WO2018023984A1 - 无机杂化多元醇醚化三聚氰胺树脂及其制备方法 - Google Patents

无机杂化多元醇醚化三聚氰胺树脂及其制备方法 Download PDF

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WO2018023984A1
WO2018023984A1 PCT/CN2017/078237 CN2017078237W WO2018023984A1 WO 2018023984 A1 WO2018023984 A1 WO 2018023984A1 CN 2017078237 W CN2017078237 W CN 2017078237W WO 2018023984 A1 WO2018023984 A1 WO 2018023984A1
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inorganic hybrid
melamine resin
polyol
etherified melamine
reaction
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French (fr)
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王洪波
李强
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常州聚博节能科技有限公司
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0016—Foam properties semi-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
    • C08G2110/0025—Foam properties rigid

Definitions

  • the invention belongs to the technical field of inorganic hybrid polymer materials, and particularly relates to an inorganic hybrid polyol etherified melamine resin and a preparation method thereof.
  • amino resins Because amino resins have a certain temperature resistance, they are used in many fields, including the coatings industry, the furniture industry, and the polyurethane industry. However, the application of high flame retardant polyurethane materials has a certain difference in high temperature resistance.
  • the present invention provides an inorganic hybrid polyol etherified melamine resin and a preparation method thereof, which are prepared by reacting hexamethylol melamine with a polyol under an acidic medium.
  • the tetramethyl etherified melamine resin or the pentamethyl etherified melamine resin is reacted with an inorganic hybrid compound to form an inorganic hybrid polyol etherified melamine resin, which has high flame retardancy and high temperature resistance.
  • X in the molecular structure is an inorganic hybrid element, including one of B or Sb;
  • R in the molecular structure is -(CH 2 ) n OH or -(CH 2 ) m O(CH 2 ) m OH or
  • the etherification reaction of hexamethylol melamine and the polyol represented by R in claim 1 is carried out under acidic conditions to obtain a polyol etherified melamine resin, and an alkali neutralization reaction is carried out by adding an alkali under stirring;
  • the etherified melamine resin is reacted with the inorganic hybrid compound at 100 to 110 ° C for 0.5-2 hours, the hybridization reaction is completed, cooled to 60-80 ° C, and the salt is filtered through a filter to obtain an inorganic hybrid polyol. Etherified melamine resin.
  • hexamethylol melamine and the polyol represented by R in claim 1 are added, and the pH is adjusted to 2.5 to 5.5 by adding acid, and the stirring speed is 60 to 80 rpm at 35 to 65 ° C.
  • the etherification reaction is carried out for 30 to 120 minutes to obtain a polyol etherified melamine resin;
  • the residual polyol added in the step (1) is distilled off under the condition of a vacuum degree of 0.090-0.1 MPa and a temperature of 100-130 ° C;
  • the method for preparing an inorganic hybrid polyol etherified melamine resin characterized in that the inorganic hybrid compound in the step (3) is: sodium borate, potassium borate, boric acid, zinc borate, boron phosphate, tetrahydrate Sodium octacarboxylate, antimony trioxide, antimony pentoxide, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate.
  • the method for preparing an inorganic hybrid polyol etherified melamine resin is characterized in that the acid used for adjusting the pH in the step (1) or the step (2) is hydrochloric acid or nitric acid, and the mass concentration thereof is 31-36%.
  • the base used is sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide or potassium carbonate at a mass concentration of 25-35%.
  • the method for preparing an inorganic hybrid polyol etherified melamine resin characterized in that the polyol in the step (1) is propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, butanediol, and One of a diol, ethylbutyl propylene glycol, polytetrahydrofuran diol, glycerol or pentaerythritol.
  • the inorganic hybrid polyol etherified melamine resin is characterized in that the inorganic hybrid polyol etherified melamine resin is used for preparing a combined polyether, and the combined polyether comprises a composite polyether for polyurethane rigid foam. Polyurethane semi-rigid combination polyether, polyurethane polyether composite polyether.
  • the use of the inorganic hybrid polyol etherified melamine resin is characterized in that: the inorganic Hybrid polyol etherified melamine resin is used to prepare paint coatings, including alkyd paint coatings, polyurethane paint coatings, epoxy resin paint coatings, acrylic paint coatings, and amino paint coatings.
  • the hybridization process of the invention is realized, because the methylol group is blocked, the active group is eliminated, and the reaction process is eliminated.
  • the temperature can be greatly increased to 110 ° C, and the molecular structure of the introduction of boron, molybdenum, antimony flame retardant elements, so that the product's stability, flame retardant properties and high temperature performance is greatly improved.
  • the hybridization crosslinking reaction of the etherified melamine resin with the inorganic hybrid compound causes the finally formed melamine resin polyol to introduce high temperature resistant flame retardant elements such as boron, bismuth, molybdenum, etc., thereby improving the amino resin polyol.
  • High temperature resistance and flame retardant performance compared with the resin before the hybridization, the high temperature resistance is improved by 50 ° C or more, and the flame retardant performance is improved by at least 20%.
  • the preparation of the inorganic hybrid polyol etherified melamine resin overcomes the technical problem of introducing a flame retardant element into the molecular structure of the polyol etherified melamine resin, and solves the influence of the externally added flame retardant on the physical and mechanical properties of the product and the flame retardant effect. Not ideal technical issues.
  • the high temperature resistant flame retardant melamine resin is prepared by using the high temperature resistant flame retardant melamine resin, and reacts with the isocyanate MDI to form an inorganic hybrid melamine polyurethane foam material with excellent physical properties, high strength, no powder, no change, completely It meets the requirements of GB50404-2007 standard waterproof insulation and GB8624-2012 standard B1 flame retardant. While ensuring physical properties, it has excellent flame retardancy and an oxygen index of more than 30%.
  • the prepared melamine resin polyol has high flame retardant property and high temperature resistance, it is not necessary to use expensive high flame retardant phosphate flame retardant when producing polyurethane foam, so that the foam cost is large. Reduced, reduced by more than 30%, and the economy is more reasonable.
  • the residual propylene glycol added in the step (1) is distilled off under the condition of a vacuum degree of 0.090 MPa and a temperature of 130 ° C;
  • a 2% diatomaceous earth filter aid was added, and the salt was filtered off with a filter to obtain a boron hybridized propylene glycol etherified melamine resin in a yield of 99.0%.
  • the residual polytetrahydrofuran diol added in the step (1) is distilled off under the condition of a vacuum degree of 0.090 MPa and a temperature of 110 ° C;
  • the residual pentaerythritol added in the step (1) is distilled off under the condition of a vacuum degree of 0.1 MPa and a temperature of 120 ° C;

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

本发明属于无机杂化高分子材料技术领域，特别涉及一种无机杂化多元醇醚化三聚氰胺树脂及其制备方法。主要包括以下步骤：(1)醚化反应，向反应釜中加入六羟甲基三聚氰胺和多元醇进行保温反应，得到四醚化或五醚化三聚氰胺树脂；(2)碱中和；(3)杂化反应；(4)蒸馏脱除残留的多元醇；(5)冷却过滤得到成品。通过本发明所述的方法制得的无机杂化多元醇醚化三聚氰胺树脂，通过与无机杂化化合物的杂化交联反应，使得最终生成的氨基树脂多元醇引入了硼、钼、锑等耐高温阻燃元素，从而提高了氨基树脂多元醇的耐高温性能和阻燃性能，主要应用于制备组合聚醚和油漆涂料。

Description

无机杂化多元醇醚化三聚氰胺树脂及其制备方法 技术领域
本发明属于无机杂化高分子材料技术领域，特别涉及一种无机杂化多元醇醚化三聚氰胺树脂以及其制备方法。
背景技术
由于氨基树脂具有一定的耐温性能，所以在很多领域，包括涂料行业，家具行业，聚氨酯行业等都有应用。但是，应用于高阻燃的聚氨酯材料上，其耐高温性能还是具有一定的差距。
由于聚氨酯泡沫塑料分子的特殊结构，决定了其容易燃烧、不耐高温的特性。随着聚氨酯节能保温硬泡应用技术的不断推广应用，对其阻燃性能的要求也越来越高，特别是GB8624-2012《建筑材料燃烧性能分级方法》和GB50016-2014《建筑设计防火规范》的颁布实施后，聚氨酯泡沫在阻燃防火性能方便面临着严峻的考验。因此，如何提高氨基树脂的耐高温和阻燃性能成了本领域亟待解决的技术难题。
发明内容
为了解决现有技术存在的上述问题，本发明提供了一种无机杂化多元醇醚化三聚氰胺树脂及其制备方法，以六羟甲基三聚氰胺为原料，在酸性介质条件下，与多元醇反应生成四甲醚化三聚氰胺树脂或五甲醚化三聚氰胺树脂，再与无机杂化化合物进行反应，生成无机杂化多元醇醚化三聚氰胺树脂，具有较高的阻燃性能和耐高温性能。
本发明所采用的技术方案如下：
无机杂化多元醇醚化三聚氰胺树脂，其特征在于：分子结构如下：
Figure PCTCN2017078237-appb-000001
Figure PCTCN2017078237-appb-000002
所述分子结构中的X为无机杂化元素，包括B或Sb中的一种；
所述分子结构中的R为－(CH2)nOH或－(CH2)mO(CH2)mOH或
－(OCH2CH2CH2CH3)KOH或－O(CH2)PCH(OH)CH2OH或－OCH2C(CH2OH)3，其中2≤n≤6，2≤m≤6，2≤p≤6，2≤k≤41。
所述的无机杂化多元醇醚化三聚氰胺树脂的制备方法，其特征在于：主要包括以下步骤：
在酸性介质条件下，将六羟甲基三聚氰胺和权利要求1中的R代表的多元醇进行醚化反应得到多元醇醚化三聚氰胺树脂，在搅拌条件下加碱进行碱中和反应；
将醚化的三聚氰胺树脂与无机杂化化合物在100～110℃的条件下反应0.5-2小时，杂化反应完成，冷却到60-80℃，用过滤机过滤出盐，得到无机杂化多元醇醚化三聚氰胺树脂。
所述的无机杂化多元醇醚化三聚氰胺树脂的制备方法，其特征在于：主要包括以下具体步骤：
(1)醚化反应
向反应釜中加入六羟甲基三聚氰胺和权利要求1中的R代表的多元醇，加酸调节pH为2.5～5.5，在35～65℃的条件下，搅拌速度为60～80转/分钟，保温30～120min进行醚化反应，得到多元醇醚化三聚氰胺树脂；
(2)碱中和
在转速40-80转/分钟条件下进行搅拌，加碱调节pH为8.0～9.0，该碱中和过程保持温度低于50℃；
(3)杂化反应
向反应釜中加入无机杂化化合物和水，升温到100-110℃反应0.5-2小时，杂化反应完成；
(4)蒸馏脱除残留的多元醇
在真空度0.090-0.1MPa，温度100-130℃的条件下，蒸出步骤(1)中加入的残存的多元醇；
(5)冷却过滤
冷却到60-80℃，加入2％～2.5％硅藻土助滤剂，用过滤机过滤出盐，得到无机杂化多元醇醚化三聚氰胺树脂。
所述的无机杂化多元醇醚化三聚氰胺树脂的制备方法，其特征在于：所述步骤(3)中的无机杂化化合物为：硼酸钠、硼酸钾、硼酸、硼酸锌、磷酸硼、四水八硼酸钠、三氧化二锑、五氧化二锑、钼酸钠、钼酸钾、钼酸锌、钼酸铵、四钼酸铵或七钼酸铵中的一种。
所述的无机杂化多元醇醚化三聚氰胺树脂的制备方法，其特征在于：所述步骤(1)或步骤(2)中调节pH所用酸为盐酸或硝酸，其质量浓度为31-36％，所用碱为氢氧化钠、碳酸钠、碳酸氢钠、氢氧化钾或碳酸钾，其质量浓度为25-35％。
所述的无机杂化多元醇醚化三聚氰胺树脂的制备方法，其特征在于：所述步骤(1)中的多元醇为丙二醇、乙二醇、二乙二醇、二丙二醇、丁二醇、己二醇、乙基丁基丙二醇、聚四氢呋喃二醇、丙三醇或季戊四醇中的一种。
所述的无机杂化多元醇醚化三聚氰胺树脂的应用，其特征在于：所述无机杂化多元醇醚化三聚氰胺树脂用于制备组合聚醚，所述组合聚醚包括聚氨酯硬泡用组合聚醚、聚氨酯半硬泡组合聚醚、聚氨酯软泡用组合聚醚。
所述的无机杂化多元醇醚化三聚氰胺树脂的应用，其特征在于：所述无机 杂化多元醇醚化三聚氰胺树脂用于制备油漆涂料，所述油漆涂料包括醇酸油漆涂料、聚氨酯油漆涂料、环氧树脂油漆涂料、丙烯酸油漆涂料、氨基油漆涂料。
本发明专利的无机杂化反应原理：
利用化合物上含有的羟甲基能与硼、钼、锑元素发生交联反应的原理，实现了本发明专利的杂化反应过程，因为封闭了羟甲基，消除了活泼基团，反应过程中的温度可以大幅度提高至110℃，并且分子结构上引入了硼、钼、锑阻燃元素，使得产品的稳定性、阻燃性能和耐高温性能大幅提升。
本发明的上述技术方案与现有技术相比，具有以下优点：
1、通过醚化的三聚氰胺树脂与无机杂化化合物的杂化交联反应，使得最终生成的三聚氰胺树脂多元醇引入了硼、锑、钼等耐高温阻燃元素，从而提高了氨基树脂多元醇的耐高温性能和阻燃性能，与未杂化之前的树脂相比，耐高温性能提高50℃以上，阻燃性能提高了至少20％。
2、该无机杂化多元醇醚化三聚氰胺树脂的制备克服了多元醇醚化三聚氰胺树脂分子结构引入阻燃元素的技术难题，解决了外添加阻燃剂对产品物理机械性能的影响和阻燃效果不理想等技术问题。
3、用此耐高温阻燃三聚氰胺树脂制备成耐高温阻燃三聚氰胺树脂多元醇，与异氰酸酯MDI反应，形成的无机杂化三聚氰胺聚氨酯泡沫材料物理性能优异，强度高，不发粉，不变型，完全达到GB50404-2007标准防水保温及GB8624-2012标准B1级阻燃的要求。在保证物理性能的同时，阻燃性能优异，其氧指数大于30％。
4、由于所制备的三聚氰胺树脂多元醇具有高阻燃性能和耐高温性能，所以在用其生产聚氨酯泡沫时，不需要使用价格昂贵的高阻燃磷酸酯阻燃剂，使泡沫成本大为的降低，降低了30％以上，经济性更合理。
具体实施方式
下面结合具体实施例详细说明本发明，但本发明并不局限于具体实施例。
实施例1
硼杂化丙二醇醚化三聚氰胺树脂的制备
分子结构式：
Figure PCTCN2017078237-appb-000003
原料配比：
Figure PCTCN2017078237-appb-000004
(1)醚化反应
按上述比例将六羟甲基三聚氰胺和丙二醇加入反应釜中，加酸调节pH为2.5，在35℃的条件下，搅拌速度为60转/分钟保温120min进行醚化反应，得到丙二醇醚化三聚氰胺树脂；
(2)碱中和
在转速40转/分钟条件下进行搅拌，加碱调节pH为8.0，该碱中和过程保持温度低于50℃；
(3)杂化反应
向反应釜中加入四水八硼酸钠和水，升温到100℃反应2小时，杂化反应完成；
(4)蒸馏脱除残留的多元醇
在真空度0.090MPa，温度130℃的条件下，蒸出步骤(1)中加入的残存的丙二醇；
(5)冷却过滤
冷却到60℃，加入2％硅藻土助滤剂，用过滤机过滤出盐，得到硼杂化丙二醇醚化三聚氰胺树脂，收率99.0％。
实施例2
锑杂化二乙二醇醚化三聚氰胺树脂的制备
分子结构式：
Figure PCTCN2017078237-appb-000005
原料配比：
Figure PCTCN2017078237-appb-000006
(1)醚化反应
按上述比例将六羟甲基三聚氰胺和二乙二醇加入反应釜中，加酸调节pH为5.5，在65℃的条件下，搅拌速度为80转/分钟，保温30min进行醚化反应，得到二乙二醇醚化三聚氰胺树脂；
(2)碱中和
在转速80转/分钟条件下进行搅拌，加碱调节pH为9.0，该碱中和过程保持温度低于50℃；
(3)杂化反应
向反应釜中加入三氧化二锑和水，升温到110℃反应0.5小时，杂化反应完成；
(4)蒸馏脱除残留的多元醇
在真空度0.1MPa，温度100℃的条件下，蒸出步骤(1)中加入的残存的二乙二醇；
(5)冷却过滤
冷却到80℃，加入2.5％硅藻土助滤剂，用过滤机过滤出盐，得到锑杂化二乙二醇醚化三聚氰胺树脂，收率98.5％。
实施例3
硼杂化聚四氢呋喃二醇醚化三聚氰胺树脂的制备
分子结构式：
Figure PCTCN2017078237-appb-000007
原料配比：
Figure PCTCN2017078237-appb-000008
(1)醚化反应
按上述比例将六羟甲基三聚氰胺和聚四氢呋喃二醇加入反应釜中，加酸调节pH为3.5，在45℃的条件下，搅拌速度为70转/分钟，保温50min进行醚化反应，得到聚四氢呋喃二醇醚化三聚氰胺树脂；
(2)碱中和
在转速50转/分钟条件下进行搅拌，加碱调节pH为8.2，该碱中和过程保持温度低于50℃；
(3)杂化反应
向反应釜中加入四水八硼酸钠和水，升温到105℃反应1小时，杂化反应完成；
(4)蒸馏脱除残留的多元醇
在真空度0.090MPa，温度110℃的条件下，蒸出步骤(1)中加入的残存的聚四氢呋喃二醇；
(5)冷却过滤
冷却到70℃，加入2％硅藻土助滤剂，用过滤机过滤出盐，得到硼杂化聚四氢呋喃二醇醚化三聚氰胺树脂，收率98.1％。
实施例4
钼杂化丙三醇醚化三聚氰胺树脂的制备
分子结构式：
Figure PCTCN2017078237-appb-000009
原料配比：
Figure PCTCN2017078237-appb-000010
(1)醚化反应
按上述比例将六羟甲基三聚氰胺和丙三醇加入反应釜中，加酸调节pH为4.5，在40℃的条件下，搅拌速度为65转/分钟，保温90min进行醚化反应，得到丙三醇醚化三聚氰胺树脂；
(2)碱中和
在转速70转/分钟条件下进行搅拌，加碱调节pH为8.5，该碱中和过程保持温度低于50℃；
(3)杂化反应
向反应釜中加入钼酸钠和水，升温到105℃反应1.5小时，杂化反应完成；
(4)蒸馏脱除残留的多元醇
在真空度0.1MPa，温度120℃的条件下，蒸出步骤(1)中加入的残存的丙三醇；
(5)冷却过滤
冷却到75℃，加入2％硅藻土助滤剂，用过滤机过滤出盐，得到钼杂化丙三醇醚化三聚氰胺树脂，收率98.2％。
实施例5
硼杂化季戊四醇醚化三聚氰胺树脂的制备
分子结构式：
Figure PCTCN2017078237-appb-000011
原料配比：
Figure PCTCN2017078237-appb-000012
(1)醚化反应
按上述比例将六羟甲基三聚氰胺和季戊四醇加入反应釜中，加酸调节pH为4.0，在60℃的条件下，搅拌速度为65转/分钟，保温110min进行醚化反应，得到季戊四醇醚化三聚氰胺树脂；
(2)碱中和
在转速50转/分钟条件下进行搅拌，加碱调节pH为8.6，该碱中和过程保持温度低于50℃；
(3)杂化反应
向反应釜中加入硼酸钠和水，升温到102℃反应1.5小时，杂化反应完成；
(4)蒸馏脱除残留的多元醇
在真空度0.1MPa，温度120℃的条件下，蒸出步骤(1)中加入的残存的季戊四醇；
(5)冷却过滤
冷却到60℃，加入2.5％硅藻土助滤剂，用过滤机过滤出盐，得到无机杂化多元醇醚化三聚氰胺树脂，收率98.0％。

Claims (8)

  1. 无机杂化多元醇醚化三聚氰胺树脂，其特征在于：分子结构如下：
    Figure PCTCN2017078237-appb-100001
    所述分子结构中的X为无机杂化元素，包括B或Sb中的一种；
    所述分子结构中的R为－(CH2)nOH或－(CH2)mO(CH2)mOH或
    －(OCH2CH2CH2CH3)KOH或－O(CH2)PCH(OH)CH2OH或－OCH2C(CH2OH)3，其中2≤n≤6，2≤m≤6，2≤p≤6，2≤k≤41。
  2. 如权利要求1所述的无机杂化多元醇醚化三聚氰胺树脂的制备方法，其特征在于：主要包括以下步骤：
    在酸性介质条件下，将六羟甲基三聚氰胺和权利要求1中的R代表的多元醇进行醚化反应得到多元醇醚化三聚氰胺树脂，在搅拌条件下加碱进行碱中和反应；
    将醚化的三聚氰胺树脂与无机杂化化合物在100～110℃的条件下反应0.5～2小时，杂化反应完成，冷却到60～80℃，用过滤机过滤出盐，得到无机杂化多元醇醚化三聚氰胺树脂。
  3. 如权利要求2所述的无机杂化多元醇醚化三聚氰胺树脂的制备方法，其 特征在于：主要包括以下具体步骤：
    (1)醚化反应
    向反应釜中加入六羟甲基三聚氰胺和权利要求1中的R代表的多元醇，加酸调节pH为2.5～5.5，在35～65℃的条件下，搅拌速度为60～80转/分钟，保温30～120min进行醚化反应，得到多元醇醚化三聚氰胺树脂；
    (2)碱中和
    在转速40～80转/分钟条件下进行搅拌，加碱调节pH为8.0～9.0，该碱中和过程保持温度低于50℃；
    (3)杂化反应
    向反应釜中加入无机杂化化合物和水，升温到100～110℃反应0.5～2小时，杂化反应完成；
    (4)蒸馏脱除残留的多元醇
    在真空度0.090～0.1MPa，温度100～130℃的条件下，蒸出步骤(1)中加入的残存的多元醇；
    (5)冷却过滤
    冷却到60～80℃，加入2％～2.5％硅藻土助滤剂，用过滤机过滤出盐，得到无机杂化多元醇醚化三聚氰胺树脂。
  4. 根据权利要求3所述的无机杂化多元醇醚化三聚氰胺树脂的制备方法，其特征在于：所述步骤(3)中的无机杂化化合物为：硼酸钠、硼酸钾、硼酸、硼酸锌、磷酸硼、四水八硼酸钠、三氧化二锑、五氧化二锑、钼酸钠、钼酸钾、钼酸锌、钼酸铵、四钼酸铵或七钼酸铵中的一种。
  5. 根据权利要求3所述的无机杂化多元醇醚化三聚氰胺树脂的制备方法，其特征在于：所述步骤(1)或步骤(2)中调节pH所用酸为盐酸或硝酸，其质量浓度为31～36％，所用碱为氢氧化钠、碳酸钠、碳酸氢钠、氢氧化钾或碳酸钾，其质量浓度为25～35％。
  6. 根据权利要求3所述的无机杂化多元醇醚化三聚氰胺树脂的制备方法，其特征在于：所述步骤(1)中的多元醇为丙二醇、乙二醇、二乙二醇、二丙二 醇、丁二醇、己二醇、乙基丁基丙二醇、聚四氢呋喃二醇、丙三醇或季戊四醇中的一种。
  7. 根据权利要求1所述的无机杂化多元醇醚化三聚氰胺树脂的应用，其特征在于：所述无机杂化多元醇醚化三聚氰胺树脂用于制备组合聚醚，所述组合聚醚包括聚氨酯硬泡用组合聚醚、聚氨酯半硬泡组合聚醚、聚氨酯软泡用组合聚醚。
  8. 根据权利要求1所述的无机杂化多元醇醚化三聚氰胺树脂的应用，其特征在于：所述无机杂化多元醇醚化三聚氰胺树脂用于制备油漆涂料，所述油漆涂料包括醇酸油漆涂料、聚氨酯油漆涂料、环氧树脂油漆涂料、丙烯酸油漆涂料、氨基油漆涂料。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112341583A (zh) * 2020-11-04 2021-02-09 上海挚纯电器有限公司 一种用于氨基树脂磷酸酯的改性氨基树脂的制备方法

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101712749A (zh) * 2009-11-19 2010-05-26 中国科学院广州化学研究所 一种氮硅杂化型环氧树脂固化剂及其制备方法和应用
CN102690661A (zh) * 2012-06-07 2012-09-26 常州大学 一种杂化阻燃剂及其制备方法
CN104987484A (zh) * 2015-05-29 2015-10-21 张家港迪蒙德节能科技有限公司 一种无机材料杂化硬质三聚氰胺聚氨酯泡沫保温材料及其制备方法和用于其中的组合聚醚
CN106366104A (zh) * 2016-08-01 2017-02-01 常州聚博节能科技有限公司 无机杂化多元醇醚化三聚氰胺树脂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101712749A (zh) * 2009-11-19 2010-05-26 中国科学院广州化学研究所 一种氮硅杂化型环氧树脂固化剂及其制备方法和应用
CN102690661A (zh) * 2012-06-07 2012-09-26 常州大学 一种杂化阻燃剂及其制备方法
CN104987484A (zh) * 2015-05-29 2015-10-21 张家港迪蒙德节能科技有限公司 一种无机材料杂化硬质三聚氰胺聚氨酯泡沫保温材料及其制备方法和用于其中的组合聚醚
CN106366104A (zh) * 2016-08-01 2017-02-01 常州聚博节能科技有限公司 无机杂化多元醇醚化三聚氰胺树脂及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112341583A (zh) * 2020-11-04 2021-02-09 上海挚纯电器有限公司 一种用于氨基树脂磷酸酯的改性氨基树脂的制备方法

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