0288] Example B5

[0289] To further optimize the insulation performance, the blowing agent can be changed to an HFO with a very low thermal conductivity in the gas phase, e.g. HFO1233zd(E). Due to the limited amount of blowing agent, the contribution of said blowing agent to the total global warming potential is limited. The improvement of the insulation performance of the product can contribute to the reduction of the CO2 footprint of the product, since less insulation is needed to obtain the same insulation value. However, this effect is not visible when the functional unit is 1 kg of insulation product.

[0290] Example B5 is prepared with resin synthesis Comp-B1 and foaming method B1. However, for the blowing agent, instead of a mixture of isopropyl chloride (iPC) and isopentane (iP), a mixture of HFO 1233zd(E) and isopentane (95 / 5 wt%) was used. For foam sample B5, resin formulation B4 was used, in which phenol and formaldehyde were completely replaced by bio-based ones.

[0291] Comparative Example Comp-B3 was prepared in the same manner as Comp-B1, except that the blowing agent was changed to a mixture of HFO1233zd(E) and isopentane in the same ratio and amount as used in B5. The product properties are shown in Tables 18 and 19. [Table 18] Table 18: Properties of foam samples Comp-B3 and B5

[0292] The GWP-total of HFO1233zd(E) in the Gabi database (version: GaBi ts 9.2 Gabi ts 9.2 (Service Packs 39)) is 11 kg / CO2eq / kg, which means that the GWP-total of the product is negatively affected. [Table 19] Table 19: Global warming potential of foam samples Comp-B3 to B5

[0293] The GWP-total of the foam includes a GWP-luluc of 0.1 kg-CO2eq / kg. For the phenol and formaldehyde, the GWP-luluc is less than 0.1 kg-CO2eq / kg.

[0294] The thermal performance of B5 is higher than B4, so 10% less material is required. However, this effect is overridden by the increase in GWP total due to the addition of HFO. However, discussions are underway to update the profile of HFO in the Gabi database. If this new profile is adopted, the GWP of HFO will decrease from 11 kg-CO2eq / kg to 3 kg-CO2eq / kg. In that case, the increase in GWP-total as a result of the addition of HFO will be 0.2 kg-CO2eq / kg, making the addition of HFO possible.

[0295] The thermal performance increases by 10%, but the GWP-total expressed per kg of foam does not increase to the same extent when compared to B1-B4. The same is observed when comparing foam formulations of section A and section B. The thermal conductivity (lambda value) of sample Comp-A1 after 50 weeks of aging at 70°C, which simulates the average thermal performance of the product over 50 years, is less than 0.026 W / mK. This is well below any bio-based insulation material, as shown in Table 3. The product foamed with cyclopentane-isopentane blowing agent has a total GWP of 2.0 kg-CO2eq / kg (cradle-to-gate). Comparing comp-A1 with comp-B1, the thermal conductivity (lambda) value after 4 weeks of aging at 110°C (which is equivalent to 50 weeks of aging at 70°C), which simulates the average performance of the foam product over 50 years, is less than 0.021 W / mK. This effect can be largely attributed to the blowing agent, which in this example is a mixture of isopropyl chloride and isopentane. It is interesting to note that the total GWP does not increase significantly. However, the insulation performance is improved by 25%, which means that the CO2 footprint to achieve the same insulation performance is significantly better. The difference is smaller when using HFO blowing agents. Based on these findings, at least 70% of the blowing agent should be composed of components with a gas phase thermal conductivity of 12 mW / mk or less at 25°C. Preferably, it is 11.8 mW / mk or less. Resin Synthesis C1 and D1

[0296] The preparation of resin types C1 and D1 is the same as resin type B4 with the following exceptions: For resin C1, the amount of formalin was reduced to 585 g of 49 w% formalin, resulting in a F / P-molar ratio of 1.8:1. After formalin addition, 270 g of water is removed by vacuum distillation. The amount of urea was reduced to 30 g. For resin D1, the amount of 49 w% formalin was increased to 715 g, resulting in a F:P-molar ratio of 2.2:1. In this preparation, 330 g of water is removed by vacuum distillation. The amount of urea was increased to 69 g.

[0297] These samples were foamed according to foam preparation Comp-B1 and the foam properties of these samples are shown in Table 20. [Table 20] Table 20: Characteristics of samples C1 and D1

[0298] Further changes in the F / P-molar ratio do not substantially change the CO2 footprint of the product, because the total GWP of biophenol and bioformaldehyde is of the same magnitude in this case when biowaste is selected as the raw material source. However, an increase in the F / P-molar ratio to 2.5:1 in the product has a negative effect on the thermal and fire performance. [Table 21] Table 21: Global Warming Potential of Foam Samples C1, B4 and D1

[0299] The GWP-total for foam includes a GWP-luluc of 0.1 kg-CO2eq / kg. The GWP-luluc for phenol and formaldehyde is less than 0.1 kg-CO2eq / kg.

[0300] When both phenol and formaldehyde are biobased, the change in F:P molar ratio does not have a significant impact on the total GWP of the insulation foam. When only partial substitutions or combinations of substitutions are used, the F:P molar ratio can be a factor to consider. Increasing the molar ratio of phenol to formaldehyde will result in an increase in the renewable weight content.

[0301] Varying the F:P molar ratio does not significantly affect PENRM.

[0302] Example E1 - Use of sulfonated kraft lignin

[0303] Resin Synthesis E1

[0304] The process was the same as described in Resin Preparation Example comp-A1, except that 20% by weight of the phenol input was replaced with sulfonated kraft lignin (Reax 100M, supplied by Ingevity). Two additives, an ethoxylated castor oil surfactant and dimethyl phthalate, were added during the cooling stage of the resin synthesis in the same ratios as described in Example comp-A1.

[0305] Reax 100M is a sulfonated kraft lignin with a molecular weight of about 2000 D. The molecular weight (Mw) of a molecule / atom is usually expressed in g / mol. However, in biochemistry and polymer chemistry, the unit Dalton (D or Da) is more often used instead of g / mol, but both units are the same: 1g / mol=1D or Da. Polymers like lignin are not well-defined chemical structures and do not have a well-defined molecular weight like, for example, water or sulfuric acid. Such compounds contain molecules that are very similar but have different molecular weights. In the case of such compounds, one must speak of a molecular weight distribution. To convert this distribution into a single number, two expressions are often used: 1) Mw = weight average molecular weight, which is the arithmetic average molecular weight. 2) Mn = number average molecular weight, taking into account the number of molecules with a certain molecular weight (weighted average). The molecular weight of such compounds is measured by GPC (Gel Permeation Chromatography). The compound is solubilized in a solvent and guided onto a porous gel. The higher the molecular weight, the longer it takes to pass through the gel column of the GPC instrument. The retention time is directly related to the molecular weight and can be determined by calibrating with compounds of known molecular weight.

[0306] The sulfonation degree is about 3.4. The sulfonation degree is measured as the input of the sulfonation process. A sulfonation degree of 1.5 means that 1.5 moles of sulfonic acid are added to 1 kg of lignin for sulfonation. (The total sulfur content is the sum of the added sulfur and the amount of sulfur added in the sulfonation.)

[0307] The cation used is sodium.

[0308] The properties of the final resin are shown in Table 22: [Table 22] Table 22: Resin properties of Example E1

[0309] Foaming process E1

[0310] 400 g of the above resin is filled into a can, and 0.96 g of a nucleating agent (perfluoro compound) and 22 g of a blowing agent (a mixture of cyclopentane and isopentane in a ratio of 70 / 30 by weight) are added and mixed to obtain a homogeneous phenolic resol blend. This chemical blend is kept at 20°C for 2 hours.

[0311] 60 g of curing acid (a mixture of sulfuric and phosphoric acids) is added to the phenolic resole blend, mixed for 20 minutes, and the reaction mixture is poured into a wooden mold preheated to 70° C. The mold is placed in a preheated oven at 70° C. for 4 hours.

[0312] After 4 hours of curing, the foam is demolded and left for 1 week at room conditions (i.e. temperature and relative humidity) before being cut into 80 mm thick samples for measurement of physical properties.

[0313] Comparative foam example Comp-E1 was prepared in the same manner as comparative foam example Comp-A1. [Table 23] Table 23: Foam properties of sample E1 with 20% replacement of phenol with Reax 100M

[0314] Example E2 - Use of sulfonated kraft lignin (2)

[0315] Resin synthesis E2

[0316] The process was the same as described in Resin Preparation Example Comp-A1, except that 20% of the input phenol was replaced with sulfonated Kraft lignin (Kraftsperse 25M from Ingevity). Two additives, ethoxylated castor oil and dimethyl phthalate, were added in the same ratios as described in Comp-A1 during the cooling stage of the resin synthesis. Kraftsperse 25M is a sulfonated Kraft lignin, with a molecular weight of about 4400 D and a degree of sulfonation of about 2.9. The cation used was sodium.

[0317] The final resin properties are shown in Table 24: [Table 24] Table 24: Resin properties of Example E1

[0318] The resin was foamed using the same foaming step E1.

[0319] Comparative Example Comp-E2 was prepared in the same manner as Comparative Example Comp-A1.

[0320] The product properties are shown in Table 25: [Table 25] Table 25: Foam properties of sample E2 with 20% replacement of phenol with Kraftsperse 25M

[0321] The introduction of sulfonated kraft lignin does not adversely affect physical properties such as density, insulating capacity, compressive strength, or crushability.

[0322] Example F1 - Use of sulfonated kraft lignin (2)

[0323] Resin Synthetic F1

[0324] The process was identical to that described in Comparative Example Comp-B1, except that 20% of the input phenol was replaced with sulfonated kraft lignin (Kraftsperse 25M supplied by Ingevity).

[0325] The obtained phenolic resin composition ResinF1 contained 10 to 13 wt % water, less than 4 wt % free phenol, and less than 1 wt % free formaldehyde.

[0326] Foaming process F1

[0327] The foaming process is the same as B1.

[0328] Comparative Example Comp-F1 was prepared in the same manner as Comp-B1. [Table 26] Table 26: Foam properties of sample F1 with 20% replacement of phenol with Kraftsperse 25M

[0329] Comparative Example comp-E3 - Use of sulfonated kraft lignin (3)

[0330] Resin synthesis comp-E3

[0331] The same process as described in Comparative Example comp-A1, except that 20% of the input phenol was replaced with sulfonated kraft lignin (Hyact, provided by Ingevity). Two additives, an ethoxylated castor oil surfactant and dimethyl phthalate, were added at the cooling stage of the resin synthesis in the same ratios as described in Comparative Example A1. Hyact is a sulfonated kraft lignin with a molecular weight of about 23000 D and a degree of sulfonation of about 0.8. The cation used was sodium.

[0332] Final properties of said resin: [Table 27] Table 27: Resin properties of Comparative Example E3

[0333] Foaming process Comp-E3 : Same as Example E1

[0334] Comparative Example E4 - Use of Sulfonated Kraft Lignin (4)

[0335] Resin synthesis Comp-E4

[0336] The same process as described in Comparative Example A1, but replacing 20% ​​of the input phenol with sulfonated kraft lignin (Polyfon from Ingevity). Two additives, ethoxylated castor oil surfactant and dimethyl phthalate, were added already at the cooling stage of the resin synthesis in the same ratios as described in Comparative Example A1. Polyfon is a sulfonated kraft lignin with a molecular weight of about 4300 D and a degree of sulfonation of about 0.7. The cation used is sodium.

[0337] Final properties of said resin: [Table 28] Table 28: Resin properties of Comparative Example E4

[0338] Foaming process Comp-E4 : Same as comparison example Comp-E1

[0339] The properties of comparative foam samples comp-E3 and comp-E4 are shown in Table 29: [Table 29] Table 29: Product characteristics of comparative examples comp-E3 and comp-E4

[0340] Comparative experiments comp-E3 and comp-E4 show that phenol can be replaced by sulfonated lignin, but long-term insulation performance and crushability are compromised compared to fully phenolic-based foams. A condition for good performance is the use of sulfonated kraft with a high degree of sulfonation (moles of sulfonic acid groups per 1,000 unit weight of lignin) of at least 1.5. The molecular weight can vary widely, from 2,000 to 23,000 D. [Table 30] Table 30: Properties of sulfonated lignin

[0341] Mechanical properties such as friability and compressive strength can be modified by the choice of surfactant and / or plasticizer. In Example E3, the surfactant is modified to improve friability.

[0342] Example E3 - Use of sulfonated kraft lignin (5)

[0343] Resin synthesis E3

[0344] The same process as described in comparative example comp-E2, where 20% of the phenol was replaced with sulfonated kraft lignin (Kraftsperse 25M from Ingevity).

[0345] Final properties of said resin: [Table 31] Table 31: Resin properties of Example E3

[0346] Foaming Process E3

[0347] Load 368g of the above resin into a 1 liter can and add 16g of surfactant (Silicone Surfactant Niax L5356) and 16g of plasticizer (Dimethyl Phthalate) and mix to a homogenous resole blend. Add 3.0g of nucleating agent (Perfluorinated compound) and 22g of blowing agent (70 / 30 wt% mixture of cyclopentane and isopentane) and mix to a homogenous blend. Hold this chemical blend at 20°C for 2 hours.

[0348] 60 g of hardening acid (a mixture of sulfuric and phosphoric acids) is added to the resol blend, mixed for 20 minutes, and the reacted mixture is poured into a wooden mold preheated to 70° C. The mixture is covered with a floating lid and placed in a preheated oven at 70° C. for 4 hours.

[0349] After 4 hours of curing, the foam is demolded and left at room temperature for one week, after which samples are cut out and their physical properties are measured.

[0350] The properties of comparative foam sample E3 are shown in Table 32: [Table 32] Table 32: Product characteristics of Example E3

[0351] Example G1 - Use of phenolized kraft lignin

[0352] Resin Synthetic G1

[0353] The same process as described in comparative example Comp-A1, but with 20% of the input phenol replaced by phenolized kraft lignin (BioPiva from UPM). Two additives, ethoxylated castor oil surfactant and dimethyl phthalate, were already added at the cooling stage of the resin synthesis in the same ratios as described in example Comp-A1.

[0354] BioPiva is phenolized using sulfuric acid prior to resin synthesis. The molecular weight does not change during phenolization (3000 to 3500 D). The phenolization process increases the aromatic OH level to approximately 4 to 6 mmol / g.

[0355] Final properties of said resin: [Table 33] Table 33: Resin properties of Example E3

[0356] Foaming Process G1 : Same as comparative example Comp-A1

[0357] Comparative Example Comp-G1 was prepared in the same manner as Comp-A1.

[0358] The properties of foam sample G1 and comparative foam sample Comp-G1 are shown in Table 34: [Table 34] Table 34: Product Properties of Example G1 BioPiva Phenolic Kraft Lignin

[0359] Example G2 - Use of phenolized kraft lignin (2)

[0360] Resin synthesis G2

[0361] Lineo Classic lignin, supplied by Stora Enso, a portion of the phenol and an acid catalyst are loaded into a laboratory reactor and phenolization is carried out. Phenolation is terminated by placing the mixture in an alkaline environment. The remaining phenol and water are added and the temperature and meter are gradually adjusted to keep all the formalin at the reaction temperature of about 80°C while the excess water is removed by distillation. Once the target MW is reached, neutralize with 85% formic acid and begin cooling to about 50°C. Water is added to correct the specification on water level and further cool to room temperature. Two additives, ethoxylated castor oil surfactant and dimethyl phthalate, are added during the cooling stage of the resin synthesis in the same ratios as described in Example Comp-A1.

[0362] Final properties of said resin: [Table 35] Table 35: Resin properties of Example G2

[0363] Foaming Process G2 : Same as comparative example Comp-A1

[0364] Comparative Example Comp-G2 was prepared in the same manner as Comp-A1.

[0365] Characteristics: [Table 36] Table 36: Product Properties Example G2 Phenolic Lineo Classic Lignin

[0366] To obtain a foam with the desired properties, the total phenolic OH should be at least 3 mmole / g. [Table 37] Table 37: Product Properties Example G2 Phenolic Lineo Classic Lignin

[0367] Example G3 - Use of phenolized kraft lignin (3)

[0368] Resin synthesis G3

[0369] The same process as described in Example G2, except that the addition of both the surfactant and the plasticizer was omitted.

[0370] Final properties of said resin: [Table 38] Table 38: Resin properties of Example G2

[0371] Foaming Process G3

[0372] Load 368g of the above resin into a 1 liter can and add 16g of surfactant (Silicone Surfactant Niax L5356) and 16g of plasticizer (Dimethyl Phthalate) and mix to a homogeneous blend. Add 3.0g of nucleating agent (Perfluorinated compound) and 22g of blowing agent (70 / 30 wt% mixture of cyclopentane and isopentane) and mix to a homogeneous blend. Hold this chemical blend at 20°C for 2 hours.

[0373] Add 60g of hardening acid (mixture of sulfuric and phosphoric acids) to the resol blend, mix for 20 seconds and pour the reacted mixture into a wooden mould preheated to 70° C. Place a floating lid on top of the mixture and place in a preheated oven at 70° C. for 4 hours.

[0374] After curing for 4 hours, the foam is demolded and left at room temperature for one week, after which a sample is cut out and the physical properties are measured.

[0375] Comparative Example Comp-G3 was prepared in the same manner as Comp-A1. [Table 39] Table 39: Product Properties Example G2 Phenolic Lineo Classic Lignin Example H1 - Use of pyrolytic lignin

[0376] Resin Composite H1

[0377] The same process as described in Comparative Example Comp-A1, except that 20% of the input phenol was replaced with pyrolytic lignin (provided by BTG), whose molecular weight was 300-5000 D. Two additives, an ethoxylated castor oil surfactant and dimethyl phthalate, were added at the cooling stage of the resin synthesis in the same ratios as described in Example 1.

[0378] Final properties of said resin: [Table 40] Table 40: Resin properties of Example H1

[0379] Foaming Process H1 : Same as comparative example Comp-A1

[0380] Comparative Example Comp-H1 was prepared in the same manner as Comp-A1.

[0381] Characteristics: [Table 41] Table 41: Product Characteristics Example H1 Pyrolytic Lignin

[0382] The fire resistance performance of samples E1-3, G1-3, H1 and their comparative examples all had a flame height of less than 100 mm (after 30 seconds) measured according to standard EN 11925-2:2020.

[0383] Examples I1-I7H1 - Use of pyrolytic lignin

[0384] Resin Synthesis I1, I3, I4 and I5

[0385] The same process as described in Comparative Example Comp-B1, except that 10% of the input phenol was replaced with the same pyrolytic lignin as in H1.

[0386] The resulting phenolic resin composition, Resin I1, contained 10.8% by weight of water, less than 5% by weight of free phenol, and less than 1% by weight of free formaldehyde.

[0387] Final resin properties: [Table 42] Table 42: Resin Properties Example I1

[0388] Resin synthesis I2 and I6

[0389] The same process as described in Comparative Example Comp-B1, except that 20% of the input phenol was replaced with pyrolytic lignin from Example H1.

[0390] Resin Properties [Table 43] Table 43: Resin Properties Example I2

[0391] Resin synthesis I7

[0392] The same process as described in Comparative Example Comp-B1, except that 30% of the input phenol was replaced with the same pyrolytic lignin as in H1.

[0393] Resin Properties [Table 44] Table 44: Resin Properties Example I7

[0394] Foaming Process I1~I7 : Same as comparative example Comp-B1

[0395] Comparative Examples Comp-I1, I3, I4 and I5 were prepared in the same manner as Comp-B1.

[0396] The foam samples produced were analyzed and the results are summarized in Table 45. [Table 45] Table 45: Product characteristics Examples I1 to I7, using 10 to 30% BTG pyrolysis lignin

[0397] Sample I4 was tested according to standard EN13823:2020 to determine the fire resistance of the foam. The sample without facer was mounted in the SBI test apparatus according to standard EN15715:2009. The measurement results are shown in Figra 0.4 =150.6W / s. Total heat dissipation (THR 600 )=4.2MJ. SMOGRA=36m 2 / s 2 , Total Smoke Rate (TSP 600 )=55.8m 2 This performance is consistent with what would be expected from standard phenolic foam without any added flame retardants. Adding flame retardants would improve fire performance, but this would have a negative impact on the environmental footprint.

[0398] This fire resistance without the need for flame retardants differentiates the product from alternative insulation materials: for example, polyurethane and extruded polystyrene require the addition of flame retardants to achieve fire resistance below 150mm per standard EN11925-2, and many bio-based insulation materials require the addition of flame retardants to achieve acceptable fire performance.

[0399] Comparative Example Comp-J2 - Use of Commercially Available Kraft Lignin

[0400] Resin synthesis Comp-J2

[0401] The process was the same as that described in comparative example Comp-A1, but 20% of the input phenol was replaced by commercial lignin (BioPiva from UPM). Two additives, ethoxylated castor oil and dimethyl phthalate, were already added at the cooling stage of the resin synthesis in the same ratios as those described in comparative resin example Comp-A1.

[0402] Final properties of said resin: [Table 46] Table 46: Resin characteristics of comparative resin Comp-J2

[0403] Foaming process Comp-J2 : Same as comparative example Comp-A1

[0404] Comparative Example Comp-J1 was prepared in the same manner as Comp-A1.

[0405] Characteristics: [Table 47] Table 47: Product characteristics of Comparative Examples J1 and J2 using BioPiva manufactured by UPM

[0406] This experiment demonstrates the importance of phenolization of this grade of lignin.

[0407] Comparative Example Comp-K2 - Use of Commercial Lignosulfonate Lignin

[0408] Resin synthesis Comp-K2

[0409] The process is identical to that described in comp-A1, but 20% of the input phenol is replaced by a commercial lignosulfonate (Lignex Mg F from Sappi). The molecular weight of this lignin is about 6,000 D. Two additives, ethoxylated castor oil and dimethyl phthalate, are added already at the cooling stage of the resin synthesis in the same ratios as described in the comparative resin example Comp-A1.

[0410] Final properties of said resin: [Table 48] Table 48: Resin properties Resin comparison example Comp-K2

[0411] Foaming process Comp-K2 : Same as comparative example Comp-A1

[0412] Comparative Example Comp-K1 was prepared in the same manner as Comp-A1.

[0413] The properties of comp-K2 could not be measured because the foam was too brittle.

[0414] Comparative Example Comp-L2 - Use of Organosolv Lignin

[0415] Resin synthesis Comp-L2

[0416] The process was identical to that described in comp-A1, but 20% of the input phenol was replaced with organosolv lignin (provided by Suzano). Two additives, an ethoxylated castor oil surfactant and dimethyl phthalate, were added already at the cooling stage of the resin synthesis in the same proportions as described in comp-A1.

[0417] Final properties of said resin: [Table 49] Table 49: Resin properties Resin comparison example Comp-L2

[0418] Foaming process Comp-L2 : Same as comparative example Comp-A1

[0419] Comparative Example Comp-L1 was prepared in the same manner as Comp-A1.

[0420] Characteristics: [Table 50] Table 50: Product characteristics Comparative examples Comp-L1 and Comp-L2 using organosol lignin (manufactured by Suzano)

[0421] Comparative Example Comp-M2 - Use of hydrolyzed lignin

[0422] Resin synthesis Comp-M2

[0423] The same process as described in Example 1, but replacing 20% ​​of the input phenol with hydrolyzed lignin (supplied by Chempolis). Two additives, ethoxylated castor oil surfactant and dimethyl phthalate, were added already at the cooling stage of the resin synthesis in the same ratios as described in the comparative resin Comp-A1.

[0424] Final properties of said resin: [Table 51] Table 51: Resin properties Comparative resin Comp-M2

[0425] Foaming process Comp-M2 : Same as comparative example Comp-A1

[0426] Comparative Example Comp-M1 was prepared in the same manner as Comp-A1.

[0427] Characteristics: [Table 52] Table 52: Product characteristics Comparative Example M2 using hydrolyzed lignin (Chempolis)

[0428] Examples G1, G2, G3, H1, I1, I3, I4, I5, I6 and I7 show that, surprisingly, good physical properties can be obtained for certain types of lignin, whereas comparative examples Comp-G1, Comp-G2, Comp-G3, Comp-H1, Comp-I1, Comp-I3, Comp-I4, Comp-I5, Comp-J1, Comp-J2, Comp-L1, Comp-L2, CompM1 and CompM2 demonstrate that in the majority of cases, product properties are adversely affected.

[0429] The main characteristics of the lignin used are as follows: [Table 53] Table 53: Summary of Lignin Properties

[0430] The addition of lignin is positive as it could increase the renewable content without the need for the addition of biophenols, as biophenols still have a greater environmental impact than lignin. The biocontent (C) measured according to the standard EN16640:2017 14 Carbon) are shown in Table 48. [Table 54] Table 54: Renewable content as a function of the amount added per lignin type

[0431] Depending on the type of lignin, the biocontent increases by 5–10% when 20% of the phenol is replaced by lignin.

[0432] Another advantage is that the resulting product has a lower GWP-total compared to replacing phenol with biophenol. The GWP-fossil of lignin is 1.5 kg-CO2eq / kg, which is lower than fossil phenol (1.8 kg-CO2eq / kg). However, the total GHG footprint depends on how the lignin is valorised. Valorising lignin means putting the waste stream to a more useful use. Lignin is currently incinerated as there is no useful use. In the case of non-valorised lignin, such as the sulfonated lignin of examples E1 and E2, there is no contribution from fractionation and therefore the footprint is very low. In the case of solvent fractionation, the footprint is almost as low as non-valorised lignin (about 5% higher). For example, BTG pyrolysis lignin is a solvent fractionated lignin.

[0433] However, when base-catalyzed depolymerization is used, the GWP increases ten-fold to 18.3 kg-CO2 eq / kg, and is therefore unfavorable from an environmental point of view.

[0434] In this example, it was assumed that the performance of non-value-added and value-added liquids was more or less equivalent since the footprint difference was less than 5%.

[0435] To illustrate the effect of lignin addition, samples N1 and N2 were prepared. These samples used the same methodology as Comp-A1, but in sample N1, formaldehyde was replaced with bioformaldehyde produced from syngas. Additionally, 20% of the phenol was replaced with Ingevity's Reax 100M. Sample N2 was prepared in an identical manner to sample N1, but fossil phenol was replaced with bio-based phenol.

[0436] Final properties of said resin: [Table 55] Table 55: Resin properties Examples N1 and N2

[0437] The foams were prepared according to the method of comp-A1. The foam properties are shown in Table 56. [Table 56] Table 56: Product characteristics Examples N1 and N2 using Reax 100M lignin

[0438] Again, there is no negative effect on product properties. The main benefit of adding lignin is the reduction of the GWP of the final product. [Table 57] Table 57: Global warming potential of Examples N1 and N2 (from the cradle to the gate)

[0439] The GWP-total for foams includes a GWP-luluc of 0.1 kg-CO2eq / kg. For phenol and formaldehyde, the GWP-luluc is less than 0.1 kg-CO2eq / kg.

[0440] By combining bioformaldehyde with a 20% phenol replacement by lignin, a significant reduction in the GWP of the product can be achieved: the GWP reduction of the final product is about 0.9 kg CO2 equivalent per kg of foam (almost a 50% reduction).

[0441] Even more interesting is the reduction when the remaining part of phenol is replaced with biophenol, in which case the GWP is reduced to approximately 0 kg-CO2eq / kg (100% reduction).

[0442] In general, it can be concluded that the addition of lignin instead of phenol could solve the problem of low bio-content in high-performance insulation foams and significantly reduce the carbon footprint during the production phase (cradle-to-grave).

[0443] Applying these findings to the final product, the density is 15 to 60 kg / m 3 , more preferably 25 to 40 kg / m 3 This can be in the range of, for example, a density of 35 kg / m 3 For an 80mm insulation foam (without facer), the GHG footprint of the incorporation of lignin into this insulation foam means that the GHG footprint is 4.2 kg-CO2eq if the formaldehyde is completely replaced by formaldehyde produced from bio-waste. A foam based on bio-phenol can achieve a value of 1.7 kg-CO2eq. The combination leads to a further reduction to 0.6 kg-CO2eq.

[0444] By replacing 20% ​​of the phenol with lignin, the product's GHG (cradle-to-gate) value reaches 3.9kg-CO2eq / kg. Further replacement with bioformaldehyde results in a footprint of 2.8kg-CO2eq / kg. Moreover, by replacing all the phenol with bio-based phenol, the footprint can be reduced to 0.

[0445] Samples O1 and O2: combination of lignin, bioformaldehyde and biophenol

[0446] To confirm these findings, sample O1 was produced in an identical manner to sample B4, but in this case 20% of the biobased phenol was replaced by phenolized lignin. The lignin phenolization process was carried out under acidic conditions and before the addition of formaldehyde, so the impact on GWP is negligible. The lignin grade was Lineo Classic, supplied by Stora Enso.

[0447] Sample O2 further replaced the remaining 80% of the fossil phenol with bio-based phenol.

[0448] Product properties were not compromised by the introduction of lignin. [Table 58] Table 58: Product characteristics Examples O1 and O2 using phenolized Lineo Classic

[0449] Additionally, the impact of these samples on the GWP potential of the final product was measured. [Table 59] Table 59: Global Warming Potential of Examples O1 and O2 using Phenolated Lineo Classic

[0450] The GWP-total for foams includes a GWP-luluc of 0.1 kg-CO2eq / kg. For phenol and formaldehyde, the GWP-luluc is less than 0.1 kg-CO2eq / kg.

[0451] Furthermore, lignin contributes positively to renewable primary energy resources (PERM) used as a raw material: [Table 60] Table 60: PERM and PENRM of Examples O1 and O2 using Phenolated Lineo Classic

[0452] Table 60 shows that when all options are combined, the product's PERM can be higher than 2.0.

[0453] The main component of insulation products is resin. However, the product footprint from cradle to gate can be further optimized by changing other components of the foam to bio-based alternatives.

[0454] For example, bio-based polyols are conceivable. In this case, phthalic acid can be replaced by its bio-based version. For example, Relement supplies this material. Fully or partially bio-based polyols are also available, for example, from Polylabs and COIM. Polyester polyols can also be the result of glycolysis of polyurethane foam scraps consisting of diethylene glycol, amine and urea polyurethane oligomers, and diethylene glycol.

[0455] Urea has a relatively high nitrogen content and a relatively low carbon content, so the conversion of urea has a relatively low impact.

[0456] When organic acids are used as catalysts, bio-based versions can also be considered. Bio-based toluene and xylene are commercially available.

[0457] When adding neutralizing agents such as CaCO3, bio-based alternatives such as sea shells can be considered.

[0458] Optimization of the blowing agent is also possible: in the case of cyclopentane, for example, grades recovered from used refrigeration units can be used.

[0459] The laminate is produced at the facer in a continuous process. The laminate foam is fed between two layers of facers in a conveyor rather than a discontinuous block foam production. If this facer has a high renewable content, the GWP is further optimized. For example, this can be a paper facer, which in optimal circumstances is produced from recycled paper. Aluminium, which is relatively often used as a facer material, is less preferred due to its high GWP. Fiberglass veils can be an interesting option if fire resistance is an important requirement of the application.

[0460] As used herein in relation to the present invention, the terms "comprises / comprising" and "having / including" are used to specify the presence of stated features, integers, steps or components, but do not exclude the presence or addition of one or more other features, integers, steps, components or sets thereof.

[0461] It is understood that certain features of the invention which are, for clarity, described in the context of separate embodiments, may also be provided in a single embodiment in combination. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.

[0462] definition

[0463] The expression "at least one X selected from the group consisting of A, B, C and combinations thereof" is defined such that X includes "at least one A" or "at least one B" or "at least one C" or "at least one A in combination with at least one B" or "at least one A in combination with at least one C" or "at least one B in combination with at least one C" or "at least one A in combination with at least one B and at least one C".

[0464] The phrase "Y may be selected from A, B, C, and combinations thereof" means that Y may be A, or B, or C, or A+B, or A+C, or B+C, or A+B+C.

[0465] The term "blowing agent" is defined as a propellant used to blow a foamable composition to form a foam. For example, a blowing agent can be used to blow / expand a resin to form a foam.

[0466] characteristics

[0467] Suitable test methods for measuring the physical properties of phenolic resins are described below. (i) Resin Viscosity The viscosity of the resins used in making the foams of the present invention can be measured by methods known to those skilled in the art, for example, using a Brookfield type viscometer (Model DV-II+Pro) equipped with a temperature controlled water bath, maintaining the sample temperature at 25° C., spindle number SC4-29 rotating at 20 rpm or appropriate rotation speed and spindle type or suitable test temperature, maintaining an intermediate torque acceptable for the accuracy of the viscosity reading. (i) % Moisture Content of Phenolic Resin The phenolic resin was dissolved in anhydrous ethanol (manufactured by Honeywell Speciality Chemicals) in a range of 25% to 75% by mass. The moisture content of the phenolic resin was calculated from the moisture content measured for this solution. The instrument used for the measurement was a Metrohm 870 KF Titrino Plus. To measure the moisture content, Hydranal® Composite 5 manufactured by Honeywell Speciality Chemicals was used as a Karl Fischer reagent, and Hydranal® Methanol Rapid manufactured by Honeywell Speciality Chemicals was used for Karl Fischer titration. To measure the titer of the Karl Fischer reagent, Hydranal® Water Standard 10.0 manufactured by Honeywell Speciality Chemicals was used. The measured moisture content was determined by the Titer IPol method set in the instrument.

[0468] Suitable test methods for measuring the physical properties of phenolic foams are described below. (i) Foam Density This was measured in accordance with European Standard BS EN1602:2013-“Thermal insulating products for building applications - Determination of the apparent density”. (i) Compressive strength It was measured according to standard EN826:2013 - Thermal insulating products for building applications - Determination of compression behaviour. The values ​​shown are those for the first crack when the sample is subjected to a deformation of 10% of its thickness. (ii) Thermal Conductivity of Foam A foam specimen with a length of 300 mm and a width of 300 mm was placed in a thermal conductivity tester (LaserComp Type FOX314 / ASF, Inventech Benelux BV) between a hot plate at 20° C. and a cold plate at 0° C. The thermal conductivity (TC) of the specimen was measured according to the European standard EN12667: “Thermal performance of building materials and products - Determination of thermal resistance by means of guarded hot plate and heat flow meter methods, Products of high and medium thermal resistance”. Thermal conductivity can also be measured according to the standard EN12939:2000 "Thermal performance of building materials and products - Determination of thermal resistance by means of guarded hot plate and heat flow meter methods - Thick products of high and medium thermal resistance". (iii) Thermal Conductivity of Foams After Accelerated Aging It was measured using European Standard EN13166:2012+A2:2016-“Thermal insulation products for buildings - Factory made products of phenolic foam (PF)”-Specification Annex C section 4.2.3. Thermal conductivity is measured after exposing foam samples to 70°C for 2 weeks, followed by 110°C for 2 weeks, and stabilizing to constant weight at 23°C and 50% relative humidity. This method gives an estimate of thermal conductivity over a 25-year period. To determine the average thermal conductivity over a 50-year period, foam samples are exposed to 70°C for 2 weeks, followed by 110°C for 4 weeks, and stabilizing to constant weight at 23°C and 50% relative humidity. Instead of aging at 110°C for 2 weeks to obtain a 25-year average, the foam can be aged at 70°C for 25 weeks and then stabilized to a constant weight at 23°C and 50% relative humidity. To obtain a 50-year estimated thermal conductivity at ambient temperature, the product can be aged for 50 weeks. For biophenol / lignin / bioformaldehyde block foams, accelerated aging at 70°C for 25 weeks and thermal conductivity after adjustment to stable weight at 23°C / 50%RH is measured to simulate 25 years of thermal performance according to standard EN14314:2015 (Heat aging B4, Annex B). Only aging at 70°C is permitted by this standard. (v) Closed bubble content The closed cell content can be measured using gas pycnometry. Suitably, the closed cell content can be measured according to the standard NEN-EN ISO4590, Rigid Cellular plastics - Determination of volume percentage of open cells and closed cells. (vi) Form Vulnerability The fragility is measured according to the test method of standard ASTM C421-08(2014). (viii) Average bubble diameter The flat section of the foam is obtained by cutting the foam board in the middle of its thickness in a direction parallel to the top and bottom surfaces. A photocopy is obtained of the cut surface of the foam, enlarged 50 times. Four straight lines, each 9 mm long, are drawn on the photocopy. According to the test method of standard JIS K6402, the number of bubbles present on each line is counted to determine the average number of bubbles. By dividing by this average number, the average bubble diameter is determined to be 1800 μm. (x) Fire resistance of foam The fire resistance performance is measured according to standard EN13501. This standard refers to standard ISO-EN11925-2:2020, which specifies the test method for measuring the ignition tendency of a product by direct impingement of a small flame under zero irradiance with vertically oriented test specimens. This standard also refers to standard EN13823:2020 Reaction to fire tests for building products. This document specifies the test method for determining the fire reaction performance of building products when exposed to thermal attack by a single burning object (SBI). The calculation procedure is given in Annex A. The calibration procedure is given in Annex C and Annex D, Annex C being a normative annex. This document is developed to measure the fire reaction performance of essentially flat products. Samples are installed in a test rig according to standard EN15715:2009. (x) Foam water vapor transmission rate The water vapor transmission rate is measured according to the standard EN12086:2013. The test conditions are according to clause 7.1 Table 1, condition B: 23℃-0 / 80% RH (drycup). Cylindrical specimens with a diameter of 130 mm are tested through the entire thickness of the product. [Brief description of the drawings]

[0469]

Claims

1. 1. A foam product comprising an expanded foam having cells defined therein and a blowing agent retained within the cells, wherein at least 5% by weight of the foam is formed from at least one component from a renewable source.

2. 10. The foam product of claim 1, wherein the foam product comprises as a plasticizer cardanol, rosin, or a polyol derived from polyethylene terephthalate; polyurethane; and / or polyisocyanurate; or combinations thereof.

3. wherein at least one component from a renewable source comprises phenolized lignin; and / or at least one component from a renewable source comprises sulfonated lignin, optionally with a weight of sulfur in the sulfonated lignin of at least 2% by weight; and / or wherein the at least one component from a renewable source comprises pyrolytic lignin; and / or said at least one component from renewable sources consisting of technical lignin derived from paper and / or pulp processes; and / or said at least one component from renewable sources comprises soda lignin; and / or wherein the at least one component from renewable sources comprises organosolv lignin; and / or wherein at least one component from a renewable source comprises depolymerized lignin; and / or wherein the at least one component from a renewable source comprises kraft lignin, and optionally the weight percent of sulfur in the sulfonated kraft lignin is at least 2 wt.%, and further optionally 3. The foam product of claim 1 or 2, wherein the sulfonated kraft lignin has a weight average molecular weight (Mw) of 2,000 to 23,000 Daltons (Da).

4. The foam product of claim 1, wherein the foam product is formed from a composition consisting of methanol, the methanol having a GWP-total of less than -0.5 measured according to standard EN 15804:2012+A2:2019, and / or the foam product is formed from a composition comprising a phenol, the phenol having a GWP-total measured according to standard EN 15804:2012+A2:2019 of less than 1; and / or 1. The foam product, wherein the foam product is formed from a composition consisting of methanol and phenol, wherein the methanol has a GWP-total of less than −0.5 as measured according to standard EN 15804:2012+A2:2019, and the phenol has a GWP-total of less than 1 as measured according to standard EN 15804:2012+A2:2019.

5. 10. A foam product according to claim 1, comprising an expanded foam having cells defined therein and a blowing agent held within the cells, wherein the foam is formed from the reaction of a phenolic material with formaldehyde, wherein at least 10% by weight of the formaldehyde used is bioformaldehyde, such as at least 20% by weight, for example at least 30% by weight, such as at least 40% by weight, desirably at least 50% by weight, and optionally The bioformaldehyde is produced from biomethanol, for example: The biomethanol is produced by fermentation of biowaste, e.g. The biomethanol is a foam product produced from synthetic gas, for example synthesis gas obtained by gasification of bio-waste such as forestry waste.

6. 10. The foam product of claim 1, comprising an expanded foam having cells defined therein and a blowing agent held within the cells, wherein the foam is formed from a reaction with a phenol, wherein at least 10% by weight of the phenol is formed from bio-phenol, such as at least 15% by weight, for example at least 20% by weight, for example at least 25% by weight, and optionally The biophenol may be produced from biobenzene, optionally using pyrolysis of biowaste such as wood waste and wood-based materials including by-products of wood processing such as papermaking, e.g. A foam product, wherein the biobenzene is made from tall oil.

7. at least 7% by weight of the foam, such as at least 10% by weight, for example at least 15% by weight, desirably at least 20% by weight, optionally at least 25% by weight, for example at least 30% by weight, is formed from at least one component from renewable sources; and / or at least 70% of the blowing agent (based on the total weight of the blowing agent) has a gas phase thermal conductivity of 12 mW / m.k or less at 25°C, e.g., 11.8 mW / m.k or less; and / or the weight of said at least one component from renewable sources comprises carbon, measured according to standard EN 16640:2017 and based on C 14 measurement; and / or 10. The foam product of claim 1, wherein the foam has a C14 carbon content greater than 3% as measured according to standard EN 16640:2017.

8. said foam product having a 25-year average thermal conductivity of less than or equal to 0.025 W / m.K as measured according to standard EN 16783:2017; and optionally the foam product has an average thermal conductivity of less than or equal to 0.026 W / m.K over a 50-year service life, measured according to standard EN 16783:2017; and / or the total global warming potential of said foam product is equal to or less than 1.7 kg-CO 2 eq / kg, such as equal to or less than 1.5 kg-CO 2 eq / kg, for example equal to or less than -0.5 kg-CO 2 eq / kg, as measured according to standard EN 16783:2017, and optionally 2. The foam product of claim 1, wherein the foam product has a Global Warming Potential - Biogenicity of less than or equal to −0.2 kg-CO 2 eq / kg, such as less than or equal to −0.4 kg-CO 2 eq / kg, measured according to standard EN 16783:2017.

9. 10. The foam product of claim 1, wherein the foam-forming ingredients have renewable primary energy resources equivalent to or less than 0.7 MJ / kg as measured according to standard EN 16783:2017.

10. the foam product exhibits a fire resistance performance in the single flame source test according to standard EN ISO 11925-2 with a flame height of <100 mm; and / or said foam product having a closed cell content of at least 90%, such as at least 92%, for example at least 94%, optionally at least 95%, as measured according to standard EN ISO 4590; and / or The foam product has a friability of less than 20% as measured by standard ASTM C421-08(2014), and / or said foam product having a compressive strength, measured according to standard EN 826:2013, of at least 100 kPa; and / or 2. The foam product according to claim 1, wherein the foam product has a density of 10 kg / m3 to 125 kg / m3, for example from about 15 kg / m3 to about 100 kg / m3, preferably from about 15 kg / m3 to about 60 kg / m3, and suitably from about 20 kg / m3 to about 35 kg / m3, as measured according to standard EN 1602:2013.

11. 10. The foam product of claim 1, wherein the foam product is a phenolic foam product.

12. Use of lignin as a color-imparting additive in a foam product comprising a foam having cells defined therein and a blowing agent retained within the cells; and / or 1. Use of lignin as a color stabilizing additive in a foam product comprising a foam having cells defined therein and a blowing agent retained within said cells.

13. The foam has a C of more than 3% as measured according to standard EN 16640:2017 １４ 10. The foam product of claim 1, wherein the foam is a phenolic foam product having a C14 carbon content of more than 3% as measured according to standard EN 16640:2017.

14. 10. The foam product of claim 1, comprising an expanded foam having cells defined therein and a blowing agent held within said cells, The foam is formed from at least one component from a renewable source, and the foam has a carbon footprint of 1.0 kg-CO for Cradle-to-gate stages (A1-A3). ２ and / or has a total GWP (Global Warming Potential) of less than eq / kg (measured according to standard EN 16783:2017); the foam has an EPD rating of 1.0 kg-CO 2 eq / kg measured according to standard EN 15804:2012+A2:2019 for life cycles A-D, and / or at least 5% by weight of said foam is formed from at least one component from renewable sources, and optionally said foam product has an average thermal conductivity over a 25-year service life of less than or equal to 0.025 W / m.K, measured according to standard EN 12667 or EN 12939; and / or 1. A foam product comprising an expanded foam having cells defined therein and a blowing agent held within the cells, wherein at least 5% by weight of the foam is formed from at least one component from renewable sources, and optionally wherein the foam product has an average thermal conductivity of 0.026 W / m.K or less over a 50-year service life as measured in accordance with standards EN 12667 or EN 12939.

15. 10. The foam product of claim 1, comprising an expanded foam having cells defined therein and a blowing agent retained within said cells, at least 5% by weight of said foam is formed from at least one component from renewable sources, and optionally the average thermal conductivity of said foam product over a 25-year service life is less than or equal to 0.025 W / m.K, measured according to standards EN 13166 and / or EN 14314; and / or 1. A foam product, wherein at least 5% by weight of said foam is formed from at least one component from renewable sources, and optionally wherein said foam product has an average thermal conductivity over a 50-year service life of less than or equal to 0.026 W / m.K as measured according to standards EN 13166 and / or EN 14314.

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