Polyurethane-polyisocyanurate foam composition

Abstract

FIELD: polyol-based foam.SUBSTANCE: mixture of polyols for producing polyurethane-polyisocyanurate foam (PUF-PIF), as well as a composition for producing PUF-PIF, a foam material made from PUF-PIF, a method for producing a foam material from PUF-PIF and the use of a foam material from PUF-PIF for thermal insulation. The method for producing a polyol blend involves mixing three different polyols and a chain extending polyol. The different polyols indicated are selected from polyether polyols and polyester polyols. The polyol blend has a viscosity below 1000 mPa⋅s at 25°C. Based on a mixture of polyols, polyurethane-polyisocyanurate foam (PUF-PIF) is obtained as a result of the reaction of this mixture with at least one polyisocyanate compound in the presence of catalysts, foaming agents and other additives.EFFECT: resulting foam material based on PUF-PIF has improved physical properties and characteristics, in particular, in terms of such indicators as density, mechanical strength and thermal conductivity.18 cl, 2 tbl, 2 ex

Description

[0001] FIELD OF TECHNOLOGY

[0002] The proposed technical solution relates to a polyol blend for producing polyurethane polyisocyanurate foam (PUF-PIR). The blend contains three different polyols and a chain-extending polyol. This blend produces PUF-PIR, which can be used, in particular, as thermal insulation. The proposed technical solution also relates to a composition for preparing said PUF-PIR composition, the resulting foam material, and a method for producing said foam material.

[0003] STATE OF THE ART

[0004] Polyurethanes - polymers consisting of one or more urethane molecules - are well known to those skilled in the art and are currently used in a wide variety of applications as insulating materials, adhesives, or compounds for the automotive, textile, or furniture industries.

[0005] In particular, polyurethanes are used in the form of foam materials: polyurethane foam (PUF), polyisocyanurate foam (PIR), and polyurethane-polyisocyanurate foam (PUF-PIR), which can be flexible or rigid. The formation of foam materials is well known to those skilled in the art and involves the polymerization or condensation reaction of polyols with isocyanate compounds. Depending on the nature of the compounds, their quantity, and the presence of additives, polyurethane foams can be produced with different characteristics and properties specific to each composition.

[0006] Polyurethane foams are used in the automotive industry as flexible foam or as thermal insulation in the form of rigid foam. Polyurethane foam-PIR and polyisocyanurate foams are also used as thermal insulation. These foams surpass polyurethane foams in fire resistance and compressive strength.

[0007] PUF, PIR and PPU-PIR are classified depending on the ratio of isocyanate to polyol, while the mechanisms of formation of polyisocyanurate foams and PPU-PIR are similar to the mechanisms of formation of polyurethane foams.

[0008] Prior art documents, including patent applications Nos. US 2010 / 0116829 and WO 2020 / 104749 or patent application No. US 8 940 803, disclose a number of compositions for preparing PPU-PIR mixtures.

[0009] However, none of them can produce a foam material that simultaneously has a good thermal coefficient and satisfactory mechanical properties and meets industry technical requirements, while the viscosity of the foam composition must ensure uniform distribution.

[0010] The authors of the present invention have succeeded in obtaining a composition for preparing a polyurethane foam composition that allows overcoming at least some of the disadvantages of currently known solutions.

[0011] STATEMENT OF TECHNICAL SOLUTION

[0012] The proposed technical solution relates to a method for producing a polyol mixture, which comprises blending three (3) different polyols and a chain-extending polyol, wherein said different polyols are selected from polyether polyols and polyester polyols. This mixture is used to prepare a polyurethane-polyisocyanurate foam (PUF-PIR) composition, wherein the foam composition comprises said polyol mixture, at least one polyisocyanate compound, and a catalyst.

[0013] The proposed technical solution relates to a method for producing a mixture of polyols, characterized in that the polyether polyols are polyols based on glycerol and sorbitol and / or polyols based on glycerol and sucrose.

[0014] The proposed technical solution relates to a method for producing a mixture of polyols, characterized in that the polyester polyols are aromatic polyester polyols, preferably derivatives of phthalic acid.

[0015] The proposed technical solution relates to a method for producing a mixture of polyols, characterized in that the chain-extending polyol is a glycol-type derivative, preferably dipropylene glycol.

[0016] The proposed technical solution relates to a method for producing a mixture of polyols, characterized in that the mixture has a viscosity of 400 to 800 mPa s at 25°C.

[0017] The proposed technical solution relates to a method for obtaining a mixture of polyols, characterized in that the following are mixed:

[0018] - from 28 parts by weight (wt.) to 100 parts by weight of polyether polyols, wherein the first polyether polyol is from 18 parts by weight to 67 parts by weight, wherein the second polyether polyol is from 10 parts by weight to 25 parts by weight,

[0019] - from 5 parts by weight to 40 parts by weight of polyester polyol, and

[0020] —from 15 parts by weight to 30 parts by weight of chain-extending polyol. Thus, the proposed technical solution also applies to a foam composition that may also contain blowing agents and additives.

[0021] Thus, the proposed technical solution also relates to a composition for obtaining PPU-PIR, characterized in that the following are mixed:

[0022] - a polyol blend comprising three (3) different polyols and a chain extending polyol as defined in the proposed technical solution,

[0023] - at least one polyisocyanate compound, and

[0024] - catalyst.

[0025] Thus, the proposed technical solution also relates to a composition for producing PPU-PIR, characterized in that the composition contains from 90 parts by weight to 120 parts by weight of polyisocyanate per 100 parts by weight of polyols.

[0026] Thus, the proposed technical solution also relates to a composition for producing PUF-PIR, characterized in that the polyisocyanate is selected from aromatic diisocyanates; preferably, the isocyanate compound is methylene diphenyl diisocyanate (MDI).

[0027] Thus, the proposed technical solution also relates to a composition for producing PPU-PIR, characterized in that the catalyst is selected from tin catalysts and potassium carboxylates or a mixture thereof.

[0028] Thus, the proposed technical solution also relates to a composition for producing PPU-PIR, characterized in that the composition additionally contains a foaming agent selected from water, CO2, fluorinated foaming agents or a mixture thereof.

[0029] Thus, the proposed technical solution also relates to a composition for producing PPU-PIR, characterized in that it additionally contains one or more additives.

[0030] Another object of the proposed technical solution is a foam material made of polyurethane foam with the following characteristics: density from 110 kg / m3 3 up to 130 kg / m 3 , thermal conductivity from 24 mW / m K to 26 mW / m K and / or compressive strength from 1.30 MPa to 1.50 MPa.

[0031] Another object of the proposed technical solution is a foam material made of polyurethane foam and polyurethane foam based on the composition described above.

[0032] Another object of the proposed technical solution is a foam material made of polyurethane foam-PIR, characterized in that the said foam material has a density of 110 to 130 kg / m3 3 .

[0033] Another object of the proposed technical solution is a foam material made of polyurethane foam-PIR, characterized in that the said foam material has a thermal conductivity of 24 to 26 mW / m K.

[0034] Another object of the proposed technical solution is a foam material made of polyurethane foam-PIR, characterized in that the said foam material has a compressive strength of 1.30 to 1.50 MPa.

[0035] The proposed technical solution additionally includes a method for producing foam material from PPU-PIR, wherein said method includes the following stages:

[0036] i) contacting at least one polyisocyanate compound and a polyol mixture comprising three (3) different polyols and a chain extending polyol, wherein said polyols are selected from polyether polyols and polyester polyols, in the presence of one or more catalysts, one or more blowing agents and one or more flame retardants and one or more additives;

[0037] ii) apply the PPU-PIR composition to a stack of glass yarns or a stack of glass mats, and

[0038] iii) allow the said composition to harden after expansion to form a foam block.

[0039] The foam material obtained in this way can be used as thermal insulation, in particular as insulation for LNG tankers.

[0040] The proposed technical solution also relates to the use of polyurethane foam-polyisocyanurate foam, characterized above or obtained by the method characterized above, for thermal insulation.

[0041] IMPLEMENTATION OF THE TECHNICAL SOLUTION

[0042] Definitions

[0043] With regard to the proposed technical solution, regardless of whether the definition “approximately” is used or not, all quantitative features in the present description, in addition to the specified specific value, include a value close to it, which can be reasonably logically deduced by a person skilled in the art, as well as values ​​equivalent to the specified value and close to the specified value, adopted taking into account the conditions of the experiment and / or measurement.For example, the term "about" when applied to a stated value or range means "within 20% of a deviation," preferably "within 15% of a deviation," more preferably "within 10% of a deviation," more preferably "within 9% of a deviation," more preferably "within 8% of a deviation," more preferably "within 7% of a deviation," more preferably "within 6% of a deviation," and more preferably "within 5% of a deviation" from the stated value or range.

[0044] For the purposes of the proposed technical solution, "polyols" are defined as any organic compound with at least two hydroxyl (-OH) groups in the molecular structure. The reactivity of polyols depends on a number of parameters, including functionality, hydroxyl number, and aromaticity.

[0045] Functionality is the average number of reactive hydroxyl groups per molecule. During foam production, hydroxyl groups react with isocyanate groups (-NCO) contained in isocyanate compounds.

[0046] The hydroxyl value, or OHV, also abbreviated as "HV," of polyols is the number of reactive hydroxyl groups (-OH) available for reaction. The hydroxyl value is the amount in milligrams (mg) of potassium hydroxide (KOH) corresponding to the number of hydroxyl groups in one gram (g) of polyols, herein referred to as "mg KOH / g polyol." That is, the hydroxyl value is determined according to ASTM D4274-16. In particular, the determination of the hydroxyl value allows one to evaluate the cross-linking efficiency of a composition.

[0047] The aromaticity of compounds is an inherent property caused by the presence of a cyclic, planar structure, which is particularly stable. A compound is considered aromatic if it complies with Hückel's rules.

[0048] "Polyether polyols" refers to polyols containing at least one ether functional group in the molecular structure. "Polyester polyols" refers to polyols containing at least one ester functional group in the molecular structure.

[0049] "Chain extending polyol" means polyol molecules that promote the formation of chemical bonds and improve the physical properties of one or more compounds obtained by covalently attaching these molecules during the synthesis of the final product.

[0050] An "isocyanate compound" or "isocyanate" means any compound containing at least one isocyanate functional group in the molecular structure. A "polyisocyanate compound" or "polyisocyanate" means any organic compound with at least two isocyanate (-NCO) groups in the molecular structure.

[0051] PUF, PIR, and PIR-PUF are products of a chemical reaction between polyols and polyisocyanates and exhibit different properties depending on the nature of the compounds and the quantitative ratios used to produce their formulations. Specifically, they are characterized by the isocyanate-to-polyol ratio (NCO / OH ratio), also known as the "index," which corresponds to the ratio of the number of isocyanate groups to the number of hydroxyl groups in the polyols or other components containing such groups.

[0052] Thus, a distinction can be made between polyurethane foams (PUF) with an NCO / OH ratio of 1:1 to 1.3:1, polyurethane foam-polyisocyanurate foams (PUF-PIR) with a ratio of 1.3:1 to 1.8:1, and polyisocyanurate foams (PIR) with a ratio of 1.8:1 to 2.8:1.

[0053] "Foam material" means a compound with a foamed three-dimensional cellular structure. Foam material is produced by a chemical reaction between polyisocyanates and polyols in the presence of other compounds, particularly catalysts or blowing agents. The resulting foam material can be rigid or flexible, with open or closed cells. According to the proposed technical solution, PUR-PIR is a rigid foam material with closed cells containing gas.

[0054] The "closed gas-containing cells" provided by the proposed technical solution contain a gas obtained either from a blowing agent as a result of a chemical reaction in the case of a chemical blowing agent, for example, carbon dioxide (CO2) if this chemical agent is water, or from a physical blowing agent, for example, molecular nitrogen (N2), dioxygen (O2), carbon dioxide (CO2), hydrocarbons, chlorofluorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, or mixtures thereof. Physical blowing agents in a gaseous or liquid state are dispersed in the mass of a liquid copolymer. During foaming, nucleation, and growth of bubbles, a structure of closed cells containing this gas is formed.

[0055] By “foaming agent” we mean compounds that stimulate, by chemical and / or physical action, the expansion of the composition at the foaming stage.

[0056] In addition to the compounds required for their composition, PUR-PIR may contain flame retardants. As the name suggests, flame retardants are compounds that reduce or prevent the combustion or heating of materials containing them.

[0057] With regard to the proposed technical solution, the various ingredients used in the PUF-PIR composition are defined as percentages of the total polyol mass. The content of these various ingredients can also be expressed as parts by weight (wt.) of the total polyol mass in the composition.

[0058] Polyol blend

[0059] The proposed technical solution relates to a mixture of polyols for producing polyurethane foam-polyisocyanurate foam (PUF-PIR), characterized in that the mixture of polyols contains three (3) different polyols and a chain-extending polyol, wherein said different polyols are selected from simple polyether polyols and polyester polyols.

[0060] Simple polyether polyols and complex polyether polyols used in compositions for the preparation of PUF-PIR compounds are well known to those skilled in the art.

[0061] Polyether polyols

[0062] Polyether polyols used in PUF-PIR compositions typically have a molecular weight of about 150 g / mol to about 1600 g / mol, a functionality of 3 to 8, and a hydroxyl number of about 250 mg KOH / g polyol to about 1000 mg KOH / g polyol.

[0063] With regard to the proposed technical solution, the polyether polyols have a relative molecular weight of no more than about 1000 g / mol, preferably no more than about 800 g / mol. In one embodiment, the polyether polyols have a relative molecular weight of at least about 200 g / mol. In another embodiment, the polyether polyols used in the PUF-PIR composition have a relative molecular weight of from about 200 g / mol to about 800 g / mol. The polyether polyols according to the technical solution advantageously have a relative molecular weight of from about 200 g / mol to about 600 g / mol, preferably from about 300 g / mol to about 600 g / mol.

[0064] In another embodiment, the polyether polyols have a molecular relative weight of from about 350 g / mol to about 600 g / mol, from about 400 g / mol to about 600 g / mol, from about 450 g / mol to 600 g / mol, or from about 500 g / mol to 600 g / mol. In another embodiment, the polyether polyols used in the PUF-PIR composition advantageously have a molecular relative weight of from about 550 g / mol to about 600 g / mol, preferably from about 580 g / mol to about 600 g / mol.

[0065] The polyether polyols contained in the polyol mixture for preparing PUF-PIR have a hydroxyl number from about 50 mg KOH / g polyols to about 850 mg KOH / g polyols. With regard to the proposed technical solution, the mixture contains polyether polyols with a hydroxyl number of no more than about 800 mg KOH / g polyols, preferably no more than about 700 mg KOH / g polyols or even no more than about 600 mg KOH / g polyols. In one embodiment, the polyether polyols have a hydroxyl number of from about 50 mg KOH / g polyols to about 600 mg KOH / g polyols, preferably from about 100 mg KOH / g polyols to about 600 mg KOH / g polyols, more preferably from about 200 mg KOH / g polyols to about 600 mg KOH / g polyols.In another embodiment, the polyether polyols have a hydroxyl number of from about 100 mg KOH / g polyols to about 300 mg KOH / g polyols, from about 200 mg KOH / g polyols to about 300 mg KOH / g polyols, from about 200 mg KOH / g polyols to about 400 mg KOH / g polyols, or from about 300 mg KOH / g polyols to 400 mg KOH / g polyols. In yet another embodiment, the hydroxyl number of the polyether polyols used in the polyol blend for preparing PUF-PIR is from about 400 mg KOH / g polyols to about 600 mg KOH / g polyols or from about 300 mg KOH / g polyols to about 500 mg KOH / g polyols. Polyether polyols advantageously have a hydroxyl value of from about 350 mg KOH / g to about 400 mg KOH / g polyols or from about 350 mg KOH / g polyols to about 500 mg KOH / g polyols.In particular, the polyether polyols have a hydroxyl number of from about 350 mg KOH / g to about 390 mg KOH / g polyols, preferably from about 350 mg KOH / g to about 360 mg KOH / g polyols. In another embodiment, the hydroxyl number of the polyether polyols is from about 390 mg KOH / g to about 500 mg KOH / g polyols, in particular from about 390 mg KOH / g to about 470 mg KOH / g polyols.

[0066] Polyether polyols can also be characterized by their functionality and their viscosity. Thus, polyether polyols used in the polyol mixture for the preparation of PUF-PIR have a functionality of 3 to 8, preferably 3 to 6. The viscosity of the polyether polyols is below 5000 mPa s at 25 ° C, preferably not higher than 4000 mPa s at 25 ° C. In one embodiment, the viscosity of the polyether polyols is from 2500 to 3000 mPa s at 25 ° C. In another embodiment, the viscosity is below 1500 mPa s at 25 ° C. In another embodiment, the viscosity of the polyether polyols is approximately 700 mPa s at 25 ° C.

[0067] For the purposes of the proposed technical solution, polyether polyols are glycerol-based polyols. Specifically, polyether polyols are glycerol- and carbohydrate-based polyols.

[0068] Examples of carbohydrates suitable for polyether polyols include sucrose, sorbitol, fructose, glucose, lactose, maltose, galactose, sorbose, xylose, arabinose, mannose, cellobiose, methyl glucoside, and mixtures thereof. In one preferred embodiment, the carbohydrate-based polyether polyols used in the polyol mixture for preparing PUF-PIR are sucrose- and / or sorbitol-based polyols.

[0069] The polyether polyols used in the polyol mixture for the preparation of PUF-PIR are preferably glycerol-sorbitol-based polyols and / or glycerol-sucrose-based polyols.

[0070] Such polyether polyols are commercially available. In particular, they include Daltolac ® R404, marketed by Huntsman Corporation, Multranol ® 9260, Multranol ® 4030 and Multranol ® 4034, marketed by Bayer Corporation, Thanol ®R-572, marketed by Arco Chemical, Poly G ® 74-53, marketed by Olin Chemical, Voranol ® 202, Voranol ® 280, Voranol ® 360, Voranol ® 370, Voranol ® 490, Voranol ® 520, Voranol ® 615 and Voranol ® 800, marketed by Dow Chemicals Co., and Rubinol ® R180 and Rubinol ® R140, sold on the market by ICI Polyurethanes.

[0071] The polyether polyols used in the polyol blend for the foam formulation are preferably those marketed by Huntsman Corporation and Dow Chemicals Co. In particular, these are Daltolac formulations ® R404 and Voranol ® 360.

[0072] The polyether polyols used in the polyol blend may be identical or different from one another, that is, they may have identical or different characteristics. In one embodiment, the polyether polyols are identical. In another embodiment, and advantageously, the polyether polyols are different from one another.

[0073] Polyether polyols

[0074] In addition to polyether polyols, the polyol mixture according to the proposed technical solution contains polyether polyols.

[0075] With reference to the proposed technical solution, the polyether polyols have a molecular relative mass of from about 180 g / mol to about 4000 g / mol. In one embodiment, the molecular relative mass of the polyester polyols is no more than about 3000 g / mol, no more than about 2000 g / mol, or even no more than about 1000 g / mol. In another embodiment, the molecular relative mass is no less than about 180 g / mol or even no less than about 200 g / mol. In another embodiment, the polyether polyols have a molecular relative mass of from about 200 g / mol to 900 g / mol, preferably from about 200 g / mol to about 800 g / mol, more preferably from about 200 g / mol to about 700 g / mol.In particular, the polyether polyols used in the polyol mixture for preparing PUF-PIR have a relative molecular weight of from about 250 g / mol to about 600 g / mol, preferably from about 250 g / mol to about 550 g / mol. The relative molecular weight of the polyether polyols is preferably from about 300 g / mol to about 550 g / mol, preferably from about 400 g / mol to about 550 g / mol. In another embodiment, the relative molecular weight of the polyether polyols is from about 420 g / mol to about 500 g / mol, from about 430 g / mol to about 500 g / mol, from about 450 g / mol to about 500 g / mol, and preferably from about 460 g / mol to about 490 g / mol.

[0076] At the same time, the polyester polyols used in the polyol mixture for preparing PUF-PIR have a hydroxyl number from about 100 mg KOH / g polyols to about 400 mg KOH / g polyols, preferably from about 150 mg KOH / g polyols to about 400 mg KOH / g polyols, more preferably from about 150 mg KOH / g polyols to about 350 mg KOH / g polyols. In another embodiment, the polyester polyols according to the proposed technical solution have a hydroxyl number from about 200 mg KOH / g to about 350 mg KOH / g polyols, preferably from about 200 mg KOH / g to about 300 mg KOH / g polyols, more preferably from about 220 mg KOH / g polyols to about 300 mg KOH / g polyols.In particular, the polyether polyols contained in the polyol mixture have a hydroxyl number of from about 220 mg KOH / g polyols to about 270 mg KOH / g polyols, from about 220 mg KOH / g polyols to about 260 mg KOH / g polyols, from about 220 mg KOH / g polyols to about 250 mg KOH / g polyols, or from about 230 mg KOH / g polyols to 250 mg KOH / g polyols.

[0077] The functionality of the polyester polyols used in the composition is from 1.5 to 5, preferably from 1.5 to 3. In one embodiment, the functionality of the polyester polyols is from 1.5 to 2.5. Advantageously, the functionality of the polyester polyols is 2.

[0078] Like polyether polyols, the viscosity of polyester polyols is lower than 5000 mPa s at 25°C. In one embodiment, the viscosity is not lower than 1000 mPa s or even not lower than 2000 mPa s. The viscosity of polyether polyols used in the polyol mixture for preparing PUF-PIR is preferably from 2500 mPa s to 4500 mPa s at 25°C, preferably from 2500 to 4000 mPa s, and more preferably from 3000 to 4000 mPa s at 25°C.

[0079] The polyester polyols used in the polyol blend may be identical or different from each other.

[0080] Commercially available polyester polyols include Stepanpol ® PS-2352, Stepanpol ® PS-1752, Stepanpol ® PS-3152 and Stepanpol ® PS-3024, sold on the market by Stepan Company.

[0081] In one embodiment, the polyester polyols used in the polyol mixture are Stepanpol brand compounds ®, in particular, Stepanpol ® PS-2352.

[0082] A blend of 3 different polyols

[0083] With regard to the proposed technical solution, the polyol mixture for preparing PUF-PIR comprises a mixture of three (3) different polyols, wherein said polyols are selected from the polyether polyols and polyester polyols described above. In one embodiment, the mixture of three (3) different polyols comprises three (3) polyether polyols. In another embodiment, the mixture of three (3) different polyols comprises two (2) polyether polyols and (1) polyester polyol. In another embodiment, the mixture of three (3) different polyols comprises one (1) polyether polyol and two (2) polyester polyols. In yet another embodiment, the mixture of three (3) different polyols comprises three (3) polyester polyols. The mixture of three (3) different polyols according to the invention preferably comprises two (2) polyether polyols and one (1) polyester polyol.

[0084] Thus, the blend of three (3) different polyols preferably comprises: a first polyether polyol with a molecular relative weight of from about 300 g / mol to about 600 g / mol, a hydroxyl number of from about 390 mg KOH / g to about 470 mg KOH / g polyols and a viscosity below 1500 mPa s at 25°C, a second polyether polyol with a molecular relative weight of from about 580 g / mol to about 600 g / mol, a hydroxyl number of from about 350 mg KOH / g to about 360 mg KOH / g polyols and a viscosity of not higher than 1500 mPa s at 25°C and a polyester polyol characterized by a molecular relative weight of from about 460 g / mol to about 490 g / mol, a hydroxyl number of from approximately 230 mg KOH / g polyols to 250 mg KOH / g polyols and a viscosity of 3000 to 4000 mPa s at 25°C.

[0085] Chain extending polyol

[0086] The polyol blend for preparing a PUF-PIR composition additionally contains a chain-extending polyol. Thus, the polyol blend contains: a blend of three (3) different polyols selected from polyether polyols and polyester polyols, and a chain-extending polyol. Chain-extending polyols are functionalized compounds that can also act as crosslinkers. These compounds typically have a molecular weight of less than 350 g / mol and contain 2 to 14 carbon atoms.

[0087] With regard to the proposed technical solution, the chain-extending polyols have a molecular relative weight of from about 50 g / mol to about 300 g / mol, preferably from about 50 g / mol to about 250 g / mol, more preferably from about 50 g / mol to about 200 g / mol. The chain-extending polyols advantageously have a molecular relative weight of from about 100 g / mol to about 150 g / mol. In one preferred embodiment, the chain-extending polyols have a molecular relative weight of about 134 g / mol.

[0088] The hydroxyl number of the chain-extending polyols used in the polyol mixture for preparing PUF-PIR is from about 100 mg KOH / g polyols to about 1000 mg KOH / g polyols. In one embodiment, the chain-extending polyols have a hydroxyl number of at least about 200 mg KOH / g polyols, preferably at least about 300 mg KOH / g polyols, more preferably at least about 500 mg KOH / g polyols. In another embodiment, the hydroxyl number of the chain-extending polyols is from about 500 mg KOH / g polyols to about 1000 mg KOH / g polyols, preferably from about 600 mg KOH / g polyols to about 1000 mg KOH / g polyols, more preferably from about 700 mg KOH / g polyols to about 1000 mg KOH / g polyols.In another embodiment, the hydroxyl number of the chain-extending polyols used in the polyol mixture according to the proposed technical solution is from about 800 mg KOH / g polyols to about 950 mg KOH / g polyols, preferably from about 800 mg KOH / g polyols to about 900 mg KOH / g polyols. The chain-extending polyols advantageously have a hydroxyl number of from about 800 mg KOH / g polyols to about 850 mg KOH / g polyols, preferably from about 820 mg KOH / g polyols to about 850 mg KOH / g polyols, in particular from about 830 mg KOH / g polyols to about 850 mg KOH / g polyols. In one preferred embodiment, the hydroxyl number of the chain-extending polyol is about 837 mg KOH / g polyols.

[0089] Another characteristic of chain-extending polyols is functionality. According to the proposed technical solution, chain-extending polyols have a functionality of approximately 2. The functionality of chain-extending polyols is preferably 2.

[0090] The viscosity of the chain-extending polyols is 50 to 500 mPa s at 25°C, preferably 100 to 300 mPa s, and more preferably 150 to 250 mPa s. In particular, the viscosity of the chain-extending polyols is 175 to 225 mPa s, preferably 190 to 210 mPa s at 25°C. The polyol mixture for preparing PUF-PIR preferably contains a chain-extending polyol with a viscosity of 200 mPa s at 25°C.

[0091] Examples of chain-extending polyols include bifunctionalized compounds such as diamines or diols, or trifunctionalized compounds such as triamines and triols. Examples include ethylene glycol, the isomers propane-1,2-diol and -1,3-diol, the isomers pentane-1,2-diol and -1,3-diol, decane-1,10-diol, the isomers dihydroxycyclohexane-1,2-diol, -1,3-diol and -1,4-diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butane-1,4-diol, hexane-1,6-diol, bis(2-hydroxyethyl)hydroquinone, the isomers 1,2,4- and 1,3,5-trihydroxycyclohexane, glycerol, trimethylolpropane, and low molecular weight polyalkylene oxide compounds with hydroxyl groups based on ethylene oxide and / or 1,2-propylene oxide, as well as the compounds characterized above.

[0092] In one embodiment, the chain-extending polyol used in the polyol mixture is a glycol derivative, selected in particular from derivatives of ethylene glycol or propylene glycol. In one preferred embodiment, the chain-extending compound is dipropylene glycol.

[0093] A blend of 4 polyols

[0094] Thus, a chain-extending polyol and a mixture of three (3) different polyols, in which said different polyols are selected from polyether polyols and polyester polyols, form a mixture of polyols for the preparation of PUF-PIR according to the proposed technical solution.

[0095] The mixture of polyols for the preparation of PPU-PIR contains, in parts by weight of the total mass of polyols:

[0096] - from about 20 parts by weight to about 100 parts by weight of polyether polyols, preferably from about 10 parts by weight to about 70 parts by weight of a first polyether polyol and from about 10 parts by weight to 40 parts by weight of a second polyether polyol,

[0097] - from about 5 parts by weight to about 50 parts by weight of polyester polyols, and

[0098] - from about 10 parts by weight to about 30 parts by weight of chain-extending polyols.

[0099] In another embodiment, the polyol mixture comprises:

[0100] - from about 28 to about 100 parts by weight of polyether polyols, preferably from about 18 to 67 parts by weight of a first polyether polyol and from about 10 parts by weight to 25 parts by weight of a second polyol,

[0101] - from about 5 parts by weight to about 40 parts by weight of polyester polyols, and

[0102] - from about 15 parts by weight to about 30 parts by weight of chain-extending polyols.

[0103] Preferably, the polyol mixture contains:

[0104] - from about 65 to about 80 parts by weight of polyether polyols, preferably from about 44 to 55 parts by weight of a first polyether polyol and from about 15 parts by weight to 25 parts by weight of a second polyol,

[0105] - from about 20 parts by weight to about 35 parts by weight of polyester polyols, and

[0106] - from about 15 parts by weight to about 25 parts by weight of chain-extending polyols.

[0107] More preferably, the polyol mixture contains:

[0108] - from about 65 to about 80 parts by weight of polyether polyols, preferably from about 48 to 55 parts by weight of a first polyether polyol and from about 17 parts by weight to 23 parts by weight of a second polyol,

[0109] - from about 25 parts by weight to about 32 parts by weight of polyester polyols, and

[0110] - from about 18 parts by weight to about 25 parts by weight of chain-extending polyols.

[0111] A polyol blend comprising three (3) different polyols and a chain extending polyol, wherein said different polyols are selected from polyether polyols and polyester polyols, preferably comprising, in parts by weight based on the total weight of the polyols:

[0112] - approximately 70 parts by weight of polyether polyols,

[0113] - approximately 30 parts by weight of polyester polyols, and

[0114] - approximately 20 parts by weight of chain-extending polyols.

[0115] In particular, the polyol mixture contains, in parts by weight of the total weight of the polyols:

[0116] - about 50 parts by weight of the first polyether polyol,

[0117] - approximately 20 parts by weight of the second polyether polyol,

[0118] - approximately 30 parts by weight of polyester polyols, and

[0119] - approximately 20 parts by weight of chain-extending polyols.

[0120] In another embodiment, the mixture of polyols for preparing PUF-PIR contains, in weight percent of the total weight of the polyols:

[0121] - from about 20% to about 85% polyether polyols, preferably about 30% to 60% of a first polyether polyol and from about 5% to about 40% of a second polyether polyol,

[0122] - from about 10% to about 50% polyester polyols, and

[0123] - from about 5% to about 35% chain extending polyols.

[0124] In another embodiment, the mixture of polyols for preparing PPU-PIR contains, in weight percent of the total weight of the polyols:

[0125] - from about 30% to about 70% polyether polyols, preferably about 35% to 50% of a first polyether polyol and from about 10% to about 35% of a second polyether polyol,

[0126] - from about 15% to about 35% polyester polyols, and

[0127] - from about 10% to about 25% chain extending polyols.

[0128] In another embodiment, the mixture of polyols for preparing PPU-PIR contains, in weight percent of the total weight of the polyols:

[0129] - from about 40% to about 60% polyether polyols, preferably about 35% to 50% of a first polyether polyol and from about 10% to about 25% of a second polyether polyol,

[0130] - from about 20% to about 30% polyester polyols, and

[0131] - from about 15% to about 25% chain extending polyols.

[0132] The polyol mixture preferably comprises, in percent by weight of the total weight of the polyols:

[0133] - about 58% polyether polyols, preferably about 42% of the first polyether polyol and about 16% of the second polyether polyol,

[0134] - approximately 24% polyester polyols, and

[0135] - approximately 18% chain extending polyols.

[0136] The polyol mixture obtained in this way and containing three (3) different polyols and a chain-extending polyol, wherein the different polyols are selected from polyester polyols and polyether polyols, has a viscosity of below 5000 mPa s at 25°C, preferably below 1000 mPa s at 25°C, more preferably not higher than 900 mPa s at 25°C. In another embodiment, the viscosity of the polyol mixture is not lower than 200 mPa s, preferably not lower than 300 mPa s, more preferably not lower than 400 mPa s at 25°C. In yet another embodiment, the polyol mixture has a viscosity of from 400 to 900 mPa s at 25°C. The polyol mixture corresponding to the proposed technical solution and used for the PUF-PIR composition preferably has a viscosity of 400 to 800 mPa s at 25°C, preferably 500 to 800 mPa s, and more preferably 600 to 800 mPa s at 25°C. In another embodiment, the viscosity of the polyol mixture is 750 mPa s at 25°C.

[0137] PPU-PIR composition

[0138] A polyol blend containing three (3) different polyols and a chain-extending polyol, wherein the different polyols are selected from polyester polyols and polyether polyols, can be used to prepare PUF-PIR.

[0139] PUF-PIR foam is a cellular structure formed by small closed cells that enclose gas. The formation of PUF-PIR foams is well known to those skilled in the art and involves a multicomponent reaction between one or more polyols, one or more polyisocyanates, and a blowing agent. This condensation reaction can be catalyzed by basic and / or nucleophilic compounds, such as tertiary amines, organometallic complexes, or alkali metal complexes.

[0140] Thus, the PPU-PIR composition according to the proposed technical solution contains a mixture of polyols containing three (3) different polyols and a chain-extending polyol, characterized above, and at least one polyisocyanate compound and a catalyst.

[0141] Polyisocyanate compounds

[0142] Polyisocyanate compounds are characterized by the presence of at least two isocyanate (-NCO) groups in the structure of their molecule.

[0143] Polyisocyanate compounds suitable for the PUF-PIR composite are known to those skilled in the art. These polyisocyanate compounds include aromatic, aliphatic, cycloaliphatic, and arylaliphatic polyisocyanates and mixtures thereof.

[0144] Polyisocyanate compounds according to the proposed technical solution are diisocyanate compounds, i.e. compounds containing two isocyanate groups, which can be aliphatic or aromatic.

[0145] The polyisocyanate compounds have a viscosity of 100 to 3000 mPa s at 25°C. The polyisocyanates used in the PUF-PIR composition have a viscosity of no more than 2000 mPa s or even less than 1000 mPa s. In one embodiment, the polyisocyanates have a viscosity of 200 to 1000 mPa s, preferably 200 to 800 mPa s, more preferably 200 to 600 mPa s at 25°C.

[0146] The functionality of the polyisocyanate compound is 2.5 to 3.5, preferably 2.7 to 3.1.

[0147] Diisocyanate compounds suitable for the present invention are hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane 4,4'-diisocyanate (H12MDI), cyclohexane 1,4-diisocyanate (CHDI), bis(isocyanatomethyl)cyclohexane (H6XDI,DDI), m-xylene diisocyanate (m-XDI), tetramethylxylylene diisocyanate (TMXDI), toluene diisocyanate (TDI), toluene 2,4- and 2,6-diisocyanate isomers (2,4-TDI and 2,6-TDI), methylene diphenyl diisocyanate (MDI), such as diphenylmethane 4,4'-, 2,4'- and 2,2'-diisocyanate isomers (2,4'-MDI, 2,4'-MDI and 2,2'-MDI), and dibenzyl diisocyanate, such as the isomers dibenzyl 4,4'- and 2,4'-diisocyanate (4,4'-DBDI and 2,4'-DBDI).

[0148] In one embodiment of the proposed technical solution, the polyisocyanate compound is an aromatic diisocyanate compound, preferably selected from toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), and dibenzyl diisocyanate (DBDI). The diisocyanate compound is preferably selected from methylene diphenyl diisocyanates (MDI).

[0149] Diisocyanate compounds can be produced commercially. Examples of such compounds include Voranate ® , Voracor ® , for example, Voracor ® CL100 or Voracor ® CE101, or PAPI ® , for example, PAPI ® 27, which is available from Dow Chemical Co., Suprasec ® S5005 and Suprasec ® S2085, which can be purchased from Huntsman, as well as Lupranate ® M20 and Lupranate ® M50, which can be purchased from BASF.

[0150] It should be understood that the diisocyanate compound according to the proposed technical solution may be a mixture of a plurality of diisocyanate compounds characterized above.

[0151] The presence of a polyisocyanate compound in addition to the polyol mixture is necessary for forming the foam material. Thus, the amount of polyisocyanate is at least about 70 parts by weight per 100 parts by weight of polyols. In one embodiment, the amount of polyisocyanate is from about 70 parts by weight to about 140 parts by weight, preferably from about 80 parts by weight to about 130 parts by weight, more preferably from about 83 parts by weight to about 128 parts by weight, per 100 parts by weight of polyols. The amount of polyisocyanate is preferably from about 85 parts by weight to about 125 parts by weight, preferably from about 87 parts by weight to about 123 parts by weight, more preferably from about 90 parts by weight to about 120 parts by weight, per 100 parts by weight of polyols.

[0152] In another embodiment, the amount of polyisocyanates is from about 80% to about 200% by weight of the total weight of the polyols. In one embodiment, the amount of polyisocyanates is from about 90% to about 180%, preferably from about 100% to about 150%. In another embodiment, the amount of polyisocyanates in the PUF-PIR composition is from about 100% to about 140%, preferably from about 110% to about 130%, more preferably from about 115% to 125%, by weight of the total weight of the polyols. The foam material according to the proposed technical solution preferably contains from about 117% to 123% polyisocyanates, preferably from about 118% to about 122% and more preferably from about 119% to about 121%, by weight of the total weight of the polyols.

[0153] Furthermore, the amount of isocyanate compound can be characterized by the isocyanate-to-polyol ratio. Examples of isocyanate-to-polyol ratios according to the proposed technical solution include 1:1 and 1.8:1. According to the proposed invention, the resulting foam materials are PUF-PIR foams and have an isocyanate-to-polyol ratio of 1 to 1.25.

[0154] Catalysts

[0155] By "catalyst" is meant any compound that accelerates the polymerization or condensation reaction between polyols and polyisocyanates.

[0156] Any compounds that typically catalyze this reaction between polyols and polyisocyanates can be used.

[0157] The catalysts may be gelling, expansion, hardening, or trimerization catalysts commonly used in the preparation of polyisocyanurate foams. Information on these can be found in the description of the compositions in the "Kunststoffhandbuch" ["Plastics Handbook"], Volume 7, "Polyurethane" ["Polyurethanes"], Carl Hanser, 3rd edition, 1993, Chapter 3.4.1.

[0158] According to the proposed technical solution, the catalysts are selected from organometallic catalysts, in particular tin catalysts or tin-based catalysts, bismuth-based catalysts and alkali metal carboxylates.

[0159] In one embodiment, the catalysts are selected from tin(II) carboxylates, e.g., tin acetate, tin octoate, ethylhexanoate tin, tin laurate, and tin(IV) carboxylates, e.g., dibutyltin diacetate, dibutyltin dilaurate (DBTDL), dibutyltin maleate, and dioctyltin diacetate.

[0160] In another embodiment, the catalysts used in the PUF-PIR composition are bismuth-based catalysts, in particular bismuth carboxylates, bismuth alkanolamines, or bismuth thiolates. Examples of such compounds include bismuth neodecanoate, bismuth 2-ethylhexanoate, and bismuth octanoate.

[0161] In another embodiment, the catalysts used are alkali metal carboxylates, preferably potassium carboxylates, in particular potassium acetate, potassium formate, or potassium octanoate. The catalyst is preferably potassium octanoate.

[0162] In another embodiment, the catalyst is a mixture of catalysts, preferably a mixture comprising a tin-based catalyst and an alkali metal carboxylate. In another embodiment, the mixture comprises a tin catalyst and potassium octanoate.

[0163] Thus, the catalyst used in the PPU-PIR composition is selected from tin catalysts, potassium carboxylates or a mixture thereof.

[0164] It is also possible to use commercially available catalysts in the PPU-PIR composition, such as Polycat® type catalysts sold on the market by Evonik Industries, in particular Polycat® 5, Polycat® 9 and Polycat® 203, or Kosmos® type catalysts, such as Kosmos® T12N sold on the market by Evonik Industries.

[0165] Foaming agents

[0166] The PUF-PIR composition additionally contains a foaming agent. This component allows for the formation of a cellular foam structure and can be physical and / or chemical. The foaming agent is preferably a combination of these two types.

[0167] Physical blowing agents are well known to those skilled in the art and include hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), or hydrofluoroolefins (HFOs).

[0168] Examples of hydrochlorofluorocarbons are HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane) and HCFC-141b (1,1-dichloro-1-fluoroethane).

[0169] Thus, in one embodiment of the invention, the blowing agent is selected from hydrofluorocarbons (HFCs), such as HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane, HFC-134a (1,1,1,2-tetrafluoroethane) and HFC-152a (1,1-difluoroethane), or hydrofluoroolefins (HFOs), such as HFO-1234yf (2,3,3,3-tetrafluoropropene), HFO-1234ze (1,3,3,3-tetrafluoropropene) or HFO-1233zd (1-chloro-3,3,3-trifluoropropene).

[0170] In another embodiment, the foaming agent is a chemical agent, in particular carbon dioxide (CO2) and / or water. In particular, water as a foaming agent causes the release of CO2, which leads to foam expansion. Water is a preferred chemical foaming agent.

[0171] Physical and chemical blowing agents can be used separately or simultaneously. According to one embodiment of the invention, the blowing agent includes a physical agent and a chemical agent. Thus, in one embodiment, the blowing agent is a mixture containing a hydrofluorocarbon (HFC), a hydrofluoroolefin (HFO) and / or carbon dioxide (CO2), wherein the hydrofluorocarbon and hydrofluoroolefin compounds are selected from the compounds mentioned above. In another embodiment, the blowing agent is a mixture containing HFC-365mfc and / or HFC-245fa in combination with water.

[0172] The PPU-PIR composition according to the invention may contain one or more foaming agents.

[0173] In one embodiment, the composition comprises a foaming agent selected from water, CO2, the above-described fluorinated foaming agents, or a mixture thereof.

[0174] The amount of physical blowing agent is calculated depending on the density of the PUF-PIR. It is preferably from 0% to about 10% by weight of the total weight of the polyols. In one embodiment, the amount of blowing agent is from about 2% to about 10%, preferably from about 5% to about 10%, by weight of the total weight of the polyols. The amount of blowing agent in the PUF-PIR composition is preferably about 7% by weight of the total weight of the polyols.

[0175] The amount of water also depends on the density of the desired foam material. According to the invention, it is preferably from 0% to about 1%, preferably from 0% to about 0.5%, more preferably from 0% to about 0.2%, by weight of the total weight of the polyols.

[0176] Fire retardants

[0177] PUR-PIR foams typically contain flame retardants to reduce flammability and improve fire resistance. Flame retardants are well known to those skilled in the art and are described in the "Kunststoffhandbuch" ["Plastics Handbook"], Volume 7, "Polyurethane," Chapter 6.1.

[0178] Compositions used as fire retardants include, in particular: brominated compound Ixol ® B251, dibromoneopentyl alcohol, tribromoneopentyl alcohol, tetrabromophthalate diol, known as PHT4-diol TM, chlorinated phosphates, in particular trichloropropyl phosphate (TCPP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCCP) and tris-(1,3-dichloroisopropyl) phosphate (TDCPP).

[0179] It is also possible to use inorganic fire retardants, in particular phosphorus or phosphorus-containing compositions, expandable graphite, aluminum hydroxide, antimony trioxide, ammonium polyphosphate, calcium sulfate, cyanuric acid derivatives such as melamine, or mixtures of at least two fire retardants, such as ammonium iophosphate and melamine.

[0180] Examples of other halogen-free liquid flame retardants include diethyl ethyl phosphate (DEEP), triethyl phosphate (TEP), dimethyl propyl phosphate (DMPP), or diphenyl cresyl phosphate (DPC).

[0181] In one embodiment, the foam composition comprises a flame retardant, preferably in an amount of 5% to 20% by weight of the total weight of the polyols.

[0182] In another embodiment, the composition does not contain a fire retardant. In a preferred embodiment of the invention, the composition does not contain any fire retardant.

[0183] Supplements

[0184] In addition, the composition may contain other additives commonly used in the preparation of PPU-PIR, such as surfactants, stabilizers, emulsifiers, plasticizers, dyes or crosslinkers.

[0185] In one embodiment, the foam composition comprises at least one additive, preferably a surfactant.

[0186] In one embodiment, the composition comprises at least one surfactant. Surfactants, also referred to as "surface-active agents" or emulsifiers, are compounds that alter the surface tension between two surfaces. Thus, they perform the function of solubilizing at least two immiscible phases. According to the proposed technical solution, the PUF-PIR composition may contain one or more surfactants. These compositions may be of the organosilicon type or non-organosilicon type, or a mixture of both. Examples of organosilicon surfactants suitable for the preparation of PUF-PIR compositions include Tegostab ®B-8427, B-2454, B-8404, B-8407, B-8409, B-8462, B-8465, B-8315, B-1048 and B-84507, marketed by Evonik, L-5130, L-5180, L-5340, L-5440, L-6100, L-6900, L-6980 and L-6980, marketed by Momentive, and DC-5374, DC-193, DC-197, DC-5582 and DC-5598, marketed by Dow Corning. Examples of non-silicon surfactants include ethoxylated alkyl phenols, ethoxylated fatty alcohols, paraffin oils, castor oil esters, ricinoleic acid esters, peanut oil, and fatty alcohols.

[0187] Properties of PPU-PIR

[0188] A polyurethane foam-PIR composition containing a mixture of polyols, a catalyst, one or more blowing agents, and one or more additives, enables, among other things, uniform distribution of the foam material in its liquid state. Uniform distribution means uniform and equal distribution of the foam material across the entire base or surface to which the liquid composition is applied before expansion. Once the foam material is obtained, it will have identical and uniform thermal and mechanical properties at any point.

[0189] Thus, the foam material has physical and chemical characteristics and special mechanical properties, due, in particular, to its composition.

[0190] Examples of physical and chemical properties are thermal conductivity, density, and compressive strength.

[0191] In a liquid state, or particularly in an emulsion, the foam exhibits stable attraction, with a rise time of approximately sixty (60) seconds. This rise time can be defined as the time between the start of mixing all ingredients and the appearance of the first bubbles, a visible change in the composition's color, or the expansion of the mixture into foam. This rise time is determined in accordance with ASTM D7487.

[0192] After the foam is formed, it will have a density of less than 150kg / m3 3 or even less than 140 kg / m 3 In one embodiment, the density of the resulting foam material is from 90 to 140 kg / m3 3 , preferably from 100 to 140 kg / m 3 , more preferably from 110 to 130 kg / m 3 In another embodiment, the PPU-PIR according to the proposed technical solution has a density of 115 to 125 kg / m3 3, preferably from 116 to 122 kg / m 3 , more preferably from 118 to 122 kg / m 3 In one preferred embodiment, the PUR-PIR has a density of approximately 120 kg / m3 3 .

[0193] At the same time, the PUR-PIR foam has a thermal conductivity of less than 30 mW / m K or even less than 27 mW / m K. Thermal conductivity characterizes the ability of the foam material to dissipate heat. Thus, the lower the thermal conductivity, the greater the insulation provided by the foam material. In one embodiment, the thermal conductivity is from 20 to 27 mW / m K, preferably from 22 to 26 mW / m K, more preferably from 23 to 26 mW / m K. In particular, the thermal conductivity of the foam material according to the invention is from 24 to 26 mW / m K. In another embodiment, the PUR-PIR foam has a thermal conductivity of approximately 25 mW / m K.

[0194] In terms of mechanical properties, the resulting foam material can be characterized by compressive strength, compressive modulus, tensile or shear strength, flexural strength, etc.

[0195] Compressive strength is a measure of a foam's ability to withstand an applied compressive load, i.e., an external load applied to the foam to change its shape and / or size.

[0196] According to the proposed technical solution, the PUF-PIR has a compressive strength of above 1.10 MPa or even above 1.20 MPa. In one embodiment, the compressive strength of the foam material is from 1.20 to 1.60 MPa, preferably from 1.30 to 1.60 MPa, more preferably from 1.30 to 1.50 MPa. The compressive strength of PUF-PIR is preferably from 1.40 to 1.50 MPa in accordance with the International Organization for Standardization (ISO) standard ISO 844.

[0197] Method for manufacturing a PPU-PIR block

[0198] After expanding the above-described liquid PPU-PIR composition, PPU-PIR is obtained.

[0199] PUF-PIR is the result of a physicochemical process in which a mixture of polyols reacts with polyisocyanates. This reaction can be described as a polymerization or condensation reaction. The exothermic reaction releases carbon dioxide, causing the foam to expand.

[0200] The method for manufacturing a PPU-PIR block according to the proposed technical solution includes the following stages, in which:

[0201] i) contacting at least one polyisocyanate compound and a polyol mixture comprising three (3) different polyols and a chain extending polyol, wherein said polyols are selected from polyether polyols and polyester polyols, in the presence of catalysts, blowing agents, as well as additives and fire retardants,

[0202] ii) applying the foam composition obtained in step i) to the substrate, and

[0203] iii) allowing said composition to harden after expansion to form a foam block.

[0204] Thus, in the first step, at least one polyisocyanate compound is contacted with a polyol mixture consisting of three different polyols and a chain-extending polyol, in the presence of catalysts, blowing agents, and additives. Mixing is preferably carried out at ambient temperature using a "low-pressure" or "high-pressure" system. "Low-pressure" and "high-pressure" systems are well known to those skilled in the art, who will be able to determine, in particular, which system to use depending on the composition and characteristics of the foam material.

[0205] Next, the mixture obtained and corresponding to the PPU-PIR composition according to the proposed technical solution is quickly poured onto the base to evenly distribute the composition over the entire base.

[0206] The polyurethane foam-PIR composite, initially in a liquid state, transforms into foam through a chemical reaction. This expansion stage of the foam material can occur freely or under the influence of force.

[0207] In one embodiment, the expansion occurs freely, i.e., without the effect of stress due to a volume closed in cross-section. In another embodiment, the expansion of the foam is physically limited by the walls of a two-belt laminator, preferably a two-belt laminator that forms a tunnel of rectangular cross-section, in which the distance between the side walls is equal to L, and the distance between the horizontally located walls is equal to E, which confines the expanding foam, thereby allowing the foam block to be formed into a specific size.

[0208] Next, the foam is allowed to harden. This final curing or curing stage can be performed at elevated temperatures or at ambient temperature.

[0209] It should be understood that, when producing a foam block under free expansion conditions, the foam block can be trimmed to obtain a foam block whose dimensions and shape meet the desired characteristics. This finishing step can be performed before or after the foam block has cured.

[0210] In one preferred embodiment, the casting is carried out on a base comprising a reinforcing material, in particular a stack of glass filaments or a stack of glass mats, to produce a block of fiber-reinforced foam material. The method comprises the following steps:

[0211] i) contacting at least one polyisocyanate compound and a polyol mixture comprising three (3) different polyols and a chain extending polyol, wherein said polyols are selected from polyether polyols and polyester polyols, in the presence of catalysts, blowing agents, as well as additives and flame retardants,

[0212] ii) applying the foam composition obtained in step i) to the stack of glass filaments or the stack of glass mats, and

[0213] iii) allowing said composition to harden after expansion to form a foam block.

[0214] In this case, the mixed PU-PIR composition is poured onto the reinforcing material so that the composition penetrates the entire thickness of the fiberglass or fiberglass mat stack. The fiberglass or fiberglass mat content can be determined, in particular, according to ISO 1172.

[0215] One of the advantages of the foam composition is, in particular, that it quickly and evenly penetrates into reinforcing materials.

[0216] The glass mats used are preferably continuous glass mats (continuous filament mats), such as those sold under the trade names Unifilo® or Advantex® by Owens Corning.

[0217] These glass yarns are bonded to each other with a binder, the content of which is preferably from about 0.6% to about 3% by weight of the total weight of the glass mats, preferably about 2.5%. The binder serves to bond the glass yarns and is preferably an epoxy resin.

[0218] The glass threads, preferably forming mats, preferably have a linear density of 20 to 40 tex, i.e. 20 to 40 g / km of threads.

[0219] Glass mats have a mass per unit area preferably from 300 to 900 g / m 2 and more, as an advantage from 300 to 600 g / m 2 , more preferably about 450 g / m 2The glass fiber content preferably ranges from 6% to 12% by weight of the total weight of the reinforced polyurethane foam-PIR. Advantageously, the glass fiber content is approximately 10% by weight of the total weight of the polyurethane foam-PIR.

[0220] To obtain acceptable mechanical properties, the number of glass mats can be from 4 to 12, depending on the amount of binder and the mass of glass mats per unit area.

[0221] The glass yarns preferably used in the second embodiment are preferably made from roving, i.e., a flattened strip of variable width formed by glass yarns that are not interwoven but run parallel to one another. The glass yarns are preferably laid using the "Webforming" technology of Plastech TT Ltd.

[0222] The glass fibers laid using this technology preferably have a linear density of 30 to 300 tex.

[0223] Application of PPU-PIR

[0224] PUR-PIR foams have a wide variety of applications due to their insulating and adhesive properties. According to the technical solution, PUR-PIR foams are characterized by stability and low thermal conductivity, as well as excellent mechanical properties, in particular shear strength, compressive strength, and Young's modulus. Moreover, these foams demonstrate uniform distribution across the entire surface of the reinforcing material. The proposed foams are particularly suitable for thermal insulation, in particular for the insulation of tanks for the transportation of liquefied gas, such as liquefied petroleum gas (LPG) or liquefied natural gas (LNG), or tanks for the transportation of low-temperature liquid products, such as ammonia or hydrogen, used in LNG tankers. The invention can also find application in the insulation of marine, onshore, or port pipelines or storage tanks.

[0225] In another embodiment, the proposed PPU-PIR are used to form insulating panels.

[0226] A composition comprising a mixture of polyols, at least one polyisocyanate compound, a catalyst, and additives is applied to a surface to form a foam block. The application rate is calculated based on the desired foam block height and density. Those skilled in the art will be able to determine several of these parameters.

[0227] After the foam has expanded and hardened, the sides, top, and / or bottom of the foam block are removed. This finishing step allows for the production of foam blocks of specific dimensions.

[0228] PUR-PIR blocks can also be cut transversely to a third of their thickness, creating two layers of primary and secondary insulation. This single cutting step allows for the simultaneous production of a primary and secondary insulation layer from a single block of foam, thereby saving material due to minimal waste and saving time, as only one step is required to produce two layers of thermal insulation.

[0229] EXAMPLES

[0230] Example 1 – Example of composition No. 1 of polyurethane foam-polyisocyanurate foam according to one aspect of the proposed technical solution

[0231] Compound Quantity (mass. parts) Quantity per 100 parts by weight of polyols (parts by weight) Polyol Daltolac® R404 50 42 Stepanpol PS 2352 30 24 DPG dipropylene glycol 20 18 Voranol® 360 RH 20 16 Catalyst T 12 / 10 0.1 0.1 Surfactant B8465 2 1 Foaming agent 365mfc 10 8 Fine Arts S5005 150 120

[0232] Example 2 – Examples of a polyurethane foam-polyisocyanurate foam composition according to one aspect of the proposed technical solution

[0233] Compound Quantity of Composition 2 (parts by weight) Quantity of Composition 3 (parts by weight) Quantity of Composition 4 (parts by weight) Polyol Daltolac® R404 60 40 35 Stepanpol PS 2352 30 30 30 DPG dipropylene glycol 15 25 23 Voranol® 360 RH 10 25 40 Catalyst T 12 / 10 0.1 0.1 0.1 Surfactant B8465 2 2 2 Foaming agent 365mfc 10 10 10 Fine Arts S5005 135 150 150

[0234] SOURCES

[0235] ─ US 2010 / 0116829.

[0236] ─ US 8 940 803.

[0237] ─ WO 2020 / 104749.

Claims

1. A method for producing a mixture of polyols for producing polyurethane foam-polyisocyanurate foam (PUF-PIR), which consists in mixing three different polyols and a chain-extending polyol, wherein said different polyols are selected from simple polyether polyols and polyester polyols, wherein the mixture of polyols has a viscosity below 1000 mPa⋅s at 25°C.

2. The method according to claim 1, characterized in that the polyether polyols are polyols based on glycerol and sorbitol and / or polyols based on glycerol and sucrose.

3. The method according to claim 1, characterized in that the polyester polyols are aromatic polyester polyols, preferably derivatives of phthalic acid.

4. The method according to claim 1, characterized in that the chain-extending polyol is a glycol-type derivative, preferably dipropylene glycol.

5. The method according to claim 1, characterized in that the mixture has a viscosity of 400 to 800 mPa⋅s at 25°C.

6. The method according to any of paragraphs 1-5, characterized in that the following are mixed: - from 28 to 100 parts by weight of polyether polyols, wherein the first polyether polyol is from 18 to 67 parts by weight, wherein the second polyether polyol is from 10 to 25 parts by weight, - from 5 to 40 parts by weight of polyester polyol, and - from 15 to 30 parts by weight of chain-extending polyol.

7. A composition for producing polyurethane foam-PIR, characterized in that the composition contains: - a mixture of polyols for producing PPU-PIR, obtained by any of the methods according to paragraphs 1-6, - at least one polyisocyanate compound, and - catalyst.

8. The composition according to claim 7, characterized in that the composition contains from 90 to 120 parts by weight of polyisocyanate per 100 parts by weight of polyols.

9. The composition according to claim 7, characterized in that the polyisocyanate is selected from aromatic diisocyanates; preferably, the isocyanate compound is methylene diphenyl diisocyanate (MDI).

10. The composition according to claim 7, characterized in that the catalyst is selected from tin catalysts and potassium carboxylates or a mixture thereof.

11. The composition according to claim 7, characterized in that the composition additionally contains a foaming agent selected from water, CO2, fluorinated foaming agents, or mixtures thereof.

12. A composition according to any one of paragraphs 7-11, characterized in that it additionally contains one or more additives.

13. Foam material made of polyurethane foam-PIR obtained from the composition according to paragraphs 7-12.

14. Foam material made of polyurethane foam-PIR according to paragraph 13, characterized in that the foam material has a density of 110 to 130 kg / m3. 3 .

15. Foam material made of polyurethane foam-PIR according to paragraph 13, characterized in that the foam material has a thermal conductivity of 24 to 26 mW / m⋅K.

16. Foam material made of polyurethane foam-PIR according to paragraph 13, characterized in that the foam material has a compressive strength of 1.30 to 1.50 MPa.

17. A method for producing foam material from polyurethane foam-PIR according to any of paragraphs 13-16, including the steps of: i) contacting at least one polyisocyanate compound and a polyol mixture comprising three different polyols and a chain extending polyol, wherein said different polyols are selected from polyether polyols and polyester polyols, wherein the polyol mixture has a viscosity below 1000 mPa⋅s at 25°C, obtained by the method of claims 1-6, in the presence of catalysts, blowing agents, fire retardants and additives, and ii) applying the foam composition obtained in step i) to the stack of glass filaments or the stack of glass mats, and iii) allowing said composition to harden after expansion to form foam material.

18. Use of polyurethane foam-pi foam material obtained by the method according to paragraph 17 for thermal insulation.