WO2020078329A1 - 一种阻燃组合聚醚、聚异氰脲酸酯板材用保温材料及其制备方法 - Google Patents

一种阻燃组合聚醚、聚异氰脲酸酯板材用保温材料及其制备方法 Download PDF

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Publication number
WO2020078329A1
WO2020078329A1 PCT/CN2019/111116 CN2019111116W WO2020078329A1 WO 2020078329 A1 WO2020078329 A1 WO 2020078329A1 CN 2019111116 W CN2019111116 W CN 2019111116W WO 2020078329 A1 WO2020078329 A1 WO 2020078329A1
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Prior art keywords
polyether
produced
catalyst
component
polyisocyanurate
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PCT/CN2019/111116
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English (en)
French (fr)
Inventor
李学庆
于楠
王光辉
郭磊
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上海东大聚氨酯有限公司
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Publication of WO2020078329A1 publication Critical patent/WO2020078329A1/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
    • C08G18/28—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
    • 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
    • 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
    • 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
    • C08J9/142—Compounds containing oxygen but no halogen atom
    • 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
    • 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
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/10—Water or water-releasing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers

Definitions

  • This application relates to the technical field of chemical synthesis, in particular, this application relates to a flame-retardant combination polyether, a thermal insulation material for polyisocyanurate plates derived from the flame-retardant combination polyether, and the polyisocyanate Preparation method of heat preservation material for urate board.
  • the mainstream foaming agents in polyurethane sheets are HCFC-141b, HFC-245fa, HFC-365mfc, pentane, etc.
  • HCFC-141b has been basically banned in this industry due to its great damage to the ozone layer.
  • HFC-245fa and HFC-365mfc have an Ozone Depletion Potential (ODP) of 0 and a Global Warming Potential (GWP) of 820 and 840, respectively, which are transitional products and also face replacement problems.
  • ODP Ozone Depletion Potential
  • GWP Global Warming Potential
  • methyl formate the biggest problem affecting the use of methyl formate is that it is easily hydrolyzed in the combined polyether system to form formic acid and methanol, and irreversible chemical reaction between formic acid and amine catalysts results in slower raw material reactivity and higher product density
  • the system storage time is short. Even if it is in the product system, slow hydrolysis will occur.
  • the hydrolysate formic acid and methanol have a greater dissolution effect on the foam product. Within three months, foam shrinkage and the product's compressive strength will drop significantly. occur. Solving the hydrolysis of methyl formate and its dissolution effect on foam products is the biggest difficulty in the application of methyl formate blowing agent.
  • methyl formate foaming solution In the existing methyl formate foaming solution, the hydrolysis of methyl formate is generally solved by a special catalyst and the amount of methyl formate is reduced, but it cannot be completely solved in practical applications.
  • the storage stability is up to 10 days in summer Around the same time, deterioration still occurs, and the dissolution effect of the foam product still exists, and its use is very limited.
  • the purpose of the present application is to provide a flame retardant combined polyether that can effectively inhibit the hydrolysis of methyl formate, thereby solving the problems in the prior art.
  • This application introduces special additives to dissolve methyl formate in it to reduce its hydrolysis and obtain good results.
  • the shelf life can be extended to more than 90 days, which can be applied to the production of most customers.
  • the dissolution effect in foam products has also been greatly improved, and the performance of the products has remained basically unchanged after being placed for at most 1 year.
  • the purpose of the present application is also to provide a thermal insulation material for polyisocyanurate sheet derived from the flame-retardant combination polyether.
  • the purpose of this application is also to provide a method for preparing a thermal insulation material for polyisocyanurate sheets.
  • the present application provides a flame retardant combination polyether, based on parts by weight, which is made of the following raw material components:
  • the total amount of the first polyether polyol, the second polyether polyol and the polyester polyol is 100 parts;
  • the polyester polyol is an aromatic polyester polyol with a flame retardant structure
  • additives include aliphatic ketones.
  • the additive is butanone.
  • the polyether polyol is polyoxypropylene alcohol using sorbitol as an initiator, and has a functionality of 5-6, a hydroxyl value of 465-515 mgKOH / g, and a viscosity of 17000- 23000mPa ⁇ s;
  • the second polyether polyol is polyoxypropylene alcohol with sucrose as an initiator, its functionality is 4.5-5, its hydroxyl value is 415-455 mgKOH / g, and its viscosity is 5400-8000 mPa ⁇ s;
  • the polyester polyol is a polyester polyol with a flame-retardant structure, its functionality is 2-2.5, its hydroxyl value is 230-250 mgKOH / g, and its viscosity is 2000-4500 mPa ⁇ s.
  • the surfactant includes a foam stabilizer
  • the first catalyst is an amine catalyst
  • the second catalyst is a metal catalyst
  • the third catalyst is a trimeric catalyst
  • the flame retardant is a commonly used chlorine-based flame retardant and / or phosphorus-based flame retardant for polyurethane;
  • the chemical blowing agent is water
  • the physical blowing agent includes methyl formate.
  • the first polyether polyol is polyether polyol NJ-6249 produced by Jurong Ningwu New Materials Co., Ltd .;
  • the second polyether polyol is polyether polyol NJ-8332 produced by Jurong Ningwu New Materials Co., Ltd. and / or polyether polyol GSU-450L produced by Shanghai Gaoqiao Petrochemical Company;
  • the polyester polyol is a polyester polyol PS-2412 produced by Nanjing Jinling Stepan Chemical Co., Ltd .;
  • the first catalyst is Polycat 9 produced by Air Chemical Products
  • the second catalyst is Dabco K15 and / or Polycat46 produced by Air Chemical Products;
  • the third catalyst is Dabco TMR-4 produced by Air Chemical Products
  • the foam stabilizer is B8462 produced by Evonik Specialty Chemicals (Shanghai) Co., Ltd. and / or AK-8808 produced by Jiangsu Meside Chemical Co., Ltd .;
  • the flame retardant is tris (2-chloropropyl) phosphate and / or diethyl ethyl phosphate;
  • the water includes deionized water.
  • the present application provides an insulation material for a polyisocyanurate sheet
  • the insulation material for a polyisocyanurate sheet is made of a first component and a second component, wherein the first The component is composed of the raw material components of the flame-retardant combination polyether as described in the first aspect; the second component is polymethylene polyphenyl polyisocyanate.
  • the second component is PM200 and PM400 produced by Yantai Wanhua Polyurethane Co., Ltd .; one or more of 44V20 produced by Bayer and M20S produced by BASF. .
  • the weight ratio of the first component and the second component is 1: 1.05-1.4.
  • the flame retardant properties of the insulation material for polyisocyanurate sheet Reach level B2.
  • the present application provides a method for preparing a thermal insulation material for a polyisocyanurate sheet as described in the second aspect, the method comprising mixing a predetermined weight ratio of the first component and the second component After the constant temperature foaming, the thermal insulation material for the polyisocyanurate board is obtained.
  • the constant temperature foaming has a foaming temperature of 40 ° C-45 ° C.
  • the beneficial effect of the present application is to solve the hydrolysis of methyl formate in the polyisocyanurate composite polyether system, and the shelf life can be increased to more than 90 days. At the same time, it is produced
  • the foam products have no shrinkage, deformation, etc., which is helpful for the promotion of methyl formate in the polyisocyanurate composite polyether system.
  • Its safety and physical properties are better than the pentane system, and the overall cost ratio HFC and HFO blowing agents are much lower, ODP, GWP, VOC values are all zero, and environmental protection is also the best among all blowing agents.
  • the numerical ranges in this application are approximate, so unless stated otherwise, they may include values outside the range.
  • the range of values includes all values from the lower limit to the upper limit increased by 1 unit, provided that there is a gap of at least 2 units between any lower value and any higher value.
  • the composition, physical or other properties are 100 to 1000, it means that all single values are clearly listed, such as 100, 101, 102, etc., and all sub-ranges, such as 100 to 166,155 to 170,198 to 200 etc.
  • compositions in this application that use the terms “comprising”, “including”, or “having” may contain any additional additives, excipients, or compounds.
  • the term “consisting essentially of” excludes any other components, steps or processes from any scope of the term described below, except for those necessary for operational performance.
  • the term “consisting of” does not include any components, steps or processes not specifically described or listed. Unless specifically stated otherwise, the term “or” refers to the listed individual members or any combination thereof.
  • the present application provides a flame retardant combination polyether.
  • the flame-retardant combination polyether of the present application is composed of the following components, the parts are mass parts, and the sum of the first polyether polyol, the second polyether polyol, and the polyester polyol is 100 parts:
  • the flame retardant combination polyether of the present application includes a first polyether polyol.
  • Polyether polyols suitable for the purposes of this application include, but are not limited to, those obtained by polymerizing epoxides (such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran) in the presence of a multifunctional initiator product.
  • Suitable initiators contain multiple active hydrogen atoms, specific examples of which include water, butylene glycol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene di Amine, diethyltoluenediamine, aniline, diphenylmethanediamine, ethylenediamine, cyclohexanediamine, cyclohexanedimethanol, resorcinol, bisphenol A, glycerin, trimethylolpropane , 1,2,6-hexanetriol, pentaerythritol or a combination thereof.
  • the first polyether polyol is preferably polyoxypropylene alcohol with sorbitol as the initiator, its functionality is 5-6, its hydroxyl value is 465-515 mgKOH / g, and its viscosity is 17000 ⁇ 23000mPa ⁇ s, the typical model is polyether polyol NJ-6249 of Jurong Ningwu New Materials Co., Ltd.
  • the second polyether polyol is polyoxypropylene alcohol with sucrose as an initiator, its functionality is 4.5-5, its hydroxyl value is 415-455 mgKOH / g, and its viscosity is 5400-8000 mPa ⁇ s, its typical model is Jurong Ningwu New Materials Co., Ltd. polyether polyol NJ-8332 and / or Shanghai Gaoqiao Petrochemical Company polyether polyol GSU-450L.
  • the flame retardant combination polyether of the present application further includes an aromatic polyester polyol with a flame retardant structure.
  • Aromatic polyester polyol refers to a polyester polyol containing a benzene ring, usually a polyester polyol synthesized from an aromatic dibasic acid (or anhydride or ester) and a diol (and / or polyol) as raw materials.
  • the raw material of polyester is generally phthalic anhydride or terephthalic acid, etc.
  • the common raw material of glycol is diethylene glycol, triol and so on.
  • the polyester polyol described herein is a polyester polyol with a flame retardant structure, its functionality is 2-2.5, its hydroxyl value is 230-250 mgKOH / g, and its viscosity is 2000-4500 mPa.
  • ⁇ S its typical model is the polyester polyol PS-2412 of Nanjing Jinling Stepan Chemical Co., Ltd.
  • the flame-retardant combination polyether of the present application also includes a surfactant, which generally supports the homogenization of the blowing agent and the polyol, and adjusts the cell structure of the polyisocyanurate foam.
  • the surfactant may include any suitable surfactant or mixture of surfactants known in the art.
  • the surfactant of the present application includes a foam stabilizer.
  • the foam stabilizer described herein is a silicone foam stabilizer, preferably B8462 of Evonik Specialty Chemicals (Shanghai) Co., Ltd. and / or AK-8808 of Jiangsu Meside Chemical Co., Ltd.
  • the flame retardant combination polyether described herein further includes a catalyst composition.
  • the catalyst is generally used to catalyze the reaction between isocyanate and polyol, and is not consumed in the reaction.
  • the flame retardant combination polyether of the present application includes at least a first catalyst, a second catalyst, and a third catalyst.
  • the first catalyst in the present invention is an amine catalyst commonly used in the field of polyurethane, and Polycat 9 (produced by Air Chemical Products) is preferred in the present invention.
  • the second catalyst of the present invention is a metal-based catalyst commonly used for polyurethane.
  • Dabco K15 manufactured by Air Chemical Products
  • Polycat 46 manufactured by Air Chemical Products
  • the third catalyst of the present invention is a trimeric catalyst commonly used for polyurethane, and Dabco TMR-4 (produced by Air Chemical Products) is preferred in the present invention.
  • the flame retardant combination polyether of the present application further includes a flame retardant.
  • the flame retardants described in this application are commonly used chlorine-based flame retardants and / or phosphorus-based flame retardants for polyurethanes, preferably tris (2-chloropropyl) phosphate (TCPP) and / or diethyl ethyl phosphate ( DEEP).
  • the flame retardant combination polyether of the present application further includes additives.
  • the additive can be used as a solvent for dissolving methyl formate and inhibiting the hydrolysis of methyl formate.
  • the additives described herein are aliphatic ketones, including but not limited to butanone, pentanone, neopentanone, cyclohexanone, and the like. In a particularly preferred embodiment, the additive described in this application is butanone.
  • the flame-retardant combination polyether of the present application may optionally also include other conventional additives, including but not limited to chain extenders, chain terminators, processing aids, adhesion promoters , Antioxidants, defoamers, water scavengers, molecular sieves, ultraviolet light stabilizers, fillers, thixotropic agents, colorants, inert diluents, or combinations thereof.
  • other conventional additives including but not limited to chain extenders, chain terminators, processing aids, adhesion promoters , Antioxidants, defoamers, water scavengers, molecular sieves, ultraviolet light stabilizers, fillers, thixotropic agents, colorants, inert diluents, or combinations thereof.
  • the flame-retardant combination polyether described in this application may further include a chemical blowing agent and a physical blowing agent.
  • a chemical blowing agent refers to a blowing agent that does not chemically react with isocyanates or polyols.
  • the physical blowing agent may be gas or liquid. Liquid physical blowing agents usually evaporate into a gas when heated, and usually return to a liquid when cooled. In a specific embodiment, the physical blowing agent described in this application is methyl formate.
  • the term "chemical blowing agent” refers to a blowing agent that chemically reacts with isocyanates, polyols, or other components and releases gas for foaming.
  • the chemical blowing agents described herein include water, especially deionized water.
  • the present application also provides a thermal insulation material for polyisocyanurate sheet material.
  • the thermal insulation material for polyisocyanurate sheet material is composed of a first component and a second component that are mechanically stirred and mixed in a certain ratio, and then pass a series of Chemical reaction.
  • the first component is formed by mixing the raw material components of the flame-retardant combination polyether as described above.
  • the first component consists of a certain proportion of polyether polyol, polyester polyol, surfactant, catalyst, additives, foaming agent, etc. after mechanical mixing;
  • the second component is polymethylene polyphenyl polyisocyanate (PAPI).
  • the polymethylene polyphenyl polyisocyanate mentioned in this application is a polymethylene polyphenyl polyisocyanate commonly used in the field of polyurethane, such as PM200 and PM400 produced by Yantai Wanhua Polyurethane Co., Ltd., 44V20 of Bayer, BASF AG M20S etc. This application prefers PM400 produced by Yantai Wanhua Polyurethane Co., Ltd.
  • the weight ratio of the first component and the second component in the present application is 1: 1.05-1.4.
  • the present application also provides a method for preparing a thermal insulation material for polyisocyanurate sheets as described in the second aspect, the method comprising mixing a first component and a second component in a predetermined weight ratio, after constant temperature foaming The thermal insulation material for the polyisocyanurate board is obtained.
  • Examples 1-4 and Comparative Examples 1-2 were prepared according to the ingredients in the following table, and the parts shown in Table 1 were all parts by mass.
  • Example 1 Example 2
  • Example 3 Example 4 Comparative Example 1 Comparative Example 2
  • NJ-6249 25 10
  • 20 15 20
  • NJ-8332 35
  • GSU-450L - 40 - 25 - - PS-2412 40 50 60 60 60 45
  • Milking time, gel time, debonding time visual observation using a stopwatch
  • Free foam density, molded foam density density test of GB / T6343-95 polyurethane foam
  • Compression strength GB / T 8813-2008 rigid foam plastic compression performance determination
  • Flame retardant performance GB / T8624-2012 building materials and products combustion performance classification.
  • the flame retardant combination polyether obtained in the present invention does not change much in reaction time and free foam density after being left for 30 days, and can be used for long-term storage, and the volume change rate is very small after being left at low temperature for 180 days after being made into a foam product. , To ensure the long-term performance of the product. Compared with the current mainstream cyclopentane foaming system, it is also found that its compressive strength, thermal conductivity, dimensional stability and other physical properties are superior to the cyclopentane system, coupled with its higher safety and large-scale The value of promotion.
  • the raw materials used in the present invention are all the raw materials sold in the market, and the raw materials have a wide source and can be produced on a large scale.

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

Abstract

提供了一种阻燃组合聚醚，以重量份数为基准计，其由下述原料组分制成：第一聚醚多元醇10-25份，第二聚醚多元醇20-40份，聚酯多元醇30-60份，表面活性剂2.5-3.5份，第一催化剂0.1-0.6份，第二催化剂0.3-1.0份，第三催化剂0.6-1.5份，阻燃剂15-30份，化学发泡剂1.5-2.3份，添加剂2.0-3.2份，物理发泡剂10-16份；其中第一聚醚多元醇、第二聚醚多元醇和聚酯多元醇用量之和为100份，聚酯多元醇为带有阻燃结构的芳香族聚酯多元醇，且添加剂包括脂肪族酮。还提供了一种聚异氰脲酸酯板材用保温材料及其制备方法，其由第一组分和第二组分制成，其中第一组分由如权上所述的阻燃组合聚醚的原料组分混合而成；第二组分为多亚甲基多苯基多异氰酸酯。

Description

一种阻燃组合聚醚、聚异氰脲酸酯板材用保温材料及其制备方法 技术领域
本申请涉及化学合成技术领域，具体来说，本申请涉及一种阻燃组合聚醚，源自所述阻燃组合聚醚的聚异氰脲酸酯板材用保温材料，以及所述聚异氰脲酸酯板材用保温材料的制备方法。
背景技术
近年来，随着我国建筑节能市场的迅速发展，聚氨酯保温材料在建筑保温领域得到了广泛应用。但国内聚氨酯保温材料在建筑保温方面的应用占比还不够高，由于聚氨酯保温材料导热系数低、耐候性好、施工方面等特点，必将在我国的建筑节能领域得到更广泛的应用。
目前聚氨酯板材中主流的发泡剂有HCFC-141b、HFC-245fa、HFC-365mfc、戊烷等，HCFC-141b由于其对臭氧层有较大的破坏作用，在该行业已经基本禁用。HFC-245fa和HFC-365mfc的臭氧消耗潜值(ODP)为0，全球变暖潜能值(GWP)分别为820和840，属于过渡产品，也面临替代的问题。
目前主流的零ODP值、低GWP值发泡剂中，戊烷由于其自身易燃易爆，危险性高，且其热导率高，制得的泡沫阻燃性能差，使用限制较大。水的热导率非常高，且相比其他使用物理发泡剂的体系用料量多，只在个别行业中有使用。第四代发泡剂如霍尼韦尔公司的LBA或者科慕公司的Opteon1100，目前的生产规模很小，且价格昂贵，也没有推广开来。甲酸甲酯的沸点及溶解度与HCFC-141b极为接近，且其成本低廉，又不含有挥发性有机物(VOC)，是目前非常理想的发泡剂替代品。
不过影响甲酸甲酯使用的最大问题是其在组合聚醚体系中极易水解，生成甲酸和甲醇，而甲酸与胺类催化剂发生不可逆的化学反应，导致原料反应活性变慢，制品密度升高，体系存储时间短。即使其在制品体系之中，也会发生缓慢的水解，水解产物甲酸和甲醇对泡沫制品有较大的溶解效应，在三个月之内即会出现泡沫收缩、制品压缩强度大幅下降等现象的发生。解决甲酸甲酯水解及对泡沫制品的溶解 效应，是甲酸甲酯发泡剂应用的最大难点。
为此，本领域迫切需要开发一种可以有效抑制甲酸甲酯水解的阻燃组合聚醚、聚异氰脲酸酯板材用保温材料及其制备方法。
发明内容
在已有的甲酸甲酯发泡解决方案中，一般通过特殊催化剂及减少甲酸甲酯的用量来解决甲酸甲酯水解的问题，但是实际应用中仍不能完全解决，储存稳定性夏季最多在10天左右，仍有变质的情况发生，且泡沫制品溶解效应依然存在，使用非常受限。
本申请之目的在于提供一种可以有效抑制甲酸甲酯水解的阻燃组合聚醚，从而解决现有技术中的问题。本申请通过引入特殊的添加剂，将甲酸甲酯溶解在其中，降低其水解情况，得到了很好的使用效果，保质期可以延长到90天以上，可以适用于绝大多数客户的生产。同时，在泡沫制品中的溶解效应也有了相当大的改善，制品最多放置1年后仍保持性能基本没有下降。前述两个问题均有了良好的解决的方案，甲酸甲酯发泡剂在聚异氰脲酸酯板材体系中的后期推广将会更加顺利。
本申请之目的还在于提供一种源自所述阻燃组合聚醚的聚异氰脲酸酯板材用保温材料。
本申请之目的还在于提供一种制备聚异氰脲酸酯板材用保温材料的方法。
为了实现上述目的，本申请提供下述技术方案。
在第一方面中，本申请提供一种阻燃组合聚醚，以重量份数为基准计，其由下述原料组分制成：
Figure PCTCN2019111116-appb-000001
Figure PCTCN2019111116-appb-000002
其中第一聚醚多元醇、第二聚醚多元醇和聚酯多元醇用量之和为100份；
其中所述聚酯多元醇为带有阻燃结构的芳香族聚酯多元醇；
其中所述添加剂包括脂肪族酮。
在第一方面的一种实施方式中，所述添加剂为丁酮。
在第一方面的一种实施方式中，所述聚醚多元醇为以山梨醇为起始剂的聚氧化丙烯醇，其官能度为5-6，羟值465～515mgKOH/g，粘度17000～23000mPa·s；
和/或，所述第二聚醚多元醇为蔗糖为起始剂的聚氧化丙烯醇，其官能度为4.5-5，羟值415～455mgKOH/g，粘度5400～8000mPa·s；
和/或，所述聚酯多元醇为带有阻燃结构的聚酯多元醇，其官能度为2-2.5，羟值230～250mgKOH/g，粘度2000～4500mPa·s。
在第一方面的一种实施方式中，所述表面活性剂包括泡沫稳定剂；
和/或，所述第一催化剂为胺类催化剂；
和/或，所述第二催化剂为金属类催化剂；
和/或，所述第三催化剂为三聚类催化剂；
和/或，所述阻燃剂为聚氨酯常用的氯系阻燃剂和/或磷系阻燃剂；
和/或，所述化学发泡剂为水；
和/或，所述物理发泡剂包括甲酸甲酯。
在第一方面的一种实施方式中，所述第一聚醚多元醇为句容宁武新材料股份有限公司生产的聚醚多元醇NJ-6249；
和/或，所述第二聚醚多元醇为句容宁武新材料股份有限公司生产的聚醚多元醇NJ-8332和/或上海高桥石油化工公司生产的聚醚多元醇GSU-450L；
和/或，所述聚酯多元醇为南京金陵斯泰潘化学有限公司生产的聚酯多元醇PS-2412；
和/或，所述第一催化剂为空气化工产品公司生产的Polycat 9；
和/或，所述第二催化剂为空气化工产品公司生产的Dabco K15和/或Polycat46；
和/或，所述第三催化剂为空气化工产品公司生产的Dabco TMR-4；
和/或，所述泡沫稳定剂为赢创特种化学(上海)有限公司生产的B8462和/或江苏美思德化学股份有限公司生产的AK-8808；
和/或，所述阻燃剂为磷酸三(2-氯丙基)酯和/或乙基磷酸二乙酯；
和/或，所述水包括去离子水。
在第二方面中，本申请提供一种聚异氰脲酸酯板材用保温材料，所述聚异氰脲酸酯板材用保温材料由第一组分和第二组分制成，其中第一组分由如第一方面所述的阻燃组合聚醚的原料组分混合而成；第二组分为多亚甲基多苯基多异氰酸酯。
在第二方面的一种实施方式中，所述第二组分为烟台万华聚氨酯股份有限公司生产的PM200、PM400；拜耳公司生产的44V20，巴斯夫股份公司生产的M20S中的一种或几种。
在第二方面的一种实施方式中，所述第一组分和第二组分的重量比例为1:1.05-1.4。
在第二方面的一种实施方式中，当根据国家标准《GB/T 8624-2012建筑材料及制品燃烧性能分级》进行测试时，所述聚异氰脲酸酯板材用保温材料的阻燃性能达到B2级。
在第三方面中，本申请提供一种制备如第二方面所述的聚异氰脲酸酯板材用保温材料的方法，所述方法包括混合预定重量比例的第一组分和第二组分，恒温发泡后得到所述聚异氰脲酸酯板材用保温材料。
在第二方面的一种实施方式中，恒温发泡的发泡温度为40℃-45℃。
与现有技术相比，本申请的有益效果在于解决了甲酸甲酯在聚异氰脲酸酯板材用组合聚醚体系中出现的水解情况，保质时间可以提高到90天以上，同时，生产出来的泡沫制品没有收缩、变形等情况发生，有助于甲酸甲酯在聚异氰脲酸酯板材用组合聚醚体系中的推广，其安全性及物理性能要优于戊烷体系，综合成本比HFC类及HFO类发泡剂低得多，ODP、GWP、VOC值均为零，环保性在所有发泡剂中也是最佳的。
具体实施方式
除非另有说明、从上下文暗示或属于现有技术的惯例，否则本申请中所有的份数和百分比都基于重量，且所用的测试和表征方法都是与本申请的提交日期同步的。在适用的情况下，本申请中涉及的任何专利、专利申请或公开的内容全部结合于此作为参考，且其等价的同族专利也引入作为参考，特别这些文献所披露的关于本领域中的合成技术、产物和加工设计、聚合物、共聚单体、引发剂或催化剂等的定义。如果现有技术中披露的具体术语的定义与本申请中提供的任何定义不一致， 则以本申请中提供的术语定义为准。
本申请中的数字范围是近似值，因此除非另有说明，否则其可包括范围以外的数值。数值范围包括以1个单位增加的从下限值到上限值的所有数值，条件是在任意较低值与任意较高值之间存在至少2个单位的间隔。例如，如果记载组分、物理或其它性质(如分子量，熔体指数等)是100至1000，意味着明确列举了所有的单个数值，例如100，101,102等，以及所有的子范围，例如100到166,155到170,198到200等。对于包含小于1的数值或者包含大于1的分数(例如1.1，1.5等)的范围，则适当地将1个单位看作0.0001，0.001，0.01或者0.1。对于包含小于10(例如1到5)的个位数的范围，通常将1个单位看作0.1。这些仅仅是想要表达的内容的具体示例，并且所列举的最低值与最高值之间的数值的所有可能的组合都被认为清楚记载在本申请中。还应指出，本文中的术语“第一”、“第二”等不限定先后顺序，只是为了区分不同结构的物质。
关于化学化合物使用时，除非明确地说明，否则单数包括所有的异构形式，反之亦然(例如，“己烷”单独地或共同地包括己烷的全部异构体)。另外，除非明确地说明，否则用“一个”，“一种”或“该”形容的名词也包括其复数形式。
术语“包含”，“包括”，“具有”以及它们的派生词不排除任何其它的组分、步骤或过程的存在，且与这些其它的组分、步骤或过程是否在本申请中披露无关。为消除任何疑问，除非明确说明，否则本申请中所有使用术语“包含”，“包括”，或“具有”的组合物可以包含任何附加的添加剂、辅料或化合物。相反，除了对操作性能所必要的那些，术语“基本上由……组成”将任何其他组分、步骤或过程排除在任何该术语下文叙述的范围之外。术语“由……组成”不包括未具体描述或列出的任何组分、步骤或过程。除非明确说明，否则术语“或”指列出的单独成员或其任何组合。
在一种具体实施方式中，本申请提供一种阻燃组合聚醚。
本申请的阻燃组合聚醚由以下成分构成，所述份数为质量份数，第一聚醚多元醇、第二聚醚多元醇和聚酯多元醇的总和为100份：
Figure PCTCN2019111116-appb-000003
Figure PCTCN2019111116-appb-000004
在一种具体实施方式中，本申请的阻燃组合聚醚包括第聚醚多元醇。适用于本申请之目的的聚醚多元醇包括但不限于通过使环氧化物(如环氧乙烷、环氧丙烷、环氧丁烷或四氢呋喃)在多官能度引发剂存在进行聚合而获得的产物。适合的引发剂含有多个活性氢原子，其具体示例包括水、丁二醇、乙二醇、丙二醇、二乙二醇、三乙二醇、二丙二醇、乙醇胺、二乙醇胺、三乙醇胺、甲苯二胺、二乙基甲苯二胺、苯胺、二苯基甲烷二胺、乙二胺、环己烷二胺、环己烷二甲醇、间苯二酚、双酚A、甘油、三羟甲基丙烷、1,2,6-己三醇、季戊四醇或它们的组合。
在一种具体实施方式中，所述第一聚醚多元醇优选地为以山梨醇为起始剂的聚氧化丙烯醇，其官能度为5-6，羟值465～515mgKOH/g，粘度17000～23000mPa·s，其典型型号为句容宁武新材料股份有限公司的聚醚多元醇NJ-6249。
在一种具体实施方式中，所述第二聚醚多元醇为以蔗糖为起始剂的聚氧化丙烯醇，其官能度为4.5-5，羟值415～455mgKOH/g，粘度5400～8000mPa·s，其典型型号为句容宁武新材料股份有限公司的聚醚多元醇NJ-8332和/或上海高桥石油化工公司的聚醚多元醇GSU-450L。
在一种具体实施方式中，本申请的阻燃组合聚醚还包括带有阻燃结构的芳香族聚酯多元醇。芳香族聚酯多元醇指含有苯环的聚酯多元醇，通常以芳香族二元酸(或酸酐、酯)与二元醇(和/或多元醇)为原料合成的聚酯多元醇。聚酯的原料一般是邻苯二甲酸酐或对苯二甲酸等，常用的二元醇原料是一缩二乙二醇、三元醇等。
在一种具体实施方式中，本申请所述聚酯多元醇为一种带有阻燃结构的聚酯多元醇，其官能度为2-2.5，羟值230～250mgKOH/g，粘度2000～4500mPa·s，其典型型号为南京金陵斯泰潘化学有限公司的聚酯多元醇PS-2412。
本申请的阻燃组合聚醚还包括表面活性剂，表面活性剂通常支持发泡剂和多 元醇的均匀化，且调节聚异氰脲酸酯泡沫的孔结构。表面活性剂可包括本领域中已知的任何合适的表面活性剂或者表面活性剂的混合物。
在一种具体实施方式中，本申请的表面活性剂包括泡沫稳定剂。本申请所述泡沫稳定剂为硅氧烷类泡沫稳定剂，优选为赢创特种化学(上海)有限公司的B8462和/或江苏美思德化学股份有限公司的AK-8808。
在一种具体实施方式中，本文所述的阻燃组合聚醚还包括催化剂组合物。催化剂通常用于催化异氰酸酯和多元醇之间的反应，且在反应中不被消耗。在一种具体实施方式中，本申请的阻燃组合聚醚包括至少第一催化剂、第二催化剂和第三催化剂。本发明所述第一催化剂为聚氨酯领域常用的胺类催化剂，本发明优选Polycat 9(空气化工产品公司生产)。本发明所述第二催化剂为聚氨酯常用的金属类催化剂，本发明优选Dabco K15(空气化工产品公司生产)和/或Polycat 46(空气化工产品公司生产)。本发明所述第三催化剂为聚氨酯常用的三聚类催化剂，本发明优选Dabco TMR-4(空气化工产品公司生产)。
在一种具体实施方式中，本申请的阻燃组合聚醚还包括阻燃剂。本申请所述阻燃剂为聚氨酯常用的氯系阻燃剂和/或磷系阻燃剂，优选为磷酸三(2-氯丙基)酯(TCPP)和/或乙基磷酸二乙酯(DEEP)。
在一种具体实施方式中，本申请的阻燃组合聚醚还包括添加剂。所述添加剂可用作溶剂，用于溶解甲酸甲酯，且抑制甲酸甲酯的水解。在一种具体实施方式中，本文所述的添加剂为脂肪族酮，其包括但不限于丁酮、戊酮、新戊酮、环己酮等。在一种特别优选地实施方式中，本申请所述的添加剂为丁酮。
在一种具体实施方式中，本申请的阻燃组合聚醚还可任选地包括其他常规添加剂，所述常规添加剂包括但不限于扩链剂、链终止剂、加工助剂、粘合促进剂、抗氧化剂、消泡剂、除水剂、分子筛、紫外光稳定剂、填料、触变剂、着色剂、惰性稀释剂或者它们的组合。
本申请所述的阻燃组合聚醚还可包括化学发泡剂和物理发泡剂。在本文中，术语“物理发泡剂”指不会与异氰酸酯或者多元醇发生化学反应的发泡剂。物理发泡剂可以是气体或液体。液体物理发泡剂通常在加热时蒸发成气体，且通常在冷却时恢复成液体。在一种具体实施方式中，本申请所述物理发泡剂为甲酸甲酯。
在本文中，术语“化学发泡剂”指与异氰酸酯、多元醇或其它组分发生化学反应且释放用于发泡的气体的发泡剂。在一种具体实施方式中，本文所述的化学发 泡剂包括水，特别是去离子水。
本申请还提供一种聚异氰脲酸酯板材用保温材料，该聚异氰脲酸酯板材用保温材料由第一组分和第二组分以一定比例经过机械搅拌混合后，通过一系列的化学反应而合成。第一组分通过如上所述的阻燃组合聚醚的原料组分混合而成。第一组分由一定比例的聚醚多元醇、聚酯多元醇、表面活性剂、催化剂、添加剂、发泡剂等经过机械混合而组成；第二组分为多亚甲基多苯基多异氰酸酯(PAPI)。
本申请所述多亚甲基多苯基多异氰酸酯为聚氨酯领域常用的多亚甲基多苯基多异氰酸酯，如烟台万华聚氨酯股份有限公司生产的PM200、PM400，拜耳公司的44V20，巴斯夫股份公司的M20S等。本申请优选烟台万华聚氨酯股份有限公司生产的PM400。
本申请所述第一组分和第二组分的重量比例为1：1.05-1.4。
本申请还提供一种制备如第二方面所述的聚异氰脲酸酯板材用保温材料的方法，所述方法包括混合预定重量比例的第一组分和第二组分，恒温发泡后得到所述聚异氰脲酸酯板材用保温材料。
实施例
下面将结合本申请的实施例，对本申请的技术方案进行清楚和完整的描述。如无特别说明，所用的试剂和原材料都可通过商业途径购买。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
实施例1-4和对比例1-2
首先，按照下表中的成分制备实施例1-4和对比例1-2的第一组分，表1所示的份数均为质量份数。
表1.实施例1-4和对比例1-2的第一组分配方
原料名称 实施例1 实施例2 实施例3 实施例4 对比例1 对比例2
NJ-6249 25 10 20 15 20 25
NJ-8332 35 - 20 - 20 30
GSU-450L - 40 - 25 - -
PS-2412 40 50 60 60 60 45
B8462 2 - 1.5 3 1.5 1
AK-8808 1 2.5 1.5 - 1.5 2
Polycat 9 0.6 0.3 0.1 0.5 0.1 0.3
Dabco K15 - - 1.0 0.8 1.0 -
Polycat 46 0.3 0.5 - - - 0.6
Dabco TMR-4 1.5 1.0 0.6 1.2 0.6 1.1
TCPP 15 5 10 30 10 15
DEEP 10 10 10 - 10 10
丁酮 2.0 2.4 3.2 3.0 - -
去离子水 2.3 1.5 1.8 2.0 1.8 1.5
甲酸甲酯 10 12 16 15 16 -
环戊烷 - - - - - 15
PAPI 151.935 162.24 203.98 194.375 199.5 190.45
将上表所述除PAPI外的其它原料按照规定比例倒入反应容器中，利用电动搅拌器混合均匀，制成第一组分；再将第一组分与第二组分的温度调节至22℃，按照相应的重量比例倒入反应容器中，然后利用电动搅拌器搅拌10-12秒钟，将混合均匀后的液体倒入恒温40-45℃的厚度10cm模具中，关好模具，在恒温45℃条件下放置20min后打开模具，可得本申请所述聚异氰脲酸酯板材用保温泡沫。
对实施例1-4和对比例1-2所得材料进行性能测试，所得结果见下文的表2。
性能测试标准：
乳白时间、凝胶时间、脱粘时间：使用秒表目测；
自由泡密度、模塑泡密度：GB/T 6343-95聚氨酯泡沫塑料的密度测试；
压缩强度：GB/T 8813-2008硬质泡沫塑料压缩性能的测定；
导热系数：GB/T 10295-2008绝热材料稳态热阻及有关特性的测定热流计法
尺寸稳定性：GB/T 6342-1996泡沫塑料与橡胶线性尺寸的测定；
阻燃性能：GB/T 8624-2012建筑材料及制品燃烧性能分级。
表2.实施例1-4及对比例1-2性能测试结果
Figure PCTCN2019111116-appb-000005
从表2可知，本发明所得阻燃组合聚醚放置30天后，反应时间及自由泡密度均没有太大的变化，可以长期储存使用，且制成泡沫制品后低温放置180天后体积变化率很小，保证了制品长期的性能。在和目前市场主流的环戊烷发泡体系进行对比，也发现其压缩强度、导热系数、尺寸稳定性等物理性能均优于环戊烷体系，再加上其安全性更高，具有大规模推广的价值。本发明所使用原料均为市面上所售原料，原料来源广泛，可进行大规模生产。
上述对实施例的描述是为了便于本技术领域的普通技术人员能理解和应用本申请。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其它实施例中而不必付出创造性的劳动。因此，本申请不限于这里的实施例，本领域技术人员根据本申请披露的内容，在不脱离本申请范围和精神的情况下做出的改进和修改都本申请的范围之内。

Claims (11)

  1. 一种阻燃组合聚醚，以重量份数为基准计，其由下述原料组分制成：
    Figure PCTCN2019111116-appb-100001
    其中第一聚醚多元醇、第二聚醚多元醇和聚酯多元醇用量之和为100份；
    其中所述聚酯多元醇为带有阻燃结构的芳香族聚酯多元醇；
    其中所述添加剂包括脂肪族酮。
  2. 如权利要求1所述的阻燃组合聚醚，其特征在于，所述添加剂为丁酮。
  3. 如权利要求1所述的阻燃组合聚醚，其特征在于，所述聚醚多元醇为以山梨醇为起始剂的聚氧化丙烯醇，其官能度为5-6，羟值465～515mgKOH/g，粘度17000～23000mPa·s；
    和/或，所述第二聚醚多元醇为蔗糖为起始剂的聚氧化丙烯醇，其官能度为4.5-5，羟值415～455mgKOH/g，粘度5400～8000mPa·s；
    和/或，所述聚酯多元醇为带有阻燃结构的聚酯多元醇，其官能度为2-2.5，羟值230～250mgKOH/g，粘度2000～4500mPa·s。
  4. 如权利要求1所述的阻燃组合聚醚，其特征在于，所述表面活性剂包括泡 沫稳定剂；
    和/或，所述第一催化剂为胺类催化剂；
    和/或，所述第二催化剂为金属类催化剂；
    和/或，所述第三催化剂为三聚类催化剂；
    和/或，所述阻燃剂为聚氨酯常用的氯系阻燃剂和/或磷系阻燃剂；
    和/或，所述化学发泡剂为水；
    和/或，所述物理发泡剂包括甲酸甲酯。
  5. 如权利要求4所述的阻燃组合聚醚，其特征在于，所述第一聚醚多元醇为句容宁武新材料股份有限公司生产的聚醚多元醇NJ-6249；
    和/或，所述第二聚醚多元醇为句容宁武新材料股份有限公司生产的聚醚多元醇NJ-8332和/或上海高桥石油化工公司生产的聚醚多元醇GSU-450L；
    和/或，所述聚酯多元醇为南京金陵斯泰潘化学有限公司生产的聚酯多元醇PS-2412；
    和/或，所述第一催化剂为空气化工产品公司生产的Polycat 9；
    和/或，所述第二催化剂为空气化工产品公司生产的Dabco K15和/或Polycat46；
    和/或，所述第三催化剂为空气化工产品公司生产的Dabco TMR-4；
    和/或，所述泡沫稳定剂为赢创特种化学(上海)有限公司生产的B8462和/或江苏美思德化学股份有限公司生产的AK-8808；
    和/或，所述阻燃剂为磷酸三(2-氯丙基)酯和/或乙基磷酸二乙酯；
    和/或，所述水包括去离子水。
  6. 一种聚异氰脲酸酯板材用保温材料，所述聚异氰脲酸酯板材用保温材料由第一组分和第二组分制成，其中第一组分由如权利要求1-5中任一项所述的阻燃组合聚醚的原料组分混合而成；第二组分为多亚甲基多苯基多异氰酸酯。
  7. 如权利要求6所述的聚异氰脲酸酯板材用保温材料，其特征在于，所述第二组分为烟台万华聚氨酯股份有限公司生产的PM200、PM400；拜耳公司生产的44V20，巴斯夫股份公司生产的M20S中的一种或几种。
  8. 如权利要求6所述的聚异氰脲酸酯板材用保温材料，其特征在于，所述第一组分和第二组分的重量比例为1:1.05-1.4。
  9. 如权利要求6所述的聚异氰脲酸酯板材用保温材料，其特征在于，当根据国家标准《GB/T 8624-2012建筑材料及制品燃烧性能分级》进行测试时，所述聚异氰脲酸酯板材用保温材料的阻燃性能达到B2级。
  10. 一种制备如权利要求6所述的聚异氰脲酸酯板材用保温材料的方法，所述方法包括混合预定重量比例的第一组分和第二组分，恒温发泡后得到所述聚异氰脲酸酯板材用保温材料。
  11. 如权利要求10所述的制备聚异氰脲酸酯板材用保温材料的方法，其特征在于，恒温发泡的发泡温度为40℃-45℃。
PCT/CN2019/111116 2018-10-16 2019-10-15 一种阻燃组合聚醚、聚异氰脲酸酯板材用保温材料及其制备方法 WO2020078329A1 (zh)

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