WO2016115751A1 - 用于聚氨酯发泡的组合物，聚氨酯泡沫及其用途 - Google Patents

用于聚氨酯发泡的组合物，聚氨酯泡沫及其用途 Download PDF

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Publication number
WO2016115751A1
WO2016115751A1 PCT/CN2015/071824 CN2015071824W WO2016115751A1 WO 2016115751 A1 WO2016115751 A1 WO 2016115751A1 CN 2015071824 W CN2015071824 W CN 2015071824W WO 2016115751 A1 WO2016115751 A1 WO 2016115751A1
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Prior art keywords
parts
composition
polyether polyol
ethylene oxide
mixture
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PCT/CN2015/071824
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English (en)
French (fr)
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王军丰
朱霞林
陈静
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万华化学（宁波）容威聚氨酯有限公司
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Priority to JP2017535925A priority Critical patent/JP6516847B2/ja
Priority to US15/540,763 priority patent/US10450403B2/en
Publication of WO2016115751A1 publication Critical patent/WO2016115751A1/zh

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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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester 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
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy 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
    • 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
    • C08G18/4829—Polyethers containing at least three hydroxy 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • 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
    • C08G18/5033—Polyethers having heteroatoms other than oxygen having nitrogen containing carbocyclic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/08—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 chemical blowing agent developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the present invention relates to a composition for polyurethane foaming, a polyurethane foam and uses thereof, and more particularly to a composition for low density all-water polyurethane foaming, a low density all-water polyurethane foam and uses thereof.
  • the composition of the present invention is reacted with polymethylene polyphenyl polyisocyanate (PAPI), and the obtained foam is applied to building insulation, heat insulation, sound insulation, moisture proof, and can also be used in the packaging industry of precision instruments.
  • PAPI polymethylene polyphenyl polyisocyanate
  • Polyurethane foam is a high-performance foam material. Its thermal insulation performance is the best among various foam materials, and it has excellent material strength. It is currently in the field of insulation for refrigerators, solar energy, heat pipes, buildings, automobiles, cold chains, etc. Optimal choice. With the emphasis on building energy conservation in China, the use of polyurethane foam insulation materials in China's construction industry has expanded year by year. At present, the foaming agent used in polyurethane foam for construction in China is mainly HCFC-141B, which is a kind of ozone-depleting substance. It has been restricted and used. Its alternative foaming agent is mainly HFC-245fa, 365mfc, cyclopentane, and all. Water foaming.
  • HFC-245fa is too expensive; 365mfc and cyclopentane are flammable and cannot be used for on-site spraying, and the foam has poor flame retardancy.
  • the whole water foaming agent is a low-cost, environmentally-friendly and easily flame-retardant HCFC-141B alternative foaming technology route, especially suitable for some buildings with thick interlayers, for example: in the roof of a single-family house, the curtain wall structure In the building, the ceiling with the cavity, the inner wall of the wooden house, and the brick structure of the cavity structure, the polyurethane foam can be filled by the on-site construction method, which is used for heat preservation, sound insulation and prevention. The tidal effect and the full use of space avoid the additional building area occupied by the additional insulation layer.
  • the flame retardant in the formulation is incompatible with water, the product is not clear and transparent; the layering is easy to occur, and the storage period is short; The mutual solubility of the components increases the storage period, a large amount of solubilizing agent needs to be added, the cost is too high, and the cells are rough;
  • the catalyst for the polyurethane foaming reaction is generally an organic tertiary amine structure, for example, the catalyst A1 commonly used in the whole water spraying foaming industry, That is, bis(diaminoethyl)ether has a strong catalytic effect on the polyurethane reaction, but its volatility is strong, and the smell is odorous and irritating to the eyes and skin.
  • One of the objects of the present invention is to provide a composition for polyurethane foaming, especially for low-density all-water polyurethane foaming, which is a transparent liquid and is less prone to delamination; Odorless.
  • Another object of the present invention is to provide a polyurethane foam which has a very low foam density (for example, 6 to 15 kg/m 3 ) and a foaming magnification of up to 100 times, and the same volume of heat insulating construction material is only ordinary foam 1 /4 ⁇ 1/5, which greatly saves cost, and has good dimensional stability.
  • the foam has a long service life and is firmly bonded to the substrate.
  • the present invention provides a composition for polyurethane foaming (also referred to as a combination polyol) comprising, by weight of the composition, the following raw materials by weight:
  • the polyether polyol A has an average functionality of 4-8, and a hydroxyl value of 300-700 mgKOH/g;
  • the polyether polyol B has an average functionality of 2 to 4 and a hydroxyl value of 20 to 200 mgKOH/g;
  • the flame retardant is a phosphate or a mixture of a plurality of phosphates, the flame retardant having a phosphorus content of 8 to 40% by weight;
  • the catalyst is a mixture of organic tertiary amines containing hydroxyl functional groups.
  • the composition of the present invention is a colorless or pale yellow transparent liquid at normal temperature, and can be stored for up to 5 months without delamination and deterioration.
  • the above raw materials are mixed at room temperature and then foamed with a polymethylene polyphenyl polyisocyanate at a mass ratio of 100:100 to 150 using a high pressure foaming process.
  • the foam obtained by using the composition of the present invention differs from the conventional polyurethane insulating rigid foam in that the foam produced by the present invention is mostly open-ended, so that it can be kept at a very low density. Dimensional stability, no shrinkage, no expansion.
  • the polyether polyol A is one or more of sorbitol, sucrose, pentaerythritol, 2,4-diaminophenol, ethylenediamine and trishydroxyl
  • propane in any ratio is used as a starting agent to polymerize with propylene oxide and ethylene oxide; wherein the molar ratio of propylene oxide to ethylene oxide is from 7:3 to 9:1, It is preferably from 7:3 to 8:2.
  • the polyether polyol A is a mixture of sucrose, trimethylolpropane and sorbitol in any ratio as a starter with propylene oxide, ethylene oxide.
  • the mass ratio of sorbitol, sucrose to trimethylolpropane may be from 100 to 150: 180 to 230: 260 to 300, preferably from 109 to 120: 200 to 205: 268 to 280.
  • the polyether polyol A is formed by polymerization of propylene oxide and ethylene oxide with 2,4-diaminophenol or/and ethylenediamine as a starting agent.
  • it is formed by polymerization of propylene oxide and ethylene oxide with 2,4-diaminophenol and ethylenediamine as starting agents; and has an average functionality of 4 to 5, preferably 4 to 4.5;
  • the hydroxyl value is from 500 to 700 mgKOH/g, preferably from 600 to 680 mgKOH/g; and the molar ratio of propylene oxide to ethylene oxide is from 7:3 to 9:1, preferably from 8:2 to 9:1.
  • the polyether polyol B is a mixture of one or more of dipropylene glycol, diethylene glycol or triethanolamine mixed with glycerin in any ratio. It is formed by polymerization with propylene oxide and ethylene oxide, and the end of the reaction is terminated with ethylene oxide, so that the terminal group of the polyether polyol B is a primary hydroxyl group. More preferably, the polyether polyol B is formed by polymerization of propylene oxide and ethylene oxide with a mixture of glycerin and triethanolamine in any ratio as a starting agent, and the reaction is terminated with epoxy B.
  • the alkane is capped such that the end group of the polyether polyol B is a primary hydroxyl group.
  • the polyether polyol B may have a hydroxyl value of 20 to 90 mgKOH/g, preferably 25 to 80 mgKOH/g; an average functionality of 2 to 3, preferably 2.5 to 3; propylene oxide and ethylene oxide.
  • the molar ratio is from 7:3 to 9:1, preferably from 7:3 to 8:2.
  • the polyether polyol B is selected from one or more of Wanol RF3135 and WanolRF3160 produced by Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.
  • the polyether polyol used in the present invention has the advantage that the polyol using the mixed initiator has a comprehensive performance advantage over the single-component polyether of the similar products in the market.
  • the two polyether polyols A and B must be used at the same time and have the right ratio to reach To the best use.
  • the high-functionality initiator of the polyether polyol A component can make the foam have fine cells, thereby maintaining an excellent heat preservation effect.
  • the polyether polyol B terminal group has a high structural activity of a primary hydroxyl group, and the reaction is fast, so that the foaming process is not easy to shrink and collapse; the lower functionality can achieve the effect of opening at the later stage of the foaming reaction, and the foam is prevented from being formed. After contraction.
  • the mixed polyether polyols A and B used in the invention have good compatibility with water, flame retardant and auxiliary agent, so that when various additives are mixed together, they are uniform, transparent, and stored at room temperature for a long time. Not easy to stratify. A transparent, stable system can be obtained without or with a very small amount of solubilizer.
  • an aliphatic chain starter such as glycerin, sorbitol, triethanolamine, trimethylolpropane or the like has good flexibility, which can reduce the brittleness of the foam and improve the adhesion.
  • the catalyst comprises a mixture of dimethylaminoethoxyethanol and trimethylhydroxyethylethylenediamine in any ratio, and also contains N, N, N'-three.
  • the catalyst is a combination of dimethylaminoethoxyethanol, trimethylhydroxyethylethylenediamine and N,N,N'-trimethyl-N'-hydroxyethyl bis-aminoethyl ether. Things.
  • the catalyst is dimethylaminoethoxyethanol:trimethylhydroxyethylethylenediamine:N,N,N'-three in a mass ratio of 1 to 3:1 to 3:0 to 3
  • the catalyst is dimethylaminoethoxyethanol:trimethylhydroxyethylethylenediamine:N,N,N'-trimethyl-N'- in a mass ratio of 3:1:1.
  • a composition of hydroxyethyl bis-aminoethyl ether is dimethylaminoethoxyethanol:trimethylhydroxyethylethylenediamine:N,N,N'-three in a mass ratio of 1 to 3:1 to 3:0 to 3
  • a composition of methyl-N'-hydroxyethyl bis-aminoethyl ether is dimethylaminoethoxyethanol:trimethylhydroxyethylethylenediamine:N,N,N'-three in a mass
  • the catalyst group used in the present invention In the middle, the amount of bis(dimethylaminoethyl)ether or dimethylcyclohexylamine can be completely zero, and it will not cause personal discomfort during construction.
  • most of the catalysts used in the present invention contain hydroxyl groups, can react with isocyanates, and are embedded in the polymer chain, and have the characteristics of low volatility and low odor.
  • the foaming machine of the present invention has almost no amine taste during construction.
  • the flame retardant is one or two of tris(2-chloropropyl) phosphate and tris(2-chloroethyl) phosphate and triethyl phosphate. a mixture of esters, wherein triethyl phosphate accounts for at least 40% of the total weight of the flame retardant; preferably, the flame retardant is triethyl phosphate and phosphoric acid in a mass ratio of 1 to 3:1 to 3 A mixture of tris(2-chloropropyl) ester. More preferably, the flame retardant is a mixture of triethyl phosphate and tris(2-chloropropyl) phosphate in a mass ratio of 1:1.
  • the flame retardant with stable chemical properties and less volatile impurities is beneficial to prolonging the storage period and reducing the odor.
  • Different kinds of flame retardants are mixed to improve the compatibility with water, so that the product can be used without collateral or with a small amount of solubilizer or emulsifier/dispersant to achieve clarification and transparency, and no stratification at normal temperature. effect.
  • the reasonable proportion of phosphorus and halogen in the flame retardant utilizes the phosphorus-halogen flame retardant synergistic effect to achieve an optimum flame retardant effect with a minimum amount of flame retardant.
  • the weight of water is from 10 to 30 parts, preferably from 13 to 18 parts. Its role is to react with isocyanate to form carbon dioxide gas during foaming to promote hair At the same time, the excess portion of the water itself volatilizes to form a gas, and functions as both a chemical foaming agent and a physical foaming agent.
  • the surfactant is formed by copolymerization of polymethylsiloxane, propylene oxide, and ethylene oxide.
  • the surfactant of the present invention is L-6186, L-5345 of American Momentive High-Tech Materials Co., Ltd. or DC-5950 of Air Chemical Company. The surfactant can maintain the effect of fine foaming and opening of the foam during the foaming process.
  • the composition of the present invention preferably, the composition further comprises 0 to 3 parts by weight, preferably 1 to 2 parts by weight, of other auxiliary agents selected from the group consisting of triethanolamine and glycerin. One or two. This will make the foam more delicate.
  • the present invention also provides a polyurethane foam obtained by the above composition. Preferably, it is obtained by reacting the above composition with polymethylene polyphenyl polyisocyanate PAPI.
  • the polyurethane foam of the present invention is preferably a low density all-water polyurethane foam, the foaming process comprising a three-stage reaction.
  • the reaction at this stage is similar to the first stage of ordinary rigid foam foaming.
  • the reaction time in this stage is about 1.5 seconds; when pouring, the reaction time in this stage is about 5 to 10 seconds.
  • the reaction time at this stage is about 5 seconds and the total chemical reaction is 90% complete. Under the pouring construction conditions, the reaction time at this stage is about 20 to 40 seconds.
  • the reaction proceeds to form a solid polymer foam. Since the polyether polyol and PAPI are all polyfunctional, a polymer foam material having a certain degree of crosslinking is formed, and the foam has a uniform polygonal shape under the action of the surfactant, and has a coarse skeleton and a cell wall. Thin special structure. The temperature and heat release of the system are maximized, and excess water vaporizes at a high temperature to break through most of the cell walls and enter the outside air, eventually forming an open-cell polyurethane foam. Under typical spraying conditions, the reaction time in this stage is about 2 to 3 seconds. Under the pouring construction conditions, the reaction time in this stage is about 10 to 20 seconds.
  • composition of the invention has the advantages that: the foam spraying machine and the casting machine used in the use can adopt almost all models commonly used in the market, and react with the PAPI mass ratio of 100:100-150, preferably the ratio range is 100:100-120 reaction. It can be applied under climatic conditions above 15 °C, and has good tolerance to construction conditions.
  • the foam prepared by the reaction of the invention with PAPI is open-cell type, has a high open porosity of 80% or more, and has an open porosity of more than 90% in most construction conditions, under natural temperature conditions. Does not shrink or deform.
  • the high-pressure foaming process usually spraying, uses a high-pressure sprayer to mix and spray the composition of the present invention and PAPI onto the wall including the inner surface of the roof, the foam immediately rises, becomes solid within 5 s, 10s After the internal curing is completed, the ripening degree is over 95% in half an hour.
  • the high-pressure foaming process of the present invention can also be a potting process, using the foam casting machine to mix the invention with PAPI and inject into the building insulation layer, starting in 5 seconds, curing in 30 seconds, and curing in one hour to 95. %the above.
  • the shape of the insulation layer is not limited, and a square, a spherical shape or a shaped space can be used.
  • the present invention also provides the use of the above-described polyurethane foam for packaging of building insulation, heat insulation, sound insulation, moisture resistance or precision instruments.
  • part means “parts by weight” unless otherwise stated; “%” means “wt%”, that is, a percentage by weight.
  • the polyether polyol 1 is a polyether polyol polymerized with ethylene oxide or propylene oxide using sorbitol, sucrose or trimethylolpropane as a starting agent, having a hydroxyl value of 450 mgKOH/g and an average functionality of 4.5.
  • the specific preparation method is as follows: 109 g of sorbitol is put into a 2.5 liter jacketed reaction vessel, 205g of sucrose, 268g of trimethylolpropane and 35g of catalyst were gradually heated to 70 ° C; stirring was started, the reaction kettle was evacuated, and excess water in the raw material was removed; then, the reactor was replaced with nitrogen, and propylene oxide 1000 g and 200 g of ethylene oxide (the molar ratio of the two was about 8:2) was slowly introduced into the reaction vessel over 2 hours while maintaining the pressure below 0.25 MPa and slowly rising to 100 ° C until the completion of the charging. Then the temperature was raised to about 120 ° C and continued for 3 hours. After the reaction is completed, the temperature is lowered to below 90 ° C, and then the pH is adjusted, refined, and filtered.
  • the polyether polyol 2 is a polyether polyol polymerized with ethylene oxide or propylene oxide as a mixed initiator of sorbitol and trimethylolpropane, having a hydroxyl value of 350 mgKOH/g and an average functionality of 5.
  • the preparation method comprises the following steps: in a 2.5 L jacketed reaction kettle, 364 g of sorbitol, 134 g of trimethylolpropane and 32 g of a catalyst are gradually added, and the temperature is gradually raised to 70 ° C; stirring is started, the reaction kettle is evacuated, and the raw materials are removed.
  • Polyether polyol 3 is a polyether polyol polymerized with ethylene oxide or propylene oxide as a mixed initiator of 2,4-diaminophenol and ethylenediamine, having a hydroxyl value of 680 mgKOH/g and a functionality of 4.
  • the specific preparation method is as follows: in a 2.5 L jacketed reactor, 366 g of 2,4-diaminophenol and 180 g of ethylenediamine are gradually added, and the temperature is gradually raised to 70 ° C; stirring is started, and then the reactor is replaced with nitrogen, and the ring is replaced.
  • the polyether polyol 4 is a polyether polyol polymerized with ethylene oxide or propylene oxide as a mixed initiator of glycerin and dipropylene glycol, having a hydroxyl value of 25 mgKOH/g and an average functionality of 2.5.
  • the specific preparation method is as follows: in a 2.5 L jacketed reactor, 645 g of glycerin, 940 g of dipropylene glycol, and 40 g of a catalyst are gradually added, and the temperature is gradually raised to 70 ° C; the stirring is started, and the reaction kettle is evacuated to remove excess water in the raw material; Then, the reaction vessel was replaced with nitrogen, and 410 g of propylene oxide was slowly introduced into the reaction vessel over 2 hours to maintain the pressure below 0.25 MPa, and the temperature was maintained at 90 to 100 ° C until the completion of the feed; 133 g (a molar ratio of propylene oxide to ethylene oxide of about 7:3) was slowly introduced into the reaction vessel over 2 hours, maintaining the pressure below 0.25 MPa until the completion of the feed. Finally, the temperature was raised to about 120 ° C for 3 hours, and after the reaction was completed, the temperature was lowered to below 90 ° C, and then refined and filtered.
  • the polyether polyol 5 is a polyether polyol polymerized with ethylene oxide or propylene oxide as a mixed initiator of glycerin and triethanolamine, having a hydroxyl value of 80 mgKOH/g and a functionality of 3.
  • the specific preparation method is as follows: in a 2.5 L jacketed reactor, 644 g of glycerin, 1044 g of triethanolamine, and 30 g of a catalyst are gradually added, and the temperature is gradually raised to 70 ° C; stirring is started, and the reaction kettle is evacuated to remove excess water in the raw material; Then, the inside of the reaction vessel was replaced with nitrogen, and 438 g of propylene oxide was slowly introduced into the reaction vessel for 2 hours to maintain the pressure below 0.25 MPa, and the temperature was maintained at 90 to 100 ° C until the completion of the feeding; 142 g (a molar ratio of propylene oxide to ethylene oxide of about 7:3) was slowly introduced into the reaction vessel over 2 hours, maintaining the pressure below 0.25 MPa until the feed was completed. Finally, the temperature is raised to about 120 ° C for 3 hours, after the reaction is completed, the temperature is lowered to below 90 ° C, and then the pH is adjusted, refined, filter.
  • the catalyst used in the above preparation examples was potassium hydroxide.
  • the polymethylene polyphenyl isocyanate used in the following examples is Yantai Wanhua PM-200.
  • the detailed parameters are shown in the following table:
  • Surfactant L-5345 American Momentive High-Tech Materials Co., Ltd.
  • composition of the formulation shown in Table 1 was foamed with Wanhua Chemical Company PM200 using a high pressure sprayer Graco A20, and the volume ratio of the two components was 1:1 (mass ratio: 1:1.1). Polyurethane foam is tested according to industry common standards, and its performance is shown in Table 2.

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Abstract

一种用于聚氨酯发泡的组合物，聚氨酯泡沫及其用途，所述组合物包含两种不同的多聚环氧乙烷、环氧丙烷醚结构的多元醇，并加入特定种类的催化剂、阻燃剂、水，同时含有少量的表面活性剂和其它小分子的醇，产品性状为浅黄色透明，长期储存不分层。上述组合物与多苯基多亚甲基多异氰酸酯(PAPI)通过发泡机生产低密度聚氨酯泡沫，保温效果好、出方率高，且该泡沫具有阻燃性能，即可用于建筑保温、也可用于包装缓冲材料，具有优良的保温、粘接、尺寸稳定性；施工过程低气味，发泡剂全部采用水，不含破坏臭氧层和气候的氯氟烃类物质。

Description

用于聚氨酯发泡的组合物，聚氨酯泡沫及其用途 技术领域
本发明涉及用于聚氨酯发泡的组合物，聚氨酯泡沫及其用途，尤其涉及一种用于低密度全水聚氨酯发泡的组合物，低密度全水聚氨酯泡沫及其用途。本发明的组合物与多亚甲基多苯基多异氰酸酯(PAPI)反应，制得的泡沫应用于建筑物填充保温、隔热、隔音、防潮，也可用于精密仪器的包装行业。
背景技术
聚氨酯泡沫塑料是一种高性能泡沫材料，其保温性能是各种泡沫材料中最优的，同时具有优异的材料强度，是目前冰箱、太阳能、热力管道、建筑、汽车、冷链等保温领域的最优选择。随着我国建筑节能的重视，聚氨酯泡沫保温材料在我国建筑行业用量逐年扩大。国内目前建筑用聚氨酯泡沫所用的发泡剂主要为HCFC-141B，是一种破坏臭氧层物质，目前已经被限制使用，它的可替代发泡剂主要为HFC-245fa、365mfc、环戊烷、全水发泡。HFC-245fa成本太高；365mfc和环戊烷可燃，无法用于现场喷涂，泡沫阻燃性差。全水做发泡剂是一种低成本、环保、易实现阻燃的HCFC-141B替代发泡技术路线，尤其适合在一些建筑具有厚夹层的场合，例如：在独栋房屋屋顶内、幕墙结构的楼房、有空腔的天花板、木质房屋的内墙、空腔结构的砖墙结构中，可以采取现场施工法填充聚氨酯泡沫，起保温、隔音、防 潮作用，且充分利用空间，避免了外加保温层占用额外的建筑面积。
目前市场已有全水聚氨酯发泡组合物，但其面临诸多问题：配方中的阻燃剂与水互不相溶，产品并非澄清透明；易发生分层，储存期短；已有技术实现各组份互溶提高储存期，需要添加大量增溶剂，成本太高，且泡孔粗糙；目前聚氨酯发泡反应的催化剂一般为有机的叔胺结构，例如：全水喷涂发泡行业常用的催化剂A1，即双(二氨基乙基)醚，对聚氨酯反应有强烈的催化作用，但其挥发性很强，且气味恶臭、刺激眼睛和皮肤。这导致施工时会对工人造成人身伤害。现有技术多采用较单一种类的聚醚导致泡孔粗糙、粘接力差、产品酥脆且容易收缩，无法兼顾多元醇产品的相溶性、施工性、泡沫性能三者的关系。
因此，需要寻求一种新的全水聚氨酯发泡组合物配方，配方各组分间相溶性良好，施工时不会产生大量挥发性物质且制备的泡沫性能良好。
发明内容
本发明的目的之一在于提供一种用于聚氨酯发泡的组合物，尤其是用于低密度全水聚氨酯发泡的组合物，该多元醇产品为透明液体，不易发生分层；施工时几乎无气味。
本发明的另一个目的在于提供一种聚氨酯泡沫，其泡沫密度极低(例如6-～15kg/m3)，发泡倍率最高可达100倍，同体积保温施工用料仅为普通泡沫的1/4～1/5，大大节约了成本，且尺寸稳定性好，泡沫 的寿命长、与基材粘接牢固。
本发明的再一个目的在于提供一种聚氨酯泡沫的用途，其可用于建筑物填充保温、隔热、隔音、防潮，也可用于精密仪器的包装。
本发明提供了一种用于聚氨酯发泡的组合物(也可以称之为组合多元醇)，以100重量份组合物计，包含如下重量份的原料：
10～30份，优选15～25份的聚醚多元醇A；
20～40份，优选25～35份的聚醚多元醇B；
10～40份，优选20～30份的阻燃剂；
10～30份，优选13～18份的水；
1～4份，优选2～3份的表面活性剂；
1～8份，优选3～6份的催化剂；
其中，所述的聚醚多元醇A的平均官能度为4～8，羟值为300～700mgKOH/g；
其中，所述的聚醚多元醇B的平均官能度为2～4，羟值为20～200mgKOH/g；
其中，所述的阻燃剂为一种磷酸酯或多种磷酸酯的混合物，所述的阻燃剂的含磷量为8～40wt％；
其中，所述的催化剂为含有羟基官能团的有机叔胺混合物。
本发明的组合物在常温下为无色或浅黄色的透明液体，储存期可长达5个月不分层、不变质。本发明的组合物在使用时，将上述原料在室温下混合后与多亚甲基多苯基多异氰酸酯按质量比100∶100～150使用高压发泡工艺发泡。
使用本发明的组合物所制得的泡沫与常规的聚氨酯保温硬泡的不同在于，使用本发明所制得的泡沫为大部分开孔，因此能保持在极低的密度下仍能保持很好的尺寸稳定性，不收缩、不膨胀。
在本发明的组合物中，优选地，所述的聚醚多元醇A是以山梨醇、蔗糖、季戊四醇、2，4-二氨基苯酚、乙二胺中的一种或多种与三羟甲基丙烷按照任意比例混合的混合物为起始剂与环氧丙烷、环氧乙烷聚合反应生成的；其中，环氧丙烷和环氧乙烷的摩尔数比例为7∶3～9∶1，更优选为7∶3～8∶2。
在本发明的组合物中，优选地，所述的聚醚多元醇A是以蔗糖、三羟甲基丙烷、山梨醇按照任意比例混合的混合物作为起始剂与环氧丙烷、环氧乙烷聚合反应生成的；其平均官能度为4～5，优选为4.5～4.8；其羟值为400～500mgKOH/g，优选为450～480mgKOH/g；环氧丙烷和环氧乙烷摩尔数比例为7∶3～8∶2。在本发明中，山梨醇、蔗糖与三羟甲基丙烷的质量比例可以为100～150∶180～230∶260～300，优选为109～120∶200～205∶268～280。
在本发明的组合物中，优选地，所述的聚醚多元醇A是以2，4-二氨基苯酚或/和乙二胺为起始剂与环氧丙烷、环氧乙烷聚合反应生成的，优选为以2，4-二氨基苯酚和乙二胺为起始剂与环氧丙烷、环氧乙烷聚合反应生成的；其平均官能度为4～5，优选为4～4.5；其羟值为500～700mgKOH/g，优选为600～680mgKOH/g；环氧丙烷和环氧乙烷的摩尔数比例为7∶3～9∶1，优选为8∶2～9∶1。
在本发明的组合物中，优选地，所述的聚醚多元醇B是以二丙二醇、二乙二醇或三乙醇胺中的一种或多种与甘油按照任意比例混合的混合物为起始剂与环氧丙烷、环氧乙烷聚合反应生成的，且反应的末期以环氧乙烷封端，从而使得所述的聚醚多元醇B的端基为伯羟基。更优选地，所述的聚醚多元醇B是以甘油和三乙醇胺按照任意比例混合的混合物为起始剂与环氧丙烷、环氧乙烷聚合反应生成的，且反应的末期以环氧乙烷封端，从而所述的聚醚多元醇B的端基为伯羟基。所述的聚醚多元醇B的羟值可以为20～90mgKOH/g，优选为25～80mgKOH/g；平均官能度为2～3，优选为2.5～3；环氧丙烷和环氧乙烷的摩尔数比例为7∶3～9∶1，优选为7∶3～8∶2。进一步优选地，所述的聚醚多元醇B选自万华化学(宁波)容威聚氨酯有限公司生产的Wanol RF3135、WanolRF3160中的一种或多种。
本发明所采用的聚醚多元醇的优点在于，采用混合起始剂的多元醇，比市场建筑用同类产品采用较单一成分的聚醚具有综合性能优势。两种聚醚多元醇A和B必须同时采用，且有恰当的比例，才能达 到最佳的使用效果。
本发明中，聚醚多元醇A组分的高官能度起始剂，可以使泡沫具有细腻的泡孔，从而保持优良的保温效果。聚醚多元醇B端基为伯羟基的结构活性高，反应快，使发泡过程不易收缩和塌泡；较低的官能度在发泡反应后期又可以达到开孔的效果，避免泡沫在成型后收缩。
本发明所采用的混合聚醚多元醇A和B具有对水、阻燃剂、助剂有良好的相容性，使多种助剂混合在一起时，均一、透明，且室温下长时间储存不容易分层。在不用或者极少量的增溶剂即可得到透明、稳定的体系。使用脂肪链起始剂例如甘油、山梨醇、三乙醇胺、三羟甲基丙烷等起始剂分子具有良好的柔韧性，可以减少泡沫的脆性，提高粘接力。
在本发明的组合物中，优选地，所述的催化剂包含二甲氨基乙氧基乙醇与三甲基羟乙基乙二胺按照任意比例的混合物，同时还包含N，N，N’-三甲基-N’-羟乙基双氨乙基醚、三甲基羟乙基丙二胺、二甲基乙醇胺中的一种或多种。优选地，所述的催化剂为二甲氨基乙氧基乙醇、三甲基羟乙基乙二胺与N，N，N’-三甲基-N’-羟乙基双氨乙基醚的组合物。更优选地，所述的催化剂为质量比为1～3∶1～3∶0～3的二甲氨基乙氧基乙醇∶三甲基羟乙基乙二胺∶N，N，N’-三甲基-N’-羟乙基双氨乙基醚的组合物。更优选地，所述的催化剂为质量比为3∶1∶1的二甲氨基乙氧基乙醇∶三甲基羟乙基乙二胺∶N，N，N’-三甲基-N’-羟乙基双氨乙基醚的组合物。
相对于目前市场上现有技术采用大量的双(二甲氨基乙基)醚和二甲基环己胺作为催化剂，总用量达到4％以上，施工时味道极为恶臭，本发明所采用的催化剂组分中，双(二甲氨基乙基)醚或二甲基环己胺用量可完全为零，在施工时不会引起人员的不适。与现有技术相比，本发明所采用的催化剂绝大部分含有羟基，可以与异氰酸酯反应，从而嵌入到高分子链中，具有低挥发性、低气味的特点。本发明用发泡机在施工时几乎无胺味。
在本发明的组合物中，优选地，所述的阻燃剂为磷酸三(2-氯丙基)酯、磷酸三(2-氯乙基)酯中的一种或两种与磷酸三乙酯的混合物，其中，磷酸三乙酯在阻燃剂总重量份中至少占40％；优选地，所述的阻燃剂为质量比为1～3∶1～3的磷酸三乙酯与磷酸三(2-氯丙基)酯的混合物。更优选地，所述的阻燃剂为质量比为1∶1的磷酸三乙酯与磷酸三(2-氯丙基)酯的混合物。
本发明所采用化学性质稳定、挥发性杂质少的阻燃剂，有利于延长储存期、减少气味。将不同种类的阻燃剂混合使用，改善对水的相容性，使产品可以不采用、或采用极少量的增溶剂或乳化剂/分散剂即可达到澄清透明、常温下不分层的稳定效果。所述的阻燃剂中的磷和卤素含量合理的比例，利用磷-卤素阻燃协同效应，以最少的阻燃剂用量达到最优的阻燃效果。
在本发明的组合物中，优选地，水的重量份为10～30份，优选13～18份。其作用是发泡时与异氰酸酯反应生成二氧化碳气体从而促进发 泡、同时过量部分的水自身挥发形成气体，兼具化学发泡剂和物理发泡剂的功能。
在本发明的组合物中，优选地，所述的表面活性剂由多聚甲基硅氧烷、环氧丙烷、环氧乙烷嵌段共聚而成。优选地，本发明的表面活性剂为美国迈图高新技术材料有限公司的L-6186、L-5345或空气化工公司的DC-5950。所述的表面活性剂可以在发泡过程中保持泡沫细腻、开孔的效果。
在本发明的组合物中，优选地，所述的组合物还包含0～3重量份，优选为1～2重量份的其他助剂，所述的其他助剂选自三乙醇胺、甘油中的一种或两种。这样可以使泡沫更加细腻。
本发明还提供了一种聚氨酯泡沫，其通过上述的组合物得到。优选地，其通过上述组合物与多亚甲基多苯基多异氰酸酯PAPI反应得到。本发明的聚氨酯泡沫优选为低密度全水聚氨酯泡沫，其发泡过程包括三个阶段的反应。
第一阶段，水与PAPI开始发生反应，放出热量、少量气体二氧化碳，泡沫开始起发；此时这个体系还是液体状态，在表面活性剂的作用下PAPI与组合物中所有组分保持均一、稳定的液体泡沫，总体积增长至最终泡沫的5％，体系中多数成分仍以小分子的状态存在。这个阶段的反应与普通硬泡发泡的第一阶段是类似的。以喷涂施工时，该阶段反应时间在1.5秒左右；以浇注施工时，该阶段反应时间在5～10秒左右。
第二阶段，水与PAPI继续发生反应，放出大量二氧化碳，泡沫体迅速膨胀；同时聚醚多元醇B、聚醚多元醇A与PAPI陆续发生反应，分子量呈几何级数增长，粘度迅速上升，泡沫体迅速生长为凝胶状态，这样在泡沫体迅速膨胀的过程中泡沫体仍能保持稳定、不塌陷。在表面活性剂的作用下泡沫仍能保持细腻、不粗糙、不并泡。在典型的喷涂施工条件下，这个阶段的反应时间为5秒左右，总的化学反应完成了90％。在浇注施工条件下，这个阶段的反应时间为20～40秒左右。
第三阶段，反应继续进行，形成固体的高分子泡沫塑料。由于聚醚多元醇、PAPI都是多官能度的，因此形成了有一定交联度的高分子泡沫材料，在表面活性剂的作用下泡沫呈均匀的多边形，且具有骨架较粗、泡孔壁较薄的特殊结构。体系的温度、热量释放达到最大，过量的水在高温下汽化冲破大部分泡孔壁进入外界空气，最终形成了开孔型的聚氨酯泡沫塑料。在典型的喷涂施工条件下，这个阶段的反应时间为2～3秒左右，在浇注施工条件下，这个阶段的反应时间为10～20秒左右。
本发明的组合物的优点在于：使用时所采用的发泡喷涂机、浇注机可采用市场通用的几乎所有型号，与PAPI质量比100∶100～150反应，优选比例范围100∶100～120反应，在15℃以上气候条件下皆可施工，对施工条件有良好的宽容度。
本发明与PAPI反应制得的泡沫，是开孔型的，具有80％以上的高开孔率，多数施工情况下具有90％以上开孔率，在自然温度条件下 不收缩、不变形。
本发明中，所述的高压发泡工艺，通常为喷涂，使用高压喷涂机将本发明的组合物和PAPI混合并喷涂于墙体包括屋顶内表面，泡沫立即起发，5s内成为固体，10s内固化完毕，半小时熟化度到95％以上。
本发明的高压发泡工艺，也可以为灌注工艺，使用泡沫浇注机将本发明与PAPI混合并注于建筑保温层内，在5秒内起发，30秒内固化，一小时熟化度到95％以上。保温层的形状不限，方形、球形、异形空间均可。
另外，本发明还提供了上述的聚氨酯泡沫的用途，其用于建筑物填充保温、隔热、隔音、防潮或精密仪器的包装。
具体实施方式
下面通过具体实施方式对本发明进行进一步的说明，其目的在于更好理解本发明的内容，但并不限制本发明的保护范围。
在本发明中，除非特别声明，“份”表示“重量份”；“％”表示“wt％”，即重量百分比。
制备例1-5
聚醚多元醇1是以山梨醇、蔗糖、三羟甲基丙烷为起始剂与环氧乙烷、环氧丙烷聚合的聚醚多元醇，羟值450mgKOH/g，平均官能度4.5。具体制备方法为：在2.5升的带夹套的反应釜中投入山梨醇109g、 蔗糖205g、三羟甲基丙烷268g、催化剂35g，逐渐升温至70℃；开动搅拌，对反应釜抽真空，抽去原料中多余的水分；然后反应釜内用氮气置换，将环氧丙烷1000g与环氧乙烷200g(二者的摩尔比约为8∶2)在2小时内同时缓慢投入反应釜中，保持压力在0.25MPa以下，缓慢上升到100℃，直至投料完毕。然后温度上升至120℃左右继续保持3小时。反应完毕后降温到90℃以下，然后调节pH值、精制、过滤。
聚醚多元醇2是以山梨醇、三羟甲基丙烷为混合起始剂与环氧乙烷、环氧丙烷聚合的聚醚多元醇，羟值350mgKOH/g，平均官能度5。具体制备方法为：在2.5L的带夹套的反应釜中投入山梨醇364g、三羟甲基丙烷134g、催化剂32g，逐渐升温至70℃；开动搅拌，对反应釜抽真空，抽去原料中多余的水分；然后反应釜内用氮气置换，将环氧丙烷1500g与环氧乙烷300g(二者的摩尔比约为8∶2)在2小时内同时缓慢投入反应釜中，保持压力在0.25MPa以下，缓慢上升到100℃。投料完毕后，温度上升至110℃左右继续保持3小时。反应完毕后降温到90℃以下，然后调节pH值、精制、过滤。
聚醚多元醇3是以2，4-二氨基苯酚和乙二胺为混合起始剂与环氧乙烷、环氧丙烷聚合的聚醚多元醇，羟值680mgKOH/g，官能度4。具体制备方法为：在2.5L的带夹套的反应釜中投入2，4-二氨基苯酚366g、乙二胺180g，逐渐升温至70℃；开动搅拌，然后反应釜内用氮气置换，将环氧丙烷1561g与环氧乙烷132g(二者摩尔比约为9∶1)在2小时内同时缓慢投入反应釜中，保持压力在0.25MPa以下， 缓慢上升到100℃。投料完毕后，温度上升至110℃左右继续保持2小时。反应完毕后降温到90℃以下，然后精制、过滤。
聚醚多元醇4是以甘油和二丙二醇为混合起始剂与环氧乙烷、环氧丙烷聚合的聚醚多元醇，羟值25mgKOH/g，平均官能度2.5。具体制备方法为：在2.5L的带夹套的反应釜中投入甘油645g、二丙二醇940g、催化剂40g，逐渐升温至70℃；开动搅拌，对反应釜抽真空，抽去原料中多余的水分；然后反应釜内用氮气置换，再将环氧丙烷410g在2小时内缓慢投入反应釜中反应，保持压力在0.25MPa以下，温度保持在90～100℃，直至投料完毕；再将环氧乙烷133g(环氧丙烷与环氧乙烷摩尔比约为7∶3)在2小时内缓慢投入反应釜中反应，保持压力在0.25MPa以下，直至投料完毕。最后将温度上升至120℃左右继续保持3小时，反应完毕后降温到90℃以下，然后精制、过滤。
聚醚多元醇5是以甘油和三乙醇胺为混合起始剂与环氧乙烷、环氧丙烷聚合的聚醚多元醇，羟值80mgKOH/g，官能度为3。具体制备方法为：在2.5L的带夹套的反应釜中投入甘油644g、三乙醇胺1044g、催化剂30g，逐渐升温至70℃；开动搅拌，对反应釜抽真空，抽去原料中多余的水分；然后反应釜内用氮气置换，再将环氧丙烷438g在2小时内缓慢投入反应釜中反应，保持压力在0.25MPa以下，温度保持在90～100℃，直至投料完毕；再将环氧乙烷142g(环氧丙烷与环氧乙烷摩尔比约为7∶3)在2小时内缓慢投入反应釜中反应，保持压力在0.25MPa以下，直至投料完毕。最后将温度上升至120℃左右继续保持3小时，反应完毕后降温到90℃以下，然后调节pH值、精制、 过滤。
以上制备例中所使用的催化剂为氢氧化钾。
以下实施例所用的多亚甲基多苯基异氰酸酯为烟台万华PM-200，详细参数如下表所示：
Figure PCTCN2015071824-appb-000001
表面活性剂L-5345：美国迈图高新技术材料有限公司。
实施例1-5：
将表1中所示配方的组合物与万华化学公司PM200使用高压喷涂机固瑞克A20发泡，两个组分的体积比为1∶1(质量比为1∶1.1)，制得的聚氨酯泡沫按照行业通用标准测试，其性能参见表2.
下表中的组分用量为重量份，EO为环氧乙烷，PO为环氧丙烷。
表1 组合物配方
Figure PCTCN2015071824-appb-000002
Figure PCTCN2015071824-appb-000003
表2 泡沫性能
Figure PCTCN2015071824-appb-000004
上述性能测试采用行业通用的检测标准，检测方法和设备都是行业熟知和常见的。

Claims (13)

  1. 一种用于聚氨酯发泡的组合物，其特征在于，以100重量份组合物计，包含如下重量份的原料：
    10～30份，优选15～25份的聚醚多元醇A；
    20～40份，优选25～35份的聚醚多元醇B；
    10～40份，优选20～30份的阻燃剂；
    10～30份，优选13～18份的水；
    1～4份，优选2～3份的表面活性剂；
    1～8份，优选3～6份的催化剂；
    其中，所述的聚醚多元醇A的平均官能度为4～8，羟值为300～700mgKOH/g；
    其中，所述的聚醚多元醇B的平均官能度为2～4，羟值为20～200mgKOH/g；
    其中，所述的阻燃剂为一种磷酸酯或多种磷酸酯的混合物，所述的阻燃剂的含磷量为8～40wt％；
    其中，所述的催化剂为含有羟基官能团的有机叔胺混合物。
  2. 根据权利要求1所述的组合物，其特征在于，所述的聚醚多元醇A是以山梨醇、蔗糖、季戊四醇、2，4-二氨基苯酚、乙二胺中的一种或多种与三羟甲基丙烷按照任意比例混合的混合物为起始剂与环氧丙烷、环氧乙烷聚合反应生成的；其中，环氧丙烷和环氧乙烷的摩尔数比例为7∶3～9∶1。
  3. 根据权利要求1所述的组合物，其特征在于，所述的聚醚多元醇A是以蔗糖、三羟甲基丙烷、山梨醇按照任意比例混合的混合物作为起始剂与环氧丙烷、环氧乙烷聚合反应生成的；其平均官能度为4～5；羟值为400～500mgKOH/g；环氧丙烷和环氧乙烷摩尔数比例为7∶3～8∶2。
  4. 根据权利要求1所述的组合物，其特征在于，所述的聚醚多元醇A是以2，4-二氨基苯酚或/和乙二胺为起始剂与环氧丙烷、环氧乙烷聚合反应生成的；其平均官能度为4～5；羟值为500～700mgKOH/g；环氧丙烷和环氧乙烷的摩尔数比例为7∶3～9∶1。
  5. 根据权利要求1所述的组合物，其特征在于，所述的聚醚多元醇B是以二丙二醇、二乙二醇或三乙醇胺中的一种或多种与甘油按照任意比例混合的混合物为起始剂与环氧丙烷、环氧乙烷聚合反应生成的，且反应的末期以环氧乙烷封端，从而使得所述的聚醚多元醇B的端基为伯羟基。
  6. 根据权利要求5所述的组合物，其特征在于，所述的聚醚多元醇B是以甘油和三乙醇胺按照任意比例混合的混合物为起始剂与环氧丙烷、环氧乙烷聚合反应生成的，其羟值为20～90mgKOH/g，且反应的末期以环氧乙烷封端，从而使得所述的聚醚多元醇B的端基为伯羟基。
  7. 根据权利要求1所述的组合物，其特征在于，所述的表面活性剂由多聚甲基硅氧烷、环氧丙烷、环氧乙烷嵌段共聚而成的，优选为美国迈图高新技术材料有限公司的L-6186、L-5345或空气化工公司的DC-5950。
  8. 根据权利要求1所述的组合物，其特征在于，所述的催化剂包含二甲氨基乙氧基乙醇与三甲基羟乙基乙二胺按照任意比例的混合物，同时还包含N，N，N’-三甲基-N’-羟乙基双氨乙基醚、三甲基羟乙基丙二胺、二甲基乙醇胺中的一种或多种；优选地，所述的催化剂为质量比为1～3∶1～3∶0～3的二甲氨基乙氧基乙醇∶三甲基羟乙基乙二胺∶N，N，N’-三甲基-N’-羟乙基双氨乙基醚的组合物。
  9. 根据权利要求1所述的组合物，其特征在于，所述的阻燃剂为磷酸三(2-氯丙基)酯、磷酸三(2-氯乙基)酯中的一种或两种与磷酸三乙酯的混合物，其中，磷酸三乙酯在阻燃剂总重量份中至少占40％；优选地，所述的阻燃剂为质量比为1～3∶1～3的磷酸三乙酯与磷酸三(2-氯丙基)酯的混合物。
  10. 根据权利要求1所述的组合物，其特征在于，所述的组合物还包含0～3％的其他助剂，所述的其他助剂选自三乙醇胺、甘油中的一种或两种。
  11. 一种聚氨酯泡沫，其通过权利要求1-10任一项所述的组合物得到。
  12. 根据权利要求11所述的聚氨酯泡沫，其通过权利要求1-10任一项所述的组合物与多亚甲基多苯基多异氰酸酯PAPI反应得到。
  13. 根据权利要求11或12所述的聚氨酯泡沫的用途，其用于建筑物填充保温、隔热、隔音、防潮或精密仪器的包装。
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