WO2020078672A1 - Rigid polyurethane foam, production method therefor and cooling device comprising the same - Google Patents

Rigid polyurethane foam, production method therefor and cooling device comprising the same Download PDF

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Publication number
WO2020078672A1
WO2020078672A1 PCT/EP2019/075604 EP2019075604W WO2020078672A1 WO 2020078672 A1 WO2020078672 A1 WO 2020078672A1 EP 2019075604 W EP2019075604 W EP 2019075604W WO 2020078672 A1 WO2020078672 A1 WO 2020078672A1
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Prior art keywords
polyurethane foam
blowing agent
rigid polyurethane
component
weight
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PCT/EP2019/075604
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French (fr)
Inventor
Orcun YUCEL
Cahit Can CANAKCI
Original Assignee
Arcelik Anonim Sirketi
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Priority to EP19782924.5A priority Critical patent/EP3867303A1/en
Publication of WO2020078672A1 publication Critical patent/WO2020078672A1/en

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    • 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
    • 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
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
    • 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
    • C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
    • 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
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2036—Heterocyclic amines; Salts thereof containing one heterocyclic ring having at least three nitrogen atoms in the ring
    • 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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • 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

Definitions

  • the present invention relates to a rigid polyurethane foam which is developed to be used for insulation purposes in cooling devices.
  • Plastic foams which are also called foamed plastics or cellular plastics, are chemical structures formed by the dispersion of the gas phase in the solid phase (polymeric matrix). Both thermoplastic and thermoset plastics can be obtained in cellular structure by changing production conditions. The chemical nature, composition, structure and size of the cells of the solid polymeric phase determine the properties of the plastic foam. Since plastic foams are very different in structure and feature, as well as light and low cost, they have different uses. With the advancement of foam technology and the discovery of new foam structures, foam materials are increasingly used in more important application areas.
  • Polyurethane foam is composed of two main raw materials and catalyst(s), surfactant(s) and blowing agent(s) which provide the chemical reaction of said raw materials.
  • 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.
  • polyurethane foams have a much better property of diffusion than other chemical products.
  • the percentages of OH and NCO of the components determine whether the foam formed is rigid, semi-rigid or flexible.
  • the application areas of polyurethane foam vary according to the chemical structure of the foam.
  • the time from the mixture of polyol and isocyanate at the desired ratio to the formation of the polyurethane foam is divided into three steps. Said three stages which determine the chemical reaction properties of polyurethane foam are cream time, string time and tack free time which are 5, 45-50 and 70-75 seconds respectively.
  • the thermal conductivity coefficients of conventional polyurethane foams are generally in the order of 21 mW/mK, and the compressive strength thereof is in the range of 120-130 kPa.
  • the state of the art United States Patent No. US8,748,501 B2 relates to 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.
  • the aim of the present invention is the realization of a high performance cooling device comprising a rigid polyurethane foam having a low thermal conductivity coefficient and high compressive strength as an insulating material.
  • the rigid polyurethane foam realized in order to attain the aim of the present invention, explicated in the first claim and the respective claims thereof is produced with the method comprising the steps of (i) pumping the base polyol, the surfactant(s), the catalyst(s) and the pure water (component B) into a separate storage tank in the injection machine so as to be stirred therein for a period of time and obtaining the formulated polyol, (ii) adding fluorine-containing additive to the blowing agent and stirring the same and then pumping this mixture to the storage tank to be mixed with the component B, or injecting the blowing agent and fluorine-containing additive into the pump at the same time and obtaining the mixture in the pump, and mixing all the materials in the storage tank wherein the component B is present, (iii) afterwards simultaneously pumping the isocyanate (component A) and the component B containing blowing agent with added fluorine-containing additive added to the injection head, (iv) mixing this mixture in the injection head and performing the polyurethane foam reaction,
  • the rigid polyurethane foam of the present invention comprises a base polyol, an isocyanate, surfactant, catalyst, pure water, blowing agent, fluorine-containing additive, and optionally bifunctional silane.
  • the rigid polyurethane foam of the present invention is used as an insulation material in the cooling devices.
  • the rigid polyurethane foam of the present invention is produced with the method comprising the steps of (i) pumping the base polyol, the surfactant(s), the catalyst(s) and the pure water (component B) into a separate storage tank in the injection machine so as to be stirred therein for a period of time and obtaining the formulated polyol, (ii) pumping the blowing agent into the storage tank and mixing the same with the component B, (iii) afterwards simultaneously pumping the isocyanate (component A) and the component B to the injection head, (iv) mixing this mixture in the injection head and performing the polyurethane foam reaction, (v) spraying the polyurethane formulation leaving the injection head into the molds and molding the same.
  • the rigid polyurethane foam of the present invention is produced with the method comprising the steps of (ii) adding fluorine-containing additive to the blowing agent and stirring the same and then pumping this mixture to the storage tank to be mixed with the component B, or injecting the blowing agent and fluorine-containing additive into the pump at the same time and obtaining the mixture in the pump, and mixing all the materials in the storage tank wherein the component B is present, (iii) afterwards simultaneously pumping the isocyanate (component A) and the component B containing blowing agent with added fluorine-containing additive added to the injection head.
  • the addition of fluorine-containing additive to the blowing agent exhibits a nucleating effect, which provides a decrease in the wall size of the polyurethane foam and an improvement in the lambda value.
  • the lambda value (thermal conductivity coefficient) of the polyurethane foam of the present invention is between 18-19 mW/Mk.
  • the use of fluorine-containing additive ensures that closed cell ratio values are 95% and above.
  • ultrasonication may be used optionally in the process step (ii), and preferably a high rotation shear mixer or high pressure mixing unit is used.
  • a liquid blowing agent selected from trans-1-chloro-3,3,3-trifluoropropene and cis-1,1,1,4,4,4-hexafluoro-2-butene or cyclopentane (CP) or isobutane/cyclopentane mixture is used as the blowing agent in the production of the rigid polyurethane foam.
  • cyclopentane or isobutane/cyclopentane mixture decreases the wall size, increases the closed cell ratio, thus increasing increases the compressive strength as well. Moreover, it also reduces the density, which reduces the viscosity, thus facilitating flow in the pump line.
  • Technical effect of using the LBA instead of the CP blowing agent is that due to its chemical structure, its thermal conductivity value is lower than cyclopentane as a gas, it can be used for producing foam with low lambda value, it has low GWP (Global warming potential) value, and it is environmentally friendly and not flammable.
  • the fluorine-containing additive is used in an amount of 1.9 to 2.3% of the weight of the component B, and for the cyclopentane or isobutane/cyclopentane mixture blowing agent the fluorine-containing additive is used in an amount of 2.1 to 2.5% of the weight of the component B.
  • perfluorocarbon PF5056
  • fluorine-containing additive PF5056
  • 1,1,1,2,3,4,5,5,5-nonafluoro-4-trifluoromethyl-pentene FA188
  • amine-based catalyst(s) is/are used in the production of the rigid polyurethane foam.
  • a catalyst selected from the group containing bis(2-dimethylaminoethyl)(methyl)amine, cyclohexyldimethylamine and/or N,N,N',N',N'',N''-hexamethyl-1,3,5-triazine-1,3,5(2H,4H,6H)-tripropanamine or the combination thereof is used in the production of rigid polyurethane foam.
  • the ratios of bis(2-dimethylaminoethyl)(methyl)amine, cyclohexyldimethylamine and N,N,N',N',N'',N''-hexamethyl-1,3,5-triazine-1,3,5 (2H, 4H, 6H)-tripropanamine in the catalyst combination are in the range of 1.50:1:0.5-1.75:1:0.8.
  • silicone-based surfactant(s) is/are used in the production of rigid polyurethane foam.
  • silicone-based surfactants positively affect particularly on the foam viscosity.
  • the surfactant is used in the production of hard polyurethane foam at a rate of 2-3 times the weight of the catalyst.
  • step (i) if cyclopentane or isobutane/cyclopentane mixture is used as blowing agent in the production of rigid polyurethane foam, in step (i), the base polyol, the surfactant(s), the catalyst(s) and the pure water (component B) and bifunctional silane are pumped into a separate storage tank in the injection machine so as to be stirred therein for a period of time,
  • bifunctional silane provides optimum lambda value and good mixture of the component A.
  • polyether or polyester is used as the polyol in the production of rigid polyurethane foam.
  • the rigid polyurethane foam produced with the polyurethane production method of the present invention comprises a base polyol, an isocyanate, surfactant, catalyst, pure water, blowing agent, fluorine-containing additive, and optionally bifunctional silane.
  • the rigid polyurethane foam produced with the polyurethane production method of the present invention comprises 35-45% formulated polyol by weight, 30-60% isocyanate by weight, 4-6% blowing gas by weight, 0.05-0.5% fluorine-containing additive by weight for the liquid blowing agent or 1-3% fluorine-containing additive by weight for the cyclopentane or isobutane/cyclopentane mixture blowing agent, and optionally 0.005-0.25% bifunctional silane by weight.
  • the ratio of catalyst weight to the total polyol weight is 0.5-2.
  • the rigid polyurethane foam comprises methyl diisocyanate (MDI) as isocyanate.
  • MDI methyl diisocyanate
  • the rigid polyurethane foam of the present invention is used in the cooling devices.
  • the rigid polyurethane foam of the present invention is used in the refrigerators.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to an insulation material which is used in cooling devices.

Description

A COOLING DEVICE
The present invention relates to a rigid polyurethane foam which is developed to be used for insulation purposes in cooling devices.
Plastic foams, which are also called foamed plastics or cellular plastics, are chemical structures formed by the dispersion of the gas phase in the solid phase (polymeric matrix). Both thermoplastic and thermoset plastics can be obtained in cellular structure by changing production conditions. The chemical nature, composition, structure and size of the cells of the solid polymeric phase determine the properties of the plastic foam. Since plastic foams are very different in structure and feature, as well as light and low cost, they have different uses. With the advancement of foam technology and the discovery of new foam structures, foam materials are increasingly used in more important application areas.
Polyurethane foam is composed of two main raw materials and catalyst(s), surfactant(s) and blowing agent(s) which provide the chemical reaction of said raw materials. 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.
As during the polyurethane polymerization reaction three dimensional progress occurs, polyurethane fills all the gaps of the container or mold wherein it is placed and takes its shape. Polyurethane foams have a much better property of diffusion than other chemical products. The percentages of OH and NCO of the components determine whether the foam formed is rigid, semi-rigid or flexible. The application areas of polyurethane foam vary according to the chemical structure of the foam.
The time from the mixture of polyol and isocyanate at the desired ratio to the formation of the polyurethane foam is divided into three steps. Said three stages which determine the chemical reaction properties of polyurethane foam are cream time, string time and tack free time which are 5, 45-50 and 70-75 seconds respectively. The thermal conductivity coefficients of conventional polyurethane foams are generally in the order of 21 mW/mK, and the compressive strength thereof is in the range of 120-130 kPa.
The state of the art United States Patent No. US8,748,501 B2 relates to 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.
The state of the art United States Patent Application No. US 5,318,996 A relates to a rigid polyurethane foam obtained from a ternary blowing agent mixture and a method of obtaining the same by reacting the same with the organic polyisocyanate and the polyol in the presence of a blowing agent mixture.
The aim of the present invention is the realization of a high performance cooling device comprising a rigid polyurethane foam having a low thermal conductivity coefficient and high compressive strength as an insulating material.
The rigid polyurethane foam realized in order to attain the aim of the present invention, explicated in the first claim and the respective claims thereof is produced with the method comprising the steps of
(i) pumping the base polyol, the surfactant(s), the catalyst(s) and the pure water (component B) into a separate storage tank in the injection machine so as to be stirred therein for a period of time and obtaining the formulated polyol,
(ii) adding fluorine-containing additive to the blowing agent and stirring the same and then pumping this mixture to the storage tank to be mixed with the component B, or injecting the blowing agent and fluorine-containing additive into the pump at the same time and obtaining the mixture in the pump, and mixing all the materials in the storage tank wherein the component B is present,
(iii) afterwards simultaneously pumping the isocyanate (component A) and the component B containing blowing agent with added fluorine-containing additive added to the injection head,
(iv) mixing this mixture in the injection head and performing the polyurethane foam reaction,
(v) spraying the polyurethane formulation leaving the injection head into the molds and molding the same.
The rigid polyurethane foam of the present invention comprises a base polyol, an isocyanate, surfactant, catalyst, pure water, blowing agent, fluorine-containing additive, and optionally bifunctional silane.
The rigid polyurethane foam of the present invention is used as an insulation material in the cooling devices.
The rigid polyurethane foam of the present invention is produced with the method comprising the steps of
(i) pumping the base polyol, the surfactant(s), the catalyst(s) and the pure water (component B) into a separate storage tank in the injection machine so as to be stirred therein for a period of time and obtaining the formulated polyol,
(ii) pumping the blowing agent into the storage tank and mixing the same with the component B,
(iii) afterwards simultaneously pumping the isocyanate (component A) and the component B to the injection head,
(iv) mixing this mixture in the injection head and performing the polyurethane foam reaction,
(v) spraying the polyurethane formulation leaving the injection head into the molds and molding the same.
The rigid polyurethane foam of the present invention is produced with the method comprising the steps of
(ii) adding fluorine-containing additive to the blowing agent and stirring the same and then pumping this mixture to the storage tank to be mixed with the component B, or injecting the blowing agent and fluorine-containing additive into the pump at the same time and obtaining the mixture in the pump, and mixing all the materials in the storage tank wherein the component B is present,
(iii) afterwards simultaneously pumping the isocyanate (component A) and the component B containing blowing agent with added fluorine-containing additive added to the injection head.
In the present invention, the addition of fluorine-containing additive to the blowing agent exhibits a nucleating effect, which provides a decrease in the wall size of the polyurethane foam and an improvement in the lambda value. The lambda value (thermal conductivity coefficient) of the polyurethane foam of the present invention is between 18-19 mW/Mk. Moreover, the use of fluorine-containing additive ensures that closed cell ratio values are 95% and above.
In the method of the present invention, ultrasonication may be used optionally in the process step (ii), and preferably a high rotation shear mixer or high pressure mixing unit is used.
In an embodiment of the invention, a liquid blowing agent (LBA) selected from trans-1-chloro-3,3,3-trifluoropropene and cis-1,1,1,4,4,4-hexafluoro-2-butene or cyclopentane (CP) or isobutane/cyclopentane mixture is used as the blowing agent in the production of the rigid polyurethane foam.
Being silica-based, the use of cyclopentane or isobutane/cyclopentane mixture as blowing agent decreases the wall size, increases the closed cell ratio, thus increasing increases the compressive strength as well. Moreover, it also reduces the density, which reduces the viscosity, thus facilitating flow in the pump line. Technical effect of using the LBA instead of the CP blowing agent is that due to its chemical structure, its thermal conductivity value is lower than cyclopentane as a gas, it can be used for producing foam with low lambda value, it has low GWP (Global warming potential) value, and it is environmentally friendly and not flammable.
In the method of the present invention, for the liquid blowing agent, the fluorine-containing additive is used in an amount of 1.9 to 2.3% of the weight of the component B, and for the cyclopentane or isobutane/cyclopentane mixture blowing agent the fluorine-containing additive is used in an amount of 2.1 to 2.5% of the weight of the component B.
In the preferred embodiment of the present invention, in the production of rigid polyurethane foam, perfluorocarbon (PF5056) is used for the liquid blowing agent as fluorine-containing additive, and 1,1,1,2,3,4,5,5,5-nonafluoro-4-trifluoromethyl-pentene (FA188) is used for the cyclopentane or isobutane/cyclopentane mixture blowing agent.
The use of said fluorine-containing additives provides a nucleation effect and reduces the thermal conductivity coefficient. By means of said nucleation effect, a homogeneous polyurethane foam with small wall size is obtained during the polyurethane reaction and the lambda value decreases due to this effect. Thus, more effective insulation can be provided thanks to the lower thermal conductivity coefficient.
In an embodiment of the present invention, amine-based catalyst(s) is/are used in the production of the rigid polyurethane foam.
By using amine-based catalyst instead of metal-containing catalyst, contamination of metal-based refrigerant pipes is prevented and puncture problem is minimized.
In an embodiment of the present invention, a catalyst selected from the group containing bis(2-dimethylaminoethyl)(methyl)amine, cyclohexyldimethylamine and/or N,N,N',N',N'',N''-hexamethyl-1,3,5-triazine-1,3,5(2H,4H,6H)-tripropanamine or the combination thereof is used in the production of rigid polyurethane foam.
In an embodiment of the present invention, in the production of rigid polyurethane foam the ratios of bis(2-dimethylaminoethyl)(methyl)amine, cyclohexyldimethylamine and N,N,N',N',N'',N''-hexamethyl-1,3,5-triazine-1,3,5 (2H, 4H, 6H)-tripropanamine in the catalyst combination are in the range of 1.50:1:0.5-1.75:1:0.8.
In an embodiment of the invention, silicone-based surfactant(s) is/are used in the production of rigid polyurethane foam.
The use of silicone-based surfactants positively affect particularly on the foam viscosity.
In the preferred embodiment of the present invention, the surfactant is used in the production of hard polyurethane foam at a rate of 2-3 times the weight of the catalyst.
The use of surfactant in this ratio provides foam viscosity and optimum lambda value.
In the preferred embodiment of the invention, if cyclopentane or isobutane/cyclopentane mixture is used as blowing agent in the production of rigid polyurethane foam, in step (i), the base polyol, the surfactant(s), the catalyst(s) and the pure water (component B) and bifunctional silane are pumped into a separate storage tank in the injection machine so as to be stirred therein for a period of time,
The use of bifunctional silane provides optimum lambda value and good mixture of the component A.
In an embodiment of the present invention, polyether or polyester is used as the polyol in the production of rigid polyurethane foam.
The rigid polyurethane foam produced with the polyurethane production method of the present invention comprises a base polyol, an isocyanate, surfactant, catalyst, pure water, blowing agent, fluorine-containing additive, and optionally bifunctional silane.
The rigid polyurethane foam produced with the polyurethane production method of the present invention comprises 35-45% formulated polyol by weight, 30-60% isocyanate by weight, 4-6% blowing gas by weight, 0.05-0.5% fluorine-containing additive by weight for the liquid blowing agent or 1-3% fluorine-containing additive by weight for the cyclopentane or isobutane/cyclopentane mixture blowing agent, and optionally 0.005-0.25% bifunctional silane by weight.
In an embodiment of the present invention, if the liquid blowing agent is used as the blowing agent, the ratio of catalyst weight to the total polyol weight is 0.5-2.
In the preferred embodiment of the present invention, the rigid polyurethane foam comprises methyl diisocyanate (MDI) as isocyanate.
In an embodiment of the present invention, the rigid polyurethane foam of the present invention is used in the cooling devices.
In the preferred embodiment of the present invention, the rigid polyurethane foam of the present invention is used in the refrigerators.

Claims (15)

  1. A rigid polyurethane foam production method comprising the steps of
    (i) pumping the base polyol, the surfactant(s), the catalyst(s) and the pure water (component B) into a separate storage tank in the injection machine so as to be stirred therein for a period of time and obtaining the formulated polyol,
    (ii) pumping the blowing agent into the storage tank and mixing the same with the component B,
    (iii) afterwards simultaneously pumping the isocyanate (component A) and the component B to the injection head,
    (iv) mixing this mixture in the injection head and performing the polyurethane foam reaction,
    (v) spraying the polyurethane formulation leaving the injection head into the molds and molding the same.
    characterized by the steps of
    - adding, in the step (ii), fluorine-containing additive to the blowing agent and stirring the same and then pumping this mixture to the storage tank to be mixed with the B component, or injecting the blowing agent and fluorine-containing additive into the pump at the same time and obtaining the mixture in the pump, and mixing all the materials in the storage tank wherein the component B is present,
    - simultaneously pumping, in the step (iii), the isocyanate (component A) and the component B containing blowing agent with added fluorine-containing additive added to the injection head.
  2. A rigid polyurethane foam production method as in Claim 1, characterized in that ultrasonication may be used optionally in the process step (ii).
  3. A rigid polyurethane foam production method as in Claim 1, characterized in that a liquid blowing agent selected from trans-1-chloro-3,3,3-trifluoropropene and cis-1,1,1,4,4,4-hexafluoro-2-butene or cyclopentane or isobutane/cyclopentane mixture is used as the blowing agent.
  4. A rigid polyurethane foam production method as in Claim 1, characterized in that for the liquid blowing agent, the fluorine-containing additive is used in an amount of 1.9 to 2.3% of the weight of the component B, and for the cyclopentane or isobutane/cyclopentane mixture blowing agent the fluorine-containing additive is used in an amount of 2.1 to 2.5% of the weight of the component B.
  5. A rigid polyurethane foam production method as in Claim 1, characterized in that perfluorocarbon (PF5056) is used as fluorine-containing additive for the liquid blowing agent, and 1,1,1,2,3,4,5,5,5-nonafluoro-4-trifluoromethyl-pentene (FA188) is used for the cyclopentane or isobutane/cyclopentane mixture blowing agent.
  6. A rigid polyurethane foam production method as in Claim 1, characterized in that a catalyst selected from the group containing bis(2-dimethylaminoethyl)(methyl)amine, cyclohexyldimethylamine and/or N,N,N',N',N'',N''-hexamethyl-1,3,5-triazine-1,3,5(2H,4H,6H)-tripropanamine or the combination thereof is used.
  7. A rigid polyurethane foam production method as in Claim 6, characterized in that a catalyst combination containing bis(2-dimethylaminoethyl)(methyl)amine, cyclohexyldimethylamine and N,N,N',N',N'',N''-hexamethyl-1,3,5-triazine-1,3,5 (2H, 4H, 6H)-tripropanamine with the ratios to each other being in the range of 1.50:1:0.5-1.75:1:0.8 is used.
  8. A rigid polyurethane foam production method as in Claim 1, characterized in that the silicone-based surfactant(s) is/are used at a rate of 2-3 times the weight of the catalyst.
  9. A rigid polyurethane foam production method as in Claim 1, characterized in that if cyclopentane or isobutane/cyclopentane mixture is used as blowing agent in the production of rigid polyurethane foam, in step (i), the base polyol, the surfactant(s), the catalyst(s) and the pure water (component B) and bifunctional silane are pumped into a separate storage tank in the injection machine so as to be stirred therein for a period of time.
  10. A rigid polyurethane foam production method as in Claim 1, characterized in that polyether polyol or polyester polyol is used as base polyol.
  11. A rigid polyurethane foam produced by the method as in Claim 1, characterized by comprising a base polyol, an isocyanate, surfactant, catalyst, pure water, blowing agent, fluorine-containing additive, and optionally bifunctional silane.
  12. A rigid polyurethane foam as in Claim 11, characterized by comprising 35-45% formulated polyol by weight, 30-60% isocyanate by weight, 4-6% blowing gas by weight, 0.05-0.5% fluorine-containing additive by weight for the liquid blowing agent or 1-3% fluorine-containing additive by weight for the cyclopentane or isobutane/cyclopentane mixture blowing agent, and optionally 0.005-0.25% bifunctional silane by weight.
  13. A rigid polyurethane foam as in Claim 11, characterized in that if the liquid blowing agent is used as the blowing agent, the ratio of catalyst weight to the total polyol weight is 0.5-2.
  14. A rigid polyurethane foam as in Claim 11, characterized in that isocyanate is methyl diisocyanate (MDI).
  15. A cooling device or a refrigerator characterized by comprising a rigid polyurethane foam as in Claim 11 as insulation material.
PCT/EP2019/075604 2018-10-16 2019-09-24 Rigid polyurethane foam, production method therefor and cooling device comprising the same WO2020078672A1 (en)

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