WO2021114920A1 - 一种制备聚硫醇类固化剂的催化剂及其应用 - Google Patents

一种制备聚硫醇类固化剂的催化剂及其应用 Download PDF

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WO2021114920A1
WO2021114920A1 PCT/CN2020/124205 CN2020124205W WO2021114920A1 WO 2021114920 A1 WO2021114920 A1 WO 2021114920A1 CN 2020124205 W CN2020124205 W CN 2020124205W WO 2021114920 A1 WO2021114920 A1 WO 2021114920A1
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catalyst
sba
curing agent
preparing
polythiol curing
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French (fr)
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梁万根
费潇瑶
崔卫华
张超
宋吻吻
孙志利
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山东益丰生化环保股份有限公司
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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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans

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  • the invention relates to the technical field of polythiol compounds, in particular to a catalyst for preparing a polythiol curing agent and its application.
  • thiol compounds there are many known methods for preparing thiol compounds, such as: (1) disulfide compound reduction method; (2) using organic halides or alcohols to first react with thiourea to form isothiourea salt, and then isosulfide Urea hydrolysis method; (3) Bunte salt method; (4) Organic halide reaction method with sodium hydrosulfide, potassium hydrosulfide and other metal salts; (5) Dithiocarbamate hydrolysis method ; (6) The method of adding olefin and hydrogen sulfide or thioacetic acid, etc.
  • the method (2) and method (4) using organic halides as starting materials are the most commonly used methods for preparing mercaptan compounds. Compared with other methods, these two methods have high yields, fewer by-products, and products. The quality is good, but the method (2) involves many reaction steps, and it is not as convenient as the direct use of metal salt for sulfhydrylation.
  • the Chinese patent with publication number CN109180926A discloses a preparation method of polyether polythiol compound, which uses organic halogen compound to react with sodium hydrosulfide to directly sulfhydryl, which can produce polythiol with high yield, effectively and cheaply.
  • Compound in addition, in a preparation method of polythiol curing agent disclosed by Liao Yibin et al. (Preparation and activity study of polythiol curing agent, Xiamen University Master of Science Dissertation, 2014.4), a polyether polysulfide was prepared alcohol.
  • the polythiol curing agent obtained by the above preparation method is mostly yellow-green or light yellow, with poor transparency, and the quaternary ammonium salt phase transfer catalyst used in the above preparation method is mostly quaternary ammonium salt phase transfer catalyst, which will remain in the product after use
  • the resulting product contains too much halogen and other residues.
  • the resulting product has a high chloride ion content, which does not meet the requirements of environmental protection; and the catalyst is not easy to recycle, the production and separation costs are high, and the industrial-scale production and application are limited.
  • the present invention provides a catalyst for preparing polythiol curing agent and its application.
  • the invention obtains a quaternary ammonium salt three-phase transfer catalyst after halogenation modification of mesoporous molecular sieve and reaction with tertiary amine, and it is applied to the preparation of polythiol curing agent.
  • the catalyst obtained by the method not only has high catalytic activity, but also can prepare a high-quality polythiol curing agent with colorless, transparent and low halogen residues, and the catalyst is easy to recover, has low separation cost, and has very good industrial application prospects.
  • the catalyst is a mesoporous molecular sieve SBA-15 modified with surface groups, denoted as QA-SBA-15, and its surface groups include the structure as shown in formula I:
  • R 1 , R 2 , and R 3 are C1-C10 linear or branched alkanes, which may be the same or different; Y is Cl or Br.
  • the inventor further provides a preparation method of the catalyst, and the specific process includes:
  • the halogenating reagent and the mesoporous molecular sieve SBA-15 are refluxed in an organic solvent, and the surface is modified by halogenation to obtain halogenated SBA-15; the obtained halogenated SBA-15 is reacted with tertiary amine to obtain Quaternary ammonium salt three-phase phase transfer catalyst QA-SBA-15.
  • the protective atmosphere is preferably nitrogen
  • the mass ratio of the halogenating reagent to the mesoporous molecular sieve SBA-15 is preferably (0.5-4):1, more preferably (0.5-3):1, still more preferably (0.8-1.5):1, and still more preferably (0.8 ⁇ 1.2):1, most preferably (1 ⁇ 1.2):1;
  • the molar ratio of halogen atom to nitrogen in tertiary amine in the reaction of halogenated SBA-15 with tertiary amine is preferably 1:(2 ⁇ 4);
  • the halogenating reagent is preferably selected from 3-chloropropyltrimethoxysilane or 3-chloropropyltriethoxysilane or 3-bromopropyltrimethoxysilane or 3-bromopropyltriethoxysilane or Combination; more preferably, the halogenating agent is selected from 3-chloropropyltriethoxysilane or 3-bromopropyltriethoxysilane.
  • the structural formula of the tertiary amine is shown in formula II, wherein R 1 , R 2 , and R 3 are C1-C10 linear or branched alkanes, which may be the same or different;
  • the tertiary amine is selected from tri-n-propylamine, tri-n-butylamine or a combination thereof.
  • the organic solvent is preferably an alcohol solvent, more preferably anhydrous ethanol;
  • the concentration of the halogenating reagent in the reaction system is preferably 30-100 mmol/L, more preferably 40-80 mmol/L, still more preferably 40-60 mmol/L, most preferably 50 mmol/L;
  • the reflux reaction time is preferably 20-24h;
  • the reaction temperature of halogenated SBA-15 and tertiary amine is preferably 70°C to 120°C, preferably 80°C; the reaction time of halogenated SBA-15 and tertiary amine is preferably 8-12h;
  • washing preferably uses an alcohol solvent, more preferably anhydrous ethanol; drying is preferably vacuum drying; the drying temperature is preferably 60°C to 100°C, more preferably 70°C to 90°C, and even more preferably 80°C; the vacuum drying time is preferably For 6-12h.
  • alcohol solvent more preferably anhydrous ethanol
  • drying is preferably vacuum drying; the drying temperature is preferably 60°C to 100°C, more preferably 70°C to 90°C, and even more preferably 80°C; the vacuum drying time is preferably For 6-12h.
  • halogenated SBA-15 and tertiary amine are preferably carried out under stirring conditions; after the reaction, it is separated by suction filtration, washed with ethanol, and dried; and then extracted with absolute ethanol for 12h with a Soxhlet extractor to remove any traces in the pores.
  • the reacted tertiary amine is finally vacuum dried to constant weight at room temperature to obtain catalyst QA-SBA-15.
  • reaction route for preparing QA-SBA-15 is as follows:
  • mesoporous molecular sieves MCM-41 and MCM-48 can also be modified by halogenation according to the above-mentioned method of the present invention, and then reacted with tertiary amines to obtain modified mesoporous molecular sieves MCM-41 and MCM-48, which can also be used for catalytic polymerization. Synthesis of mercaptan curing agent.
  • the above catalyst QA-SBA-15 is used to synthesize polythiol curing agent, including the following steps: NaSH, catalyst QA-SBA-15, and halogenated polyether polyol are reacted under normal pressure H 2 S gas environment Then, the catalyst is separated to obtain a crude product; the crude product is washed and dried in sequence to obtain a high-quality polythiol curing agent for epoxy resin.
  • the addition amount of the catalyst QA-SBA-15 is 0.1% to 10% of the mass of the halogenated polyether polyol, more preferably 0.5 to 6%; the addition amount of the NaSH is preferably in accordance with NaSH and halogenated The molar ratio of halogen atoms in the polyether polyol (0.5-3):1 is added, and it is more preferably (0.9-1.5):1.
  • the NaSH is added in the form of a NaSH aqueous solution; the mass fraction of the NaSH aqueous solution is preferably 10%-50%, more preferably 20%-44%, most preferably 20-25%.
  • the reaction temperature is preferably 60°C to 150°C, more preferably 80°C to 110°C, most preferably 90°C;
  • the reaction time is preferably 2h to 20h, more preferably 5h to 7h , Most preferably 6h.
  • the water washing process is preferably specifically as follows: adding the obtained crude product to water for one water washing, adjusting the pH of the organic phase to 5-7, and leaving it to stand for stratification after stabilization, and taking out the lower layer After the substance and water are evenly mixed, let it stand for 10h-14h, and then cut out the product to complete the water washing process; more preferably, take out the lower layer substance and mix it evenly with water and let it stand for 12h.
  • the acid washing + water washing method it is beneficial to remove the salt formed by the reaction.
  • the drying method is preferably vacuum dehydration; the vacuum degree of the vacuum dehydration is preferably less than or equal to -0.095MPa; the vacuum dehydration temperature is preferably 60°C to 70°C, and more Preferably it is 65°C; the vacuum dehydration time is preferably 1h to 3h, more preferably 2h.
  • distilled water is used to obtain a high-quality polythiol curing agent for epoxy resin.
  • the present invention does not have special restrictions on the sources of the mesoporous molecular sieve SBA-15, halogenated polyether polyols and NaSH.
  • Commercially available products or self-made products well known to those skilled in the art are used (NaSH is mainly passed through hydrogen sulfide in an alkaline solution). It can be prepared).
  • the mesoporous molecular sieve SBA-15 is prepared with reference documents "Xiaoyao Fei, Shaoyun Chen, Dai Liu, Chunjie Huang, Yongchun Zhang. Comparison of amino and epoxy functionalized SBA-15 used for carbonic anhydrase immobilization.Journal of BioengineeringJand Bioengineering. ].2016,122(3):314-321".
  • the structure of the halogenated polyether polyol is as shown in formula III:
  • m, n, and p are independently selected from an integer of 2 to 5, and R is a C1-C10 linear alkyl group or a C1-C10 branched chain alkyl group or a substituted aryl group or an unsubstituted aryl group, X is one or more of F, Cl and Br.
  • R is a C2-C4 straight-chain alkyl group or a C2-C4 branched-chain alkyl group;
  • X is Cl.
  • the synthesis of the polythiol curing agent also includes recycling the separated catalyst QA-SBA-15.
  • the reaction between the halogenated polyether polyol and NaSH is carried out in the presence of H 2 S, which can efficiently carry out this reaction, and at the same time, can also improve product quality.
  • the present invention has no special restrictions on the source of the H 2 S.
  • the invention provides a catalyst for preparing a polythiol curing agent, which is used in the synthesis of a polythiol curing agent for epoxy resin.
  • the catalyst QA-SBA-15 has high activity, good mechanical strength, is easy to separate from the product and can be recycled, reduces waste water discharge, can greatly reduce the cost of raw materials, production and separation, and greatly reduces the reaction time. Very good industrial application prospects.
  • Experimental results show that the chromaticity of the polythiol curing agent for epoxy resin obtained by using the catalyst and preparation method provided by the present invention is less than 20, and the halogen content is within 200 ppm.
  • the present invention adopts a specific type of catalyst and carries out a solvent-free three-phase transfer catalyzed synthesis of a polythiol curing agent for epoxy resin under a specific preparation process.
  • the prepared product is colorless and transparent, has low halogen residue; and the used catalyst is easy to recover, has low separation cost, can be recycled, and has a very good industrial application prospect.
  • the preparation method provided by the present invention has a better conversion rate (product conversion rate of more than 90%) and a higher yield, and the process is simple, the conditions are mild, and the amount of waste water produced is greatly reduced. It is suitable for industrial manufacturing and is compared with traditional methods. It greatly reduces the reaction time and production cost, and has broad application prospects.
  • FIG. 1 is a hydrogen nuclear magnetic 1HNMR detection spectrum of a product obtained by the preparation method provided in Example 4 of the present invention.
  • halogenated polyether polyol used in the following examples was synthesized in the laboratory, and was specifically prepared according to the method described in the patent CN109180926A, specifically:
  • the mesoporous molecular sieve SBA-15 is based on the literature "Xiaoyao Fei, Shaoyun Chen, Dai Liu, Chunjie Huang, Yongchun Zhang.Comparison of amino and epoxy functionalized SBA-15 used for carbonic anhydrase immobilization.Journal of Bioscience] and Bioengineering [J]. , 122(3):314-321" method.
  • Example 1 To prepare catalyst QA-SBA-15, and choose 3-bromopropyltriethoxysilane (1.2) as the halogenating reagent.
  • the product obtained by the preparation method of this Example 4 is colorless and transparent.
  • the chromaticity (Hazen) measured by the Hunterley colorimeter is 16 and the halogen content (chlorine residue) measured by the Coulometric chlorine meter is 154 ppm; at the same time, the obtained
  • the product was tested by hydrogen nuclear magnetic 1HNMR, and the result is shown in Figure 1. It can be seen from Figure 1 that the product is a polyether polythiol compound with the structure shown in formula IV.
  • m, n, and p are independently selected from 2 to 5, and R is a C3 linear alkyl group.
  • Synthetic polythiol curing agent Add 237.9g of 18% NaSH aqueous solution (the molar ratio of NaSH to epichlorohydrin is 1.2:1) and 5.5g of QA-SBA- prepared in Example 2 into the reactor. 15 Catalyst. After sealing the reactor, check the air tightness. After replacement, H 2 S gas is introduced into the reactor to keep the inside of the reactor at normal pressure. The reaction system is heated to 85°C through an oil bath, and then the reactor is kept warm for 6 hours, and then the reactor is opened.
  • the product obtained by the preparation method provided in Example 2 of the present invention is colorless and transparent.
  • the chromaticity (Hazen) measured by the Hunterley colorimeter is 18, and the halogen content (chlorine residue) is 181 ppm measured by the Coulometric chlorine meter.
  • crude product A is obtained; the crude product A is added to 175 g of deionized water for one wash, and the pH of the organic phase is adjusted to 5-7 with hydrochloric acid.
  • crude product B Let stand for layering, take out the lower layer material is crude product B; add 175g of deionized water to crude product B, mix well and let stand for 10 hours, then cut out the product and remove water under the condition of vacuum ⁇ -0.095MPa, The water removal temperature was 65° C., and the time was 2 hours to obtain 154.2 g of a colorless and transparent polyether polythiol product.
  • Example 4 The preparation method provided in Example 4 is used to obtain a polythiol curing agent; the difference is that 12.5 g of phase transfer catalyst tetrabutylammonium chloride is used instead of 3.5 g of catalyst QA-SBA-15 in Example 4.
  • the product obtained by the preparation method provided in Comparative Example 1 is colorless and transparent.
  • the chromaticity (Hazen) tested by the Hunterley colorimeter is 27, and the halogen content (chlorine residue) is 589ppm by the Coulometric chlorine tester.
  • Example 4 The preparation method provided in Example 4 is used to obtain a polythiol curing agent; the difference is that 16 g of phase transfer catalyst benzyltriethylammonium chloride is used instead of the catalyst QA-SBA-15 in Example 4.
  • the product obtained by the preparation method provided in Comparative Example 2 is colorless and transparent.
  • the chromaticity (Hazen) measured by the Hunterley colorimeter is 21, and the halogen content (chlorine residue) is 673 ppm measured by the Coulometric chlorine meter.
  • the polythiol curing agent for epoxy resin synthesized by solvent-free three-phase phase transfer catalysis is colorless and transparent in appearance, with a chromaticity of less than 20, and the residual chlorine is only 100ppm-200ppm, which is obviously better than the polythiol curing agent prepared by the conventional method in the comparative example.
  • the preparation method provided by the present invention can produce environmentally friendly colorless, transparent and high-viscosity polythiol products with low chlorine residues.
  • the reaction process does not require the use of organic solvents, and the organic polymer polymer is used to solidify the phase transfer catalyst.
  • the present invention reduces the difficulty of post-processing and three-waste treatment while reducing the raw material cost and production cost, and can further expand its application field due to the environmental protection of the product, and has a very good industrial application prospect.

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Abstract

本发明涉及聚硫醇化合物技术领域，具体涉及一种制备聚硫醇类固化剂的催化剂及其应用。本发明通过对介孔分子筛进行卤化改性并与叔胺反应后获得一种季铵盐三相相转移催化剂，并将其应用到聚硫醇固化剂的制备中。该方法所获得的的催化剂不仅催化活性高，能够制备获得无色透明、卤素残留低的高品质聚硫醇类固化剂，且该催化剂易回收、分离成本低，具有非常好的工业化应用前景。

Description

一种制备聚硫醇类固化剂的催化剂及其应用 技术领域
本发明涉及聚硫醇化合物技术领域，具体涉及一种制备聚硫醇类固化剂的催化剂及其应用。
背景技术
已知的硫醇化合物的制备方法有很多种，例如：(1)二硫醚化合物还原法；(2)使用有机卤化物或醇类先与硫脲反应生成异硫脲盐，再将异硫脲水解的方法；(3)经由Bunte盐的方法；(4)使用有机卤化物与硫氢化钠、硫氢化钾等金属盐反应的方法；(5)由二硫代氨基甲酸酯水解的方法；(6)使烯与硫化氢或硫代乙酸加成的方法等。其中，由有机卤化物为起始原料的方法(2)和方法(4)是最常用的硫醇化合物的制备方法，与其他方法相比，这两种方法收率高、副产物少、产品品质好，但方法(2)涉及的反应步骤较多，不如直接使用金属盐进行巯基化操作方便。
公开号为CN109180926A的中国专利公开了一种聚醚型多硫醇化合物的制备方法，使用有机卤素化合物与硫氢化钠反应，直接巯基化，能以高收率且有效、廉价地制备多硫醇化合物；此外，在廖毅彬等公开的一种聚硫醇固化剂的制备方法(聚硫醇固化剂的制备及其活性研究，厦门大学理学硕士学位论文，2014.4)中，制得了聚醚型聚硫醇。
但是，上述制备方法得到的聚硫醇类固化剂，产品多为黄绿色或浅黄色，透明度差，并且上述制备方法中所使用的多为季铵盐类相转移催化剂，使用后会残留在产品中导致卤素等残留过多，如所得产品氯离子含量高，不满足绿色环保的要求；并且催化剂不易回收，生产和分离成本高，工业规模生产应用局限性大。
发明内容
针对现有技术缺陷，本发明提供了一种制备聚硫醇类固化剂的催化剂及其应用。本发明通过对介孔分子筛进行卤化改性并与叔胺反应后获得一种季铵盐三相相转移催化剂，并将其应用到聚硫醇固化剂的制备中。该方法所获得的的催化剂不仅催化活性高，能够制备获得无色透明、卤素残留低的高品质聚硫醇类固化剂，且该催化剂易回收、分离成本低，具有非常好的工业化应用前景。
首先，一种制备聚硫醇类固化剂的催化剂，该催化剂为表面基团改性的介孔分子筛SBA-15，记为QA-SBA-15，其表面基团包括结构如式Ⅰ：
Figure PCTCN2020124205-appb-000001
其中，左侧竖直加粗黑线代表介孔分子筛SBA-15基体骨架，R 1、R 2、R 3为C1～C10的直链或支链烷烃，可相同也可不同；Y为Cl或Br。
发明人进一步提供了该催化剂的制备方法，具体过程包括：
在保护气氛下，将卤化试剂与介孔分子筛SBA-15在有机溶剂中进行回流反应，对其进行表面卤化改性，得到卤化SBA-15；将所得卤化SBA-15与叔胺进行反应，得到季铵盐三相相转移催化剂QA-SBA-15。
所述保护气氛优选为氮气；
所述卤化试剂与介孔分子筛SBA-15的质量比优选为(0.5～4)：1，更优选为(0.5～3)：1，进一步优选为(0.8～1.5)：1，更进一步优选为(0.8～1.2)：1，最优选为(1～1.2)：1；卤化SBA-15与叔胺反应中卤原子与叔胺中的氮的摩尔比优选为1：(2～4)；
所述的卤化试剂优选自3-氯丙基三甲氧基硅烷或3-氯丙基三乙氧基硅烷或3-溴丙基三甲氧基硅烷或3-溴丙基三乙氧基硅烷或其组合；更为优选的，卤化试剂选自3-氯丙基三乙氧基硅烷或3-溴丙基三乙氧基硅烷。
优选的，所述的叔胺结构式如式Ⅱ所示，其中R 1、R 2、R 3为C1～C10的直链或支链烷烃，可相同也可不同；
Figure PCTCN2020124205-appb-000002
更为优选的，所述的叔胺选自三正丙胺或三正丁胺或其组合。
所述有机溶剂优选为醇溶剂，更优选为无水乙醇；
所述反应体系中卤化试剂的浓度优选为30～100mmol/L，更优选为40～80mmol/L，再优选为40～60mmol/L，最优选为50mmol/L；
所述回流反应的时间优选为20～24h；
卤化SBA-15与叔胺反应的温度优选为70℃～120℃，优选为80℃；卤化SBA-15与叔胺反应的时间优选为8～12h；
优选的，回流反应结束后，还包括过滤，洗涤，干燥步骤。洗涤优选采用醇溶剂，更优选采用无水乙醇；干燥优选为真空干燥；干燥的温度优选为60℃～100℃，更优选为70℃～90℃，再优选为80℃；真空干燥的时间优选为6～12h。
将所得卤化SBA-15与叔胺进行反应时，优选加入二氯乙烷和无水乙醇作为溶剂；
卤化SBA-15与叔胺反应优选在搅拌的条件下进行；反应结束后，抽滤分离，乙醇洗涤，晾干；然后用索氏提取器加入无水乙醇抽提12h，以除去在孔道内没有反应的叔胺，最后室温下真空干燥至恒重，得到催化剂QA-SBA-15。
下面以3-氯丙基三乙氧基硅烷作为卤化试剂为例，制备QA-SBA-15的反应路线如下所示：
Figure PCTCN2020124205-appb-000003
另外，介孔分子筛MCM-41与MCM-48也可以参照本发明上述方法进行卤化改性，然后与叔胺反应，得到改性的介孔分子筛MCM-41与MCM-48，同样可用于催化聚硫醇固化剂的合成。
更进一步利用上述催化剂QA-SBA-15进行聚硫醇固化剂的合成，包括以下步骤：将NaSH、催化剂QA-SBA-15、卤代聚醚多元醇在常压H 2S气体环境下进行反应，再分离出催化剂，得到粗产品；再将粗产品依次进行水洗和干燥，得到环氧树脂用高品质聚硫醇类固化剂。
优选的，所述催化剂QA-SBA-15的加入量为卤代聚醚多元醇质量的0.1％～10％，更为优选为0.5～6％；所述NaSH的加入量优选按照NaSH与卤代聚醚多元醇中的卤素原子的摩尔比(0.5～3)：1添加，更优选为(0.9～1.5)：1。
优选的，所述NaSH以NaSH水溶液的形式添加；所述NaSH水溶液的质量分数优选为10％～50％，更优选为20％～44％，最优选为20-25％。
本发明聚硫醇固化剂的合成中，反应温度优选为60℃～150℃，更优选为80℃～110℃，最优选为90℃；反应时间优选为2h～20h，更优选为5h～7h，最优选为6h。
本发明聚硫醇固化剂的合成中，所述水洗的过程优选具体为：将得到的粗产品加入水中进行一次水洗，调节有机相pH至5～7，待稳定后静置分层，取出下层物质与水混合均匀后静置10h～14h，然后切出产物，完成水洗过程；更优选的，取出下层物质与水混合均匀后静置12h。本发明通过上述酸洗涤+水洗涤的水洗方式，有利于脱除反应生成的盐。
本发明聚硫醇固化剂的合成中，所述干燥的方式优选为真空脱水；所述真空脱水的真空度优选小于等于-0.095MPa；所述真空脱水的温度优选为60℃～70℃，更优选为65℃；所述真空脱水的时间优选为1h～3h，更优选为2h。本发明通过上述干燥过程，使蒸水得到环氧树脂用高品质聚硫醇类固化剂。
本发明对所述介孔分子筛SBA-15、卤代聚醚多元醇和NaSH的来源没有特殊限制，采用本领域技术人员熟知的市售商品或自制品(NaSH主要通过向碱溶液中通入硫化氢来制备)均可。
优选的，介孔分子筛SBA-15制备参考文献“Xiaoyao Fei,Shaoyun Chen,Dai Liu,Chunjie Huang,Yongchun Zhang.Comparison of amino and epoxy functionalized SBA-15 used for carbonic anhydrase immobilization.Journal of Bioscience and Bioengineering[J].2016,122(3):314-321”。
优选的，所述卤代聚醚多元醇，其结构如式Ⅲ所示：
Figure PCTCN2020124205-appb-000004
其中，m、n、p独立地选自2～5的整数，R为C1～C10的直链烷基或C1～C10的支链烷基或经取代的芳基或未经取代的芳基，X为F，Cl，Br中的一种或多种。
优选的，R为C2～C4的直链烷基或C2～C4的支链烷基；X为Cl。
所述聚硫醇固化剂的合成还包括将分离出的催化剂QA-SBA-15进行重复利用。
在本发明中，所述卤代聚醚多元醇与NaSH的反应在H 2S存在下进行，能高效的进行此反应，同时，也可以提高产品品质。本发明对所述H 2S的来源没有特殊限制。
本发明提供了一种制备聚硫醇类固化剂的催化剂，并将其用于环氧树脂用聚硫醇类固化剂的合成。与传统方法相比，催化剂QA-SBA-15活性高、机械强度好，易与产品分离并可循环使用，减少废水排放量，可大幅度降低原料、生产及分离成本，大幅降低反应时间，具有非常好的工业化应用前景。实验结果表明，利用本发明提供的催化剂及制备方法得到的环氧树脂用聚硫醇类固化剂的色度小于20，卤素含量在200ppm以内。
与现有技术相比，本发明采用特定种类的催化剂，在特定制备工艺下进行无溶剂法三相转移催化合成环氧树脂用聚硫醇类固化剂。制备得到的产品无色透明、卤素残留低；并且所用的催化剂易回收、分离成本低，可循环使用，具有非常好的工业化应用前景。
本发明提供的制备方法具有较好的转化率(产品转化率超过90％)和较高的收率，且工艺简单、条件温和，产生废水量大幅降低，适合于工业制造，与传统方法相比大幅降低反应时间和生产成本，具有广阔的应用前景。
附图说明
图1为本发明实施例4提供的制备方法得到的产品的氢核磁1HNMR的检测图谱。
具体实施方式
以下通过实施例形式的具体实施方式，对本发明的上述内容做进一步的详细说明，但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范围，除特殊说明外，下述实施例中均采用常规现有技术完成。
以下实施例中所用的卤代聚醚多元醇为实验室合成，具体按照专利CN109180926A中记载的方法制备，具体为：
取89.6g聚醚多元醇和0.46g路易斯酸催化剂BF3，升温至65℃使催化剂全部溶解后，滴加87.9g环氧氯丙烷，滴加过程中控制反应温度在100℃，反应时间为7h，反应完成后，得到氯代聚醚多元醇。
介孔分子筛SBA-15为按照文献“Xiaoyao Fei,Shaoyun Chen,Dai Liu,Chunjie Huang,Yongchun Zhang.Comparison of amino and epoxy functionalized SBA-15 used for carbonic anhydrase immobilization.Journal of Bioscience and Bioengineering[J].2016,122(3):314-321”方法制备。
其他原料均为市售商品。
实施例1
制备催化剂QA-SBA-15：
(1)卤化SBA-15过程：在N 2氛围下，将2g SBA-15加入浓度为50mM的3-氯丙基三乙氧基硅烷(2g)的无水乙醇溶液中，回流24h后，将混合物抽滤，用无水乙醇洗涤，80℃真空条件下干燥过夜，所得固体即为卤化SBA-15。
(2)QA-SBA-15的合成：将2g干燥后的卤化SBA-15置于150mL的三口瓶中，加入50mL的1,2-二氯乙烷和50mL无水乙醇的混合溶剂。按照摩尔比n(Cl)：n(胺)＝1：3加入三正丁胺，回流反应12h，抽滤分离，乙醇洗涤，晾干。然后用索氏提取器加入无水乙醇抽提12h，以除去在孔道内没有反应的叔胺，最后室温下真空干燥至恒重，得到催化剂QA-SBA-15。
实施例2
参照实施例1制备催化剂QA-SBA-15，卤化试剂选择3-溴丙基三乙氧基硅烷(1.2)，QA-SBA-15合成时，n(Cl):n(胺)＝1:4.2，其余反应条件均不变。
实施例3
参照实施例1制备催化剂QA-SBA-15，卤化试剂选择3-氯丙基三乙氧基硅烷(3.2g)，QA-SBA-15合成时，n(Cl):n(胺)＝1:2.7，叔胺选择三正丙烷，其余反应条件均不变。
实施例4
合成聚硫醇类固化剂：
(1)向反应釜内加入258.4g质量分数为23％的NaSH水溶液和3.5g实施例1制备的催化剂QA-SBA-15，然后加入168.4g氯代聚醚，将反应釜封闭后检查气密性，之后向釜内通入H 2S气体使釜内处于常压，通过油浴加热反应体系至90℃后保温反应6h，然后开启反应釜的放空阀并用N 2置换，过滤出催化剂后，将产物静置分层，得到粗产品A。
(2)将粗产品A加入175g去离子水中进行一次水洗，用盐酸调节有机相pH至5～7，待稳定后静置分层，取出下层物质即为粗产品B；再向粗产品B中加入175g去离子水混合均匀后静置12h，然后切出产物并在真空度≤-0.095MPa条件下进行除水，除水温度为65℃，时间为2h，得到环氧树脂用高品质聚硫醇类固化剂152.7g。
本实施例4的制备方法得到的产品无色透明，通过亨特立色度仪测试色度(Hazen) 为16，通过库仑测氯仪测试卤素含量(氯残留)为154ppm；同时，对得到的产品进行氢核磁1HNMR检测，结果如图1所示，由图1可以看出，该产品为式IV所示结构的聚醚型多硫醇化合物。
Figure PCTCN2020124205-appb-000005
式IV中，m、n、p独立的选自2～5，R为C3的直链烷基。
实施例5
合成聚硫醇类固化剂：向反应釜内加入237.9g质量分数为18％的NaSH水溶液(NaSH与环氧氯丙烷的摩尔比为1.2：1)和5.5g实施例2制备的QA-SBA-15催化剂，将反应釜封闭后检查气密性，置换后向釜内通入H 2S气体使釜内处于常压，通过油浴加热反应体系至85℃后保温反应6小时，然后开启反应釜的放空阀并用N 2置换，产物静置分层后，得到粗产品A；将粗产品A加入180g去离子水中进行一次水洗，用盐酸调节有机相pH至3～4，待稳定后静置分层，取出下层物质即为粗产品B；向粗产品B中加入180g去离子水混合均匀后静置10小时，然后切出产物并在真空度≤-0.095MPa条件下进行除水，除水温度为65℃，时间为2小时，得到无色透明聚醚型多硫醇产物156.8g。
本发明实施例2提供的制备方法得到的产品无色透明，通过亨特立色度仪测试色度(Hazen)为18，通过库仑测氯仪测试卤素含量(氯残留)为181ppm。
实施例6
向反应釜内加入220.6g质量分数为18％的NaSH水溶液(NaSH与环氧氯丙烷的摩尔比为1.2：1)和4.2g实施例3制备的相转移催化剂QA-SBA-15，然后加入161.0g氯代聚醚，将反应釜封闭后检查气密性，置换后向釜内通入H 2S气体使釜内处于常压，通过油浴加热反应体系至85℃后保温反应6小时，然后开启反应釜的放空阀并用N 2置换，产物静置分层后，得到粗产品A；将粗产品A加入175g去离子水中进行一次水洗，用盐酸调节有机相pH至5～7，待稳定后静置分层，取出下层物质即为粗产品B；向粗产品B中加入175g去离子水混合均匀后静置10小时，然后切出产物并在真空度≤-0.095MPa条件下进行除水，除水温度为65℃，时间为2小时，得到无色透明聚醚型多 硫醇产物154.2g。
对比例1
采用实施例4提供的制备方法得到聚硫醇类固化剂；区别在于：使用12.5g相转移催化剂四丁基氯化铵代替实施例4中的3.5g催化剂QA-SBA-15。
对比例1提供的制备方法得到的产品无色透明，通过亨特立色度仪测试色度(Hazen)为27，通过库仑测氯仪测试卤素含量(氯残留)为589ppm。
对比例2
采用实施例4提供的制备方法得到聚硫醇类固化剂；区别在于：使用16g相转移催化剂苄基三乙基氯化铵代替实施例4中的催化剂QA-SBA-15。
对比例2提供的制备方法得到的产品无色透明，通过亨特立色度仪测试色度(Hazen)为21，通过库仑测氯仪测试卤素含量(氯残留)为673ppm。
综上所述，采用本发明提供的制备方法，通过无溶剂法三相相转移催化合成得到的环氧树脂用聚硫醇类固化剂产品外观无色透明，色度小于20，氯残留仅为100ppm～200ppm，明显优于对比例中常规方法制备得到的聚硫醇类固化剂。由此可知，本发明提供的制备方法能制造产品环保的氯残留低的无色透明高粘度聚硫醇产品，反应过程无需使用有机溶剂，且使用有机高分子聚合物将相转移催化剂固载后，实现了昂贵催化剂回收再利用的目标，由于催化剂易回收，使产品除盐、除卤素的处理难度降低，得到产品氯残留在100ppm～200ppm范围。因此，本发明在降低原料成本、生产成本的同时，降低后处理难度及三废处理难度，且由于产品环保可进一步拓展其应用领域，具有非常好的工业化应用前景。

Claims (10)

  1. 一种制备聚硫醇类固化剂的催化剂，其特征在于，该催化剂为表面基团改性的介孔分子筛SBA-15，记为QA-SBA-15，其表面基团包括结构如式Ⅰ：
    Figure PCTCN2020124205-appb-100001
    其中，左侧竖直加粗黑线代表介孔分子筛SBA-15基体骨架，R 1、R 2、R 3为C1～C10的直链或支链烷烃，可相同也可不同；Y为Cl或Br。
  2. 如权利要求1所述的一种制备聚硫醇类固化剂的催化剂的制备方法，其特征在于，在保护气氛下，将卤化试剂与介孔分子筛SBA-15在有机溶剂中进行回流反应，对其进行表面卤化改性，得到卤化SBA-15；将所得卤化SBA-15与叔胺进行反应，得到季铵盐三相相转移催化剂QA-SBA-15。
  3. 根据权利要求2所述的一种制备聚硫醇类固化剂的催化剂的制备方法，其特征在于，所述卤化试剂与介孔分子筛SBA-15的质量比为(0.5～4)：1；卤化SBA-15与叔胺反应中卤原子与叔胺中的氮的摩尔比为1：(2～4)。
  4. 根据权利要求2所述的一种制备聚硫醇类固化剂的催化剂的制备方法，其特征在于，所述保护气氛为氮气；所述的卤化试剂选自3-氯丙基三甲氧基硅烷或3-氯丙基三乙氧基硅烷或3-溴丙基三甲氧基硅烷或3-溴丙基三乙氧基硅烷或其组合；所述有机溶剂为醇溶剂；所述的叔胺结构式如式Ⅱ所示：
    Figure PCTCN2020124205-appb-100002
    其中R 1、R 2、R 3为C1～C10的直链或支链烷烃，可相同也可不同；
    所述反应体系中卤化试剂的浓度为30～100mmol/L；所述回流反应的时间为20～24h；卤化SBA-15与叔胺反应的温度为70℃～120℃；卤化SBA-15与叔胺反应的时间为8～12h。
  5. 根据权利要求4所述的一种制备聚硫醇类固化剂的催化剂的制备方法，其特征在 于，所述的叔胺选自三正丙胺或三正丁胺或其组合。
  6. 根据权利要求2所述的一种制备聚硫醇类固化剂的催化剂的制备方法，其特征在于，将所得卤化SBA-15与叔胺进行反应时，加入二氯乙烷和无水乙醇作为溶剂。
  7. 利用权利要求1所述的催化剂合成聚硫醇固化剂的方法，其特征在于，包括以下步骤：将NaSH、催化剂QA-SBA-15、卤代聚醚多元醇在常压H 2S气体环境下进行反应，再分离出催化剂，得到粗产品；再将粗产品依次进行水洗和干燥，得到环氧树脂用聚硫醇类固化剂。
  8. 根据权利要求7所述的合成聚硫醇固化剂的方法，其特征在于，所述催化剂QA-SBA-15的加入量为卤代聚醚多元醇质量的0.1％～10％；所述NaSH的加入量按照NaSH与卤代聚醚多元醇中的卤素原子的摩尔比(0.5～3)：1添加；所述NaSH以NaSH水溶液的形式添加，NaSH水溶液的质量分数为10％～50％；所述卤代聚醚多元醇，其结构如式Ⅲ所示：
    Figure PCTCN2020124205-appb-100003
    其中，m、n、p独立地选自2～5的整数，R为C1～C10的直链烷基或C1～C10的支链烷基或经取代的芳基或未经取代的芳基，X为F，Cl，Br中的一种或多种。
  9. 根据权利要求7所述的合成聚硫醇固化剂的方法，其特征在于，聚硫醇固化剂的合成中，反应温度为60℃～150℃，反应时间为2h～20h。
  10. 根据权利要求7所述的合成聚硫醇固化剂的方法，其特征在于，所述水洗的过程具体为：将得到的粗产品加入水中进行一次水洗，调节有机相pH至5～7，待稳定后静置分层，取出下层物质与水混合均匀后静置10h～14h，然后切出产物，完成水洗过程；所述干燥的方式为真空脱水，真空脱水的真空度小于等于-0.095MPa，真空脱水的温度为60℃～70℃，真空脱水的时间为1h～3h。
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