Bio-based amine curing agents and polyurea compositions

Abstract

The present invention provides 14 The present invention relates to low carbon footprint (LCF) amine curing agent compositions characterized by the presence of the C radioactive carbon isotope, LCF polyurea compositions, methods of making LCF-amine curing agent compositions, and methods of making LCF polyurea compositions.

Description

[Technical Field]

[0001] The field of the invention is 14 The present invention relates to novel low carbon footprint (LCF) polyurea compositions and LCF-amine curing agent compositions characterized by the presence of the C radioactive carbon isotope. The invention also relates to products from a process for preparing the LCF-curing agent using raw materials produced by fermentation of biomass. The invention also relates to methods for producing polyurea polymers, in which the majority of the raw materials have very low greenhouse gas emissions into the environment. The LCF-amine curing agent is used to produce the polyurea polymer by reaction with an organic isocyanate. The LCF-amine curing agent and the isocyanate each have at least two functional groups. The LCF-curing agent is preferably an organic diamine produced from sustainable, biobased raw materials with a low carbon footprint, and the process used to produce the curing agent significantly reduces greenhouse gas emissions.

[0002] Background of the Invention Alkanediol-p-diaminobenzoate diesters have been used as curing agents to prepare polyureas. These curing agents can be prepared in several different ways, the prior art of which is described below.

[0003] One representative series of curing agents used in the production of polyurea is obtained by esterifying the two terminal hydroxyl groups of petrochemical-based polytetramethylene ether glycols (PTMEG) of various molecular weights with p-aminobenzoic acid (PABA) to produce difunctional amine curing agents. When these curing agents are reacted with difunctional or polyfunctional isocyanates, they can produce polyurea films with excellent mechanical properties that offer high performance in terms of abrasion resistance and toughness.

[0004] The existing methods for preparing petrochemical-based aromatic amine curing agents described in the prior art utilize only carbon-intensive raw materials and processes that burden the environment by generating large amounts of carbon dioxide emissions during production as well as by depleting irreplaceable fossil fuels. Some of these conventional methods are described in the following documents:

[0005] U.S. Pat. No. 3,932,360 describes an isocyanate-terminated urethane prepolymer, formula: [ka]

[0010] discloses the preparation of petrochemical-based diamine-cured polyurethane products by combining a compound of the formula: [wherein X is an alkylene or cycloalkylene group having 2 to 12 carbon atoms]. These products are made exclusively from fossil fuel-based materials, 14 The C content is zero.

[0006] U.S. Patent No. 4,283,549 discloses a method for producing petrochemical-based alkanediol-diaminobenzoate esters, which involves esterifying nitrobenzoic acid with a specific diol in the melt, then dissolving the intermediate in a poorly water-soluble solvent, such as an aromatic hydrocarbon, ether, or ester, and reducing it with hydrogen gas. This product is made exclusively from fossil fuel-based materials, 14 It has zero carbon content and emits at least twice as much greenhouse gas as this new invention.

[0007] U.S. Patent No. 4,476,318 discloses a process for preparing petrochemical-based 1,3-propanediol bis(p-aminobenzoate) by reacting an alkali metal salt of p-aminobenzoic acid with a dihalogenated propane in an aprotic polar solvent. According to this process, the diesterification proceeds under mild conditions without causing any undesired side reactions, providing 1,3-propanediol bis(p-aminobenzoate) diester with high purity and high yield. This product is made solely from fossil fuel-based materials.14 The C content is zero and there are no environmental benefits compared to this new invention.

[0008] U.S. Patent No. 6,111,129 discloses a process for the direct preparation of alkanediol-diaminobenzoate diesters, which involves transesterifying an alkyl-p-aminobenzoate with a diol in the presence of a transesterification catalyst. These products are prepared exclusively from fossil fuel-based materials, and therefore, 14 C is not among them.

[0009] European Patent Application Publication No. 0677542 discloses a petrochemical-based polyurethaneurea elastomer made with 2-methyl-1,3-propanediol-bis-p-aminobenzoate, the hydrogenation reduction product of 2-methyl-1,3-propanediol-bis-p-nitrobenzoate. The 2-methyl-1,3-propanediol-bis-p-nitrobenzoate composition is preferably prepared by esterifying p-nitrobenzoic acid with 2-methyl-1,3-propanediol using a stoichiometric excess of the diol to facilitate the esterification process, followed by further reaction with an acid, removal of the volatile free diol while continuing esterification of the unreacted acid, and transesterification of the formed monoester to a diester. It is also claimed that this process is broadly applicable to the esterification of other nitroaromatic acids with other aliphatic diols, does not require external solvents for processability, and can produce high yields of diesters with only water as a by-product. This product is made exclusively from fossil fuel-based materials, 14 The C content is zero.

[0010] The hardeners provided by all the above processes are 14 It is a petrochemical-based material with zero C radiocarbon content, is made solely from fossil fuel-based materials, and has process drawbacks such as at least twice the greenhouse gas emissions compared to the new process of the present invention.

[0011] Other features and advantages of the present invention will be apparent from the following more detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of the invention.

[0012] Summary of the Invention The present invention relates to aromatic amine curing agents that can be produced using chemical processes with a positive carbon footprint (absorption of carbon dioxide from the atmosphere), a neutral carbon footprint (no carbon dioxide emissions or releases into the atmosphere), or a minimal carbon footprint (minimal or no carbon dioxide emissions into the atmosphere). The new aromatic amine curing agents also provide polyurea compositions containing the reaction product of an organic isocyanate and an organic amine, each having at least two functional groups. The polyurea compositions also provide polyurea polymers with optimal physical and chemical properties while meeting the requirements for a zero-carbon or low-carbon footprint.

[0013] The new LCF-amine curing agents as well as the resulting polyurea polymers 14 It is characterized by the presence of the C radioactive carbon isotope. Biocarbon content is based on the amount of biogenic carbon present and is defined as the amount of biocarbon in a material / product, either by weight or mass or as a weight percent or mass percent of the total organic carbon in the material / product. Biocarbon content determinations are typically obtained using the ASTM D6866 method. In this method, the percent biobased carbon content is [bio(organic) carbon / total organic carbon] x 100. ASTM D6866 is the standard test method for determining the biobased content of solid, liquid, and gas samples using radiocarbon analysis.

[0014] Carbon is a primary element that is the building block of polymeric materials, fuels, and living organisms. There is growing concern that CO2 released into the environment by human activities will continue to increase without additional fixation and removal. Reducing the carbon footprint and addressing imbalances in the carbon cycle is one of the major challenges facing modern human society. Producing plastics and products using renewable, bio-based chemical feedstocks offers an alternative path toward a zero- or neutral-carbon footprint value proposition.

[0015] The concentration of carbon dioxide in the atmosphere is approximately 380 ppm. If the concentration of CO2 begins to exceed this value, it will increase the heat retained in the atmosphere, leading to global warming, which can be life-threatening due to increased anthropogenic emissions of carbon (CO2) and other greenhouse gases into the atmosphere. Therefore, it is an undeniable fact that if atmospheric CO2 levels continue to rise uncontrollably, it will lead to global warming, which will have adverse effects on life.

[0016] Therefore, a zero-carbon emissions approach is necessary to prevent CO2 levels from rising. The fixation of atmospheric CO2 to form petroleum / fossil fuels is typically estimated in millions of years, while the timescale for their release into the environment at end of life is typically one to ten years. Therefore, if CO2 emissions from human activities are much greater than the fixation rate, it is not sustainable. This leads to increased carbon emissions, with the attendant effects of global warming and climate change. By using renewable biomass crops as feedstocks to produce carbon-based products, the CO2 released at the end of the product's life is captured by cultivating new crops or biomass plantations. Specifically, the rate and timescale of CO2 released into the environment at end of life equals the rate of photosynthesis, which captures and converts CO2 into biomass for next-generation products with a net-zero carbon footprint.

[0017] Bio-based materials are 14They may contain 100% biogenic carbon containing the C radioactive carbon isotope, or may be mixed (physically, chemically, or biologically) with fossil / petroleum-based carbon. Therefore, the biobased content needs to be defined by the amount of biogenic carbon contained in the product. 14 Measurement of C isotope content forms the basis for the identification and quantification of biobased materials. Atmospheric CO2 is radioactive 14 It is in equilibrium with CO2. Radiocarbon is produced by cosmic ray neutrons in the upper atmosphere. 14 It is then formed by acting on N, which then enters plant life through photosynthesis and then animal life to become radioactive 14 Oxidized to CO2. Plants and animals 14 Organisms use the carbon food chain to absorb carbon dioxide. 14 C concentration and the non-radioactive carbon atoms remain roughly the same over time.

[0018] When a plant or animal dies, its metabolism stops, carbon absorption stops, and radiocarbon 14 Carbon is not incorporated and its concentration gradually decreases. The half-life of carbon is about 5730 years, so fossil materials formed over millions of years contain 14 Therefore, this technique allows for the identification and quantification of biobased content, standardized using ASTM D6866. The method involves burning the test material with oxygen to produce carbon dioxide gas. This gas is then analyzed to determine the product's 14 C / 12 It provides a baseline for C content and is compared to the modern carbon-based oxalate radiocarbon Standard Reference Material (SRM) 4990c, which is 100% biocarbon. As stated in the ASTM D6866 standard, 14 C / 12 Three different methods can be used to obtain the C ratio. 14 C / 12 The most accurate method for determining the C ratio is magnetic accelerator mass spectrometry, which can provide measurements with an uncertainty of approximately 3%.

[0019] Thus, the present invention provides a compound of formula: [ka] [wherein n=1 to 40, more preferably n=1 to 30], and 14 having a % biomass content in the range of 100% to 10%, preferably 100% to 50%, more preferably 90% to 50%, as measured by the presence of the C isotope, and a MW in the range of 76 g / mol to 3040 g / mol, preferably 76 g / mol to 2280 g / mol; 14 The present invention relates to an LCF-amine curing agent composition comprising at least one compound prepared using C-containing biobased 1,3-propylene diol and / or poly(1,3-propylene diol), where the 1,3-propylene diol and / or poly(1,3-propylene diol) is produced by fermentation of biomass and / or polycondensation of 1,3-propylene diol obtained by fermentation of biomass. Additionally, the new composition also discloses a unique isomer distribution, as indicated by the range of "n" in the formula, which allows the curing agent to remain liquid or not form solids for extended periods of time, resulting in a substantially liquid amine curing agent without the need to provide heat for melting, resulting in improved processability.

[0020] definition The following definitions are provided to aid those skilled in the art in understanding the detailed description of the present invention. PPDO: Poly-1,3-propylene diol PABA: Para-aminobenzoic acid PTMEG: Polytetramethylene glycol LCF: Low Carbon Footprint

[0021] Detailed Description of the Invention The present invention relates to a compound of formula: [ka] [wherein n=1 to 40], and 14 They have a % biomass content ranging from 100% to 10%, as measured by the presence of the C isotope, and a MW ranging from 76 g / mol to 3040 g / mol. 14 The present invention is directed to an LCF-amine curing agent composition comprising at least one compound prepared using C-containing bio-based 1,3-propylene diol and / or poly(1,3-propylene diol), wherein the 1,3-propylene diol and / or poly(1,3-propylene diol) is produced by fermentation of biomass and / or polycondensation of 1,3-propylene diol obtained by fermentation of biomass. Preferably, in one embodiment, the at least one compound has n=1 to 30. Preferably, in one embodiment, the at least one compound is prepared using the method of ASTM D6866. 14 Preferably, in another embodiment, at least one compound has a % biomass content in the range of 100% to 10% as measured by the presence of the C isotope. 14 The % biomass content, as measured by the presence of the C isotope, ranges from 90% to 50%. Preferably, in one embodiment, at least one compound has a MW ranging from 76 g / mol to 2280 g / mol. 14 The novel compositions are prepared using C-containing bio-based 1,3-propylene diol and / or poly(1,3-propylene diol). Additionally, the novel compositions also disclose a unique isomer distribution, as indicated by the range of "n" in formula (I), which allows the curing agent to remain liquid or not form solids for extended periods of time, resulting in a substantially liquid amine curing agent without the need to provide heat for melting, resulting in improved processability.

[0022] In another embodiment, the present invention relates to the product of a process in which biobased or optionally non-biobased p-aminobenzoic acid or p-aminobenzoic acid ester is contacted with biobased 1,3-propanediol or biobased poly(1,3-propanediol), the mixture is dried with excess toluene using a Dean-Stark apparatus, and then the metal catalyst Ti(BuO)4 is added to the toluene-containing mixture and the temperature is increased to drive esterification to about 99% completion to yield the biobased amine curing agent 1,3-propylene glycol bis(4-aminobenzoate) or poly(1,3-propylene glycol) bis(4-aminobenzoate).

[0023] Amine hardeners are produced using chemical processes that have a negative carbon footprint (absorption of carbon dioxide from the atmosphere), a neutral carbon footprint (no net emission or release of carbon dioxide into the atmosphere), or a positive carbon footprint (minimal emission of carbon dioxide into the atmosphere).

[0024] In another embodiment, the present invention provides a method for producing a hydroxybenzoate comprising the steps of: [ka] [wherein n=1 to 40, more preferably n=1 to 30], and 14 having a % biomass content in the range of 100% to 10%, preferably 100% to 50%, more preferably 90% to 50%, as measured by the presence of the C isotope, and a MW in the range of 76 g / mol to 3040 g / mol, preferably 76 g / mol to 2280 g / mol; 14The present invention relates to an LCF polyurea composition prepared using a C-containing bio-based 1,3-propylene diol and / or poly(1,3-propylene diol), wherein the 1,3-propylene diol and / or poly(1,3-propylene diol) is produced by fermentation of biomass and / or polycondensation of 1,3-propylene diol obtained by fermentation of biomass, comprising reacting with an LCF-amine curing agent composition comprising at least one compound.

[0025] In another embodiment, the present invention provides at least one diisocyanate or polyisocyanate having the formula: [ka] [wherein n=1 to 40, more preferably n=1 to 30], and 14 having a % biomass content in the range of 100% to 10%, preferably 100% to 50%, more preferably 90% to 50%, as measured by the presence of the C isotope, and a MW in the range of 76 g / mol to 3040 g / mol, preferably 76 g / mol to 2280 g / mol; 14 and a method for making an LCF polyurea composition, the method comprising contacting an LCF-amine curing agent composition with at least one compound prepared using a C-containing biobased 1,3-propylene diol and / or poly(1,3-propylene diol), wherein the 1,3-propylene diol and / or poly(1,3-propylene diol) is produced by fermentation of biomass and / or polycondensation of 1,3-propylene diol obtained by fermentation of biomass.

[0026] In another embodiment, the present invention relates to a method for making LCF polyurea polymers by contacting a bio-based amine curing agent 1,3-propylene glycol bis(4-aminobenzoate) or poly-(1,3-propylene glycol) bis(4-aminobenzoate) with a diisocyanate or polyisocyanate to obtain a polyurea polymer.

[0027] The polyureas of the present invention are prepared by reacting at least one organic isocyanate with an amine curing agent composition. Preferably, the at least one organic isocyanate is a diisocyanate or polyisocyanate. Preferably, the diisocyanate or polyisocyanate is an aliphatic, arylaliphatic, or aromatic isocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate isomers (MDI), hydrated MDI, and 1,5-naphthalene diisocyanate.

[0028] Preferred examples of aliphatic isocyanates include, but are not limited to, polymethylene diisocyanates such as ethylene diisocyanate, propylene-1,2-diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, and dodecane-1,12-diisocyanate. Additionally, alicyclic isocyanates such as dicyclohexylmethane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, cyclohexane-1,3-diisocyanate, and mixtures of these isomers, such as 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, can also be used. Arylaliphatic diisocyanates such as 1,3-xylene diisocyanate; perchlorinated aryl polyisocyanates, polyphenylpolymethylene polyisocyanates obtained by aniline formaldehyde condensation followed by phosgenation, m- and p-isocyanatophenylsulfonyl isocyanates, and the like can also be used.

[0029] Preferred aromatic isocyanates that can be used in the present invention include 3,3'-dimethyl-4,4'-biphenylene diisocyanate (o-tolidine diisocyanate, TODI), toluene-2,4- or 2,6-diisocyanate (TDI), and mixtures of these isomers, such as 80% 2,4-toluene diisocyanate and 20% Mixtures with 2,6-toluene diisocyanate; phenylene-1,4-diisocyanate; diphenylmethane-2,4'-diisocyanate; diphenylmethane-4,4'-diisocyanate (MDI); diphenylether-4,4'-diisocyanate; naphthylene-1,5-diisocyanate (NDI); p-phenylene diisocyanate (PPDI); p,p'-diphenyl diisocyanate; hexahydrophenylene-1,3-diisocyanate; hexahydrophenylene-1,4-diisocyanate; triphenylmethane-4,4',4''-triisocyanate; perhydrodiphenylmethane-2,4'-diisocyanate; perhydrodiphenylmethane-4,4'-diisocyanate, etc., preferably MDI. Other preferred isocyanates that can be used include polyisocyanates containing carbodiimide groups, polyisocyanates containing allophanate groups, polyisocyanates containing isocyanurate groups, polyisocyanates containing urea groups, polyisocyanates containing acylated urea groups, polyisocyanates containing biuret groups, polyisocyanates prepared by telomerization reactions, polyisocyanates containing ester groups, reaction products of the above-mentioned isocyanates with acetals, and polyisocyanates containing polymeric fatty acid groups; isophorone diisocyanate and ester diisocyanates of carboxylic acids of the type described in EP-A-0 269 869; triisocyanates, such as p,p',p''-triphenylmethane triisocyanate, can also be used.

[0030] It is desirable for polyurea compositions to provide optimal physical and chemical properties for polyurea polymers while meeting zero or low carbon footprint requirements. These products can be measured using ASTM D6866. 14 It is characterized by the presence of C content.

[0031] In one embodiment of the present invention, the amine curing agent composition of the present invention further comprises zero 14 The polyurea composition includes at least one amine co-curing agent made exclusively from fossil fuel-based materials having a C content. A wide range of amine co-curing agents can be used. The choice of amine co-curing agent affects the hardness obtained in the polyurea product. Preferably, the at least one amine co-curing agent is an organic diamine or organic triamine. Preferably, in another embodiment, the at least one amine co-curing agent is an aromatic diamine. Preferably, the amine co-curing agent is selected from the group consisting of polymethylene-di-p-aminobenzoate, polyethylene glycol bis(4-aminobenzoate), and the like. Preferably, the aromatic diamine is a compound represented by the formula A): [ka] polymethylene-di-p-aminobenzoates having the formula: wherein X=an alkylene or cycloalkylene group having 2 to 12 carbon atoms, the alkylene and cycloalkylene groups represented by X being substituted or unsubstituted, and suitable substituents include alkyl groups having 1 to 5 carbon atoms, halogens, preferably chlorine or fluorine, and aryl groups, preferably phenyl; B) Formula: [ka] polyethylene glycol-bis(4-aminobenzoate) having the formula: [wherein n=2 to 4]; C) Formula: [ka] Polydimethylsiloxane-bis(4-aminobenzoate) having the formula: [wherein n=2 to 4]; and D) Formula: [ka] wherein n=1 to 40.

[0032] In addition to the negative environmental impact, the use of petrochemical-derived PTMEG-based aromatic diamines also presents several limitations regarding their physical state. PTMEG has a high Tg and is well known to form amorphous solids, and when curing agents are made by esterification with p-aminobenzoic acid, solidification is highly likely to limit their usefulness. Of the commercially available curing agents made with PTMEG and PABA, only one has a melting point below 15°C, and most are solid at room temperature. Although the products can be heated during processing at room temperature, solid-phase separation occurs in all applications requiring storage, such as in polyurea coatings and adhesives, making the manufacturing process more complicated.

[0033] In some applications, polyurea polymers are used rather than polyurethane polymers because they typically have better mechanical performance in applications requiring high abrasion resistance and toughness. System manufacturers currently use PTMEG-based curing agents because of their beneficial physical properties, but the challenge remains that PTMEG-based aromatic diamines made from PABA are very viscous and typically solid or tend to solidify over time.

[0034] Another major drawback of PTMEG-based curing agents is the energy-intensive process and raw materials utilized in the manufacturing process. PTMEG is made by the acid-catalyzed polymerization of tetrahydrofuran, which is commercially produced by converting acetylene from fossil fuels, starting with natural gas. The acetylene is then reacted with formaldehyde to produce butynediol, which is further hydrogenated to butanediol. The butanediol is then catalytically converted to tetrahydrofuran. Not only is this process for making PTMEG energy-intensive, resulting in significant greenhouse gas emissions, but it also uses non-renewable resources.

[0035] The new bio-based curing agents of the present invention are characterized by a low or zero carbon footprint (no release of CO2 into the environment) or a negative carbon footprint effect (net absorption of CO2 from the environment). The new amine curing agent compositions are 14 It is characterized by the presence of the C radiocarbon isotope, which is completely absent in petrochemical-based hardeners and 14 The concentration of C is zero. The new bio-based curing agents of the present invention are made using a process that is essentially carbon neutral, with precursors obtained, for example, by bacterial fermentation of plant-based glucose, making the overall amine curing process more energy efficient and resulting in significantly lower greenhouse gas emissions.

[0036] Thus, the present invention exemplifies, by way of example, the use of corn-based 1,3-propanediol and related materials obtained by oligomerization and polymerization of 1,3-propanediol to produce the 1,3-propanediol used in the synthesis of the LCF-amine curing agents of the present invention. Bio-based 1,3-propanediol is typically obtained by a fermentation process of plant-derived glucose instead of using petroleum-based feedstocks.

[0037] The present invention provides new curing agents made by esterifying bio-based 1,3-propanediol or bio-based poly(1,3-propanediol) with PABA to create bio-based aromatic diamines that can provide wear-resistant polyureas comparable to those made using petrochemicals. Surprisingly, the bio-based poly-1,3-propanediol / PABA diester amines are liquids at room temperature and can therefore be more easily used in applications where conventional PTMEG diamines cannot be used due to their high melting points and difficult processability.

[0038] Optionally, the present invention provides new LCF-amine curing agents made by esterifying bio-based 1,3-propanediol or bio-based poly(1,3-propanediol) with bio-based PABA produced by bacterial fermentation of sugar-containing biomass to make a bio-based aromatic diamine that can provide wear-resistant polyureas comparable to those made using petrochemicals.

[0039] Oligomeric diamine LCF-curing agents made by esterifying PABA and / or optionally bio-based PABA with bio-based poly-1,3-propanediol (PPDO) of three different molecular weights—approximately 650, approximately 1000, and approximately 2000—surprisingly result in products that are liquid at room temperature. The time window during which these curing agents remain liquid is much longer than that of conventional PTMEG curing agents, eliminating the need for heating when using the new LCF-curing agents made from bio-based PPDO. Thus, while a typical PTMEG / PABA curing agent with a MW of approximately 2000 is solid at room temperature (melting point approximately 36°C), a similar product made with bio-based PPDO / PABA of approximately the same MW (approximately 2000) is liquid at room temperature. The same is true for a MW of approximately 1000; in this case, the bio-based PPDO / PABA curing agent is liquid at room temperature, while the corresponding PTMEG / PABA curing agent becomes a cloudy liquid due to partial solidification. Only at low MW (about 650) will the bio-based PPDO / PABA hardener have a lower viscosity, although both the bio-based PPDO / PABA and PTMEG / PABA are liquid at room temperature.

[0040] Due to global concerns about climate change and the impact of greenhouse gas emissions into the environment, the chemical industry is moving toward a more circular economy in which chemical processes are designed to minimize their environmental impact, as measured, for example, by the carbon footprint of the new chemical process. Thus, there is a need for new, environmentally friendly chemical processes that can provide chemical products with minimal or no environmental impact. In response to these needs, the present invention provides a composition comprising: 14 The present invention provides new LCF-amine curing agent compositions characterized by the presence of the C radioactive carbon isotope. The present invention also provides products resulting from a process for making the new curing agents using fully or partially biobased raw materials with low or no carbon footprint. Additionally, the present invention provides methods for making these new LCF-amine curing agents.

[0041] The following invention is directed to the following aspects: <1> formula: [ka] wherein n=1 to 40; 14 An LCF-amine curing agent composition comprising at least one compound having a % biomass content in the range of 100% to 10% as measured by the presence of the C isotope.

[0042] <2> At least one compound has n=1 to 30. <1> The LCF-amine curing agent composition described herein.

[0043] <3> At least one compound is 14 An embodiment having a % value of biomass content ranging from 100% to 50% as measured by the presence of the C isotope. <1> or <2> The LCF-amine curing agent composition described herein.

[0044] <4> At least one compound is 14 and an embodiment having a % biomass content in the range of 90% to 50% as measured by the presence of the C isotope. <1> from <3> 1. The LCF-amine curing agent composition according to any one of claims 1 to 10.

[0045] <5> At least one compound has a MW in the range of 76 g / mol to 3040 g / mol 14 C-containing bio-based 1,3-propylene diol and / or bio-based poly(1,3-propylene diol). <1> from <4> 1. The LCF-amine curing agent composition according to any one of claims 1 to 10.

[0046] <6> At least one compound has a MW in the range of 76 g / mol to 2280 g / mol 14 C-containing bio-based 1,3-propylene diol and / or bio-based poly(1,3-propylene diol). <1> from <4> 1. The LCF-amine curing agent composition according to any one of claims 1 to 10.

[0047] <7> Bio-based 1,3-propylene diol is produced by fermentation of biomass. <5> or <6> The LCF-amine curing agent composition described herein.

[0048] <8> An embodiment in which the bio-based poly(1,3-propylene diol) is produced by fermentation of biomass and / or polycondensation of bio-based 1,3-propylene diol. <5> or <6> The LCF-amine curing agent composition described herein.

[0049] <9> zero 14

[0023] An embodiment further comprising at least one amine co-curing agent made exclusively from fossil fuel-based materials having a C content. <1> from <8> 1. The LCF-amine curing agent composition according to any one of claims 1 to 10.

[0050] <10> an embodiment in which at least one amine co-curing agent is an organic diamine or organic triamine; <9> The LCF-amine curing agent composition described herein.

[0051] <11> an embodiment in which at least one amine co-curing agent is an aromatic diamine; <8> or <9> The LCF-amine curing agent composition described herein.

[0052] <12> The aromatic diamine is A) Formula: [ka] polymethylene-di-p-aminobenzoate having the formula: [wherein X is an alkylene group or cycloalkylene group having 2 to 12 carbon atoms, and the alkylene group and cycloalkylene group represented by X may be substituted or unsubstituted]; B) Formula: [ka] polyethylene glycol-bis(4-aminobenzoate) having the formula: [wherein n=2 to 4]; C) Formula: [ka] Polydimethylsiloxane-bis(4-aminobenzoate) having the formula: [wherein n=2 to 4]; and D) Formula: [ka] wherein n=1 to 40. <11> The LCF-amine curing agent composition described herein.

[0053] <13> At least one isocyanate and an embodiment <1> from <12> 1. An LCF polyurea composition comprising a reaction with an LCF-amine curing agent composition according to any one of claims 1 to 10.

[0054] <14> an embodiment in which at least one isocyanate is a diisocyanate or polyisocyanate; <13> The LCF polyurea composition described.

[0055] <15> the diisocyanate or polyisocyanate is an aliphatic, arylaliphatic, or aromatic isocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate isomers, hydrated diphenylmethane diisocyanate isomers, and 1,5-naphthalene diisocyanate; <14> The LCF polyurea composition described.

[0056] <16> The diisocyanate or polyisocyanate may be <1> from <12> 10. A method of making an LCF polyurea composition comprising contacting an LCF-amine curing agent composition with the LCF-amine curing agent composition of any one of claims 1 to 9.

[0057] <17> the diisocyanate or polyisocyanate is an aliphatic, arylaliphatic, or aromatic isocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate isomers, hydrated diphenylmethane diisocyanate isomers, and 1,5-naphthalene diisocyanate; <16> The method described.

[0058] <18> A method for making an LCF polyurea polymer comprising contacting a bio-based amine curing agent 1,3-propylene glycol bis(4-aminobenzoate) or poly(1,3-propylene glycol) bis(4-aminobenzoate) with a diisocyanate or polyisocyanate.

[0059] Example These examples are provided to illustrate particular aspects of the present invention and do not limit the scope of the claims appended hereto.

[0060] Example 1: Synthesis of bio-based PDO oligomer-based curing agent Procedure for synthesis of bio-based curing agent with average MW of about 855: A mixture of ethyl p-aminobenzoate (300 g, 1.81 mol), poly(1,3-propanediol) (588.5 g, 0.95 mol) with a hydroxyl number of 181.75 mg KOH / g sample (MW = 617), and 200 g of toluene was charged to a 2 L round-bottom flask equipped with an overhead stirrer, thermocouple, short-path distillation head, and nitrogen sweep. The flask was purged with nitrogen, and the mixture was then heated to 100 °C under vacuum until 50 g of toluene had been removed, rendering the reaction mixture water-free. The vacuum was discontinued and replaced with a nitrogen sweep. 1.77 g of titanium(IV) butoxide was added to the flask, and the temperature was then raised to 165 °C and maintained at that temperature until the concentration of ethyl p-aminobenzoate was less than 1 wt %. Residual toluene was then removed under vacuum. This new hardener has an average MW of 855 g / mol and a calculated % biobased carbon of approximately 69%.

[0061] Synthesis procedure for bio-based hardener with average MW 1300: A mixture of 200 g of ethyl p-aminobenzoate, 676 g of poly(1,3-propanediol) with a hydroxyl number of 105.3 mg KOH / g, and 200 g of toluene was charged to a 2 L round-bottom flask equipped with an overhead stirrer, thermocouple, short-path distillation head, and nitrogen sweep. The flask was purged with nitrogen, and the mixture was then heated to 100 °C under vacuum until 50 g of toluene was removed, rendering the reaction mixture water-free. The vacuum was discontinued and replaced with a nitrogen sweep. 1.75 g of titanium IV butoxide was added to the flask, and the temperature was then raised to 165 °C and maintained there until the concentration of ethyl p-aminobenzoate was less than 1 wt%. Residual toluene was then removed under vacuum. This new curing agent has an average MW of 1300 g / mol and a calculated % biobased carbon of approximately 79%.

[0062] Synthesis procedure for bio-based hardener with average MW 2013: A mixture of 125 g of ethyl p-aminobenzoate, 709.4 g of poly(1,3-propanediol) with a hydroxyl number of 63.08 mg KOH / g, and 200 g of toluene was charged to a 2 L round-bottom flask equipped with an overhead stirrer, thermocouple, short-path distillation head, and nitrogen sweep. The flask was purged with nitrogen, and the mixture was then heated to 100 °C under vacuum until 50 g of toluene had been removed, rendering the reaction mixture water-free. The vacuum was discontinued and replaced with a nitrogen sweep. 1.67 g of titanium IV butoxide was added to the flask, and the temperature was then raised to 165 °C and held there until the ethyl p-aminobenzoate content was less than 1 wt%. Residual toluene was then removed under vacuum. This new curing agent has an average MW of 2013 g / mol and a calculated % biobased carbon of approximately 87%.

[0063] Example 2: Cast Elastomer In cast elastomers, the isocyanate prepolymer and curative components are typically preheated and the streams are mixed hot. The mixed components are then pumped through heated lines, usually into a heated mold. Specialized machinery is commercially available for this type of processing. The physical state of the raw materials is generally not an issue to the manufacturer, since they are melted and heated.

[0064] Each oligomer diamine was cured with carbodiimide-modified 4,4'-MDI (methylene diphenyl diisocyanate) and compared with a low-free-release TDI (toluene diisocyanate) prepolymer of comparable hardness. Additionally, for comparison, both PTMEG and PPG-based prepolymers were used to demonstrate the inherent differences in performance between PTMEG and PPG at normalized hardness, as these systems are the most well-known methods for producing polyurea cast elastomeric parts. TDI prepolymers were cured with dimethylthiotoluene diamine. The stoichiometry for all systems was 95% (amine:isocyanate). The prepolymer and oligomer diamine were melted and preheated to 70°C before casting. The isocyanate and curing agent were mixed at a 95% stoichiometry (amine:isocyanate). Parts made with TDI prepolymers were cured at 100°C for 16 hours, while parts made with oligomer diamines were cured at 70°C for 16 hours. Generally, higher cure temperatures result in harder parts. However, in general, the mechanical properties of the PPD-based diamine systems are comparable to traditional PTMEG systems and significantly improved over PPG systems. In particular, abrasion resistance and split tear strength are comparable to PTMEG performance, and this is consistent across all three hardness systems.

[0065] [Table 1]

[0066] [Table 2]

[0067] [Table 3]

[0068] Typically, for coating and adhesive applications, systems are sold pre-blended. Pre-blended systems are expected to be stable for several months, allowing the end user to use them with little or no pretreatment. The following three examples demonstrate the performance of oligomeric aromatic diamines in various applications requiring some degree of liquid stability.

[0069] Example 3: Spray-applied Polyurea This application relies on an off-the-shelf system that requires some phase stability at room temperature (20-25°C). Traditional PTMEG-based amines are solid and therefore cannot be used for this application. Adding PTMEG to the resin side improves the mechanical properties of the spray coating, especially its abrasion resistance.

[0070] Typically, the formulation consists of a PPG or PTMEG-based MDI prepolymer with a mixture of 2,4'-MDI and 4,4'-MDI with an NCO of 14-18%. The curing agent side preferably consists of a PPG-based di- or tri-functional polyetheramine, an amine chain extender, and additives that can facilitate processing, such as UV scavengers, wetting agents, defoamers, and / or adhesion promoters.

[0071] The following examples use simplified formulations to demonstrate performance based on oligomer diamines. The isocyanate side was a PTMEG-based MDI prepolymer with 16% NCO. The curing agent side consisted of 61% by weight of a 2000 MW amine, 13% by weight of diethyltoluenediamine, and 26% by weight of 4,4'-methylenebis(N-sec-butylaniline). The 2000 MW amines compared were a PPG-based aliphatic primary diamine (designated D2000), a PPD-based aromatic diamine (PPD2000), and a PTMEG-based aromatic diamine (P2000). All reactants were preheated to 70°C. Sides A and B were placed in 1:1 capacity cartridges attached to a low-pressure air gun with a static mixer. Films approximately 0.15 inches thick were produced using a spray pressure of 80-90 psi. All films were post-cured at room temperature for two weeks before physical property testing.

[0072] Because the actual spraying process is carried out at high temperatures, P2000 can be used to prepare the spray. However, in practice, the system must be phase stable over the shelf life. P2000 has a relatively high melting point of 36°C, well above the standard storage temperature of approximately 25°C, which precludes its use even if the final film properties are very good. PPD-2000 is more compatible with the system and does not solidify at room temperature. Although there is a solvent effect when mixed with the chain extender, P2000 has been observed to drop out of the batch after several days of storage at 23-25°C.

[0073] [Table 4]

[0074] Example 4: Conventionally applied coating (i.e., roller, squeegee) The main difference between this system and spray-applied coatings is its long pot life. The reactivity between aromatic amines and isocyanates is sufficiently slow that the material can be hand-mixed and conventionally applied; linear primary polyetheramines, traditionally used in spray systems, are rarely used in roll coatings because they react too quickly with isocyanates. This example demonstrates a simplified system consisting of an 80 / 20 weight ratio of curing agent and a small amount of filler. Films are made by curing with carbodiimide-modified 4,4'-liquid MDI (29% NCO) and stretching to a specified thickness. A comparison is made with a fully optimized commercial system that contains a large amount of filler (e.g., talc, calcium carbonate, or barium sulfite) as well as other additives for performance enhancement, such as driers, wetting agents, adhesion promoters, degassing agents, and / or UV scavengers. All films are stretched to the specified thickness and then post-cured at room temperature for one day. Adhesion specimens are post-cured at 25°C for seven days before testing. This commercial system is also likely based on PPG, but uses additional materials to enhance performance, whereas PPD-based systems (PPD1000) can meet these performance criteria without the aid of additional materials. As with spray coatings, PPD1000 can be useful here due to its phase stability and viscosity. P1000-based systems are more stable than P2000 at room temperature because this material has a lower melting point of approximately 18-20°C.

[0075] [Table 5]

[0076] Example 5: Adhesion PPD-based systems can also be used as resins for adhesives. Demonstration of adhesive strength indicates that PPD1000 and PPD650 materials produce adhesive strengths comparable to PTMEG-based systems. Similar to coatings, adhesive systems are typically preblended and are expected to maintain phase stability over time at ambient conditions. In general, a typical adhesive formulation includes a base resin (a di- or trifunctional polyol (preferably a polyether) with a molecular weight of 700 to 3500), a chain extender (preferably a diol), a filler such as talc, calcium carbonate, or barium sulfate, and processing additives such as adhesion promoters, rheology modifiers, UV scavengers, wetting agents, drying agents, and defoamers.

[0077] The oligomer diamine was cured with liquid 4,4'-MDI (29% NCO) at a 95% stoichiometry (amine:isocyanate). The mixed resin was applied to pre-cleaned cold-rolled steel coupons with a 5 mm adhesive line. No primer was applied. Samples were allowed to cure for one week under ambient conditions before tensile testing to determine lap shear strength.

[0078] The lap shear strength of adhesives made with PPD-based oligomer diamines is comparable to that made with PTMEG and to the fully formulated system. These results are obtained without adding any additional additives to the system that might promote adhesion (i.e., aminosilanes for adhesion promotion, silicone surfactants for wetting).

[0079] [Table 6]

[0080] Example 6: Environmental benefits & reduced CO2 emissions Poly(1,3-propylene glycol) with a hydroxyl number of 105.3 mg KOH / g (MW approximately 1063 g / mol) was used as a sustainable alternative to petrochemical-based poly(tetramethylene ether) glycol (PTMEG). A mixture of 200 g of ethyl p-aminobenzoate, 676 g of poly(1,3-propanediol) with a hydroxyl number of 105.3 mg KOH / g, and 200 g of toluene was charged to a 2 L round-bottom flask equipped with an overhead stirrer, thermocouple, short-path distillation head, and nitrogen sweep. The flask was purged with nitrogen, and the mixture was then heated to 100 °C under vacuum until 50 g of toluene was removed, rendering the reaction mixture water-free. The vacuum was discontinued and replaced with a nitrogen sweep. 1.75 g of titanium IV butoxide was added to the flask, and the temperature was then raised to 165 °C and maintained there until the concentration of ethyl p-aminobenzoate was less than 1 wt%. Residual toluene was then removed under vacuum. This new curing agent has an average MW=1300 g / mol and a calculated % biobased carbon of about 79%.

[0081] Substituting PTMEG MW ≈1000g / mol with bio-based poly(1,3-propylene glycol) MW ≈1000g / mol 1:1 reduces the carbon footprint by over 50%. Thus, PTMEG MW ≈1000 releases 9.61Kg CO₂ per equivalent of amine curing agent, while bio-based poly(1,3-propylene glycol) MW ≈1000g / mol releases 4.67Kg CO₂ per equivalent of amine curing agent, a 50% reduction in carbon emissions. [Table 7]

[0082] Example 7: MALDI and GPC analysis of new hardeners (prophetic) MALDI and GPC analysis of the new compositions also disclose a unique isomer distribution, as indicated by the range of "n" in the general formula, which allows the curing agent to remain liquid or not form solids for extended periods of time, resulting in a substantially liquid amine curing agent without the need to provide heat for melting, resulting in improved processability. [ka]

Claims

1. formula: 【Chemistry 1】 wherein n=1 to 40; １４ An LCF-amine curing agent composition comprising at least one compound having a percent biomass content ranging from 100% to 10% as measured by the presence of the C isotope.

2. The LCF-amine curing agent composition of claim 1, wherein said at least one compound has n=1-30.

3. The at least one compound is １４ 3. The LCF-amine curing agent composition of claim 1 or 2 having a percent biomass content ranging from 100% to 50% as measured by the presence of C isotope.

4. The at least one compound is １４ 4. The LCF-amine curing agent composition of any one of claims 1 to 3 having a % biomass content in the range of 90% to 50% as measured by the presence of C isotope.

5. The at least one compound has a MW in the range of 76 g / mol to 3040 g / mol. １４ 5. The LCF-amine curing agent composition of any one of claims 1 to 4, prepared using a C-containing bio-based 1,3-propylene diol and / or a bio-based poly(1,3-propylene diol).

6. The at least one compound has a MW in the range of 76 g / mol to 2280 g / mol. １４ 5. The LCF-amine curing agent composition of any one of claims 1 to 4, prepared using a C-containing bio-based 1,3-propylene diol and / or a bio-based poly(1,3-propylene diol).

7. 7. The LCF-amine curing agent composition of claim 5 or 6, wherein the bio-based 1,3-propylene diol is produced by fermentation of biomass.

8. 7. The LCF-amine curing agent composition of claim 5 or 6, wherein the bio-based poly(1,3-propylene diol) is produced by fermentation of biomass and / or polycondensation of bio-based 1,3-propylene diol.

9. zero １４ 9. The LCF-amine curing agent composition of any one of claims 1 to 8, further comprising at least one amine co-curing agent made exclusively from fossil fuel-based materials having a C content.

10. 10. The LCF-amine curing agent composition of claim 9, wherein the at least one amine co-curing agent is an organic diamine or organic triamine.

11. 10. The LCF-amine curing agent composition of claim 8 or 9, wherein the at least one amine co-curing agent is an aromatic diamine.

12. The aromatic diamine E) Formula: 【Chemistry 2】 polymethylene-di-p-aminobenzoates having the formula: wherein X is an alkylene or cycloalkylene group having 2 to 12 carbon atoms, and the alkylene and cycloalkylene groups represented by X may be substituted or unsubstituted; F) Formula: 【Transformation 3】 polyethylene glycol-bis(4-aminobenzoate) having the formula: wherein n=2 to 4; G) Formula: 【Chemistry 4】 Polydimethylsiloxane-bis(4-aminobenzoate) having the formula: wherein n=2 to 4; and H) Formula: 【Transformation 5】 12. The LCF-amine curing agent composition of claim 11, wherein the LCF-amine curing agent is selected from the group consisting of polytetramethylene ether glycol-di-p-aminobenzoates having the formula: wherein n=1 to 40.

13. 13. An LCF polyurea composition comprising the reaction of at least one isocyanate with the LCF-amine curing agent composition of any one of claims 1-12.

14. 14. The LCF polyurea composition of claim 13, wherein the at least one isocyanate is a diisocyanate or polyisocyanate.

15. 15. The LCF polyurea composition of claim 14, wherein the diisocyanate or polyisocyanate is an aliphatic, arylaliphatic, or aromatic isocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate isomers, hydrated diphenylmethane diisocyanate isomers, and 1,5-naphthalene diisocyanate.

16. A method of making an LCF polyurea composition comprising contacting a diisocyanate or polyisocyanate with the LCF-amine curing agent composition of any one of claims 1-12.

17. 17. The method of claim 16, wherein the diisocyanate or polyisocyanate is an aliphatic, arylaliphatic, or aromatic isocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate isomers, hydrated diphenylmethane diisocyanate isomers, and 1,5-naphthalene diisocyanate.

18. A method for making an LCF polyurea polymer comprising contacting a bio-based amine curing agent 1,3-propylene glycol bis(4-aminobenzoate) or poly(1,3-propylene glycol) bis(4-aminobenzoate) with a diisocyanate or polyisocyanate.

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