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CN114940738B - Polyurethane composition, polyurethane foam, and preparation method and application thereof - Google Patents

Polyurethane composition, polyurethane foam, and preparation method and application thereof Download PDF

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Publication number
CN114940738B
CN114940738B CN202210623817.9A CN202210623817A CN114940738B CN 114940738 B CN114940738 B CN 114940738B CN 202210623817 A CN202210623817 A CN 202210623817A CN 114940738 B CN114940738 B CN 114940738B
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Prior art keywords
polyether polyol
polyurethane composition
catalyst
foaming agent
polyurethane
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CN202210623817.9A
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CN114940738A (en
Inventor
郑礼倩
叶俊
徐毅
黄雷刚
朱霞林
钟仁升
王诗文
陈文靖
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Wanhua Chemical Ningbo Rongwei Polyurethane Co Ltd
Wanhua Chemical Yantai Rongwei Polyurethane Co Ltd
Original Assignee
Wanhua Chemical Ningbo Rongwei Polyurethane Co Ltd
Wanhua Chemical Yantai Rongwei Polyurethane Co Ltd
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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
    • C08G18/28—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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic 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
    • C08G18/28—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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • 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
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • F25D23/06—Walls
    • F25D23/065—Details
    • F25D23/066—Liners
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • 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
    • C08G2110/0075—Foam properties prepared with an isocyanate index of 60 or lower
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D2201/00—Insulation
    • F25D2201/10—Insulation with respect to heat
    • F25D2201/12—Insulation with respect to heat using an insulating packing material

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a polyurethane composition, polyurethane foam, a preparation method and application thereof, wherein the polyurethane composition comprises the following components in parts by mass: 67-100 parts of polyether polyol, 0-33 parts of polyester polyol, 0.5-9 parts of surfactant, 1-15 parts of composite catalyst, 0.5-7 parts of water and 8-60 parts of composite foaming agent, so that isocyanate with an isocyanate index of 1.0-1.5; wherein the composite foaming agent comprises 10-75% of pentane, 5-70% of hydrofluoroolefin foaming agent and 2-30% of propane by taking the total mass as 100%. The composite foaming agent in the invention has synergistic effect, so that the problems caused by the independent use of each physical foaming agent can be effectively avoided, and the rigid polyurethane foam with good performance can be obtained.

Description

Polyurethane composition, polyurethane foam, and preparation method and application thereof
Technical Field
The invention relates to a polyurethane composition, in particular to a polyurethane composition, polyurethane foam, a preparation method and application thereof.
Background
The rigid polyurethane foam is prepared by polymerization reaction of polyurethane polyol composite material and isocyanate in the presence of catalyst and other auxiliary agents, has the characteristics of excellent heat insulation performance, sound insulation, light weight, high specific strength, good processability and the like, and is widely used as a heat-insulating and cold-insulating material, such as a refrigerator. In order to achieve better heat insulation effect, a certain amount of physical foaming agent with low boiling point and low heat conductivity coefficient is added into the foam material, and unfortunately, the traditional polyurethane foaming agent CFC-11 has serious damage to an ozone layer, the second generation foaming agent HCFC-141b is the most used hydrochlorofluorocarbon foaming agent, but the HCFC-141b is forbidden in China in 2020, and can be used for replacing HCFC-141b foaming agents at present, such as all water, pentane, HFC-245fa, HFC-134a, HFC-152a, R600, HFO foaming agents and the like;
of these, CFC-11 is monofluorotrichloromethane, HCFC-141b is monofluorodichloroethane, HFC-245fa is 1, 3-pentafluoropropane, HFC-134a is 1, 2-tetrafluoroethane, HFC-152a is 1, 1-difluoroethane, R600 is n-butane, and the HFO blowing agent is a hydrofluoroolefin blowing agent.
Compared with halogenated hydrocarbon foaming agents, alkane foaming agents (such as pentane, butane and the like) have no halogen atoms, ozone Depletion Potential (ODP) is zero, and greenhouse effect potential (GWP) is approximately zero. Is environment-friendly and relatively low in price, is one of ideal alternatives to the foaming agent, however, the boiling point of Cyclopentane (CP) is as high as 49 ℃, the boiling points of n-butane and isobutane are both lower than 0 ℃, the boiling points are too high or too low to be suitable as physical foaming agents, and the foaming agents have certain plasticization and are easy to deteriorate the dimensional stability of foam. It is generally necessary to increase the filling amount to increase the mass density of the foam to ensure the dimensional stability of the foam, but this greatly increases the production cost of the foam; meanwhile, the liner corrosion phenomenon of pentane and butane is serious, and under the condition of high and low temperature, liner pits can be formed, so that the appearance of the refrigerator is influenced.
The hydrofluoroolefin foaming agent has ODP of almost 0 and GWP value of less than 10, is a better fourth generation foaming agent, and the refrigerator polyurethane foam used by the foaming agent has low heat conductivity coefficient and better comprehensive performance. However, the foaming agent is expensive, the polyurethane foam prepared by singly using the foaming agent as the foaming agent has high cost, and a large amount of the foaming agent is used to easily form a complex with a milky white catalyst, so that the stability of the foaming agent is reduced, and meanwhile, the plastic liner material of the refrigerator is easily corroded, so that the liner is cracked, swelled and the like.
The invention aims to overcome the respective defects of the foaming agents and provide a polyurethane composition prepared from an environment-friendly composite foaming agent so as to meet the requirement of low manufacturing cost, and the prepared foam has the advantages of small density, good stability, low conductivity, high strength and weak corrosiveness to the refrigerator liner.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polyurethane composition, polyurethane foam, a preparation method and application thereof.
According to one aspect of the present invention, there is provided a polyurethane composition comprising a polyether polyol and an isocyanate capable of reacting therewith; the foaming agent adopted by the polyurethane composition is a composite foaming agent and is a mixture composed of pentane, hydrofluoroolefin foaming agent and propane. The composite foaming agents have synergistic effect, so that the problems caused by the independent use of each physical foaming agent can be effectively avoided, and the rigid polyurethane foam with good performance can be obtained.
According to another aspect of the present invention, there is also provided a polyurethane foam prepared from the above polyurethane composition.
Based on the third aspect of the invention, a preparation method of the polyurethane foam is also provided.
In accordance with a fourth aspect of the present invention, there is also provided a refrigerator comprising the aforementioned polyurethane foam.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a polyurethane composition comprising the following components in parts by mass:
67 to 100 parts of polyether polyol,
0 to 33 parts of polyester polyol,
0.5 to 9 portions of surfactant,
1 to 15 parts of composite catalyst,
0.5 to 7 parts of water,
8 to 60 parts of composite foaming agent,
an isocyanate having an isocyanate index of 1.0 to 1.5;
wherein the composite foaming agent comprises 10-75% of pentane, 5-70% of hydrofluoroolefin foaming agent and 2-30% of propane by taking the total mass as 100%.
Propane (R290) is poorly soluble in polyols, less useful in rigid foam polyurethane foams, and has a lower boiling point (-44 ℃) and more stringent operating process requirements, and when propane alone is used to foam, it tends to escape from the reactants, causing increased foam surface blisters, which can adversely affect foam properties.
According to the invention, through continuous research, the pentane, hydrofluoroolefin foaming agent and propane form the composite foaming agent, so that the performance defect caused by independently taking each component as the foaming agent can be solved, the foam performance is improved, the prepared foam cells are fine and smooth, the polyurethane foam with good heat conductivity coefficient can be reduced, the foam mass density can be reduced under the condition of keeping the foam stability, the raw material cost is controlled, the corrosiveness to the plastic liner is lower, and the polyurethane foam is more suitable for preparing heat preservation and cold insulation materials.
In the invention, the mass content of the hydrofluoroolefin foaming agent in the composite foaming agent is not more than 70%, so that the corrosion to the plastic liner material of the refrigerator can be reduced, the cracking and swelling risks of the liner of the refrigerator can be effectively reduced, and the complexing probability with the milky white catalyst can be reduced; the pentane content in the mixed foaming agent is kept above 10%, and a certain amount of R290 is added, wherein the weight of R290 in the composite foaming agent is not more than 30%, so that the initial foaming capacity of the composition can be improved, the fluidity can be improved, the dimensional stability of the foam can be enhanced, meanwhile, the escape of propane gas to the surface of the foam caused by the addition of a large amount can be avoided, the surface defect of the foam can be effectively reduced, and the filling amount can be reduced to reduce the consumption of polyurethane foam and the production cost because the vapor pressure of the propane is high; furthermore, the mixed blowing agent system used herein also increases the maximum allowable amount of blowing agent added to the composition, thereby reducing foam density.
In a preferred embodiment of the present invention, the polyether polyol is composed of polyether polyol a, polyether polyol B, polyether polyol C, polyether polyol D;
the polyether polyol A has a hydroxyl value of 200-550 mgKOH/g and a functionality of 6-8 and is prepared by an addition reaction of at least one of sucrose and sorbitol serving as an initiator and alkylene oxide;
the polyether polyol B is amino polyether polyol with a hydroxyl value of 300-550 mgKOH/g and a functionality of 4-6, and is prepared by addition reaction of o-toluenediamine and alkylene oxide;
the polyether polyol C has a hydroxyl value of 250-495 mgKOH/g and a functionality of 3-6, and is prepared by an addition reaction of at least one of palm oil and soybean oil serving as an initiator and alkylene oxide;
the polyether polyol D has hydroxyl value of 100-300 mgKOH/g and functionality of 2-4 and is prepared by the addition reaction of at least one of diethylene glycol, glycerol and propylene glycol as an initiator and alkylene oxide.
In a preferred embodiment of the invention, the polyether polyol comprises the following components in percentage by weight, based on 100% by weight of the total mass:
5 to 85%, preferably 5 to 72%,
polyether polyol B2-85%, preferably 10-70%,
polyether polyol C0-80%, preferably 10-70%,
polyether polyol D0-30%, preferably 5-20%.
The high-functionality polyether used in the polyether polyol can provide enough crosslinking degree and rigidity for the foam, the amine polyether with self-catalysis can improve the initial viscosity of a system at the initial stage of reaction, wrap the escape of low-boiling-point propane, so that the propane can be more wrapped in the foam, the fluidity of the foam is improved, the density difference of the foam is reduced, the density distribution is uniform, the strength of the foam is improved, and the foam defect is reduced.
In a preferred embodiment of the present invention, the hydroxyl value of the polyester polyol is 150 to 400mgKOH/g, the functionality is 2 to 5, and the phthalic anhydride polyester polyol is obtained by condensing phthalic anhydride with a polyol.
The benzene ring structure is contained in the phthalic anhydride polyester polyol, so that the prepared foam has high strength, good dimensional stability and low heat conductivity coefficient, and meanwhile, the phthalic anhydride polyester has high activity, so that the initial viscosity can be improved, the foaming agent is wrapped, the dimensional stability of the foam is improved, the shrinkage rate of the foam is reduced, and the foam cost is reduced.
In a preferred embodiment of the present invention, the surfactant is a silicon-carbon surfactant, preferably at least one of silicone oil AK8830, silicone oil L6863, silicone oil B84806, and silicone oil B8492.
In a preferred scheme of the invention, the composite catalyst comprises a foaming catalyst, a gel catalyst and a trimerization catalyst, wherein the mass ratio of the foaming catalyst to the gel catalyst to the trimerization catalyst is (0-1): (0.2-5): (0-2), preferably (0-1): (1-4): (0.5-2);
preferably, the foaming catalyst is one or a mixture of more of pentamethyldiethylenetriamine, tetramethylhexamethylenediamine and bis-dimethylaminoethyl ether in any proportion;
preferably, the gel catalyst is a mixture of one or more of methylimidazole, N-dimethylcyclohexylamine, N-methylpyrrolidone and neo-classical chemical PT303 in any proportion;
preferably, the trimerization catalyst is one or a mixture of more than one of potassium formate, 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine, 2-hydroxy-N, N, N-trimethyl-1-propylamine formate (TMR-2) and potassium acetate in any proportion.
Preferably, the pentane is at least one of cyclopentane and isopentane, more preferably cyclopentane or a mixture of cyclopentane and isopentane, and the content of the cyclopentane and the isopentane in the mixture is 30-95% and the content of the isopentane in the mixture is 5-70%.
Preferably, the hydrofluoroolefin blowing agent is trans-1-chloro-3, 3-trifluoropropene (LBA), cis-1, 4-hexafluoro-2-butene (OPteon-1100), trans-1, 4-hexafluoro-2-butene (OPteon-1150) at least one of trans-1, 3-tetrafluoropropene (GBA), further preferred is the blowing agent trans-1-chloro-3, 3-trifluoropropene (LBA), which is currently the most widely used in the industry.
In a preferred embodiment of the invention, the isocyanate is a polymeric MDI, preferably a polymeric MDI having an NCO content of 29 to 32%, more preferably one or more of the group consisting of vancomic PM-200, vancomic PM-2010 and vancomic PM-400.
The present invention also provides a polyurethane foam made from the polyurethane composition described above.
The present invention also provides a process for preparing a polyurethane foam from the polyurethane composition described hereinbefore, comprising the steps of:
1) Uniformly mixing polyether polyol, polyester polyol, surfactant, composite catalyst, water and composite foaming agent, and cooling to below 10 ℃ to obtain a mixture;
2) Mixing the mixture obtained in the step 1) with isocyanate, and foaming at high pressure to obtain rigid polyurethane foam;
preferably, the high-pressure foaming condition is gun head pressure of 130-150 Kpa and temperature of 15-19 ℃.
The invention also provides the use of polyurethane foams prepared from the polyurethane compositions described above as refrigerator materials.
The polyurethane composition has the following beneficial effects:
(1) The polyurethane foam prepared by the polyurethane composition has ODP and GWP of almost 0, is environment-friendly and is environment-friendly;
(2) The polyurethane foam prepared by the polyurethane composition has high strength, and can effectively reduce the filling amount of foaming materials, thereby reducing the production cost of the foam and improving the income of clients;
(3) The polyurethane foam prepared by the polyurethane composition has fine and uniform foam holes, low heat conductivity coefficient and good heat insulation performance, and can reduce the energy consumption of the refrigerator;
(4) The polyurethane foam prepared by the composition has good fluidity, uniform density distribution and small expansion rate after demolding, can effectively wrap a low-boiling point foaming agent, reduces surface defects and improves the appearance of products.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The sources of the main materials and reagents involved in the following embodiments are as follows:
trans-1-chloro-3, 3-trifluoropropene (LBA): honiswell
Cis-1, 4-hexafluoro-2-butene (OPteon-1100): kemu (a kind of medical herb)
Trans-1, 4-hexafluoro-2-butene (OPteon-1150): kemu (a kind of medical herb)
Trans-1, 3-tetrafluoropropene (GBA): honiswell
Cyclopentane (CP): longshan chemical industry
Isopentane (IP): longshan chemical industry
Propane: gas for metallocene pattern
Polymeric MDI: wanhua PM-200
Silicone oil B8492: drawing by a man
Silicone oil B84806: drawing by a man
Silicone oil L6863: drawing by a man
Silicone oil AK8830: demeishichuang (Demeishichuang)
Pentamethyldiethylenetriamine: classical chemistry
Bis-dimethylaminoethyl ether: light-starting enterprise
Tetramethyl hexamethylenediamine: de-metallocene chemical industry
Methylimidazole: merck chemistry
Potassium formate: fengtai chemical industry
1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine: classical chemistry
N, N-dimethylcyclohexylamine: classical chemistry
N-methylpyrrolidone: basoff' s
2-hydroxy-N, N-trimethyl-1-propylamine formate (TMR-2): classical chemistry
Potassium acetate: android chemical engineering
Polyether polyol A1: sucrose as initiator, hydroxyl value of 200mgKOH/g, functionality of 6.3, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol A2: sucrose as initiator, hydroxyl value of 350mgKOH/g, functionality of 7.1, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol A3: sucrose as initiator, hydroxyl value of 550mg KOH/g, functionality of 7.9, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol A4: sorbitol as initiator, hydroxyl value of 278mgKOH/g, functionality of 6.5, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol A5: sorbitol as initiator, hydroxyl value of 510mgKOH/g, functionality of 7.7, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol B1: o-toluenediamine is used as an initiator, the hydroxyl value is 310mgKOH/g, the functionality is 4.1, and the Wanhua chemistry (Ningbo) Rong Wei
Polyether polyol B2: o-toluenediamine is used as an initiator, the hydroxyl value is 450mgKOH/g, the functionality is 5.4, and the Wanhua chemistry (Ningbo) Rong Wei
Polyether polyol B3: o-toluenediamine is used as an initiator, the hydroxyl value is 530mgKOH/g, the functionality is 5.8, and the Wanhua chemistry (Ningbo) is Rong Wei
Polyether polyol C1: palm oil as initiator, hydroxyl value of 250mgKOH/g, functionality of 3.2, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol C2: palm oil as initiator, hydroxyl value of 315mgKOH/g, functionality of 4.3, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol C3: palm oil as initiator, hydroxyl value of 450mgKOH/g, functionality of 5.1, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol C4: palm oil as initiator, hydroxyl value of 480mgKOH/g, functionality of 5.8, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol C5: soybean oil is used as an initiator, the hydroxyl value is 470mgKOH/g, the functionality is 5.5, and Wanhua chemistry (Ningbo) Rong Wei
Polyether polyol C6: soybean oil is used as an initiator, the hydroxyl value is 270mgKOH/g, the functionality is 3.4, and Wanhua chemistry (Ningbo) Rong Wei
Polyether polyol D1: diethylene glycol as initiator, hydroxyl value of 110mgKOH/g, functionality of 2.3, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol D2: diethylene glycol as initiator, hydroxyl value of 240mgKOH/g, functionality of 3.1, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol D3: diethylene glycol as initiator, hydroxyl value of 290mgKOH/g, functionality of 3.9, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol D4: propylene glycol is used as an initiator, the hydroxyl value is 125mgKOH/g, the functionality is 2.5, and Wanhua chemistry (Ningbo) Rong Wei
Polyether polyol D5: propylene glycol as initiator, hydroxyl value of 280mgKOH/g, functionality of 3.7, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol D6: glycerin as initiator, hydroxyl value of 130mgKOH/g, functionality of 2.6, wanhua chemistry (Ningbo) Rong Wei
Polyether polyol D7: glycerin as initiator, hydroxyl value of 295mgKOH/g, functionality of 4, wanhua chemistry (Ningbo) Rong Wei
Phthalic anhydride polyester polyol E1: hydroxyl value of 370mgKOH/g, functionality of 4.7, nanjing stent Pan Gongsi
Phthalic anhydride polyester polyol E2: hydroxyl value of 170mgKOH/g, functionality of 2.5, nanjing stent Pan Gongsi
Phthalic anhydride polyester polyol E3: hydroxyl value of 230mgKOH/g, functionality of 3.1, nanjing stent Pan Gongsi
The following detailed description relates to polyurethane foam performance testing methods as follows:
foam core density test was as per standard: GB/T6343-2009
Foam thermal conductivity test was as per standard: GB/T10295-2008
And (3) demolding expansion rate test: the size of the inner cavity of the die is long x wide x high=70 cm x 35cm x 10cm, and the temperature in the die is 45 ℃; the ambient temperature was 25℃and the humidity 45%. In the evaluation test, the mold was placed horizontally (i.e., 10cm was oriented upward), a foam material having a constant temperature (18 ℃) was injected into the mold, the foam was removed within 10 minutes, and the expansion coefficient of the foam in the thickness direction of 10cm was measured, namely, the mold release expansion.
Foam compression strength test was as per standard: GB/T8813-2008
Foam dimensional stability test was as per standard: GB/T8811-2008
Surface air bubble test: adopting a Lanzhi mold test method, wherein the size of the inner cavity of the mold is 5cm x 20cm x 200cm, and the temperature in the mold is 45 ℃; the ambient temperature was 25℃and the humidity 45%. In the evaluation test, the mold was placed vertically (i.e., 200cm was oriented upward), 650g of a foam material having a constant temperature (18 ℃) was injected into the mold, and after curing, the foam was taken out, and the surface bubble level was evaluated based on the size and number of bubbles. Specifically, bubbles with the longest dimension of 3-6cm are marked as class A bubbles, and bubbles with the longest dimension of more than 6cm are marked as class B bubbles; the number of class a and class B bubbles on the foam surface was counted and one class B bubble was counted as two class a bubbles. Dividing the surface bubble level into I, II and III grades, wherein the I grade represents that the number of class A bubbles is 1-10; the II grade indicates that the number of the class A bubbles is 10 to 20; class III indicates that the number of class A bubbles is > 20.
Flow index: adopting a Lanzhi mold test method, wherein the size of the inner cavity of the mold is 5cm x 20cm x 200cm, and the temperature in the mold is 45 ℃; the ambient temperature was 25℃and the humidity 45%. In the evaluation test, the mold was placed vertically (i.e., 200cm in the upward direction), 500g of foam raw material at a constant temperature (18 ℃) was injected into the mold, and the initial height of the foam was recorded; after curing, the foam was removed and the rise height of the foam was measured, and the flow index was: foam height/foam weight.
Overfill rate: adopting a Lanzhi mold test method, wherein the size of the inner cavity of the mold is 5cm x 20cm x 200cm, and the temperature in the mold is 45 ℃; the ambient temperature was 25℃and the humidity 45%. In the evaluation experiment, the mold is vertically placed (namely 200cm is in the upward direction), foam raw materials with constant temperature (18 ℃) are injected into the mold, the foam raw materials which just fill the mold are found, the injection quantity is just filled (g), and then the specified injection quantity (g) is injected, wherein the overfilling rate is: prescribed perfusion amount/exact fill 100%.
[ example 1 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 75% of cyclopentane, 23% of GBA and 2% of propane by total mass of 100%.
The polyether polyol is formed by combining 85% of polyether polyol A4, 2% of polyether polyol B1, 11% of polyether polyol C2 and 2% of polyether polyol D3;
the polyester polyol is polyester polyol E1;
the composite catalyst comprises N, N-dimethylcyclohexylamine with the mass content of 100%.
The isocyanate is polymeric MDI, wanhua PM-200.
[ example 2 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 10% of isopentane, 115060% of OPteon and 30% of propane by total mass of 100%.
The polyether polyol is formed by combining 5% of polyether polyol A1, 85% of polyether polyol B3 and 10% of polyether polyol D4;
the polyester polyol is polyester polyol E2;
in the composite catalyst, pentamethyldiethylenetriamine: n, N-dimethylcyclohexylamine: potassium acetate=0.2:2:0.5 in mass ratio.
The isocyanate is polymeric MDI, vancomic PM-2010.
[ example 3 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 20% of cyclopentane, 70% of LBA and 10% of propane based on 100% of the total mass.
The polyether polyol is formed by combining 10% of polyether polyol A3, 10% of polyether polyol B2 and 80% of polyether polyol C6;
the polyester polyol is polyester polyol E3;
in the composite catalyst, bis-dimethylaminoethyl ether: n-methylpyrrolidone: TMR-2=0.5:2.5:1 in mass ratio.
The isocyanate is polymeric MDI, wanhua PM-200.
[ example 4 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 70% of pentane mixture (cyclopentane and isopentane 19:1), OPteon-1150 5% and propane 25% based on 100% of total mass.
The polyether polyol is formed by combining 25% of polyether polyol A2, 20% of polyether polyol B2, 25% of polyether polyol C1 and 30% of polyether polyol D5;
the polyester polyol is polyester polyol E1;
in the composite catalyst, pentamethyldiethylenetriamine: n-methylpyrrolidone: potassium formate=0.7:3:1.5 in mass ratio.
The isocyanate is polymeric MDI, wanhua PM-400.
[ example 5 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises, based on 100% of the total mass, 30% of a pentane mixture (cyclopentane and isopentane 3:7), OPteon-1100 65% and propane 5%.
The polyether polyol is formed by combining 55% of polyether polyol A5, 30% of polyether polyol B3, 10% of polyether polyol C3 and 5% of polyether polyol D2;
the polyester polyol is polyester polyol E3;
in the composite catalyst, bis-dimethylaminoethyl ether: n-methylpyrrolidone: potassium acetate=0.8:4:1.8 in mass ratio.
The isocyanate is polymeric MDI, wanhua PM-200.
[ example 6 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 41% of pentane mixture (cyclopentane and isopentane 5:5), 51% of GBA and 8% of propane based on 100% of total mass.
The polyether polyol is formed by combining 20% of polyether polyol A5, 40% of polyether polyol B1, 20% of polyether polyol C5 and 20% of polyether polyol D6;
the polyester polyol is polyester polyol E2;
in the composite catalyst, bis-dimethylaminoethyl ether: n, N-dimethylcyclohexylamine: TMR-2=1:5:2 in mass ratio.
The isocyanate is polymeric MDI, vancomic PM-2010.
[ example 7 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 57% of isopentane, 115030% of OPteon and 13% of propane by total mass of 100%.
The polyether polyol is formed by combining 75% of polyether polyol A4, 5% of polyether polyol B3, 5% of polyether polyol C4 and 15% of polyether polyol D7;
the polyester polyol is polyester polyol E1;
the composite catalyst comprises methylimidazole with the mass content of 100%.
The isocyanate is polymeric MDI, wanhua PM-200.
[ example 8 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 47% of cyclopentane, 37% of LBA and 16% of propane based on 100% of the total mass.
The polyether polyol is formed by combining 35% of polyether polyol A2, 50% of polyether polyol B1, 9% of polyether polyol C1 and 6% of polyether polyol D3;
the polyester polyol is polyester polyol E2;
in the composite catalyst, tetramethyl hexamethylenediamine: n, N-dimethylcyclohexylamine: potassium acetate=0.2:2:0.5 in mass ratio.
The isocyanate is polymeric MDI, vancomic PM-2010.
[ example 9 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 20% of pentane (cyclopentane: isopentane 4:6), 20% of OPteon-1100 44% and 19% of propane by total mass of 100%.
The polyether polyol is formed by combining 15% of polyether polyol A1, 8% of polyether polyol B2, 65% of polyether polyol C2 and 12% of polyether polyol D2;
the polyester polyol is polyester polyol E3;
in the composite catalyst, bis-dimethylaminoethyl ether: n-methylpyrrolidone: TMR-2=0.5:2.5:1 in mass ratio.
The isocyanate is polymeric MDI, wanhua PM-200.
[ example 10 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises, based on 100% of the total mass, 60% of a pentane mixture (cyclopentane and isopentane 6:4), OPteon-1100 17% and 23% of propane.
The polyether polyol is formed by combining 8% of polyether polyol A3, 70% of polyether polyol B2, 14% of polyether polyol C3 and 8% of polyether polyol D1;
the polyester polyol is polyester polyol E1;
in the composite catalyst, pentamethyldiethylenetriamine: methylimidazole: potassium acetate=0.7:3:1.5 in mass ratio.
The isocyanate is polymeric MDI, wanhua PM-400.
[ example 11 ]
A polyurethane composition comprising the following components by weight:
wherein the compound foaming agent comprises 61% of pentane mixture (cyclopentane and isopentane 7:3), 11% of LBA and 28% of propane based on 100% of total mass.
The polyether polyol is formed by combining 27% of polyether polyol A3, 18% of polyether polyol B1, 40% of polyether polyol C4 and 15% of polyether polyol D4;
in the composite catalyst, tetramethyl hexamethylenediamine: n-methylpyrrolidone: potassium formate=0.8:4:1.8 in mass ratio.
The isocyanate is polymeric MDI, wanhua PM-200.
Comparative example 1
A polyurethane composition was provided with reference to substantially the same method as in example 1, except that: the composite blowing agent was replaced with LBA of the same mass.
Comparative example 2
A polyurethane composition was provided with reference to substantially the same method as in example 1, except that: the composite blowing agent was replaced with cyclopentane of the same mass.
[ comparative example 3 ]
A polyurethane composition was provided with reference to substantially the same method as in example 1, except that: the composite blowing agent was replaced with the same mass of propane.
[ comparative example 4 ]
A polyurethane composition was provided with reference to substantially the same method as in example 1, except that: the composite blowing agent was replaced with a mixture of cyclopentane and LBA of the same mass, in a mass ratio of 14:60.
comparative example 5
A polyurethane composition was provided with reference to substantially the same method as in example 1, except that: the composite blowing agent was replaced with a mixture of LBA and propane of the same mass ratio of 60:26.
[ comparative example 6 ]
A polyurethane composition was provided with reference to substantially the same method as in example 1, except that: the material proportion in the composite foaming agent is modified to be that the composite foaming agent comprises 7% of cyclopentane, 58% of LBA and 35% of propane by taking the total mass as 100%.
[ application example ]
Polyurethane foams were prepared according to the following methods using the polyurethane compositions prepared in examples 1 to 11 and comparative examples 1 to 6, respectively:
1) Uniformly mixing polyether polyol, polyester polyol, surfactant, composite catalyst, water and composite foaming agent, and cooling to below 10 ℃ to obtain a mixture;
2) Mixing the mixture obtained in the step 1) with isocyanate, and foaming at high pressure to obtain rigid polyurethane foam;
the high-pressure foaming condition is gun head pressure 140Kpa and temperature 18 ℃.
The polyurethane foams prepared from the polyurethane compositions of the examples and comparative examples were subjected to the performance test in Table 1, and the test results are shown in Table 1. As can be seen from Table 1, the polyurethane foam prepared by the scheme of the invention has the advantages of lower heat conductivity, demoulding expansion coefficient, lower air bubble, good strength and better performances than those of the comparative example under the condition of the same overfill rate, so that the raw material filling quantity can be effectively reduced, the foam density can be reduced, and the production cost can be reduced by adopting the technical scheme of the invention under the condition of the same technological parameters.
TABLE 1 polyurethane foam Performance parameter Table

Claims (17)

1. The polyurethane composition is characterized by comprising the following components in parts by mass:
67 to 100 parts of polyether polyol,
0 to 33 parts of polyester polyol,
0.5 to 9 portions of surfactant,
1 to 15 parts of composite catalyst,
0.5 to 7 parts of water,
8 to 60 parts of composite foaming agent,
an isocyanate having an isocyanate index of 1.0 to 1.5;
wherein the composite foaming agent comprises 10-75% of pentane, 5-70% of hydrofluoroolefin foaming agent and 2-30% of propane by taking the total mass as 100%; the pentane is at least one of cyclopentane and isopentane;
the polyether polyol is formed by combining polyether polyol A, polyether polyol B, polyether polyol C and polyether polyol D;
the polyether polyol A has a hydroxyl value of 200-550 mgKOH/g and a functionality of 6-8 and is prepared by an addition reaction of at least one of sucrose and sorbitol serving as an initiator and alkylene oxide;
the polyether polyol B is amino polyether polyol with a hydroxyl value of 300-550 mgKOH/g and a functionality of 4-6, and is prepared by addition reaction of o-toluenediamine and alkylene oxide;
the polyether polyol C has a hydroxyl value of 250-495 mgKOH/g and a functionality of 3-6, and is prepared by an addition reaction of at least one of palm oil and soybean oil serving as an initiator and alkylene oxide;
the polyether polyol D has a hydroxyl value of 100-300 mgKOH/g and a functionality of 2-4 and is prepared by an addition reaction of at least one of diethylene glycol, glycerol and propylene glycol serving as an initiator and alkylene oxide;
the polyether polyol is calculated by 100 percent of total mass, and the weight ratio of each component is as follows:
5 to 85 percent of polyether polyol A,
polyether polyol B2-85%,
5 to 80 percent of polyether polyol C,
polyether polyol D2-30%;
the hydroxyl value of the polyester polyol is 150-400 mgKOH/g, the functionality is 2-5, and the phthalic anhydride polyester polyol is formed by condensing phthalic anhydride and polyol.
2. The polyurethane composition according to claim 1, wherein the polyether polyol has a total mass of 100% and the respective components have the following ratios:
5 to 72 percent of polyether polyol A,
10 to 70 percent of polyether polyol B,
10 to 70 percent of polyether polyol C,
5-20% of polyether polyol D.
3. The polyurethane composition of claim 1, wherein the surfactant is a silicon-carbon type surfactant.
4. A polyurethane composition according to claim 3, wherein the surfactant is at least one of silicone oil AK8830, silicone oil L6863, silicone oil B84806, silicone oil B8492.
5. The polyurethane composition according to any one of claims 1 to 4, wherein the composite catalyst comprises a foaming catalyst, a gel catalyst and a trimerization catalyst, wherein the mass ratio of the foaming catalyst, the gel catalyst and the trimerization catalyst is (0-1): 0.2-5): 0-2.
6. The polyurethane composition according to claim 5, wherein the composite catalyst comprises a foaming catalyst, a gel catalyst and a trimerization catalyst, wherein the mass ratio of the foaming catalyst, the gel catalyst and the trimerization catalyst is (0-1): 1-4): 0.5-2.
7. The polyurethane composition according to claim 5, wherein the foaming catalyst is a mixture of one or more of pentamethyldiethylenetriamine, tetramethylhexamethylenediamine and bis-dimethylaminoethyl ether in any ratio.
8. The polyurethane composition according to claim 5, wherein the gel catalyst is a mixture of one or more of methylimidazole, N-dimethylcyclohexylamine, N-methylpyrrolidone and PT303 in any ratio.
9. The polyurethane composition according to claim 5, wherein the trimerization catalyst is one or more of potassium formate, 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine, 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, and potassium acetate in any ratio.
10. A polyurethane composition as claimed in any one of claims 1 to 4, wherein, the hydrofluoroolefin foaming agent is trans-1-chloro-3, 3-trifluoropropene, cis-1, 4-hexafluoro-2-butene trans-1, 4-hexafluoro-2-butene at least one of trans-1, 3-tetrafluoropropene.
11. The polyurethane composition of any of claims 1-4, wherein the isocyanate is a polymeric MDI.
12. The polyurethane composition of claim 11, wherein the isocyanate is a polymeric MDI having an NCO content of 29 to 32%.
13. The polyurethane composition of claim 12, wherein the isocyanate is one or more of vancomfrey PM-200, vancomfrey PM-2010, and vancomfrey PM-400.
14. A polyurethane foam made from the polyurethane composition of any one of claims 1-13.
15. A process for preparing a polyurethane foam from the polyurethane composition of any one of claims 1 to 13, comprising the steps of:
1) Uniformly mixing polyether polyol, polyester polyol, surfactant, composite catalyst, water and composite foaming agent, and cooling to below 10 ℃ to obtain a mixture;
2) Mixing the mixture obtained in the step 1) with isocyanate, and foaming at high pressure to obtain the rigid polyurethane foam.
16. The method for preparing polyurethane foam according to claim 15, wherein the high pressure foaming condition is gun head pressure of 130 to 150Kpa and temperature of 15 to 19 ℃.
17. Use of a polyurethane foam prepared from the polyurethane composition of any one of claims 1 to 13 as a refrigerator material.
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