WO2018023985A1 - 无机杂化三聚氰胺树脂多元醇及其制备方法 - Google Patents

无机杂化三聚氰胺树脂多元醇及其制备方法 Download PDF

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WO2018023985A1
WO2018023985A1 PCT/CN2017/078238 CN2017078238W WO2018023985A1 WO 2018023985 A1 WO2018023985 A1 WO 2018023985A1 CN 2017078238 W CN2017078238 W CN 2017078238W WO 2018023985 A1 WO2018023985 A1 WO 2018023985A1
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melamine resin
inorganic hybrid
reaction
methanol
acid
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PCT/CN2017/078238
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French (fr)
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王洪波
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常州聚博节能科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C07D251/70—Other substituted melamines
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3897—Low-molecular-weight compounds having heteroatoms other than oxygen containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—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
    • 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
    • C08G18/65—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 melamine resin polyol 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 melamine resin polyol and a preparation method thereof, which are prepared by reacting hexamethylol with hexamethylol melamine as a raw material under an acidic medium to form tetramethyl ether.
  • the melamine resin or the pentamethyl etherified melamine resin is reacted with the inorganic hybrid compound to form an inorganic hybrid etherified melamine resin, and then subjected to an ether exchange reaction with the polyol to form an inorganic hybrid melamine resin polyol, which has a high Flame retardant 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
  • hexamethylol melamine and methanol are etherified to obtain etherified melamine resin; alkali neutralization reaction is carried out by adding alkali under stirring;
  • the etherified melamine resin and the inorganic hybrid compound are subjected to a hybridization reaction at 100 to 110 ° C for 0.5 to 2 hours, and methanol and water are distilled off, cooled to 60 to 80 ° C, and filtered to obtain an inorganic hybrid etherified melamine resin. ;
  • the inorganic hybrid melamine resin is added to the inorganic hybrid etherified melamine resin to carry out an ether exchange reaction at 100 to 120 ° C, and the residual methanol is removed by distillation to obtain an inorganic hybrid melamine resin polyol.
  • the method for preparing the inorganic hybrid melamine resin polyol is characterized by comprising the following Specific steps:
  • the inorganic hybrid compound and water are added to the reaction vessel, and the temperature is raised to 100 to 110 ° C for 0.5 to 2 hours. Under the condition of 80 to 100 ° C, methanol is distilled off under normal pressure, and the vacuum is carried out at 100 to 110 ° C under vacuum. The water is distilled off under the condition of 0.090-0.095 MPa, and the water content reaches 0.5% or less;
  • the residual methanol was distilled off under the conditions of a vacuum of 0.090 to 0.1 MPa and a temperature of 95 to 120 ° C, and the mixture was cooled to room temperature to obtain an inorganic hybrid melamine resin polyol.
  • the method for preparing an inorganic hybrid melamine resin polyol characterized in that the inorganic hybrid compound in the step (3) is: sodium borate, potassium borate, boric acid, zinc borate, boron phosphate, tetrahydrate octaborate
  • the inorganic hybrid compound in the step (3) is: sodium borate, potassium borate, boric acid, zinc borate, boron phosphate, tetrahydrate octaborate
  • sodium, antimony trioxide, antimony pentoxide, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate sodium borate, potassium borate, boric acid, zinc borate, boron phosphate, tetrahydrate octaborate
  • sodium, antimony trioxide, antimony pentoxide sodium molybdate, potassium molybdate, zinc molybdate, ammonium moly
  • the preparation method of the inorganic hybrid melamine resin polyol is characterized in that: the step The acid used in the adjustment of pH in (1) or step (2) is hydrochloric acid or nitric acid, and the mass concentration thereof is 31 to 36%, and the alkali used is sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide or potassium carbonate, the quality thereof. The concentration is 25 to 35%.
  • the method for preparing an inorganic hybrid melamine resin polyol characterized in that the polyol in the step (5) is propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, butanediol, hexanediol One of ethyl butyl propylene glycol, polytetrahydrofuran diol, glycerol or pentaerythritol.
  • the use of the inorganic hybrid melamine resin polyol is characterized in that the inorganic hybrid melamine resin polyol is used for preparing a combined polyether, and the combined polyether comprises a combined polyether for polyurethane rigid foam and a semi-hard polyurethane. Combination polyether, polyether for polyurethane soft foam.
  • the use of the inorganic hybrid melamine resin polyol is characterized in that the inorganic hybrid melamine resin polyol is used for preparing a paint coating, and the paint coating comprises an alkyd paint paint, a polyurethane paint paint, an epoxy resin paint. Coatings, acrylic paints, amino paints.
  • 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 melamine resin polyol overcomes the technical problem of introducing a flame retardant element into the molecular structure of the polyol, and solves the technical problems of the effect of the externally added flame retardant on the physical and mechanical properties of the product and the unsatisfactory flame retardant effect.
  • 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, fully meet 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 methanol was distilled off under the conditions of a vacuum of 0.090 MPa and a temperature of 95 ° C, and the mixture was cooled to room temperature to obtain a boron-hybrid melamine resin propylene glycol in a yield of 99.0%.
  • the antimony trioxide and water were added to the reaction vessel, and the mixture was heated to 110 ° C for 0.5 hour. Under the condition of 100 ° C, methanol was distilled off under normal pressure, and the water was distilled off under the condition of a vacuum degree of 0.095 MPa at 110 ° C. , to a water content of less than 0.5%;
  • the residual methanol was distilled off under the conditions of a vacuum of 0.1 MPa and a temperature of 120 ° C, and the mixture was cooled to room temperature to obtain a doped melamine resin propylene glycol.
  • Diethylene glycol and oxalic acid are added, and an ether exchange reaction is carried out at 105 ° C, and the produced methanol is continuously distilled off under normal pressure until the mass of the distilled methanol reaches a theoretical amount, and the ether exchange is completed;
  • the residual methanol was distilled off under the conditions of a vacuum of 0.090 to 0.1 MPa and a temperature of 95 to 105 ° C, and the mixture was cooled to room temperature to obtain a molybdenum melamine resin diethylene glycol in a yield of 98.0%.
  • the hexamethylol melamine and methanol were added to the reaction kettle in the above ratio, and the pH was adjusted to 3.0 by adding hydrochloric acid.
  • the stirring speed was 65 rpm at 55 ° C, and the etherification reaction was carried out for 80 min to obtain an etherified melamine resin. ;
  • the residual methanol was distilled off under the conditions of a vacuum of 0.1 MPa and a temperature of 105 ° C, and the mixture was cooled to room temperature to obtain a boron-rich melamine resin polytetrahydrofuran diol in a yield of 98.0%.
  • the residual methanol was distilled off under the conditions of a vacuum of 0.1 MPa and a temperature of 105 ° C, and the mixture was cooled to room temperature to obtain an inorganic hybrid melamine resin polyol in a yield of 98.0%.
  • the inorganic hybrid compound and water were added to the reaction vessel, and the mixture was heated to 105 ° C for 1 hour. Under the condition of 90 ° C, methanol was distilled off under normal pressure, and the water was distilled off under the condition of a vacuum degree of 0.090 MPa at 100 ° C. , to a water content of less than 0.5%;
  • the residual methanol was distilled off under the conditions of a vacuum of 0.090 MPa and a temperature of 100 ° C, and the mixture was cooled to room temperature to obtain an inorganic hybrid melamine resin polyol in a yield of 98.0%.

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Wood Science & Technology (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三聚氰胺树脂多元醇及其制备方法。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甲醇进行保温反应；(2)碱中和；(3)杂化反应；(4)冷却过滤；(5)醚交换反应；(6)蒸馏脱除残留的甲醇得到成品。通过本发明所述的方法制得的无机杂化三聚氰胺树脂多元醇，通过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、钼、锑等耐高温阻燃元素，从而提高了三聚氰胺树脂多元醇的耐高温性能和阻燃性能，其主要应用于制备组合聚醚及油漆涂料。

Description

无机杂化三聚氰胺树脂多元醇及其制备方法 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三聚氰胺树脂多元醇以及其制备方法。
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三聚氰胺树脂多元醇及其制备方法，以六羟甲基三聚氰胺为原料，在酸性介质条件下，与甲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，生成无机杂化醚化三聚氰胺树脂，再与多元醇进行醚交换反应，生成无机杂化三聚氰胺树脂多元醇，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：
无机杂化三聚氰胺树脂多元醇，其特征在于：分子结构如下：
Figure PCTCN2017078238-appb-000001
Figure PCTCN2017078238-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。
所述的无机杂化三聚氰胺树脂多元醇的制备方法，其特征在于：主要包括以下步骤：
在酸性介质条件下，六羟甲基三聚氰胺和甲醇进行醚化反应得到醚化的三聚氰胺树脂；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℃的条件下进行杂化反应0.5～2小时，蒸出甲醇和水，冷却到60～80℃后过滤得到无机杂化醚化三聚氰胺树脂；
在无机杂化醚化三聚氰胺树脂中加入多元醇和酸在100～120℃下进行醚交换反应，蒸馏脱除残留的甲醇，即得到无机杂化三聚氰胺树脂多元醇。
所述的无机杂化三聚氰胺树脂多元醇的制备方法，其特征在于：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甲醇，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，得到醚化三聚氰胺树脂；
(2)碱中和
在转速40～80转/分钟条件下搅拌，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，在80～100℃的条件下，常压蒸出甲醇，在100～110℃的条件下，在真空度为0.090～0.095MPa条件下蒸出水，至含水量达到0.5％以下；
(4)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，得到无机杂化三聚氰胺树脂；
(5)醚交换反应
加入多元醇，及盐酸、硝酸、磷酸、硫酸、草酸、甲酸或对苯二甲酸中的一种酸，在100～120℃下，进行醚交换反应，常压下不断蒸出生成的甲醇，至计量蒸出的甲醇质量达到理论量，醚交换完成；
(6)蒸馏脱除残留的甲醇
在真空度0.090～0.1MPa，温度95～120℃的条件下，蒸出残存的甲醇，冷却到室温，即得到无机杂化三聚氰胺树脂多元醇。
所述的无机杂化三聚氰胺树脂多元醇的制备方法，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。
所述的无机杂化三聚氰胺树脂多元醇的制备方法，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％。
所述的无机杂化三聚氰胺树脂多元醇的制备方法，其特征在于：所述步骤(5)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。
所述的无机杂化三聚氰胺树脂多元醇的应用，其特征在于:所述无机杂化三聚氰胺树脂多元醇用于制备组合聚醚，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。
所述的无机杂化三聚氰胺树脂多元醇的应用，其特征在于:所述无机杂化三聚氰胺树脂多元醇用于制备油漆涂料，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、该无机杂化三聚氰胺树脂多元醇的制备克服了多元醇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
硼杂化三聚氰胺树脂丙二醇的制备
分子结构式：
Figure PCTCN2017078238-appb-000003
原料配比：
Figure PCTCN2017078238-appb-000004
(1)醚化反应
按上述比例将六羟甲基三聚氰胺和甲醇加入反应釜中，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，得到醚化三聚氰胺树脂；
(2)碱中和
在转速40转/分钟条件下搅拌，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，在80℃的条件下，常压蒸出甲醇，在100℃的条件下，在真空度为0.090MPa条件下蒸出水，至含水量达到0.5％以下；
(4)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，得到硼杂化醚化三聚氰胺树脂；
(5)醚交换反应
加入丙二醇，及盐酸，在100℃下，进行醚交换反应，常压下不断蒸出生成的甲醇，至计量蒸出的甲醇质量达到理论量，醚交换完成；
(6)蒸馏脱除残留的甲醇
在真空度0.090MPa，温度95℃的条件下，蒸出残存的甲醇，冷却到室温，即得到硼杂化三聚氰胺树脂丙二醇，收率99.0％。
实施例2
锑杂化三聚氰胺树脂丙二醇的制备
分子结构式：
Figure PCTCN2017078238-appb-000005
原料配比：
Figure PCTCN2017078238-appb-000006
(1)醚化反应
按上述比例将六羟甲基三聚氰胺和甲醇加入反应釜中，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，得到醚化三聚氰胺树脂；
(2)碱中和
在转速80转/分钟条件下搅拌，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，在100℃的条件下，常压蒸出甲醇，在110℃的条件下，在真空度为0.095MPa条件下蒸出水，至含水量达到0.5％以下；
(4)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，得到锑杂化醚化三聚氰胺树脂；
(5)醚交换反应
加入丙二醇，及硝酸，在120℃下，进行醚交换反应，常压下不断蒸出生成的甲醇，至计量蒸出的甲醇质量达到理论量，醚交换完成；
(6)蒸馏脱除残留的甲醇
在真空度0.1MPa，温度120℃的条件下，蒸出残存的甲醇，冷却到室温，即得到锑杂化三聚氰胺树脂丙二醇。
实施例3
钼杂化三聚氰胺树脂二乙二醇的制备
分子结构式：
Figure PCTCN2017078238-appb-000007
原料配比：
Figure PCTCN2017078238-appb-000008
(1)醚化反应
按上述比例将六羟甲基三聚氰胺和甲醇加入反应釜中，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60min进行醚化反应，得到醚化三聚氰胺树脂；
(2)碱中和
在转速50转/分钟条件下搅拌，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
向反应釜中加入钼酸钠和水，升温到105℃反应1小时，在90℃的条件下，常压蒸出甲醇，在100℃的条件下，在真空度为0.090MPa条件下蒸出水，至含水量达到0.5％以下；
(4)冷却过滤
冷却到65℃，加入2.5％硅藻土助滤剂，用过滤机过滤出盐，得到钼杂化醚化三聚氰胺树脂；
(5)醚交换反应
加入二乙二醇，及草酸，在105℃下，进行醚交换反应，常压下不断蒸出生成的甲醇，至计量蒸出的甲醇质量达到理论量，醚交换完成；
(6)蒸馏脱除残留的甲醇
在真空度0.090～0.1MPa，温度95～105℃的条件下，蒸出残存的甲醇，冷却到室温，即得到钼杂化三聚氰胺树脂二乙二醇，收率98.0％。
实施例4
硼杂化三聚氰胺树脂聚四氢呋喃二醇的制备
分子结构式：
Figure PCTCN2017078238-appb-000009
原料配比：
Figure PCTCN2017078238-appb-000010
(1)醚化反应
按上述比例将六羟甲基三聚氰胺和甲醇加入反应釜中，加盐酸调节pH为3.0，在55℃的条件下，搅拌速度为65转/分钟，保温80min进行醚化反应，得到醚化三聚氰胺树脂；
(2)碱中和
在转速50转/分钟条件下搅拌，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
向反应釜中加入四水八硼酸钠和水，升温到105℃反应1小时，在90℃的条件下，常压蒸出甲醇，在100℃的条件下，在真空度为0.090MPa条件下蒸出水，至含水量达到0.5％以下；
(4)冷却过滤
冷却到65℃，加入2.5％硅藻土助滤剂，用过滤机过滤出盐，得到硼杂化醚 化三聚氰胺树脂；
(5)醚交换反应
加入聚四氢呋喃二醇，及对苯二甲酸，在110℃下，进行醚交换反应，常压下不断蒸出生成的甲醇，至计量蒸出的甲醇质量达到理论量，醚交换完成；
(6)蒸馏脱除残留的甲醇
在真空度0.1MPa，温度105℃的条件下，蒸出残存的甲醇，冷却到室温，即得到硼杂化三聚氰胺树脂聚四氢呋喃二醇，收率98.0％。
实施例5
钼杂化三聚氰胺树脂丙三醇的制备
分子结构式：
Figure PCTCN2017078238-appb-000011
原料配比：
Figure PCTCN2017078238-appb-000012
(1)醚化反应
按上述比例将六羟甲基三聚氰胺和甲醇加入反应釜中，加硝酸调节pH为5.0，在50℃的条件下，搅拌速度为70转/分钟，保温100min进行醚化反应，得到醚化三聚氰胺树脂；
(2)碱中和
在转速70转/分钟条件下搅拌，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
向反应釜中加入钼酸钠和水，升温到105℃反应1.5小时，在90℃的条件下，常压蒸出甲醇，在105℃的条件下，在真空度为0.095MPa条件下蒸出水，至含水量达到0.5％以下；
(4)冷却过滤
冷却到70℃，加入2.5％硅藻土助滤剂，用过滤机过滤出盐，得到钼杂化醚化三聚氰胺树脂；
(5)醚交换反应
加入丙三醇，及甲酸，在105℃下，进行醚交换反应，常压下不断蒸出生成的甲醇，至计量蒸出的甲醇质量达到理论量，醚交换完成；
(6)蒸馏脱除残留的甲醇
在真空度0.1MPa，温度105℃的条件下，蒸出残存的甲醇，冷却到室温，即得到无机杂化三聚氰胺树脂多元醇，收率98.0％。
实施例6
硼杂化三聚氰胺树脂季戊四醇的制备
分子结构式：
Figure PCTCN2017078238-appb-000013
原料配比：
Figure PCTCN2017078238-appb-000014
(1)醚化反应
按上述比例将六羟甲基三聚氰胺和甲醇加入反应釜中，加盐酸调节pH为3.5，在55℃的条件下，搅拌速度为70转/分钟，保温80min进行醚化反应，得 到醚化三聚氰胺树脂；
(2)碱中和
在转速60转/分钟条件下搅拌，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
向反应釜中加入无机杂化化合物和水，升温到105℃反应1小时，在90℃的条件下，常压蒸出甲醇，在100℃的条件下，在真空度为0.090MPa条件下蒸出水，至含水量达到0.5％以下；
(4)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，得到硼杂化醚化三聚氰胺树脂；
(5)醚交换反应
加入季戊四醇，及磷酸在105℃下，进行醚交换反应，常压下不断蒸出生成的甲醇，至计量蒸出的甲醇质量达到理论量，醚交换完成；
(6)蒸馏脱除残留的甲醇
在真空度0.090MPa，温度100℃的条件下，蒸出残存的甲醇，冷却到室温，即得到无机杂化三聚氰胺树脂多元醇，收率98.0％。

Claims (8)

  1. 无机杂化三聚氰胺树脂多元醇，其特征在于：分子结构如下：
    Figure PCTCN2017078238-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所述的无机杂化三聚氰胺树脂多元醇的制备方法，其特征在于：主要包括以下步骤：
    在酸性介质条件下，六羟甲基三聚氰胺和甲醇进行醚化反应得到醚化的三聚氰胺树脂；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℃的条件下进行杂化 反应0.5～2小时，蒸出甲醇和水，冷却到60～80℃后过滤得到无机杂化醚化三聚氰胺树脂；
    在无机杂化醚化三聚氰胺树脂中加入多元醇和酸在100～120℃下进行醚交换反应，蒸馏脱除残留的甲醇，即得到无机杂化三聚氰胺树脂多元醇。
  3. 如权利要求2所述的无机杂化三聚氰胺树脂多元醇的制备方法，其特征在于：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甲醇，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，得到醚化三聚氰胺树脂；
    (2)碱中和
    在转速40～80转/分钟条件下搅拌，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，在80～100℃的条件下，常压蒸出甲醇，在100～110℃的条件下，在真空度为0.090～0.095MPa条件下蒸出水，至含水量达到0.5％以下；
    (4)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，得到无机杂化醚化三聚氰胺树脂；
    (5)醚交换反应
    加入多元醇，及盐酸、硝酸、磷酸、硫酸、草酸、甲酸或对苯二甲酸中的一种酸，在100～120℃下，进行醚交换反应，常压下不断蒸出生成的甲醇，至计量蒸出的甲醇质量达到理论量，醚交换完成；
    (6)蒸馏脱除残留的甲醇
    在真空度0.090～0.1MPa，温度95～120℃的条件下，蒸出残存的甲醇，冷却到室温，即得到无机杂化三聚氰胺树脂多元醇。
  4. 根据权利要求3所述的无机杂化三聚氰胺树脂多元醇的制备方法，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所述的无机杂化三聚氰胺树脂多元醇的制备方法，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所述的无机杂化三聚氰胺树脂多元醇的制备方法，其特征在于：所述步骤(5)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所述的无机杂化三聚氰胺树脂多元醇的应用，其特征在于:所述无机杂化三聚氰胺树脂多元醇用于制备组合聚醚，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所述的无机杂化三聚氰胺树脂多元醇的应用，其特征在于:所述无机杂化三聚氰胺树脂多元醇用于制备油漆涂料，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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