EP4263647A1 - A polyurethane foam and a refrigerator comprising polyurethane foam - Google Patents

A polyurethane foam and a refrigerator comprising polyurethane foam

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Publication number
EP4263647A1
EP4263647A1 EP21907282.4A EP21907282A EP4263647A1 EP 4263647 A1 EP4263647 A1 EP 4263647A1 EP 21907282 A EP21907282 A EP 21907282A EP 4263647 A1 EP4263647 A1 EP 4263647A1
Authority
EP
European Patent Office
Prior art keywords
polyurethane foam
units
catalyst
foam composition
blowing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP21907282.4A
Other languages
German (de)
French (fr)
Inventor
Cahit Can ÇANAKÇI
Orçun YÜCEL
Sefa Yasin UZEN
Aycan GÜRKA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arcelik AS
Original Assignee
Arcelik AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arcelik AS filed Critical Arcelik AS
Publication of EP4263647A1 publication Critical patent/EP4263647A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0019—Use of organic additives halogenated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2330/00—Thermal insulation material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers

Definitions

  • the present invention relates to a polyurethane foam composition with improved thermal insulation and a refrigerant comprising polyurethane.
  • Polyurethane foam is composed of two main raw materials and catalysts which provides the chemical reaction of said raw materials, surfactants and blowing agent(s) which provide(s) the foaming reaction.
  • These two main raw materials are base polyol (containing hydroxyl group) and isocyanate.
  • Polyol systems are composed of a mixture of catalyst, surfactant, blowing agent and other chemicals added in appropriate proportions to polyether or polyester-based polyols. Said mixtures carry free hydroxyls (OH).
  • isocyanates are chemicals which react exothermically when mixed with the polyol system and carry free NCOs. Isocyanates are recognized and named according to the percentage of NCO they carry.
  • polyurethanes are formed.
  • the polymerization is exothermic, and polyurethanes with different structures can be obtained by using polyol and isocyanates with different molecular structures.
  • the thermal conductivity coefficients of conventional polyurethane foams are generally in the order of 20-21 mW/mK, and the compressive strength thereof is in the range of 120-130 kPa.
  • Polyol which is the main reactant in polyurethane formation, is generally obtained from petroleum-based polyether. It is known that polyurethane is used in many sectors such as automotive, white goods for thermal insulation purposes. Obtaining polyurethane, which has a wide range of uses, from petrochemical derivative raw materials, is not environmentally friendly and sustainable. In the state of the art, vegetable oils such as sunflower, sesame, canola, castor, soybean oil, etc. are known as raw materials for polyol in polyurethane reactions.
  • the aim of the present invention is the realization of a polyurethane foam composition wherein the thermal insulation is improved by decreasing the thermal conductivity coefficient.
  • polyurethane foam composition of the present invention in order to obtain 100 units of polyol by weight, 50 units of biopolyol at the most obtained from vegetable sources such as of soybean, sunflower, castor, sesame oil, etc., and at least 50 units of petroleum-based polyether polyol mixture are used.
  • the viscosity of the polyether polyol used must be between 2000-3000 cP (centipoise).
  • the viscosity of the total polyol mixture is decreased by adding the polyether polyol with low viscosity to the plant-based polyols with very high viscosity.
  • the biobased polyol in the polyurethane foam composition of the present invention can be obtained by the reaction of sunflower, olive, castor, or sesame oil in epoxy with a functional initiator such as sorbitol or sucrose.
  • refrigerator cabins can be produced with 10- 15% faster moldability (curing time) than polyurethane foams based on petroleum -based polyether polyol. Moreover, a polyurethane foam in a more fluid form can be obtained.
  • the isocyanate used is methylene diphenyl diisocyanate.
  • the polyurethane foam composition of the present invention comprises at least one trimerization catalyst, at least one blowing amine catalyst, at least one gelling catalyst, and at least one surfactant.
  • Polycat41 (N,N',N"-Tris (3-dimethylaminopropyl)hexahydro-S-triazine) is used as the trimerization catalyst.
  • the trimerization catalyst enables the polyurethane foam to reach the desired strength values.
  • Polycat5 is used as the blowing amine catalyst, and the blowing amine catalyst is a catalyst required for obtained a closed-cell foam.
  • the amine-based Polyat8 is used as the gelling catalyst.
  • the gelling catalyst is used to accelerate the urethane reaction.
  • water is added to the composition for carbon dioxide reaction.
  • the polyurethane foam composition of the present invention comprises trans- 1-chloro- 3, 3, 3 -trifluoropropene and/or cis- 1,1, 1,4, 4, 4-hexafluoro-2 -butene as the blowing gas.
  • said blowing gases can be used together with the cyclopentane or isobutane-cyclopentane mixture.
  • bifunctional silane surfactant must be added to provide the thermal insulation improvement in the polyurethane foam composition.
  • the compressive strength of the polyurethane foam of the present invention is between 110-120 kPa, wherein the closed cell ratio value is 90% or above.
  • a polyurethane foam composition of which the surface energy is decreased with new generation blowing gases and a refrigerator comprising said polyurethane foam are realized.
  • the polyurethane foam composition comprises a mixture of plant-based polyol and petroleum-based polyether polyol, isocyanate, at least one trimerization catalyst, at least one blowing amine catalyst and at least one gelling catalyst, and at least one silicone-based surfactant.
  • the polyurethane foam composition of the present invention comprises a blowing gas comprising trans-l-chloro-3,3,3-trifhroropropene and/or cis-l,l,l,4,4,4-hexafluoro-2- butene.
  • the polyurethane foam composition of the present invention comprises a main reactant polyol composed of a mixture of plant-based biopolyol and petroleum-based polyether polyol.
  • the polyol reacts with the blowing gas and is treated with chemicals including isocyanate, catalysts and surfactant, and then urethane and polymerization reactions occur and the polyurethane foam composition is obtained.
  • a polyurethane foam with improved insulation performance is obtained by decreasing the thermal conductivity coefficient without requiring to use a surfactant such as bifunctional silane.
  • the polyurethane foam composition at least one nucleating agent selected from l,l,l,2,3,4,5,5,5-nonafhioro-4-trifluoromethyl-pentene and/or perfluorinated carbon chain.
  • the nucleating agent contributes to decrease the thermal conductivity coefficient.
  • the polyurethane foam comprises a blowing gas of cyclopentane or isobutane-cyclopentane mixture and a bifunctional silane surfactant in addition to trans-l-chloro-3,3,3-trifluoropropene and/or cis- 1,1, 1,4,4, 4-hexafluoro-2- butene.
  • old generation blowing gases such as cyclopentane and its mixtures are used by being mixed with new generation gases.
  • the polyurethane foam composition comprises N,N',N"-tris (3 -dimethylaminopropyl) hexahydro-S triazine (Polycat 41) as trimerization catalyst; N, N, N', N', N”-Pentamethyldiethylenetriamine (Polycat 5) as blowing amine catalyst; and amine-based N,N-dimethylcyclohexylamine (Polycat 8) as gelling catalyst.
  • the polyurethane foam composition comprises methylene diphenyl diisocyanate.
  • the polyurethane foam composition comprises 50 units of plant-based biopolyol at the most and at least 50 units of polyether polyol in order to obtain 100 units of polyol mixture, 32 units of blowing gas which is trans-l-chloro- 3, 3, 3 -trifluoropropene and/or cis-l,l,l,4,4,4-hexafluoro-2-butene, 130-152 units of methylene diphenyl diisocyanate and 1-4 units of silicone-based surfactant and 0.5-3 units of trimerization catalyst and 0.01-2 units of blowing amine catalyst and 0.01-4.5 units of gelling catalyst and 0.5-3 units of water.
  • the polyurethane foam composition 1-3 units by weight of at least one nucleating agent selected from l,l,l,2,3,4,5,5,5-nonafluoro-4- trifluoromethyl-pentene and/or perfluorinated carbon chain.
  • Said mixing ratios by weight are the values required to obtain the polyurethane foam composition under optimum mechanical and physical conditions.
  • said ratios by weight are required in order to provide properties such as compressive strength, thermal conductivity coefficient, closed cell ratio, viscosity, etc. under optimum conditions.
  • the polyurethane foam of the present invention is used in a refrigerator as insulation material.
  • a polyurethane foam composition of which the thermal conductivity coefficient is improved by 10% is realized.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to a polyurethane foam composition comprising a mixture of plant-based polyol and petroleum-based polyether polyol, isocyanate, at least one trimerization catalyst, at least one blowing amine catalyst and at least one gelling catalyst, and at least one silicone-based surfactant, and also relates to a refrigerator comprising said polyurethane foam.

Description

A POLYURETHANE FOAM AND A REFRIGERATOR COMPRISING POLYURETHANE FOAM
The present invention relates to a polyurethane foam composition with improved thermal insulation and a refrigerant comprising polyurethane.
Polyurethane foam is composed of two main raw materials and catalysts which provides the chemical reaction of said raw materials, surfactants and blowing agent(s) which provide(s) the foaming reaction. These two main raw materials are base polyol (containing hydroxyl group) and isocyanate. Polyol systems are composed of a mixture of catalyst, surfactant, blowing agent and other chemicals added in appropriate proportions to polyether or polyester-based polyols. Said mixtures carry free hydroxyls (OH). On the other hand, isocyanates are chemicals which react exothermically when mixed with the polyol system and carry free NCOs. Isocyanates are recognized and named according to the percentage of NCO they carry. As a result of the repeated polymerization of isocyanates containing NCO group and polyols containing OH group, polyurethanes are formed. The polymerization is exothermic, and polyurethanes with different structures can be obtained by using polyol and isocyanates with different molecular structures. The thermal conductivity coefficients of conventional polyurethane foams are generally in the order of 20-21 mW/mK, and the compressive strength thereof is in the range of 120-130 kPa.
Polyol, which is the main reactant in polyurethane formation, is generally obtained from petroleum-based polyether. It is known that polyurethane is used in many sectors such as automotive, white goods for thermal insulation purposes. Obtaining polyurethane, which has a wide range of uses, from petrochemical derivative raw materials, is not environmentally friendly and sustainable. In the state of the art, vegetable oils such as sunflower, sesame, canola, castor, soybean oil, etc. are known as raw materials for polyol in polyurethane reactions.
In the state of the art United States Patent No. US8748501B2, a polyurethane foam composition comprising polyol, isocyanate, a catalyst, a surfactant, a physical blowing agent, a chemical blowing agent, a nucleating agent, and a silsesquioxane compound is obtained.
The aim of the present invention is the realization of a polyurethane foam composition wherein the thermal insulation is improved by decreasing the thermal conductivity coefficient.
In the polyurethane foam composition of the present invention, in order to obtain 100 units of polyol by weight, 50 units of biopolyol at the most obtained from vegetable sources such as of soybean, sunflower, castor, sesame oil, etc., and at least 50 units of petroleum-based polyether polyol mixture are used. The viscosity of the polyether polyol used must be between 2000-3000 cP (centipoise). Thus, the viscosity of the total polyol mixture is decreased by adding the polyether polyol with low viscosity to the plant-based polyols with very high viscosity.
The biobased polyol in the polyurethane foam composition of the present invention can be obtained by the reaction of sunflower, olive, castor, or sesame oil in epoxy with a functional initiator such as sorbitol or sucrose.
By means of the vegetable oil-based biopolyol content with high OH functionality in the polyurethane foam of the present invention, refrigerator cabins can be produced with 10- 15% faster moldability (curing time) than polyurethane foams based on petroleum -based polyether polyol. Moreover, a polyurethane foam in a more fluid form can be obtained.
In an embodiment of the present invention, the isocyanate used is methylene diphenyl diisocyanate.
The polyurethane foam composition of the present invention comprises at least one trimerization catalyst, at least one blowing amine catalyst, at least one gelling catalyst, and at least one surfactant.
In the polyurethane foam composition of the present invention, Polycat41, (N,N',N"-Tris (3-dimethylaminopropyl)hexahydro-S-triazine) is used as the trimerization catalyst. The trimerization catalyst enables the polyurethane foam to reach the desired strength values.
Polycat5 is used as the blowing amine catalyst, and the blowing amine catalyst is a catalyst required for obtained a closed-cell foam. The amine-based Polyat8 is used as the gelling catalyst. The gelling catalyst is used to accelerate the urethane reaction.
In the polyurethane foam composition of the present invention, water is added to the composition for carbon dioxide reaction.
The polyurethane foam composition of the present invention comprises trans- 1-chloro- 3, 3, 3 -trifluoropropene and/or cis- 1,1, 1,4, 4, 4-hexafluoro-2 -butene as the blowing gas.
In an embodiment of the present invention, said blowing gases can be used together with the cyclopentane or isobutane-cyclopentane mixture. In this embodiment, bifunctional silane surfactant must be added to provide the thermal insulation improvement in the polyurethane foam composition.
The compressive strength of the polyurethane foam of the present invention is between 110-120 kPa, wherein the closed cell ratio value is 90% or above.
By means of the invention, a polyurethane foam composition of which the surface energy is decreased with new generation blowing gases and a refrigerator comprising said polyurethane foam are realized.
The polyurethane foam composition comprises a mixture of plant-based polyol and petroleum-based polyether polyol, isocyanate, at least one trimerization catalyst, at least one blowing amine catalyst and at least one gelling catalyst, and at least one silicone-based surfactant.
The polyurethane foam composition of the present invention comprises a blowing gas comprising trans-l-chloro-3,3,3-trifhroropropene and/or cis-l,l,l,4,4,4-hexafluoro-2- butene.
The polyurethane foam composition of the present invention comprises a main reactant polyol composed of a mixture of plant-based biopolyol and petroleum-based polyether polyol. First, the polyol reacts with the blowing gas and is treated with chemicals including isocyanate, catalysts and surfactant, and then urethane and polymerization reactions occur and the polyurethane foam composition is obtained. By means of to the reaction of the blowing gas, which is trans- l-chloro-3, 3, 3 -trifluoropropene and/or cis-1, 1,1, 4,4,4- hexafIuoro-2-butene and the biobased polyol in the polyurethane composition, a polyurethane foam with improved insulation performance is obtained by decreasing the thermal conductivity coefficient without requiring to use a surfactant such as bifunctional silane.
In an embodiment of the present invention, the polyurethane foam composition at least one nucleating agent selected from l,l,l,2,3,4,5,5,5-nonafhioro-4-trifluoromethyl-pentene and/or perfluorinated carbon chain. The nucleating agent contributes to decrease the thermal conductivity coefficient.
In an embodiment of the present invention, the polyurethane foam comprises a blowing gas of cyclopentane or isobutane-cyclopentane mixture and a bifunctional silane surfactant in addition to trans-l-chloro-3,3,3-trifluoropropene and/or cis- 1,1, 1,4,4, 4-hexafluoro-2- butene. In this embodiment, old generation blowing gases such as cyclopentane and its mixtures are used by being mixed with new generation gases. However, when cyclopentane or isobutane-cyclopentane mixture is added to the trans-l-chloro-3,3,3-trifluoropropene and/or cis-l,l,l,4,4,4-hexafluoro-2-butene to obtain improved thermal insulation performance, the bifunctional silane surfactant is also added.
In an embodiment of the present invention, the polyurethane foam composition comprises N,N',N"-tris (3 -dimethylaminopropyl) hexahydro-S triazine (Polycat 41) as trimerization catalyst; N, N, N', N', N”-Pentamethyldiethylenetriamine (Polycat 5) as blowing amine catalyst; and amine-based N,N-dimethylcyclohexylamine (Polycat 8) as gelling catalyst.
In an embodiment of the present invention, the polyurethane foam composition comprises methylene diphenyl diisocyanate.
In an embodiment of the present invention, the polyurethane foam composition comprises 50 units of plant-based biopolyol at the most and at least 50 units of polyether polyol in order to obtain 100 units of polyol mixture, 32 units of blowing gas which is trans-l-chloro- 3, 3, 3 -trifluoropropene and/or cis-l,l,l,4,4,4-hexafluoro-2-butene, 130-152 units of methylene diphenyl diisocyanate and 1-4 units of silicone-based surfactant and 0.5-3 units of trimerization catalyst and 0.01-2 units of blowing amine catalyst and 0.01-4.5 units of gelling catalyst and 0.5-3 units of water. In an embodiment of the present invention, the polyurethane foam composition 1-3 units by weight of at least one nucleating agent selected from l,l,l,2,3,4,5,5,5-nonafluoro-4- trifluoromethyl-pentene and/or perfluorinated carbon chain. Said mixing ratios by weight are the values required to obtain the polyurethane foam composition under optimum mechanical and physical conditions. For example, said ratios by weight are required in order to provide properties such as compressive strength, thermal conductivity coefficient, closed cell ratio, viscosity, etc. under optimum conditions.
In an embodiment, the polyurethane foam of the present invention is used in a refrigerator as insulation material. By means of the present invention, a polyurethane foam composition of which the thermal conductivity coefficient is improved by 10% is realized.

Claims

CLAIMS A polyurethane foam composition comprising a mixture of plant-based polyol and petroleum-based polyether polyol, isocyanate, at least one trimerization catalyst, at least one blowing amine catalyst and at least one gelling catalyst, and at least one silicone -based surfactant, characterized by a blowing gas comprising trans- 1- chloro-3,3,3-trifluoropropene and/or cis- 1, 1, 1,4,4, 4-hexafluoro-2 -butene. A polyurethane foam composition as in Claim 1, characterized by at least one nucleating agent selected from l,l,l,2,3,4,5,5,5-nonafhioro-4-trifluoromethyl- pentene and/or perfluorinated carbon chain. A polyurethane foam composition as in Claim 1 or 2, characterized by the blowing gas further comprising cyclopentane or isobutane-cyclopentane mixture and a bifunctional silane surfactant. A polyurethane foam composition as in any one of the above claims, characterized by N,N',N"-tris (3 -dimethylaminopropyl) hexahydro-S triazine (Poly cat 41) as trimerization catalyst; N, N, N', N', N”-Pentamethyldiethylenetriamine (Polycat 5) as blowing amine catalyst; and amine -based N,N-dimethylcyclohexylamine (Polycat 8) as gelling catalyst. A polyurethane foam composition as in any one of the above claims, characterized by methylene diphenyl diisocyanate. A polyurethane foam composition comprising 50 units of plant-based biopolyol at the most and at least 50 units of polyether polyol in order to obtain 100 units of polyol mixture, 32 units of blowing gas which is trans-l-chloro-3,3,3- trifluoropropene and/or cis- 1,1, 1,4, 4, 4-hexafluoro-2 -butene, 130-152 units of methylene diphenyl diisocyanate and 1-4 units of silicone-based surfactant and 0.5- 3 units of trimerization catalyst and 0.01-2 units of blowing amine catalyst and 0.01-4.5 units of gelling catalyst and 0.5-3 units of water. A polyurethane foam composition as in Claim 6, characterized by 1-3 units by weight of at least one nucleating agent selected from 1,1,1,2,3,4,5,5,5-nonafluoro- 4-trifluoromethyl-pentene and/or perfluorinated carbon chain.
6
8. A refrigerator comprising a polyurethane foam as in any one of the above claims.
7
EP21907282.4A 2020-12-16 2021-07-08 A polyurethane foam and a refrigerator comprising polyurethane foam Withdrawn EP4263647A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2020/20698A TR202020698A1 (en) 2020-12-16 2020-12-16 A REFRIGERATOR CONTAINING A POLYURETHANE FOAM COMPOSITION AND POLYURETHANE FOAM
PCT/TR2021/050707 WO2022132075A1 (en) 2020-12-16 2021-07-08 A polyurethane foam and a refrigerator comprising polyurethane foam

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EP4263647A1 true EP4263647A1 (en) 2023-10-25

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Publication number Priority date Publication date Assignee Title
EP4446353A1 (en) 2023-04-14 2024-10-16 Covestro Deutschland AG Polyurethane foam with improved dimensional stability

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KR100850995B1 (en) * 2002-01-04 2008-08-12 주식회사 엘지이아이 A composition for preparing rigid polyurethane foam and rigid polyurethane foam made therefrom
US8258198B2 (en) * 2004-05-28 2012-09-04 Air Products And Chemicals, Inc. Fast demold/extended cream time polyurethane formulations

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