WO2018023860A1 - 异氰脲酸酯聚醚多元醇及其制备方法和涂料固化剂的制备方法 - Google Patents

异氰脲酸酯聚醚多元醇及其制备方法和涂料固化剂的制备方法 Download PDF

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WO2018023860A1
WO2018023860A1 PCT/CN2016/099461 CN2016099461W WO2018023860A1 WO 2018023860 A1 WO2018023860 A1 WO 2018023860A1 CN 2016099461 W CN2016099461 W CN 2016099461W WO 2018023860 A1 WO2018023860 A1 WO 2018023860A1
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isocyanurate
polyether polyol
curing agent
coating curing
added
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PCT/CN2016/099461
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English (en)
French (fr)
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孙兆任
李剑锋
周玉波
王玉
杨凯
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山东一诺威新材料有限公司
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Publication of WO2018023860A1 publication Critical patent/WO2018023860A1/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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds 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
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the invention relates to an isocyanurate polyether polyol, a preparation method thereof and a preparation method of a coating curing agent, and belongs to the technical field of polyether polyol and polyurethane synthesis.
  • polyurethane curing agents commonly used in the market include polyurethane prepolymer curing agents and trimer curing agents.
  • Polyurethane prepolymer curing agents are mostly prepared by using a prepolymer solution of trimethylolpropane (TMP) and toluene diisocyanate (TDI) in a solvent.
  • TMP trimethylolpropane
  • TDI toluene diisocyanate
  • the trimer curing agent is produced by the polymerization of a trimeric isocyanate under the action of a trimerization catalyst to form an isocyanurate ring structure, and then a polymerization inhibitor is added to lose the catalytic activity of the trimerization catalyst poisoning, and the production process is complicated. The quality of the product is not easy to control.
  • the trimerization reaction requires a special catalyst, and different isocyanates are used to prepare the trimer curing agent, and the polymerization yield control is also different; the polymerization product contains a large amount of free monomers, which needs to be removed, the equipment investment is huge, and the production cost is high. high.
  • the pure TDI trimer curing agent coating film has poor toughness, and it is often necessary to modify it with a polyether.
  • the special HDI trimer curing agent when the HDI monomer is only reacted to 21% of the total monomer mass during the production process, it is necessary to separate a large amount of monomers of unreacted monomers by a process such as thin film evaporation.
  • trimer curing agents on the market mainly include TDI trimers, HDI trimers, IPDI trimers, TDI and HDI mixed trimers, TDI and MDI mixed trimers, and the like.
  • the polyurethane prepolymer curing agent has a simple production process and good production controllability; the trimer curing agent has excellent mechanical properties due to the isocyanurate ring structure contained in the molecule, but the production process is complicated.
  • a polyether polyol containing an isocyanurate ring is prepared, a trimer-like coating curing agent can be prepared by a synthetic route of the polyurethane prepolymer, which can obtain a similar chemical structure of the trimer coating curing agent, and It can simplify the production process, improve efficiency and yield, reduce cost, safety and environmental protection.
  • the polyether modification of trimer improves the compatibility of curing agent and resin, reduces the brittleness of coating and improves flexibility. Sex. In this way, through the solution of raw material production and the simultaneous improvement of the synthetic process, the simple production of high-end paint curing agent is realized, which has great social and economic value.
  • the object of the present invention is to provide an isocyanurate polyether polyol which can be prepared by using a simple polyurethane prepolymer synthesis route with any polyisocyanate to prepare a similar three-containing isocyanurate structure.
  • the coating curing agent of the polymer curing agent is simple, efficient, safe and environmentally friendly; the invention also provides a preparation method thereof and a preparation method of the coating curing agent.
  • the isocyanurate polyether polyol of the present invention uses trishydroxyethyl isocyanurate as a starting agent to form an alkylene oxide by coordination polymerization under the action of a double metal cyanide complex catalyst The ring-opening polymerization of the compound gives an isocyanurate polyether polyol.
  • the pretreatment method is: after the mixture of trishydroxyethyl isocyanurate and distilled water is mixed at a mass ratio of 1:0.5-1, acetone is added in an amount of 10 to 100% by weight of trishydroxyethyl isocyanurate and distilled water, and stirred. Uniformly, add phosphoric acid containing 0.001 to 0.005% of total mass of trishydroxyethyl isocyanurate, distilled water and acetone, stir well, recycle by filtration, remove water and acetone under vacuum, and dry to a moisture content of ⁇ 0.05 wt.%.
  • the double metal cyanide complex catalyst is one or both of a solid powder catalyst or an emulsion catalyst in an amount of 0.002% to 0.05% by weight of the sum of both the initiator and the alkylene oxide compound.
  • the isocyanurate polyether polyol obtained by the present invention has a hydroxyl value of 56 to 445 mgKOH/g.
  • the alkylene oxide compound is one or more of propylene oxide, ethylene oxide or butylene oxide, and the resulting polyether polyol is capped with propylene oxide or butylene oxide.
  • the preparation method of the isocyanurate polyether polyol is as follows: firstly pretreating the initiator trishydroxyethyl isocyanurate, and then treating the treated trishydroxyethyl isocyanurate
  • the acid ester and double metal cyanide complex catalyst are added to the pressure resistant reactor, the temperature is raised to 130 ° C ⁇ 2 ° C, the vacuum is evacuated to -0.095 MPa, nitrogen is bubbled for 1 h; then the ring of 10-20% by weight of the starter is added.
  • the oxane compound is subjected to an initiation reaction. When the pressure of the reactor is lowered to 0.01 MPa, the continuous alkylene oxide compound is continuously added dropwise for continuous polymerization. After the reaction is completed, the monomer is evacuated for 1 hour, and the isocyanurate polyether is sampled and detected.
  • the hydroxyl value of the alcohol is OHv, and the temperature is lowered and stored.
  • the method for preparing a coating curing agent for the isocyanurate polyether polyol is to first react an isocyanurate polyether polyol and an isocyanate in an organic solvent at a molar ratio of 1:3 to obtain -
  • the NCO group-terminated polyurethane prepolymer is then added to a polymerization inhibitor to obtain a coating curing agent having an isocyanurate ring structure.
  • the isocyanate is toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (pure MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), methyl ring
  • TDI toluene diisocyanate
  • pure MDI 4,4-diphenylmethane diisocyanate
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • HMDI dicyclohexylmethane diisocyanate
  • the organic solvent is selected from some low-toxic or non-toxic ester solvents: ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, ethylene glycol ethyl acetate or propylene glycol methyl ether acetate.
  • One or more mixtures preferably one or both of ethyl acetate and butyl acetate; the amount of polyamine obtained by reacting isocyanurate polyether polyol and isocyanate
  • the ester prepolymer has a mass of 25 to 100%.
  • the polymerization inhibitor is phosphoric acid, sulfuric acid or benzoyl chloride; preferably phosphoric acid or benzoyl chloride; the amount is 0.002 to 0.008% of the total mass of the curing agent.
  • the method for the coating curing agent specifically comprises the steps of: introducing an organic solvent and an isocyanate into a reaction vessel, protecting with nitrogen and stirring the temperature to 40 to 45 ° C in 10 minutes, continuously adding isocyanurate polyether polyol, feeding After the temperature is stabilized, the temperature is raised to 65-70 ° C in 30 min, the heat preservation reaction is 1.5 ⁇ 4 h, then the temperature is raised to 80-85 ° C in 20 min, the heat preservation reaction is 1-3 h, and the -NCO content is sampled and detected. When the -NCO content reaches the set After the value, the polymerization inhibitor was added, stirred for 30 min, cooled to 50 ° C to discharge, and sealed with nitrogen.
  • the polyether contains an isocyanurate ring structure, which imparts excellent heat resistance, structural stability and flame retardancy to the polyether.
  • the curing agent is introduced into the isocyanurate ring structure through the polyether end, instead of being introduced by the trimerization reaction of the isocyanate, the production process is simple, easy to control, high in yield, low in cost, and safe and environmentally friendly.
  • the polyether segment structure is introduced during the synthesis of the curing agent, which avoids the complicated steps of modifying the trimer curing agent specifically by polyether, and has good compatibility with the resin.
  • It can be prepared by reacting various isocyanates such as IPDI, HDI, HTDI, HMDI or a part of TDI and MDI mixture to prepare various types of coating curing agents, and has wide applicability.
  • 395 g of trishydroxyethyl isocyanurate was added to a 2 L autoclave at room temperature, 300 g of distilled water was added, stirred and dissolved, and then 300 g of acetone solution was stirred. Then, 0.03 g of 85 wt.% phosphoric acid was added dropwise, and the temperature was raised to 100 ° C, stirring evenly and circulating filtration, then vacuuming off water and acetone, drying to a moisture content of 0.05wt.%; adding 0.05g of solid powder DMC catalyst under nitrogen atmosphere, gradually heating to 130 ⁇ 2 ° C, vacuuming to -0.095MPa, nitrogen bubbling for 1h; 40g of propylene oxide was added to initiate the reaction.
  • HDI hexamethylene diisocyanate
  • HDI hexamethylene diisocyanate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

提供一种异氰脲酸酯聚醚多元醇及其制备方法和涂料固化剂的制备方法。异氰脲酸酯聚醚多元醇是以三羟乙基异氰脲酸酯作为起始剂，在双金属氰化物络合催化剂的作用下，通过配位聚合使环氧烷烃化合物开环聚合得到。异氰脲酸酯聚醚多元醇与异氰酸酯按照摩尔比1:3的比例在有机溶剂中进行预聚体反应制备具有异氰脲酸酯环结构的聚醚改性类三聚体涂料固化剂。该聚醚多元醇及涂料固化剂生产工艺简单，产品收率高，成本低，安全环保。

Description

异氰脲酸酯聚醚多元醇及其制备方法和涂料固化剂的制备方法 技术领域
本发明涉及一种异氰脲酸酯聚醚多元醇及其制备方法和涂料固化剂的制备方法，属于聚醚多元醇及聚氨酯合成技术领域。
背景技术
目前，市场上常用的聚氨酯涂料固化剂包括聚氨酯预聚体固化剂和三聚体固化剂两大类。聚氨酯预聚体固化剂多是采用三羟甲基丙烷(TMP)与甲苯二异氰酸酯(TDI)在溶剂中反应生成的预聚体溶液制备而成。三聚体固化剂的生产是在三聚催化剂的作用下，三分子异氰酸酯发生聚合反应，生成异氰脲酸酯环结构，然后再加入阻聚剂使三聚催化剂中毒失去催化活性，生产工艺复杂，产品质量不易控制。而且三聚反应需要有专用的催化剂，采用不同的异氰酸酯制备三聚体固化剂，聚合产率控制也不同；聚合产物中含有大量的游离单体，需要进行脱除处理，设备投资巨大，生产成本高。另外，纯TDI三聚体固化剂涂膜韧性差，常需要利用聚醚对其进行改性处理。而对于特种的HDI三聚体固化剂，生产过程中HDI单体只反应到总单体质量的21％时，就需要通过薄膜蒸发等工艺把大量未反应单体的单体分离，产品收率低，单体损失大，产品成本高，只有一些高档领域才会用到此类固化剂。目前市面上的三聚体固化剂主要有TDI三聚体，HDI三聚体、IPDI三聚体、TDI和HDI混合三聚体、TDI和MDI混合三聚体等。
不难发现，聚氨酯预聚体固化剂生产工艺简单，生产操控性好；三聚体固化剂由于分子中含有异氰脲酸酯环结构而具有优异的力学性能，但是生产工艺复杂。如果制备出含有异氰脲酸酯环的聚醚多元醇，通过聚氨酯预聚体的合成路线制备类三聚体结构的涂料固化剂，既可以得到三聚体涂料固化剂类似的化学结构，又可以简化生产工艺制造流程，提高效率和收率，降低成本，安全环保；同时又对三聚体进行了聚醚改性，提高了固化剂与树脂的相容性，降低涂料的脆性，提高柔韧性。如此通过原料生产的解决和合成工艺的同步改进，实现高端涂料固化剂的简单化生产，具有极大的社会和经济价值。
目前，国内外还未发现含有异氰脲酸酯环的聚醚多元醇以及以异氰脲酸酯聚醚多元醇为原料制备的涂料固化剂的相关报道。
发明内容
本发明的目的是提供一种异氰脲酸酯聚醚多元醇，采用该聚醚多元醇可与任何异氰酸酯通过简单的聚氨酯预聚体合成技术路线来制备含有异氰脲酸酯结构的类似三聚体固化剂的涂料固化剂，简单高效，安全环保；本发明同时提供其制备方法以及涂料固化剂的制备方法。
本发明所述的异氰脲酸酯聚醚多元醇，以三羟乙基异氰脲酸酯作为起始剂，在双金属氰化物络合催化剂的作用下，通过配位聚合使环氧烷烃化合物开环聚合得到异氰脲酸酯聚醚多元醇。
其中：
先对三羟乙基异氰脲酸酯进行预处理，再在双金属氰化物络合催化剂的作用下，通过配位聚合使环氧烷烃化合物开环聚合；
预处理方法为：三羟乙基异氰脲酸酯与蒸馏水按照质量比1:0.5～1混合后，加入占三羟乙基异氰脲酸酯和蒸馏水总质量10～100％的丙酮，搅拌均匀，加入占三羟乙基异氰脲酸酯、蒸馏水和丙酮总质量0.001～0.005％的磷酸，搅拌均匀，循环过滤，真空脱出水分和丙酮，干燥至水分≤0.05wt.％使用。
所述的双金属氰化物络合催化剂为固体粉末状催化剂或乳液状催化剂中的一种或两种，用量为起始剂和环氧烷烃化合物两者重量之和的0.002～0.05％。
本发明得到的异氰脲酸酯聚醚多元醇羟值为56～445mgKOH/g。
所述的环氧烷烃化合物为环氧丙烷、环氧乙烷或环氧丁烷中的一种或一种以上的混合物，得到的聚醚多元醇以环氧丙烷或环氧丁烷封端。
所述的异氰脲酸酯聚醚多元醇的制备方法，具体步骤如下：首先对起始剂三羟乙基异氰脲酸酯进行预处理，然后将处理后的三羟乙基异氰脲酸酯和双金属氰化物络合催化剂加入到耐压反应釜中，升温至130℃±2℃，抽真空至-0.095MPa，氮气鼓泡1h；然后加入起始剂重量10～20％的环氧烷烃化合物进行引发反应，待反应釜压力下降至0.01MPa时，开始连续滴加剩余环氧烷烃化合物进行连续聚合，反应结束后抽真空脱单体1h，取样检测异氰脲酸酯聚醚多元醇羟值OHv，降温出料保存。
所述的异氰脲酸酯聚醚多元醇制备涂料固化剂的方法，是先将异氰脲酸酯聚醚多元醇与异氰酸酯按照摩尔比1:3的比例在有机溶剂中反应，得到以-NCO基团封端的聚氨酯预聚物，然后加入阻聚剂，得到具有异氰脲酸酯环结构的涂料固化剂。
其中：
所述的异氰酸酯为甲苯二异氰酸酯(TDI)、4,4-二苯基甲烷二异氰酸酯(纯MDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、甲基环己基二异氰酸酯(HTDI)或二环己基甲烷二异氰酸酯(HMDI)中的一种或一种以上的混合物。
所述的有机溶剂选自一些低毒或无毒的酯类溶剂：乙酸乙酯、乙酸丁酯、醋酸异丙酯、醋酸异丁酯、乙二醇乙醚醋酸酯或丙二醇甲醚醋酸酯中的一种或一种以上的混合物；优选乙酸乙酯、乙酸丁酯中的一种或两种；用量为异氰脲酸酯聚醚多元醇和异氰酸酯反应所得聚氨 酯预聚物质量的25～100％。
所述的阻聚剂为磷酸、硫酸或苯甲酰氯；优选磷酸或苯甲酰氯；用量为固化剂总质量的0.002～0.008％。
所述涂料固化剂的方法具体包括以下步骤：将有机溶剂和异氰酸酯投入反应釜，充氮气保护并在10min内搅拌升温至40～45℃，连续滴加异氰脲酸酯聚醚多元醇，加料完毕待温度稳定之后，30min内升温至65～70℃，保温反应1.5～4h，然后20min内升温至80～85℃，保温反应1～3h，取样检测-NCO含量，当-NCO含量达到设定值后，加入阻聚剂，搅拌30min，降温至50℃出料，氮气密封保存。
本发明具有以下有益效果：
(1)聚醚中含有异氰脲酸酯环结构，赋予聚醚优异的耐热性、结构稳定性和阻燃性等特点。
(2)固化剂通过聚醚端引入异氰脲酸酯环结构，而非通过异氰酸酯的三聚反应引入，生产工艺简单，易控制，收率高，成本低，安全环保性好。
(3)固化剂合成过程中就引入了聚醚链段结构，避免了三聚体固化剂专门采用聚醚进行改性的繁琐步骤，与树脂的相容性好。
(4)可以与IPDI、HDI、HTDI、HMDI或部分TDI、MDI混合物等各种异氰酸酯反应制备各种类型的涂料固化剂，适用性广。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
室温下于2L高压反应釜中加入790g三羟乙基异氰脲酸酯，加入790g的蒸馏水，搅拌溶解，然后300g丙酮溶液，搅拌均匀后滴入0.05g的85wt.％浓度的磷酸，升温至100℃，搅拌均匀并循环过滤，然后抽真空脱出水分和丙酮，干燥至水分为0.04wt.％；氮气保护环境下加入0.15g的固体粉末DMC催化剂，逐步升温至130±2℃，抽真空至-0.095MPa，氮气鼓泡1h；加入80g的环氧丙烷进行引发反应，待反应釜压力下降至0.01MPa时开始连续滴加剩余634g环氧丙烷进行连续聚合，反应结束后抽真空脱单体1h，取样检测OHv＝335.9mgKOH/g，降温至90℃出料保存，得到异氰脲酸酯聚醚多元醇A。
将550g甲苯二异氰酸酯(TDI)和284g乙酸乙酯加入到反应釜中，充氮气保护，开动加热和搅拌，10min内升温至45℃，连续滴加500g聚醚多元醇A，加料完毕待温度稳定之后，30min内缓慢升温至68℃，保温反应2h，然后20min内升温至83℃保温反应2h，取样检测-NCO含量，-NCO％＝10.5，停止反应，加入0.065g磷酸，搅拌30min，降温至50℃出料， 氮气密封保存，得到TDI型涂料固化剂。
实施例2
室温下于2L高压反应釜中加入395g三羟乙基异氰脲酸酯，加入300g的蒸馏水，搅拌溶解，然后300g丙酮溶液，搅拌均匀后滴入0.03g的85wt.％浓度的磷酸，升温至100℃，搅拌均匀并循环过滤，然后抽真空脱出水分和丙酮，干燥至水分为0.05wt.％；氮气保护环境下加入0.05g的固体粉末DMC催化剂，逐步升温至130±2℃，抽真空至-0.095MPa，氮气鼓泡1h；加入40g的环氧丙烷进行引发反应，待反应釜压力下降至0.01MPa时开始连续滴加剩余1067g环氧丙烷进行连续聚合，反应结束后抽真空脱单体1h，取样检测OHv＝168.5mgKOH/g，降温至90℃出料保存，得到异氰脲酸酯聚醚多元醇B。
将750g 4,4-二苯基甲烷二异氰酸酯(纯MDI)和525g乙酸丁酯加入到反应釜中，充氮气保护，开动加热和搅拌，10min内升温至40℃，连续滴加1000g聚醚多元醇B，加料完毕待温度稳定之后，30min内缓慢升温至65℃，保温反应2h，然后20min内升温至80℃保温反应1.5h，取样检测-NCO含量，-NCO％＝5.54，停止反应，加入0.13g磷酸，搅拌30min，降温至50℃出料，氮气密封保存，得到MDI型涂料固化剂。
实施例3
室温下于2L高压反应釜中加入786g三羟乙基异氰脲酸酯，加入700g的蒸馏水，搅拌溶解，然后750g丙酮溶液，搅拌均匀后滴入0.1g的85wt.％浓度的磷酸，升温至100℃，搅拌均匀并循环过滤，然后抽真空脱出水分和丙酮，干燥至水分为0.03wt.％；氮气保护环境下加入0.23g的乳液状DMC催化剂，逐步升温至130±2℃，抽真空至-0.095MPa，氮气鼓泡1h；加入150g的环氧丙烷进行引发反应，待反应釜压力下降至0.01MPa时开始连续滴加剩余204g环氧丙烷进行连续聚合，反应结束后抽真空脱单体1h，取样检测OHv＝445.1mgKOH/g，降温至90℃出料保存，得到异氰脲酸酯聚醚多元醇C。
将505g六亚甲基二异氰酸酯(HDI)和800g醋酸异丁酯加入到反应釜中，充氮气保护，开动加热和搅拌，10min内升温至45℃，连续滴加378g聚醚多元醇C，加料完毕待温度稳定之后，30min内缓慢升温至70℃，保温反应4h，然后20min内升温至85℃保温反应2h，取样检测-NCO含量，-NCO％＝7.52，停止反应，加入0.06g磷酸，搅拌30min，降温至50℃出料，氮气密封保存，得到耐黄变型HDI涂料固化剂。

Claims (10)

  1. 一种异氰脲酸酯聚醚多元醇，其特征在于：以三羟乙基异氰脲酸酯作为起始剂，在双金属氰化物络合催化剂的作用下，通过配位聚合使环氧烷烃化合物开环聚合得到异氰脲酸酯聚醚多元醇。
  2. 根据权利要求1所述的异氰脲酸酯聚醚多元醇，其特征在于：先对三羟乙基异氰脲酸酯进行预处理，再在双金属氰化物络合催化剂的作用下，通过配位聚合使环氧烷烃化合物开环聚合；
    预处理方法为：三羟乙基异氰脲酸酯与蒸馏水按照质量比1:0.5～1混合后，加入占三羟乙基异氰脲酸酯和蒸馏水总质量10～100％的丙酮，搅拌均匀，加入占三羟乙基异氰脲酸酯、蒸馏水和丙酮总质量0.001～0.005％的磷酸，搅拌均匀，循环过滤，真空脱出水分和丙酮，干燥至水分≤0.05wt.％使用。
  3. 根据权利要求1所述的异氰脲酸酯聚醚多元醇，其特征在于：双金属氰化物络合催化剂为固体粉末状催化剂或乳液状催化剂中的一种或两种，用量为起始剂和环氧烷烃化合物两者重量之和的0.002～0.05％；异氰脲酸酯聚醚多元醇羟值为56～445mgKOH/g。
  4. 根据权利要求1所述的异氰脲酸酯聚醚多元醇，其特征在于：环氧烷烃化合物为环氧丙烷、环氧乙烷或环氧丁烷中的一种或一种以上的混合物，得到的聚醚多元醇以环氧丙烷或环氧丁烷封端。
  5. 一种权利要求1～4任一所述的异氰脲酸酯聚醚多元醇的制备方法，其特征在于包括以下步骤：首先对起始剂三羟乙基异氰脲酸酯进行预处理，然后将处理后的三羟乙基异氰脲酸酯和双金属氰化物络合催化剂加入到耐压反应釜中，升温至130℃±2℃，抽真空至-0.095MPa，氮气鼓泡1h；然后加入起始剂重量10～20％的环氧烷烃化合物进行引发反应，待反应釜压力下降至0.01MPa时，开始连续滴加剩余环氧烷烃化合物进行连续聚合，反应结束后抽真空脱单体1h，取样检测异氰脲酸酯聚醚多元醇羟值OHv，降温出料保存。
  6. 一种权利要求1～4任一所述的异氰脲酸酯聚醚多元醇制备涂料固化剂的方法，其特征在于：先将异氰脲酸酯聚醚多元醇与异氰酸酯按照摩尔比1:3的比例在有机溶剂中反应，得到以-NCO基团封端的聚氨酯预聚物，然后加入阻聚剂，得到具有异氰脲酸酯环结构的涂料固化剂。
  7. 根据权利要求6所述的异氰脲酸酯聚醚多元醇制备涂料固化剂的方法，其特征在于：异氰酸酯为甲苯二异氰酸酯、4,4-二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、甲基环己基二异氰酸酯或二环己基甲烷二异氰酸酯中的一种或一种以上的混合物。
  8. 根据权利要求6所述的异氰脲酸酯聚醚多元醇制备涂料固化剂的方法，其特征在于： 有机溶剂为乙酸乙酯、乙酸丁酯、醋酸异丙酯、醋酸异丁酯、乙二醇乙醚醋酸酯或丙二醇甲醚醋酸酯中的一种或一种以上的混合物；优选乙酸乙酯、乙酸丁酯中的一种或两种；用量为异氰脲酸酯聚醚多元醇和异氰酸酯反应所得聚氨酯预聚物质量的25～100％。
  9. 根据权利要求6所述的异氰脲酸酯聚醚多元醇制备涂料固化剂的方法，其特征在于：阻聚剂为磷酸、硫酸或苯甲酰氯；用量为固化剂总质量的0.002～0.008％。
  10. 根据权利要求6所述的异氰脲酸酯聚醚多元醇制备涂料固化剂的方法，其特征在于包括以下步骤：将有机溶剂和异氰酸酯投入反应釜，充氮气保护并在10min内搅拌升温至40～45℃，连续滴加异氰脲酸酯聚醚多元醇，加料完毕待温度稳定之后，30min内升温至65～70℃，保温反应1.5～4h，然后20min内升温至80～85℃，保温反应1～3h，取样检测-NCO含量，当-NCO含量达到设定值后，加入阻聚剂，搅拌30min，降温至50℃出料，氮气密封保存。
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