WO2020244371A1 - 一种用于与异氰酸酯反应的组合物 - Google Patents

一种用于与异氰酸酯反应的组合物 Download PDF

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WO2020244371A1
WO2020244371A1 PCT/CN2020/090670 CN2020090670W WO2020244371A1 WO 2020244371 A1 WO2020244371 A1 WO 2020244371A1 CN 2020090670 W CN2020090670 W CN 2020090670W WO 2020244371 A1 WO2020244371 A1 WO 2020244371A1
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parts
polyol
hydroxyl value
viscosity
polyether polyol
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PCT/CN2020/090670
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English (en)
French (fr)
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邢益辉
孔玉荣
熊丽媛
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红宝丽集团股份有限公司
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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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • 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
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom 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
    • C08G18/28—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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic groups
    • 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
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • 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
    • 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 invention relates to a composition for reacting with isocyanate to produce rigid polyurethane foam.
  • Rigid polyurethane foam is made by polymerization of isocyanate reactant and isocyanate in the presence of catalysts and other additives. It has the characteristics of excellent thermal insulation, sound insulation, insulation, light weight, high specific strength, and good processing performance. , Is widely used as heat preservation and cold preservation materials. In order to achieve better thermal insulation effect, a certain amount of physical foaming agent with low boiling point and low thermal conductivity must be added to the foam material. Unfortunately, the traditional polyurethane foaming agent-fluorotrichloromethane (CFC-11) can severely destroy the ozone layer. After the signing of the "Montreal Protocol" in 1987, countries have started researches on CFC-11 replacement foaming agents.
  • alkane foaming agents such as pentane, butane, etc.
  • ODP is zero
  • GWP is approximately zero.
  • They are environmentally friendly and relatively inexpensive, making them ideal
  • the boiling point of cyclopentane is as high as 49°C, and it has a certain degree of plasticization, which easily deteriorates the dimensional stability of the foam.
  • the dimensional stability of the foam is ensured by increasing the foam density, which increases the production cost of the foam.
  • the fourth-generation foaming agent made by foaming rigid polyurethane foam for refrigerators, has low thermal conductivity and good overall performance.
  • the foaming agent is expensive, and the rigid polyurethane foam prepared by using it alone as the foaming agent has a high cost and is difficult to promote.
  • the foaming material contains a large amount of trans-1-chloro-3,3,3-trifluoropropene, it is likely to corrode the plastic liner material of the refrigerator, causing the liner to crack and swell.
  • the present invention aims to overcome the respective shortcomings of the aforementioned foaming agents, and provide an environment-friendly ternary compound foaming system for reacting with isocyanates to prepare rigid polyurethane foams with excellent performance.
  • the invention aims to solve the deficiencies of the existing foaming technology, and provides an isocyanate reactant of an environment-friendly ternary compound foaming system to prepare a rigid polyurethane foam with excellent performance.
  • composition for reacting with isocyanate comprising the following components:
  • Composite polyol 100 parts, the composite polyol includes 70 to 95 parts by weight of polyether polyol, 0 to 15 parts by weight of polyester polyol, and 0 to 15 parts of polycarbonate polyol;
  • Amine catalyst 2.0 ⁇ 5.1 parts
  • Silicone surfactant 1.5 ⁇ 4.5 parts
  • the mixed blowing agent includes 7 to 15 parts of cyclopentane, 2 to 10 parts of trans-1-chloro-3,3,3-trifluoropropene and 1 to 5 of butane Copies.
  • the use of the above-mentioned ratio of mixed foaming agents can make various foaming agents play a synergistic effect, effectively avoiding the problems caused when each foaming agent is used alone, so as to obtain a rigid polyurethane foam with good performance.
  • the mixed foaming system of the present invention is mainly based on alkane foaming agent, and is matched with an appropriate amount of trans-1-chloro-3,3,3-trifluoropropene, which is beneficial to improve the foam performance and produce fine cells.
  • Rigid polyurethane foam with uniform and good thermal insulation properties can effectively control the cost of foam materials.
  • the weight content of trans-1-chloro-3,3,3-trifluoropropene in the mixed blowing agent does not exceed 56%, which can reduce the corrosion of the inner liner material and effectively reduce the cracking and swelling of the refrigerator liner And other risks; the weight content of cyclopentane in the mixed blowing agent is roughly maintained above 32%, and a certain amount of butane is added, of which the weight content of butane in the mixed blowing agent does not exceed 36%, which can be improved
  • the initial foaming ability of the composition enhances the low-temperature dimensional stability of the foam, and at the same time prevents butane from escaping from the foam surface due to excessive addition, thereby effectively reducing foam surface defects.
  • the hybrid foaming system used in the present application can also increase the maximum allowable addition amount of foaming agent in the composition, thereby reducing foam density and reducing production costs.
  • the components of the composition of the present invention have good compatibility and can work in synergy with each other, the prepared foam has uniform density distribution, good thermal insulation performance, improved compression strength and high and low temperature dimensional stability, and good overall performance.
  • the polyether polyol is made of one or more of sucrose, sorbitol, pentaerythritol, glycerol, trimethylolpropane, toluene diamine, ethylene diamine, etc. as the initiator and alkylene oxide
  • the viscosity of the polyether polyol is 10000-35000 mPa ⁇ s, and the hydroxyl value is 350-480 mgKOH/g.
  • Polyether polyol is the most used polyol raw material in the polyurethane foam industry.
  • the high-functionality polyether polyol can provide sufficient crosslinking degree and rigidity for the foam, and the foam has good heat resistance.
  • the toluene diamine polyether polyol with autocatalysis can rapidly increase the viscosity of the system at the initial stage of the reaction and reduce the escape of low-boiling butane. The rapid expansion of butane improves the fluidity of the reaction solution, and makes the prepared foam have good fluidity and uniform density distribution.
  • the polyester polyol is a modified phthalic anhydride polyester polyol with an average functionality of 2.2-2.5, a viscosity of 800-5000 mPa ⁇ s, and a hydroxyl value of 360-450 mgKOH/g.
  • the modified phthalic anhydride polyester polyol contains a rigid benzene ring structure in the molecule, and the prepared foam has high strength, good dimensional stability and reduced thermal conductivity.
  • the polycarbonate polyol is formed by the reaction of carbon dioxide and olefin oxide, the viscosity of the polycarbonate polyol is 500-3500 mPa ⁇ s, and the hydroxyl value is 110-250 mgKOH/g.
  • the molecular structure of carbonate polyol contains a large number of carbonyl groups, and the intermolecular cohesion energy is large, which can bring excellent mechanical properties to the foam material, increase the foam strength, and reduce the stable density of the foam.
  • excessive dosage will cause the reaction material The viscosity of the product is obviously increased and the operability is decreased.
  • the amine catalyst is selected from pentamethyldiethylenetriamine, bis-(dimethylamino)ethyl ether, triethylenediamine, tetramethylethylenediamine, tetramethylhexyl Diamine, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, dimethylethanolamine, triethanolamine, 2-hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethyl Acetyl amine, 2-hydroxypropyl trimethyl octanoic acid amine, 2,4,6-tris(dimethylaminomethyl)phenol or 1,3,5-tris(dimethylaminopropyl)-hexahydrotris A mixture of two or more of azines.
  • the above-mentioned catalysts can be compounded according to actual needs to ensure stable reaction balance.
  • the silicon surfactant is a silicon-carbon surfactant, which is formed by the reaction of a hydrogen-containing silicone oil and an unsaturated polyether polyol.
  • the selection of silicon-carbon surfactants is well known to those skilled in the art. Specifically, it can be selected from commercially available ones, such as Niax L-6863, Niax L-6988, Niax L-6861, Niax L-6866 of Momentive; AK-8805, AK-8832, and AK-8860 of Mestel.
  • Silicon-carbon surfactants have good stability, excellent hydrolysis resistance, can be stored for a long time without deterioration, have a strong foam emulsification ability, can effectively reduce the escape tendency of these alkane blowing agents, and act as nucleation in the early stage of the foaming reaction
  • the role of the agent is conducive to the formation of a large number of fine bubble nuclei, increasing the nucleation speed and the degree of cell density, and can improve the viscoelasticity of the cell wall in the middle of the reaction, effectively inhibit the rupture of cells, reduce surface pores, and improve foam performance.
  • the butane is n-butane, or isobutane, or a mixture of n-butane and isobutane in any ratio.
  • the isocyanate When using the composition and isocyanate of the present invention to produce rigid polyurethane foam, the isocyanate generally adopts polymethylene polyphenyl polyisocyanate, which can be selected from commercially available ones, such as Bayer's 44V-10L, 44V-20L, 44V -40L, Suprasec 5005, Suprasec 2085, Suprasec 5000 of Huntsman, M20S of BASF, MR200 and MR100 of Mitsui, PM2010, PM200 of Yantai Wanhua, PAPI27, PAPI135 of Dow, etc.
  • polymethylene polyphenyl polyisocyanate which can be selected from commercially available ones, such as Bayer's 44V-10L, 44V-20L, 44V -40L, Suprasec 5005, Suprasec 2085, Suprasec 5000 of Huntsman, M20S of BASF, MR200 and MR100 of Mitsui, PM2010, PM200 of Yantai Wanhua, PA
  • the weight ratio of the composition to the isocyanate is controlled to 1:(0.95 ⁇ 1.35).
  • the composition and the isocyanate are mixed at a weight ratio of 1:(0.95 ⁇ 1.35) on the foaming gun head in one step and injected into the closed mold. It is prepared after curing and molding, and the set process parameters are well known to those skilled in the art. Generally, the material temperature is controlled at 15-30°C, the mold temperature is controlled at 35-55°C, and the overfill coefficient is 105% ⁇ 130%. Manual foaming can also be used.
  • the isocyanate is quickly poured into the composition, and the mixture is quickly stirred for 3 to 6 seconds, and then poured into a mold to be cured to obtain a rigid polyurethane foam.
  • composition of the present invention has the following advantages:
  • the rigid polyurethane foam prepared by using the composition of the present invention has high specific strength and can reduce the injection volume of foaming material, thereby reducing the production cost of the foam.
  • the rigid polyurethane foam prepared by using the composition of the present invention has fine and uniform cells, low thermal conductivity and good thermal insulation performance.
  • the rigid polyurethane foam prepared by using the composition of the present invention has good high and low temperature dimensional stability, low expansion rate after demolding, and few surface defects.
  • the mixed foaming agent used in the present invention has extremely low ODP and GWP, is green and environmentally friendly, and is environmentally friendly.
  • the density, thermal conductivity, compression strength, expansion rate, and high and low temperature dimensional change rate of the foam in the present invention are respectively in accordance with the national standards GB/T 6343-2009, GB/T 3399-1982, GB/T 8813-2008, GB/T 20673 -2006, GB/T8811-2008 is measured, among them, the foam core density refers to the foam forming composition is injected into a closed mold with a certain strength 1100 ⁇ 300 ⁇ 50mm to foam, after the foam is taken out, the skin is removed and then measured The density of the foam core layer.
  • the isocyanate is referred to as the second component
  • the composition used to react with the isocyanate is referred to as the first component
  • the low-density rigid polyurethane foam is produced according to the following steps:
  • the parts in the following examples and comparative examples are parts by weight, and in each example, 100 parts of the composite polyol are used as a reference.
  • the first component is a first component
  • Compound polyol hydroxyl value of 370mgKOH/g, 100 parts, including:
  • Polyether polyol A sorbitol polyether polyol, the hydroxyl value is 380 ⁇ 440mgKOH/g, the viscosity is 15000 ⁇ 30000mPa ⁇ s, 60 parts;
  • Polyether polyol B toluene diamine polyether polyol, the hydroxyl value is 340 ⁇ 400mgKOH/g, the viscosity is 10000 ⁇ 28000mPa ⁇ s, 25 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 500 ⁇ 3500mPa ⁇ s, 15 parts;
  • Amine catalyst 2.8 parts, including 0.5 parts of pentamethyldiethylenetriamine, 1.5 parts of N,N-dimethylcyclohexylamine, and 0.8 parts of 2-hydroxypropyltrimethyloctanoic acid amine;
  • Silicon surfactant 2.5 parts, including 1.5 parts Niax L-6863, 1.0 parts Niax L-6988;
  • the second component 44V-20L, 125 parts.
  • the first component is a first component
  • Compound polyol hydroxyl value of 430mgKOH/g, 100 parts, including:
  • Polyether polyol A sucrose polyether polyol, the hydroxyl value is 440 ⁇ 480mgKOH/g, the viscosity is 20000 ⁇ 35000mPa ⁇ s, 60 parts;
  • Polyether polyol B toluene diamine polyether polyol, the hydroxyl value is 340 ⁇ 400mgKOH/g, the viscosity is 10000 ⁇ 28000mPa ⁇ s, 30 parts;
  • Modified phthalic anhydride polyester polyol hydroxyl value is 360 ⁇ 450mgKOH/g, viscosity is 800 ⁇ 5000mPa ⁇ s, 10 parts;
  • Amine catalyst 2.0 parts, including 0.4 parts of bis-(dimethylamino) ethyl ether and 1.6 parts of N,N-dimethylbenzylamine;
  • Silicone surfactant AK-8860, 1.5 parts;
  • the second component Suprasec 5005,126 copies.
  • the first component is a first component
  • Compound polyol hydroxyl value of 410mgKOH/g, 100 parts, including:
  • Polyether polyol sucrose polyether polyol, the hydroxyl value is 400 ⁇ 450mgKOH/g, the viscosity is 18000 ⁇ 32000mPa ⁇ s, 85 parts;
  • Modified phthalic anhydride polyester polyol hydroxyl value is 360 ⁇ 450mgKOH/g, viscosity is 800 ⁇ 5000mPa ⁇ s, 15 parts;
  • Amine catalyst 2.5 parts, including 0.5 part of pentamethyldiethylenetriamine, 0.2 part of triethylenediamine, 1.0 part of N,N-dimethylcyclohexylamine, 2-hydroxypropyltrimethylammonium acetate 0.8 copies;
  • Silicon surfactant 3.0 parts, including 1.5 parts Niax L-6988, 0.5 parts Niax L-6861, 1.0 parts AK-8832;
  • the second component 44V-10L, 144 parts.
  • the first component is a first component
  • Compound polyol hydroxyl value of 390mgKOH/g, 100 parts, including:
  • Polyether polyol A sucrose polyether polyol, the hydroxyl value is 400 ⁇ 460mgKOH/g, the viscosity is 18000 ⁇ 32000mPa ⁇ s, 50 parts;
  • Polyether polyol A glycerin polyether polyol, with a hydroxyl value of 350-400 mgKOH/g and a viscosity of 10,000-20,000 mPa ⁇ s, 20 parts;
  • Modified phthalic anhydride polyester polyol hydroxyl value is 360 ⁇ 450mgKOH/g, viscosity is 800 ⁇ 5000mPa ⁇ s, 15 parts;
  • Polycarbonate polyol the hydroxyl value is 110 ⁇ 220mgKOH/g, the viscosity is 500 ⁇ 3200mPa ⁇ s, 15 parts;
  • Amine catalyst 3.5 parts, including 0.6 parts of pentamethyldiethylenetriamine, 1.7 parts of N,N-dimethylbenzylamine, 1.2 parts of 2,4,6-tris(dimethylaminomethyl)phenol,
  • Silicon surfactant 4.0 parts, 2 parts including Niax L-6866, 1 part Niax L-6988, 1 part Niax L-6861;
  • the second component Suprasec2085, 144 parts.
  • the first component is a first component
  • Hydroxyl value is 380mgKOH/g, 100 parts, including:
  • Polyether polyol A sorbitol polyether polyol, with a hydroxyl value of 350-400 mgKOH/g and a viscosity of 15000-25000 mPa ⁇ s, 60 parts;
  • Polyether polyol B toluene diamine polyether polyol, the hydroxyl value is 340 ⁇ 400mgKOH/g, the viscosity is 10000 ⁇ 28000mPa ⁇ s, 25 parts;
  • Modified phthalic anhydride polyester polyol hydroxyl value is 360 ⁇ 450mgKOH/g, viscosity is 800 ⁇ 5000mPa ⁇ s, 10 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 1500 ⁇ 3500mPa ⁇ s, 5 parts;
  • Amine catalyst 5.1 parts, including 0.4 parts of bis-(dimethylamino)ethyl ether, 0.5 parts of tetramethylethylenediamine, 1.0 part of N,N-dimethylcyclohexylamine, 2.0 parts of dimethylethanolamine, 1.2 parts of 2,4,6-tris(dimethylaminomethyl)phenol,
  • Silicone surfactant 3.5 parts, 2.0 parts including AK-8832, 1.5 parts AK-8860;
  • Mixed blowing agent 22 parts, including 10 parts of cyclopentane, 10 parts of trans-1-chloro-3,3,3-trifluoropropene, and 2 parts of n-butane;
  • the second component Suprasec 5000, 120 copies.
  • the first component is a first component
  • Compound polyol hydroxyl value of 390mgKOH/g, 100 parts, including:
  • Polyether polyol A sucrose polyether polyol, the hydroxyl value is 400 ⁇ 480mgKOH/g, the viscosity is 18000 ⁇ 35000mPa ⁇ s, 65 parts;
  • Polyether polyol B glycerin polyether polyol, the hydroxyl value is 350 ⁇ 380mgKOH/g, the viscosity is 10000 ⁇ 18000mPa ⁇ s, 15 parts;
  • Modified phthalic anhydride polyester polyol hydroxyl value is 360 ⁇ 450mgKOH/g, viscosity is 800 ⁇ 5000mPa ⁇ s, 8 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 500 ⁇ 3500mPa ⁇ s, 12 parts;
  • Amine catalyst 4.2 parts, including 0.6 parts of pentamethyldiethylenetriamine, 0.8 parts of tetramethylhexamethylenediamine, 0.8 parts of N,N-dimethylbenzylamine, 1.5 parts of triethanolamine, 1,3,5 -0.5 parts of tris(dimethylaminopropyl)-hexahydrotriazine;
  • Silicon surfactant 4.5 parts, including 1.5 parts Niax L-6863, 1.0 parts Niax L-6861, 2.0 parts AK-8805;
  • the second component PM2010, 127 copies.
  • the first component is a first component
  • Compound polyol hydroxyl value of 370mgKOH/g, 100 parts, including:
  • Polyether polyol A sorbitol polyether polyol, with a hydroxyl value of 350-400 mgKOH/g and a viscosity of 15000-25000 mPa ⁇ s, 80 parts;
  • Polyether polyol B glycerin polyether polyol, the hydroxyl value is 350 ⁇ 380mgKOH/g, the viscosity is 10000 ⁇ 18000mPa ⁇ s, 10 parts;
  • Modified phthalic anhydride polyester polyol hydroxyl value is 360 ⁇ 450mgKOH/g, viscosity is 800 ⁇ 5000mPa ⁇ s, 5 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 500 ⁇ 3500mPa ⁇ s, 5 parts;
  • Amine catalyst 3.0 parts, including 0.3 parts of bis-(dimethylamino) ethyl ether, 0.8 parts of N,N-dimethylcyclohexylamine, 0.7 parts of dimethylethanolamine, 2,4,6-tris(two 1.2 parts of methylaminomethyl)phenol;
  • Silicon surfactant 3.8 parts, including 2.5 parts Niax L-6866, 1.3 parts Niax L-6861;
  • the second component PAPI27, 122 parts.
  • the first component is a first component
  • hydroxyl value is 420mgKOH/g, 100 parts, including:
  • Polyether polyol sucrose polyether polyol, the hydroxyl value is 400 ⁇ 480mgKOH/g, the viscosity is 18000 ⁇ 35000mPa ⁇ s, 80 parts;
  • Modified phthalic anhydride polyester polyol hydroxyl value is 360 ⁇ 450mgKOH/g, viscosity is 800 ⁇ 5000mPa ⁇ s, 10 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 500 ⁇ 3500mPa ⁇ s, 10 parts;
  • Amine catalyst 4.5 parts, including 0.5 parts of pentamethyldiethylenetriamine, 1.8 parts of N,N-dimethylbenzylamine, 1.0 part of dimethylethanolamine, 2,4,6-tris(dimethylamino) 1.2 parts of methyl)phenol;
  • Silicone surfactant 4.2 parts, including 1.5 parts AK-8832, 1.5 parts AK-8860, 1.2 parts AK-8805;
  • the second component PM200, 130 parts.
  • the first component is a first component
  • Compound polyol hydroxyl value of 410mgKOH/g, 100 parts, including:
  • Polyether polyol A sucrose polyether polyol, the hydroxyl value is 400 ⁇ 480mgKOH/g, the viscosity is 18000 ⁇ 35000mPa ⁇ s, 45 parts;
  • Polyether polyol B sorbitol polyether polyol, the hydroxyl value is 380 ⁇ 440mgKOH/g, the viscosity is 15000 ⁇ 30000mPa ⁇ s, 40 parts;
  • Polyether polyol C toluene diamine polyether polyol, the hydroxyl value is 340 ⁇ 400mgKOH/g, the viscosity is 10000 ⁇ 28000mPa ⁇ s, 10 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 500 ⁇ 3500mPa ⁇ s, 5 parts;
  • Amine catalyst 3.8 parts, including 0.6 parts of pentamethyldiethylenetriamine, 0.4 parts of triethylenediamine, 1.2 parts of tetramethylhexanediamine, 0.8 parts of dimethylethanolamine, 2-hydroxypropyltrimethylformic acid 0.8 parts of ammonium;
  • Silicon surfactant 2.2 parts, 1.2 parts including Niax L-6861, 1.0 part AK-8860;
  • the second component PAPI135, 123 parts.
  • the first component is a first component
  • Compound polyol hydroxyl value of 390mgKOH/g, 100 parts, including:
  • Polyether polyol A sorbitol polyether polyol, the hydroxyl value is 380 ⁇ 440mgKOH/g, the viscosity is 15000 ⁇ 30000mPa ⁇ s, 70 parts;
  • Polyether polyol B toluene diamine polyether polyol, with a hydroxyl value of 340-400 mgKOH/g and a viscosity of 10000-28000 mPa ⁇ s, 15 parts;
  • Modified phthalic anhydride polyester polyol the hydroxyl value is 360 ⁇ 450mgKOH/g, the viscosity is 800 ⁇ 5000mPa ⁇ s, 7 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 500 ⁇ 3500mPa ⁇ s, 8 parts;
  • Amine catalyst 3.2 parts, including 0.4 parts of bis-(dimethylamino) ethyl ether, 1.3 parts of N,N-dimethylcyclohexylamine, 2,4,6-tris(dimethylaminomethyl)phenol 1.5 copies;
  • Silicone surfactant 2.8 parts, including 2 parts AK-8832, 0.8 parts AK-8860;
  • the second component M20S, 132 parts.
  • the first component is a first component
  • Compound polyol hydroxyl value of 390mgKOH/g, 100 parts, including:
  • Polyether polyol A sorbitol polyether polyol, the hydroxyl value is 380 ⁇ 440mgKOH/g, the viscosity is 15000 ⁇ 30000mPa ⁇ s, 70 parts;
  • Polyether polyol B toluene diamine polyether polyol, with a hydroxyl value of 340-400 mgKOH/g and a viscosity of 10000-28000 mPa ⁇ s, 15 parts;
  • Modified phthalic anhydride polyester polyol the hydroxyl value is 360 ⁇ 450mgKOH/g, the viscosity is 800 ⁇ 5000mPa ⁇ s, 7 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 500 ⁇ 3500mPa ⁇ s, 8 parts;
  • Amine catalyst 3.2 parts, including 0.4 parts of bis-(dimethylamino) ethyl ether, 1.3 parts of N,N-dimethylcyclohexylamine, 2,4,6-tris(dimethylaminomethyl)phenol 1.5 copies;
  • Silicone surfactant 2.8 parts, including 2 parts AK-8832, 0.8 parts AK-8860;
  • the second component M20S, 132 parts.
  • the first component is a first component
  • Compound polyol hydroxyl value of 390mgKOH/g, 100 parts, including:
  • Polyether polyol A sorbitol polyether polyol, the hydroxyl value is 380 ⁇ 440mgKOH/g, the viscosity is 15000 ⁇ 30000mPa ⁇ s, 70 parts;
  • Polyether polyol B toluene diamine polyether polyol, with a hydroxyl value of 340-400 mgKOH/g and a viscosity of 10000-28000 mPa ⁇ s, 15 parts;
  • Modified phthalic anhydride polyester polyol the hydroxyl value is 360 ⁇ 450mgKOH/g, the viscosity is 800 ⁇ 5000mPa ⁇ s, 7 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 500 ⁇ 3500mPa ⁇ s, 8 parts;
  • Amine catalyst 3.2 parts, including 0.4 parts of bis-(dimethylamino) ethyl ether, 1.3 parts of N,N-dimethylcyclohexylamine, 2,4,6-tris(dimethylaminomethyl)phenol 1.5 copies;
  • Silicone surfactant 2.8 parts, including 2 parts AK-8832, 0.8 parts AK-8860;
  • Blowing agent 14 parts of cyclopentane
  • the second component M20S, 132 parts.
  • the first component is a first component
  • Compound polyol hydroxyl value of 390mgKOH/g, 100 parts, including:
  • Polyether polyol A sorbitol polyether polyol, the hydroxyl value is 380 ⁇ 440mgKOH/g, the viscosity is 15000 ⁇ 30000mPa ⁇ s, 70 parts;
  • Polyether polyol B toluene diamine polyether polyol, the hydroxyl value is 340 ⁇ 400mgKOH/g, the viscosity is 10000 ⁇ 28000mPa ⁇ s, 15 parts;
  • Modified phthalic anhydride polyester polyol the hydroxyl value is 360 ⁇ 450mgKOH/g, the viscosity is 800 ⁇ 5000mPa ⁇ s, 7 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 500 ⁇ 3500mPa ⁇ s, 8 parts;
  • Amine catalyst 3.2 parts, including 0.4 parts of bis-(dimethylamino) ethyl ether, 1.3 parts of N,N-dimethylcyclohexylamine, 2,4,6-tris(dimethylaminomethyl)phenol 1.5 copies;
  • Silicone surfactant 2.8 parts, including 2 parts AK-8832, 0.8 parts AK-8860;
  • Blowing agent 12 parts of n-butane
  • the second component M20S, 132 parts.
  • the first component is a first component
  • Compound polyol hydroxyl value of 390mgKOH/g, 100 parts, including:
  • Polyether polyol A sorbitol polyether polyol, the hydroxyl value is 380 ⁇ 440mgKOH/g, the viscosity is 15000 ⁇ 30000mPa ⁇ s, 70 parts;
  • Polyether polyol B toluene diamine polyether polyol, the hydroxyl value is 340 ⁇ 400mgKOH/g, the viscosity is 10000 ⁇ 28000mPa ⁇ s, 15 parts;
  • Modified phthalic anhydride polyester polyol the hydroxyl value is 360 ⁇ 450mgKOH/g, the viscosity is 800 ⁇ 5000mPa ⁇ s, 7 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 500 ⁇ 3500mPa ⁇ s, 8 parts;
  • Amine catalyst 3.2 parts, including 0.4 parts of bis-(dimethylamino) ethyl ether, 1.3 parts of N,N-dimethylcyclohexylamine, 2,4,6-tris(dimethylaminomethyl)phenol 1.5 copies;
  • Silicone surfactant 2.8 parts, including 2 parts AK-8832, 0.8 parts AK-8860;
  • the second component M20S, 132 parts.
  • the first component is a first component
  • Compound polyol hydroxyl value of 390mgKOH/g, 100 parts, including:
  • Polyether polyol A sorbitol polyether polyol, the hydroxyl value is 380 ⁇ 440mgKOH/g, the viscosity is 15000 ⁇ 30000mPa ⁇ s, 70 parts;
  • Polyether polyol B toluene diamine polyether polyol, the hydroxyl value is 340 ⁇ 400mgKOH/g, the viscosity is 10000 ⁇ 28000mPa ⁇ s, 15 parts;
  • Modified phthalic anhydride polyester polyol the hydroxyl value is 360 ⁇ 450mgKOH/g, the viscosity is 800 ⁇ 5000mPa ⁇ s, 7 parts;
  • Polycarbonate polyol the hydroxyl value is 220 ⁇ 250mgKOH/g, the viscosity is 500 ⁇ 3500mPa ⁇ s, 8 parts;
  • Amine catalyst 3.2 parts, including 0.4 parts of bis-(dimethylamino) ethyl ether, 1.3 parts of N,N-dimethylcyclohexylamine, 2,4,6-tris(dimethylaminomethyl)phenol 1.5 copies;
  • Silicone surfactant 2.8 parts, including 2 parts AK-8832, 0.8 parts AK-8860;
  • the second component M20S, 132 parts.
  • the rigid polyurethane foam prepared by the composition of the present invention under the same overfill coefficient, the raw material pouring amount and foam core density of Examples 1-10 are significantly lower than those of Comparative Examples 1-4.
  • the thermal conductivity is lower, the thermal insulation performance is better, and the dimensional stability is better, and the linear expansion rate is low after demolding for 5 minutes.
  • Example 11 has similar injection volume and foam density, but all properties are significantly better than Comparative Examples.
  • the composition of the present invention can obviously improve the application performance of the foam. Therefore, under the same process parameters, the technical solution of the present invention can effectively reduce the amount of raw material poured, reduce the foam density, and thereby reduce the production cost.

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Abstract

本发明公开了一种用于与异氰酸酯反应的组合物，按重量份计，包括如下组分：复合多元醇：100份，该复合多元醇包括聚醚多元醇70～95重量份、聚酯多元醇0～15重量份和聚碳酸酯多元醇0～15份；胺催化剂：2.0～5.1份；硅表面活性剂：1.5～4.5份；水：1.1～2.8份；混合发泡剂：12～22份，该混合发泡剂包括环戊烷7～15份、反式-1-氯-3,3,3-三氟丙烯2～10份和丁烷1～5份。该组合物对环境友好，流动性好，制得的泡沫综合性能优良，导热系数低，可有效减少原料的灌注量，降低泡沫生产成本。

Description

一种用于与异氰酸酯反应的组合物 技术领域
本发明涉及一种用于与异氰酸酯反应，以生产硬质聚氨酯泡沫的组合物。
背景技术
硬质聚氨酯泡沫是由异氰酸酯反应物与异氰酸酯在催化剂和其他助剂的存在下经聚合反应而制成的，具有隔热性能优异、隔音、绝缘、质轻、比强度高、加工性能良好等特点，被广泛用作保温保冷材料。为了达到更好的绝热保温效果，需向泡沫材料中加入一定量的低沸点、低导热系数的物理发泡剂。不幸的是，传统的聚氨酯发泡剂一氟三氯甲烷(CFC-11)会严重破坏臭氧层。1987年《蒙特利尔议定书》签订后，各国纷纷展开了CFC-11替代发泡剂的研究。1997年《京都议定书》签订后，人们开始同时注重保护臭氧层和减少温室效应。目前，世界各国正致力于开发新型的绿色节能的零臭氧消耗潜值(ODP)和零全球变暖潜值(GWP)的发泡体系，以缓解全球日益严重的环境问题。
与卤代烃类发泡剂相比，烷烃类发泡剂(如戊烷、丁烷等)无卤素原子，ODP为零，GWP近似为零，对环境友好，价格相对低廉，是理想的发泡剂替代方案之一。然而，环戊烷沸点高达49℃，且有一定的增塑性，易使泡沫尺寸稳定性变差。一般情况是通过提高泡沫密度来保证泡沫的尺寸稳定性，这却增大了泡沫的生产成本。
丁烷在多元醇中溶解性差，较少用于硬质聚氨酯泡沫，并且其沸点偏低，其中，正丁烷的沸点为-0.5℃，异丁烷的沸点-11.73℃，它们对操作工艺的要求更严格，当单独采用丁烷发泡时，它们容易从反应物料中逸出，造成泡沫表面气孔增多，对泡沫性能带来不利影响。
反式-1-氯-3,3,3-三氟丙烯，分子式为ClCH＝CHCF 3，沸点为19℃，臭氧层消耗潜值(ODP)几乎为0，GWP值小于7，是一种较好的第四代发泡剂，以之发泡制得的冰箱用硬质聚氨酯泡沫导热系数低，综合性能较好。然而，该发泡剂价格昂贵，单独采用它作发泡剂制备的硬质聚氨酯泡沫成本高，难以推广。而且，发泡料中若含有大量的反式-1-氯-3,3,3-三氟丙烯，容易腐蚀冰箱的塑料内胆材料，致使内胆开裂、溶胀等。
本发明旨在克服上述发泡剂各自的缺点，提供一种采用对环境友好的三元复配发泡体系的用于与异氰酸酯反应的组合物，制备性能优异的硬质聚氨酯泡沫。
发明内容
本发明旨在解决现有发泡技术的不足，提供一种对环境友好的三元复配发泡体系的异氰酸酯反应物，以制备性能优异的硬质聚氨酯泡沫。
具体的技术方案为：
1、一种用于与异氰酸酯反应的组合物，按重量份计，包括如下组分：
复合多元醇：100份，该复合多元醇包括聚醚多元醇70～95重量份、聚酯多元醇0～15重量份和聚碳酸酯多元醇0～15份；
胺催化剂：2.0～5.1份；
硅表面活性剂：1.5～4.5份；
水：1.1～2.8份；
混合发泡剂：12～22份，该混合发泡剂包括环戊烷7～15份、反式-1-氯-3,3,3-三氟丙烯2～10份和丁烷1～5份。
本发明中，采用上述比例的混合发泡剂，能够使各种发泡剂发挥协同作用，有效地避免各发泡剂单独使用时，所带来的问题，以获得性能良好的硬质聚氨酯泡沫。本发明的混合发泡体系是以烷烃发泡剂为主，并配以适量的反式-1-氯-3,3,3-三氟丙烯，既有利于改善泡沫性能，制得泡孔细密均匀、绝热性能良好的硬质聚氨酯泡沫，又能有效控制泡沫的原料成本。
本发明中，混合发泡剂中反式-1-氯-3,3,3-三氟丙烯的重量含量不超过56％，能够减少对内胆材料的腐蚀，有效降低冰箱内胆开裂、溶胀等风险；环戊烷在混合发泡剂中的重量含量大致保持在32％以上，并加入一定量的丁烷，其中，丁烷在混合发泡剂中的重量含量不超过36％，可以改善组合物初期的发泡能力，增强泡沫的低温尺寸稳定性，同时又可以避免因加入量太大而造成丁烷逃逸出泡沫表面，从而有效减少泡沫表面缺陷。此外，本申请所用混合发泡体系还能增大组合物中发泡剂的最大可允许添加量，从而降低泡沫密度，减少生产成本。
本发明中的组合物各组分之间具有良好的相容性，能够相互协同作用，制得的泡沫密度分布均匀，绝热性能良好，压缩强度和高低温尺寸稳定性提高，综合性能良好。
上述组合物中，所述聚醚多元醇是由蔗糖、山梨醇、季戊四醇、甘油、三羟甲基丙烷、甲苯二胺、乙二胺等中的一种或几种为起始剂与氧化烯烃反应而成，所述聚醚多元醇的粘度为10000～35000mPa·s，羟值为350～480mgKOH/g。
聚醚多元醇是聚氨酯泡沫塑料业用量最大的多元醇原料。高官能度的聚醚多元醇能为 泡沫提供足够的交联度和刚性，且泡沫耐热性能好。另外，具有自催化作用的甲苯二胺聚醚多元醇，会迅速提高反应初期的体系的粘度，可减少低沸点丁烷的逸出。而丁烷的迅速膨胀，提高了反应液的流动性能，使得所制备的泡沫流动性好、密度分布均匀。
上述组合物中，所述聚酯多元醇是改性苯酐聚酯多元醇，平均官能度为2.2～2.5、粘度为800～5000mPa·s，羟值为360～450mgKOH/g。
改性苯酐聚酯多元醇分子内含有刚性的苯环结构，制得的泡沫强度高，尺寸稳定性好，导热系数降低。
上述组合物中，所述聚碳酸酯多元醇是由二氧化碳和氧化烯烃反应而成，所述聚碳酸酯多元醇粘度为500～3500mPa·s，羟值为110～250mgKOH/g。
碳酸酯多元醇分子结构中含有大量的羰基，分子间内聚能大，能够为泡沫材料带来优良的力学性能，可以提高泡沫强度，从而降低泡沫的稳定密度，但用量过多会致使反应物料的粘度明显上升，操作性下降。
上述组合物中，所述胺催化剂选自五甲基二亚乙基三胺、双-(二甲基氨基)乙基醚、三亚乙基二胺、四甲基乙二胺、四甲基己二胺、N,N-二甲基环已胺、N,N-二甲基苄胺、二甲基乙醇胺、三乙醇胺、2-羟基丙基三甲基甲酸铵、2-羟基丙基三甲基乙酸胺、2-羟基丙基三甲基辛酸胺、2,4,6-三(二甲基氨基甲基)苯酚或1,3,5-三(二甲氨基丙基)-六氢三嗪中的两种或两种以上的混合物。
在具体的生产中，可以根据实际需要，将上述催化剂进行复配，保证反应平衡稳定地进行。
上述组合物中，所述硅表面活性剂是硅-碳类表面活性剂，是由含氢硅油和不饱和聚醚多元醇反应而成。硅-碳类表面活性剂的选择本领域内技术人员都熟知。具体地，可选自市售的，如迈图的Niax L-6863、Niax L-6988、Niax L-6861、Niax L-6866；美思德的AK-8805、AK-8832、AK-8860。
硅-碳类表面活性剂稳定性好，耐水解性能优越，能长期存放不变质，对泡沫乳化能力强，能够有效减少这些烷烃发泡剂的逃逸倾向，并且在发泡反应初期起到成核剂的作用，有利于形成大量细密的气泡核，提高成核速度和泡孔细密程度，在反应中期能够提高孔壁的粘弹性，有效抑制泡孔的破裂，减少表面气孔，提升泡沫性能。
上述组合物中，所述丁烷为正丁烷，或异丁烷，或正丁烷和异丁烷以任意比例组成的混合物。
在采用本发明中的组合物与异氰酸酯生产硬质聚氨酯泡沫时，异氰酸酯一般采用多亚 甲基多苯基多异氰酸酯，可选自市售的，如Bayer公司的44V-10L、44V-20L、44V-40L，Huntsman公司的Suprasec 5005、Suprasec 2085、Suprasec 5000，BASF公司的M20S，日本三井公司的MR200、MR100，烟台万华公司的PM2010、PM200，Dow公司的PAPI27、PAPI135等。
组合物与异氰酸酯的重量比控制为1:(0.95～1.35)，在生产时，将组合物与异氰酸酯按重量比为1:(0.95～1.35)在发泡枪头上一步混合，注入密闭的模具中，待固化成型后制得，所设工艺参数为本领域内的技术人员熟知，一般地，料温控制为15～30℃，模温控制为35～55℃，过填充系数为105％～130％。也可采用手工发泡的方法，配制好组合物后，将异氰酸酯迅速倒入到组合物中，并立即快速搅拌3～6秒，再倒入模具中固化制得硬质聚氨酯泡沫。
总体而言，本发明中的组合物具有如下优势：
1)采用本发明中的组合物所制得的硬质聚氨酯泡沫的比强度高，能够减少发泡料的注射量，从而降低泡沫的生产成本。
2)采用本发明中组合物所制得的硬质聚氨酯泡沫中的泡孔细密均匀，导热系数低，绝热性能良好。
3)采用本发明中组合物所制得的硬质聚氨酯泡沫的高低温尺寸稳定性好，脱模后膨胀率小，表面缺陷少。
4)本发明所用的混合发泡剂的ODP和GWP极低，绿色环保，对环境友好。
具体实施方式
实施例中未注明具体技术或条件的，可按照本领域内的公知技术进行。
本发明中泡沫的密度、导热系数、压缩强度、膨胀率以及高低温尺寸变化率分别按照国家标准GB/T 6343-2009、GB/T 3399-1982、GB/T 8813-2008、GB/T 20673-2006、GB/T8811-2008进行测定，其中，泡沫芯密度是指将泡沫形成组合物注入具有一定强度的密闭模具1100×300×50mm中发泡，待泡沫成型取出后，去除表皮再测得的泡沫芯层的密度。
在以下各实施例中，将异氰酸酯称为第二组分，将用于与异氰酸酯反应的组合物称为第一组分，且均按照如下步骤生产低密度硬质聚氨酯泡沫：
(1)配制第一组分：按设定比例将复合多元醇、胺催化剂、硅表面活性剂、水和混合发泡剂加入到混合釜中，搅拌均匀，得第一组分。并输送至第一储罐，并控制第一组分的温 度为20℃，待用。
(2)配制第二组分：将第二组分输送至第二储罐，并控制第二组分的温度为20℃，待用。
(3)混合注射：将第一组分与第二组分按1:(1.0～1.25)的重量比通过高压机枪头混合注入密闭模具(1100×300×50mm)中，充分反应，模温控制为40℃，发泡物料在模具中过填充系数为110％～118％，经6min脱模后即可得到硬质聚氨酯泡沫。
在各具体实施例及对比例中涉及参数均已列在表1和表2中。
以下各实施例及对比例中的份数均为重量份数，且各实施例中，均以100份复合多元醇为基准。
实施例1
第一组分：
复合多元醇：羟值为370mgKOH/g，100份，包括：
(1)聚醚多元醇A：山梨醇聚醚多元醇，羟值为380～440mgKOH/g，粘度为15000～30000mPa·s，60份；
(2)聚醚多元醇B：甲苯二胺聚醚多元醇，羟值为340～400mgKOH/g，粘度为10000～28000mPa·s，25份；
(3)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为500～3500mPa·s，15份；
胺催化剂：2.8份，包括五甲基二亚乙基三胺0.5份，N,N-二甲基环已胺1.5份，2-羟基丙基三甲基辛酸胺0.8份；
硅表面活性剂：2.5份，包括1.5份Niax L-6863，1.0份Niax L-6988；
水：2.0份；
混合发泡剂：14份，包括环戊烷7份，反式-1-氯-3,3,3-三氟丙烯2份，正丁烷2份，异丁烷3份；
第二组分：44V-20L，125份。
实施例2
第一组分：
复合多元醇：羟值为430mgKOH/g，100份，包括：
(1)聚醚多元醇A：蔗糖聚醚多元醇，羟值为440～480mgKOH/g，粘度为20000～35000mPa·s，60份；
(2)聚醚多元醇B：甲苯二胺聚醚多元醇，羟值为340～400mgKOH/g，粘度为10000～28000mPa·s，30份；
(3)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，10份；
胺催化剂：2.0份，包括双-(二甲基氨基)乙基醚0.4份，N,N-二甲基苄胺1.6份；
硅表面活性剂：AK-8860，1.5份；
水：1.1份；
混合发泡剂：19份，包括环戊烷15份，反式-1-氯-3,3,3-三氟丙烯3份，异丁烷1份；
第二组分：Suprasec 5005，126份。
实施例3
第一组分：
复合多元醇：羟值为410mgKOH/g，100份，包括：
(1)聚醚多元醇：蔗糖聚醚多元醇，羟值为400～450mgKOH/g，粘度为18000～32000mPa·s，85份；
(2)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，15份；
胺催化剂：2.5份，包括五甲基二亚乙基三胺0.5份，三亚乙基二胺0.2份，N,N-二甲基环已胺1.0份，2-羟基丙基三甲基乙酸铵0.8份；
硅表面活性剂：3.0份，包括1.5份Niax L-6988、0.5份Niax L-6861、1.0份AK-8832；
水：2.5份；
混合发泡剂：16份，包括环戊烷7份，反式-1-氯-3,3,3-三氟丙烯8份，正丁烷1份；
第二组分：44V-10L，144份。
实施例4
第一组分：
复合多元醇：羟值为390mgKOH/g，100份，包括：
(1)聚醚多元醇A：蔗糖聚醚多元醇，羟值为400～460mgKOH/g，粘度为18000～32000mPa·s，50份；
(2)聚醚多元醇A：甘油聚醚多元醇，羟值为350～400mgKOH/g，粘度为10000～20000mPa·s，20份；
(3)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，15 份；
(4)聚碳酸酯多元醇：羟值为110～220mgKOH/g，粘度为500～3200mPa·s，15份；
胺催化剂：3.5份，包括五甲基二亚乙基三胺0.6份，N,N-二甲基苄胺1.7份，2,4,6-三(二甲基氨基甲基)苯酚1.2份，
硅表面活性剂：4.0份，2份包括Niax L-6866，1份Niax L-6988，1份Niax L-6861；
水：2.8份；
混合发泡剂：12份，包括环戊烷7份，反式-1-氯-3,3,3-三氟丙烯2份，正丁烷2份，异丁烷1份；
第二组分：Suprasec2085，144份。
实施例5
第一组分：
复合多元醇：羟值为380mgKOH/g，100份，包括：
(1)聚醚多元醇A：山梨醇聚醚多元醇，羟值为350～400mgKOH/g，粘度为15000～25000mPa·s，60份；
(2)聚醚多元醇B：甲苯二胺聚醚多元醇，羟值为340～400mgKOH/g，粘度为10000～28000mPa·s，25份；
(3)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，10份；
(4)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为1500～3500mPa·s，5份；
胺催化剂：5.1份，包括双-(二甲基氨基)乙基醚0.4份，四甲基乙二胺0.5份，N,N-二甲基环已胺1.0份，二甲基乙醇胺2.0份，2,4,6-三(二甲基氨基甲基)苯酚1.2份，
硅表面活性剂：3.5份，2.0份包括AK-8832，1.5份AK-8860；
水：1.4份；
混合发泡剂：22份，包括环戊烷10份，反式-1-氯-3,3,3-三氟丙烯10份，正丁烷2份；
第二组分：Suprasec 5000，120份。
实施例6
第一组分：
复合多元醇：羟值为390mgKOH/g，100份，包括：
(1)聚醚多元醇A：蔗糖聚醚多元醇，羟值为400～480mgKOH/g，粘度为18000～35000mPa·s，65份；
(2)聚醚多元醇B：甘油聚醚多元醇，羟值为350～380mgKOH/g，粘度为10000～18000mPa·s，15份；
(3)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，8份；
(4)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为500～3500mPa·s，12份；
胺催化剂：4.2份，包括五甲基二亚乙基三胺0.6份，四甲基己二胺0.8份，N,N-二甲基苄胺0.8份，三乙醇胺1.5份，1,3,5-三(二甲氨基丙基)-六氢三嗪0.5份；
硅表面活性剂：4.5份，包括1.5份Niax L-6863，1.0份Niax L-6861，2.0份AK-8805；
水：1.6份；
混合发泡剂：19份，包括环戊烷10份，反式-1-氯-3,3,3-三氟丙烯7份，正丁烷1份，异丁烷1份；
第二组分：PM2010，127份。
实施例7
第一组分：
复合多元醇：羟值为370mgKOH/g，100份，包括：
(1)聚醚多元醇A：山梨醇聚醚多元醇，羟值为350～400mgKOH/g，粘度为15000～25000mPa·s，80份；
(2)聚醚多元醇B：甘油聚醚多元醇，羟值为350～380mgKOH/g，粘度为10000～18000mPa·s，10份；
(3)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，5份；
(4)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为500～3500mPa·s，5份；
胺催化剂：3.0份，包括双-(二甲基氨基)乙基醚0.3份，N,N-二甲基环已胺0.8份，二甲基乙醇胺0.7份，2,4,6-三(二甲基氨基甲基)苯酚1.2份；
硅表面活性剂：3.8份，包括2.5份Niax L-6866，1.3份Niax L-6861；
水：1.8份；
混合发泡剂：17份，包括环戊烷11份，反式-1-氯-3,3,3-三氟丙烯4份，正丁烷2份；
第二组分：PAPI27，122份。
实施例8
第一组分：
复合多元醇：羟值为420mgKOH/g，100份，包括：
(1)聚醚多元醇：蔗糖聚醚多元醇，羟值为400～480mgKOH/g，粘度为18000～35000mPa·s，80份；
(2)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，10份；
(3)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为500～3500mPa·s，10份；
胺催化剂：4.5份，包括五甲基二亚乙基三胺0.5份，N,N-二甲基苄胺1.8份，二甲基乙醇胺1.0份，2,4,6-三(二甲基氨基甲基)苯酚1.2份；
硅表面活性剂：4.2份，包括1.5份AK-8832，1.5份AK-8860，1.2份AK-8805；
水：1.5份；
混合发泡剂：18份，包括环戊烷9份，反式-1-氯-3,3,3-三氟丙烯5份，异丁烷4份；
第二组分：PM200，130份。
实施例9
第一组分：
复合多元醇：羟值为410mgKOH/g，100份，包括：
(1)聚醚多元醇A：蔗糖聚醚多元醇，羟值为400～480mgKOH/g，粘度为18000～35000mPa·s，45份；
(2)聚醚多元醇B：山梨醇聚醚多元醇，羟值为380～440mgKOH/g，粘度为15000～30000mPa·s，40份；
(3)聚醚多元醇C：甲苯二胺聚醚多元醇，羟值为340～400mgKOH/g，粘度为10000～28000mPa·s，10份；
(4)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为500～3500mPa·s，5份；
胺催化剂：3.8份，包括五甲基二乙烯三胺0.6份，三亚乙基二胺0.4份，四甲基己二胺1.2份，二甲基乙醇胺0.8份，2-羟基丙基三甲基甲酸铵0.8份；
硅表面活性剂：2.2份，1.2份包括Niax L-6861，1.0份AK-8860；
水：1.2份；
混合发泡剂：20份，包括环戊烷12份，反式-1-氯-3,3,3-三氟丙烯6份，正丁烷2份；
第二组分：PAPI135，123份。
实施例10
第一组分：
复合多元醇：羟值为390mgKOH/g，100份，包括：
(1)聚醚多元醇A：山梨醇聚醚多元醇，羟值为380～440mgKOH/g，粘度为15000～30000mPa·s，70份；
(2)聚醚多元醇B：甲苯二胺聚醚多元醇，，羟值为340～400mgKOH/g，粘度为10000～28000mPa·s，15份；
(3)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，7份；
(4)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为500～3500mPa·s，8份；
胺催化剂：3.2份，包括双-(二甲基氨基)乙基醚0.4份，N,N-二甲基环已胺1.3份，2,4,6-三(二甲基氨基甲基)苯酚1.5份；
硅表面活性剂：2.8份，包括2份AK-8832，0.8份AK-8860；
水：2.0份；
混合发泡剂：15份，包括环戊烷8份，反式-1-氯-3,3,3-三氟丙烯3份，正丁烷4份；
第二组分：M20S，132份。
实施例11
第一组分：
复合多元醇：羟值为390mgKOH/g，100份，包括：
(1)聚醚多元醇A：山梨醇聚醚多元醇，羟值为380～440mgKOH/g，粘度为15000～30000mPa·s，70份；
(2)聚醚多元醇B：甲苯二胺聚醚多元醇，，羟值为340～400mgKOH/g，粘度为10000～28000mPa·s，15份；
(3)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，7份；
(4)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为500～3500mPa·s，8份；
胺催化剂：3.2份，包括双-(二甲基氨基)乙基醚0.4份，N,N-二甲基环已胺1.3份，2,4,6-三(二甲基氨基甲基)苯酚1.5份；
硅表面活性剂：2.8份，包括2份AK-8832，0.8份AK-8860；
水：2.0份；
混合发泡剂：15份，包括环戊烷8份，反式-1-氯-3,3,3-三氟丙烯3份，正丁烷4份；
第二组分：M20S，132份。
对比例1
第一组分：
复合多元醇：羟值为390mgKOH/g，100份，包括：
(1)聚醚多元醇A：山梨醇聚醚多元醇，羟值为380～440mgKOH/g，粘度为15000～30000mPa·s，70份；
(2)聚醚多元醇B：甲苯二胺聚醚多元醇，，羟值为340～400mgKOH/g，粘度为10000～28000mPa·s，15份；
(3)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，7份；
(4)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为500～3500mPa·s，8份；
胺催化剂：3.2份，包括双-(二甲基氨基)乙基醚0.4份，N,N-二甲基环已胺1.3份，2,4,6-三(二甲基氨基甲基)苯酚1.5份；
硅表面活性剂：2.8份，包括2份AK-8832，0.8份AK-8860；
水：2.0份；
发泡剂：环戊烷14份；
第二组分：M20S，132份。
对比例2
第一组分：
复合多元醇：羟值为390mgKOH/g，100份，包括：
(1)聚醚多元醇A：山梨醇聚醚多元醇，羟值为380～440mgKOH/g，粘度为15000～30000mPa·s，70份；
(2)聚醚多元醇B：甲苯二胺聚醚多元醇，羟值为340～400mgKOH/g，粘度为 10000～28000mPa·s，15份；
(3)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，7份；
(4)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为500～3500mPa·s，8份；
胺催化剂：3.2份，包括双-(二甲基氨基)乙基醚0.4份，N,N-二甲基环已胺1.3份，2,4,6-三(二甲基氨基甲基)苯酚1.5份；
硅表面活性剂：2.8份，包括2份AK-8832，0.8份AK-8860；
水：2.0份；
发泡剂：正丁烷12份；
第二组分：M20S，132份。
对比例3
第一组分：
复合多元醇：羟值为390mgKOH/g，100份，包括：
(1)聚醚多元醇A：山梨醇聚醚多元醇，羟值为380～440mgKOH/g，粘度为15000～30000mPa·s，70份；
(2)聚醚多元醇B：甲苯二胺聚醚多元醇，羟值为340～400mgKOH/g，粘度为10000～28000mPa·s，15份；
(3)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，7份；
(4)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为500～3500mPa·s，8份；
胺催化剂：3.2份，包括双-(二甲基氨基)乙基醚0.4份，N,N-二甲基环已胺1.3份，2,4,6-三(二甲基氨基甲基)苯酚1.5份；
硅表面活性剂：2.8份，包括2份AK-8832，0.8份AK-8860；
水：2.0份；
混合发泡剂：反式-1-氯-3,3,3-三氟丙烯28份；
第二组分：M20S，132份。
对比例4
第一组分：
复合多元醇：羟值为390mgKOH/g，100份，包括：
(1)聚醚多元醇A：山梨醇聚醚多元醇，羟值为380～440mgKOH/g，粘度为15000～30000mPa·s，70份；
(2)聚醚多元醇B：甲苯二胺聚醚多元醇，羟值为340～400mgKOH/g，粘度为10000～28000mPa·s，15份；
(3)改性苯酐聚酯多元醇：羟值为360～450mgKOH/g，粘度为800～5000mPa·s，7份；
(4)聚碳酸酯多元醇：羟值为220～250mgKOH/g，粘度为500～3500mPa·s，8份；
胺催化剂：3.2份，包括双-(二甲基氨基)乙基醚0.4份，N,N-二甲基环已胺1.3份，2,4,6-三(二甲基氨基甲基)苯酚1.5份；
硅表面活性剂：2.8份，包括2份AK-8832，0.8份AK-8860；
水：2.0份；
混合发泡剂：15份，包括环戊烷2份，反式-1-氯-3,3,3-三氟丙烯5份，丁烷8份；
第二组分：M20S，132份。
表1实施例1-7原料配比及泡沫性能
Figure PCTCN2020090670-appb-000001
表2实施例8-11及对比例1-4原料配比及泡沫性能
Figure PCTCN2020090670-appb-000002
从上述表1和表2可知，采用本发明的组合物制备的硬质聚氨酯泡沫，在相同的过填充系数下，实施例1～10的原料灌注量和泡沫芯密度明显小于对比例1～4，但是导热系数更低，绝热性能更好，同时具有更好的尺寸稳定性，脱模5min后线性膨胀率低。而实施例11与对比例1～4相比，注射量和泡沫密度相近，但是各项性能均明显优于对比例。本发明的组合物能明显改善泡沫的应用性能。因此，在相同工艺参数下，采用本发明的技术方案能够有效减少原料灌注量，降低泡沫密度，从而降低生产成本。

Claims (6)

  1. 一种用于与异氰酸酯反应的组合物，其特征在于，按重量份计，包括如下组分：
    复合多元醇：100份，该复合多元醇包括聚醚多元醇70～95重量份、聚酯多元醇0～15重量份和聚碳酸酯多元醇0～15份；
    胺催化剂：2.0～5.1份；
    硅表面活性剂：1.5～4.5份；
    水：1.1～2.8份；
    混合发泡剂：12～22份，该混合发泡剂包括环戊烷7～15份、反式-1-氯-3,3,3-三氟丙烯2～10份和丁烷1～5份。
  2. 根据权利要求1所述的组合物，其特征在于，所述聚醚多元醇的粘度为10000～35000mPa·s，羟值为350～480mgKOH/g。
  3. 根据权利要求1所述的组合物，其特征在于，所述聚酯多元醇是改性苯酐聚酯多元醇，平均官能度为2.2～2.5，粘度为800～5000mPa·s，羟值为360～450mgKOH/g。
  4. 根据权利要求1所述的组合物，其特征在于，所述聚碳酸酯多元醇是由二氧化碳和氧化烯烃反应而成，聚碳酸酯多元醇的粘度为500～3500mPa·s，羟值为110～250mgKOH/g。
  5. 根据权利要求1所述的组合物，其特征在于，所述硅表面活性剂是硅-碳类表面活性剂，是由含氢硅油和不饱和聚醚多元醇反应而成。
  6. 根据权利要求1所述的组合物，其特征在于，所述丁烷为正丁烷或异丁烷，或正丁烷和异丁烷以任意比例组成的混合物。
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