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CN101497691A - High activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol and preparation thereof - Google Patents

High activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol and preparation thereof Download PDF

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CN101497691A
CN101497691A CNA2008101877053A CN200810187705A CN101497691A CN 101497691 A CN101497691 A CN 101497691A CN A2008101877053 A CNA2008101877053 A CN A2008101877053A CN 200810187705 A CN200810187705 A CN 200810187705A CN 101497691 A CN101497691 A CN 101497691A
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hydroxyl
activityhydroxyl
zinc
terminated polyepichlorohydrin
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顾尧
孙兆任
冯新武
吴如舟
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Qingdao Xinyutian Chemical Co Ltd
Qingdao University of Science and Technology
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Qingdao Xinyutian Chemical Co Ltd
Qingdao University of Science and Technology
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Abstract

一种制备工艺简单、产品颜色好的高活性端羟基聚环氧氯丙烷醚多元醇及其制备方法。技术方案是:其分子结构为带有大量亚甲基氯侧基的以环氧乙烷或环氧丙烷封端的端羟基聚醚多元醇,平均相对分子质量500~9000、平均羟基官能度2~3。制备方法为在耐压反应釜中加入小分子量起始剂、双金属氰化物络合物催化剂,真空脱出易挥发性组分,加入部分环氧氯丙烷,加热至100~140℃,在氮气保护和高速搅拌下反应;激活后逐步滴加剩余环氧氯丙烷。聚合反应完成后降温至90~120℃,滴加环氧丙烷或环氧乙烷进行封端,反应完毕,真空脱出残留单体,得到端羟基聚环氧氯丙烷醚多元醇。A highly active hydroxyl-terminated polyepichlorohydrin ether polyol with simple preparation process and good product color and a preparation method thereof. The technical solution is: its molecular structure is a hydroxyl-terminated polyether polyol capped with ethylene oxide or propylene oxide with a large number of methylene chloride side groups, the average relative molecular mass is 500~9000, and the average hydroxyl functionality is 2~ 3. The preparation method is to add a small molecular weight initiator and a double metal cyanide complex catalyst in a pressure-resistant reactor, remove the volatile components in a vacuum, add part of epichlorohydrin, heat to 100~140°C, and protect it under nitrogen React with high-speed stirring; after activation, gradually add the remaining epichlorohydrin dropwise. After the polymerization reaction is completed, the temperature is lowered to 90~120°C, and propylene oxide or ethylene oxide is added dropwise for capping. After the reaction is completed, the residual monomer is removed in a vacuum to obtain a hydroxyl-terminated polyepichlorohydrin ether polyol.

Description

一种高活性端羟基聚环氧氯丙烷醚多元醇及其制备方法 A kind of highly active hydroxyl-terminated polyepichlorohydrin ether polyol and preparation method thereof

技术领域 technical field

本发明属于聚合物合成材料聚醚多元醇技术领域,具体涉及一种高活性端羟基聚环氧氯丙烷醚多元醇及其制备方法。The invention belongs to the technical field of polymer synthetic material polyether polyol, and in particular relates to a highly active hydroxyl-terminated polyepichlorohydrin ether polyol and a preparation method thereof.

背景技术 Background technique

聚醚多元醇是合成聚氨酯材料的主要原料之一,现已被广泛的应用于聚氨酯硬泡、聚氨酯软泡、聚氨酯弹性体、聚氨酯微孔弹性体、聚氨酯涂料以及聚氨酯胶粘剂等各个方面的合成。其优异的力学性能和方便的可操作加工性使得其在现代生活中具有广阔的发展空间。目前,已经大规模工业化和广泛应用的聚醚多元醇大都是采用阴离子聚合的聚环氧丙烷醚、聚环氧乙烷醚、环氧丙烷和环氧乙烷共聚醚以及用环氧乙烷封端的聚环氧丙烷醚。此类聚醚多元醇醚键内聚能较低,易于旋转,故由它制备的聚氨酯材料低温柔顺性好,耐曲挠性能优良,并且具有较好的耐水性、耐霉菌等性能。但是,其耐水性只是相对于淡水来说的,由于海水中含有大量的各种金属离子,具有很强的腐蚀性,使得这种聚醚多元醇在耐海水性能方面大打折扣,不能被很好的应用在海洋方面。随着研究和应用的不断深入,人们发现端羟基聚环氧氯丙烷多元醇(PECH)由于其分子链上带有大量亚甲基氯侧基,含氯量高达38%,具有非常好的耐腐蚀能力,同时大量亚甲基氯侧基的存在还增大了分子间的内摩擦,使得含PECH的材料具有很高的阻尼系数,可以用作耐海水、耐油、阻尼的胶粘剂和灌封材料,因而推断其将拥有广泛的应用前景。Polyether polyol is one of the main raw materials for the synthesis of polyurethane materials, and has been widely used in the synthesis of polyurethane rigid foam, polyurethane soft foam, polyurethane elastomer, polyurethane microcellular elastomer, polyurethane coating and polyurethane adhesive. Its excellent mechanical properties and convenient operability make it have a broad development space in modern life. At present, most of the polyether polyols that have been industrialized and widely used are anionically polymerized polypropylene oxide ether, polyethylene oxide ether, propylene oxide and ethylene oxide copolyether, and sealed with ethylene oxide. terminal polypropylene oxide ether. This type of polyether polyol ether bond has low cohesive energy and is easy to rotate, so the polyurethane material prepared from it has good low-temperature flexibility, excellent flex resistance, and has good water resistance and mold resistance. However, its water resistance is only relative to fresh water. Since sea water contains a large amount of various metal ions and is highly corrosive, this polyether polyol is greatly reduced in sea water resistance and cannot be used well. applications in the ocean. With the continuous deepening of research and application, it has been found that hydroxyl-terminated polyepichlorohydrin polyol (PECH) has a very good resistance Corrosion ability, at the same time, the presence of a large number of methylene chloride side groups also increases the internal friction between molecules, making PECH-containing materials have a high damping coefficient, and can be used as seawater-resistant, oil-resistant, damping adhesives and potting materials , so it is inferred that it will have a wide range of application prospects.

目前,有关端羟基聚环氧氯丙烷醚的开发利用相对较少,国内几乎没有,国外具有较小规模的工业化生产。这可能跟目前的催化体系有关。由于环氧氯丙烷单体分子结构上含有一个氯原子,因此不能用传统的NaOH或KOH等阴离子催化体系催化其聚合。当前端羟基聚环氧氯丙烷醚的合成都是采用BF3、SnCl4等阳离子聚合催化剂来实现的。众所周知,阳离子聚合具有很多的弊病,例如反应剧烈不易控制,极易发生链转移而使得聚合物相对分子质量不高,聚合物分子量分布宽,聚合物不饱和度高,聚合物端羟基含量少等等,这对制备高性能聚氨酯材料极为不利。不仅如此,目前采用阳离子聚合合成端羟基聚环氧氯丙烷醚还有很多其他方面的缺点,例如专利US4340749、US4391970、US4431845、US2327053、US2380185中以金属卤化物SnCl4为催化剂可以合成端羟基聚环氧氯丙烷醚,但这种阳离子聚合生成的聚醚为黑色,严重制约了其应用。而且以SnCl4为催化剂合成的PECH含有10-20%的杂质,如低聚物、不含羟基的官能团等副产品,并且制备分子量越大,杂质愈多。产生环状齐聚物是阳离子聚合的一大特点。如需去除杂质,则必须进行费时的蒸馏和提取。另外,采用阳离子催化聚合的产品分子量分布宽,影响材料的物理性能。专利US4879419采用SnCl4为主催化剂,以羧酸为共催化剂来合成PECH。产品的分子量分布变窄了,一般低于1.5(分子量小于2000时),好的达到1.2以下(采用共催化剂时)。而且1000分子量的产品中环状低聚物含量在2%以下,当采用共催化剂时甚至没有低聚物(当产品的分子量不是太大时),而且颜色变浅。但是随着分子量的增大,还是有副产物产生的,而且分子量分布也会逐渐变宽。At present, there is relatively little development and utilization of hydroxyl-terminated polyepichlorohydrin ethers, almost none in China, and small-scale industrial production abroad. This may be related to the current catalytic system. Since the molecular structure of epichlorohydrin monomer contains a chlorine atom, it cannot be catalyzed by traditional anion catalyst systems such as NaOH or KOH to catalyze its polymerization. At present, the synthesis of end-hydroxy polyepichlorohydrin ether is realized by cationic polymerization catalysts such as BF 3 and SnCl 4 . As we all know, cationic polymerization has many disadvantages, such as violent reaction is difficult to control, chain transfer is very easy to occur so that the relative molecular weight of the polymer is not high, the molecular weight distribution of the polymer is wide, the degree of unsaturation of the polymer is high, and the content of the terminal hydroxyl group of the polymer is small, etc. etc., which is extremely unfavorable for the preparation of high-performance polyurethane materials. Not only that, there are still many other shortcomings in the synthesis of hydroxyl-terminated polyepichlorohydrin ethers by cationic polymerization. For example, in patents US4340749, US4391970, US4431845, US2327053, and US2380185, metal halide SnCl4 can be used as a catalyst to synthesize hydroxyl-terminated polycyclic Oxychloropropane ether, but the polyether produced by this cationic polymerization is black, which seriously restricts its application. Moreover, PECH synthesized with SnCl4 as a catalyst contains 10-20% impurities, such as by-products such as oligomers and functional groups without hydroxyl groups, and the larger the molecular weight of the preparation, the more impurities. The generation of cyclic oligomers is a major feature of cationic polymerization. Time-consuming distillation and extraction are necessary to remove impurities. In addition, the molecular weight distribution of the product using cationic catalytic polymerization is wide, which affects the physical properties of the material. Patent US4879419 uses SnCl 4 as the main catalyst and carboxylic acid as the co-catalyst to synthesize PECH. The molecular weight distribution of the product is narrowed, generally lower than 1.5 (when the molecular weight is less than 2000), and well below 1.2 (when a co-catalyst is used). And the cyclic oligomer content is below 2% in the product of 1000 molecular weights, even do not have oligomer (when the molecular weight of product is not too large) when adopting co-catalyst, and color becomes lighter. However, with the increase of molecular weight, there are still by-products, and the molecular weight distribution will gradually broaden.

目前所合成的这些端羟基聚环氧氯丙烷醚大多都是以仲羟基封端的,其反应活性相对伯羟基要低了很多,而且由于端羟基旁边带有空间位阻极大的亚甲基氯基团,使得羟基的活性进一步降低。针对这些问题专利EP0042505、US5164521等介绍了其在改进端羟基聚ECH醚的端基活性方面所做的贡献,其利用环氧乙烷等进行封端处理,从而得到带有伯羟基的端羟基聚环氧氯丙烷醚。此类催化剂在催化环氧氯丙烷聚合时,反应时间长达二十多小时,进行封端处理的话,反应时间还会进一步增长。Most of these hydroxyl-terminated polyepichlorohydrin ethers currently synthesized are terminated with secondary hydroxyl groups, and their reactivity is much lower than that of primary hydroxyl groups. group, which further reduces the activity of the hydroxyl group. In response to these problems, patents EP0042505, US5164521, etc. introduced their contributions to improving the end group activity of hydroxyl-terminated poly ECH ethers. They used ethylene oxide to perform end-capping treatment, thereby obtaining hydroxyl-terminated polyethers with primary hydroxyl groups. Epichlorohydrin ether. When this type of catalyst catalyzes the polymerization of epichlorohydrin, the reaction time is as long as more than 20 hours. If the end-capping treatment is performed, the reaction time will be further increased.

发明内容 Contents of the invention

针对以上问题,本专利发明了一种新的制备高活性端羟基聚环氧氯丙烷醚多元醇的方法。此方法是采用双金属氰化物络合物催化剂(DMC)通过配位聚合来制备高活性端羟基聚环氧氯丙烷醚多元醇。此方法催化效率高,催化剂在聚合物中的含量极少,产品中金属离子Zn2+和Co3+残留量低,从而免除产品的提纯、催化剂分离等后处理工序,制备工艺简单,产品颜色好(为略带黄色或黄绿色的透明状粘稠液体),分子量高低可任意调节,分子量分布窄,而且聚合过程中不会有副产物产生。Aiming at the above problems, this patent has invented a new method for preparing polyepichlorohydrin ether polyol with high activity terminal hydroxyl groups. The method adopts a double metal cyanide complex catalyst (DMC) to prepare high-activity hydroxyl-terminated polyepichlorohydrin ether polyol through coordination polymerization. This method has high catalytic efficiency, the content of the catalyst in the polymer is very small, and the residual amount of metal ions Zn 2+ and Co 3+ in the product is low, thereby eliminating the post-treatment procedures such as product purification and catalyst separation. The preparation process is simple and the product color Good (it is slightly yellow or yellowish green transparent viscous liquid), the molecular weight can be adjusted arbitrarily, the molecular weight distribution is narrow, and there will be no by-products during the polymerization process.

本发明的技术方案是:一种高活性端羟基聚环氧氯丙烷醚多元醇,其特征在于该聚醚多元醇分子结构为带有大量亚甲基氯侧基的端羟基聚醚多元醇,其平均相对分子质量在500~9000、平均羟基官能度在2~3之间。The technical scheme of the present invention is: a kind of highly reactive hydroxyl-terminated polyepichlorohydrin ether polyol, characterized in that the molecular structure of the polyether polyol is a hydroxyl-terminated polyether polyol with a large amount of methylene chloride side groups, Its average relative molecular weight is 500-9000, and the average hydroxyl functionality is between 2-3.

所述的端羟基聚环氧氯丙烷醚多元醇是一种端基为伯羟基或仲羟基的遥爪聚合物。The hydroxyl-terminated polyepichlorohydrin ether polyol is a telechelic polymer whose terminal group is a primary or secondary hydroxyl group.

本发明的高活性端羟基聚环氧氯丙烷醚多元醇是采用双金属氰化物络合物催化剂(DMC)通过配位聚合机理来催化环氧氯丙烷均聚,然后再以环氧乙烷或环氧丙烷封端得到的高活性聚醚多元醇。The high-activity hydroxyl-terminated polyepichlorohydrin ether polyol of the present invention adopts a double metal cyanide complex catalyst (DMC) to catalyze the homopolymerization of epichlorohydrin through a coordination polymerization mechanism, and then ethylene oxide or Highly active polyether polyol obtained by capping propylene oxide.

该端羟基聚环氧氯丙烷醚多元醇的平均相对分子质量在500~2000、平均羟基官能度在2~3之间时,可以作为合成聚氨酯的原料与甲苯而二异氰酸酯、二苯基甲烷二异氰酸酯、多亚甲基多苯基多异氰酸酯、多异氰酸酯预聚体中的一种或一种以上的混合物反应制备耐油、耐海水、耐酸、碱聚氨酯胶粘剂、聚氨酯涂料等。When the average molecular mass of the hydroxyl-terminated polyepichlorohydrin ether polyol is 500-2000 and the average hydroxyl functionality is between 2 and 3, it can be used as a raw material for synthesizing polyurethane with toluene diisocyanate and diphenylmethane diisocyanate. One or more mixtures of isocyanate, polymethylene polyphenyl polyisocyanate, and polyisocyanate prepolymer are reacted to prepare oil-resistant, seawater-resistant, acid-resistant, alkali-resistant polyurethane adhesives, polyurethane coatings, etc.

该端羟基聚环氧氯丙烷醚多元醇的平均相对分子质量在2000~9000、平均羟基官能度在2~3之间时,可以作为合成聚氨酯的原料与甲苯而二异氰酸酯、二苯基甲烷二异氰酸酯、多亚甲基多苯基多异氰酸酯、多异氰酸酯预聚体中的一种或一种以上的混合物反应制备各种耐海水、耐油的电缆插头的密封胶、阻尼聚氨酯弹性体、阻尼聚氨酯涂料等。When the average molecular mass of the hydroxyl-terminated polyepichlorohydrin ether polyol is between 2000 and 9000 and the average hydroxyl functionality is between 2 and 3, it can be used as a raw material for synthesizing polyurethane with toluene diisocyanate and diphenylmethane diisocyanate. One or more mixtures of isocyanate, polymethylene polyphenyl polyisocyanate, and polyisocyanate prepolymer are used to prepare various seawater-resistant and oil-resistant sealants for cable plugs, damping polyurethane elastomers, and damping polyurethane coatings wait.

本发明的高活性端羟基聚环氧氯丙烷醚多元醇的制备方法如下:The preparation method of the highly active hydroxyl-terminated polyepichlorohydrin ether polyol of the present invention is as follows:

(1)在耐压反应釜中加入小分子量起始剂、双金属氰化物络合物催化剂,真空脱出易挥发性组分,加入部分环氧氯丙烷,然后加热至100~140℃,在氮气保护和高速搅拌的条件下进行反应;反应激活后逐步滴加剩余环氧氯丙烷。(1) Add a small molecular weight initiator and a double metal cyanide complex catalyst into a pressure-resistant reactor, remove volatile components in a vacuum, add part of epichlorohydrin, then heat to 100-140°C, Under the conditions of protection and high-speed stirring, the reaction is carried out; after the reaction is activated, the remaining epichlorohydrin is gradually added dropwise.

(2)第(1)步中环氧氯丙烷聚合完成以后,将反应釜内温度降至90~120℃,再滴加环氧丙烷或环氧乙烷进行封端,反应完毕,真空脱出残留单体,得到平均相对分子质量在500~9000、平均羟基官能度在2~3的端羟基聚环氧氯丙烷醚多元醇。(2) After the polymerization of epichlorohydrin in step (1) is completed, the temperature in the reactor is lowered to 90-120°C, and then propylene oxide or ethylene oxide is added dropwise for capping. After the reaction is completed, the residual monomers to obtain hydroxyl-terminated polyepichlorohydrin ether polyols with an average relative molecular mass of 500-9000 and an average hydroxyl functionality of 2-3.

上述步骤(1)中的小分子量起始剂是丙二醇、1,4-丁二醇、4,4-二羟基二苯基丙烷、相对分子质量为400的两官能度聚醚多元醇、丙三醇、三羟乙基异氰尿酸酯、相对分子质量为250的三官能度聚醚多元醇、相对分子质量为700的三官能度聚醚多元醇中的一种或一种以上的混合物。The low-molecular-weight starter in the above-mentioned step (1) is propylene glycol, 1,4-butanediol, 4,4-dihydroxydiphenylpropane, the two-functionality polyether polyol that relative molecular mass is 400, glycerine Alcohol, trihydroxyethyl isocyanurate, trifunctional polyether polyol with a relative molecular mass of 250, and trifunctional polyether polyol with a relative molecular mass of 700, or a mixture of more than one.

上述步骤(1)中的一部分环氧氯丙烷与剩余部分环氧氯丙烷的质量比在100:0~1:99之间。The mass ratio of a part of epichlorohydrin to the remaining part of epichlorohydrin in the above step (1) is between 100:0 and 1:99.

上述步骤(1)中小分子量起始剂与环氧氯丙烷的摩尔比在1:4~1:100之间。The molar ratio of the small molecular weight initiator to epichlorohydrin in the above step (1) is between 1:4 and 1:100.

上述步骤(1)中双金属氰化物络合物催化剂是叔丁醇为配体之一的双金属氰化物络合物催化剂为分散相、含活泼氢的低聚物多元醇为连续相的乳液状双金属氰化物络合物催化剂。其中双金属氰化物络合物催化剂用量占所合成的聚醚多元醇质量的300~800ppm.In the above step (1), the double metal cyanide complex catalyst is an emulsion in which the double metal cyanide complex catalyst is one of the ligands as the dispersed phase and the oligomer polyol containing active hydrogen is the continuous phase. double metal cyanide complex catalyst. The amount of double metal cyanide complex catalyst accounts for 300-800ppm of the quality of the synthesized polyether polyol.

上述步骤(1)中双金属氰化物络合物催化剂是六氰合钴酸钾与锌盐在水、叔丁醇、聚醚多元醇存在下经络合反应、洗涤、干燥等工序制备的。The double metal cyanide complex catalyst in the above step (1) is prepared by complexing reaction, washing, drying and other processes in the presence of potassium hexacyanocobaltate and zinc salt in the presence of water, tert-butanol and polyether polyol.

上述的双金属氰化物络合物催化剂的制备方法,其特征在于上述锌盐是氯化锌、溴化锌、碘化锌、硫酸锌、硝酸锌、磷酸锌、碳酸锌、草酸锌中的一种或一种以上的混合物,锌盐与六氰钴酸钾的摩尔比在1.5:1~20:1之间,其中溴化锌与六氰钴酸钾的摩尔比在1.8:1~15:1之间。The preparation method of above-mentioned double metal cyanide complex catalyst is characterized in that above-mentioned zinc salt is one of zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, zinc phosphate, zinc carbonate, zinc oxalate A mixture of one or more kinds, the molar ratio of zinc salt to potassium hexacyanocobaltate is between 1.5:1 and 20:1, and the molar ratio of zinc bromide to potassium hexacyanocobaltate is 1.8:1 to 15: between 1.

上述步骤(2)中聚环氧氯丙烷醚与环氧乙烷或环氧丙烷的摩尔比在1:1~1:3之间。The molar ratio of polyepichlorohydrin ether to ethylene oxide or propylene oxide in the above step (2) is between 1:1 and 1:3.

本发明与现有技术相比具有以下优点:Compared with the prior art, the present invention has the following advantages:

本发明的高活性端羟基聚环氧氯丙烷醚多元醇是采用双金属氰化物络合物催化剂催化环氧氯丙烷聚合的,属于配位聚合机理,它不同于传统的阳离子聚合。利用此催化体系聚合物分子量大小可任意调节,分子量分布窄,不饱和度低,可以用于高性能要求的聚氨酯材料的合成;聚合过程中无副产物产生,催化剂的催化活性高,聚合过程中催化剂的加入量少,产品中金属离子Zn2+和Co3+残留量低,从而免除产品的提纯、催化剂分离等后处理工序,制备工艺简单;所合成的聚合物是以伯羟基或仲羟基封端的端羟基聚环氧氯丙烷醚多元醇,与异氰酸酯反应时反应活性高;聚合物产品为略带黄色或黄绿色的透明状粘稠液体,较阳离子聚合得到的黑色或琥珀色端羟基聚环氧氯丙烷醚在颜色上有了极大的改观。易于实现工业化生产和达到工业产品色度要求。The high-activity hydroxyl-terminated polyepichlorohydrin ether polyol of the present invention uses a double metal cyanide complex catalyst to catalyze the polymerization of epichlorohydrin, which belongs to the mechanism of coordination polymerization, which is different from traditional cationic polymerization. Using this catalytic system, the molecular weight of the polymer can be adjusted arbitrarily, the molecular weight distribution is narrow, and the degree of unsaturation is low, which can be used for the synthesis of polyurethane materials with high performance requirements; no by-products are produced during the polymerization process, and the catalytic activity of the catalyst is high. The amount of catalyst added is small, and the residual amount of metal ions Zn 2+ and Co 3+ in the product is low, thereby eliminating the post-treatment procedures such as product purification and catalyst separation, and the preparation process is simple; the synthesized polymer is based on primary or secondary hydroxyl groups End-capped hydroxyl-terminated polyepichlorohydrin ether polyols have high reactivity when reacting with isocyanate; the polymer product is a slightly yellow or yellow-green transparent viscous liquid, which is black or amber in color compared with cationic polymerization-terminated hydroxyl-terminated polyols. Epichlorohydrin ethers show a dramatic improvement in color. It is easy to realize industrialized production and meet the chromaticity requirements of industrial products.

具体实施方式 Detailed ways

实施例1.一种高活性端羟基聚环氧氯丙烷醚多元醇的制备方法。在耐压反应釜中加入15g 4,4-二羟基二苯基丙烷、0.099g双金属氰化物络合物催化剂(DMC),真空脱出易挥发性组分,加入90g环氧氯丙烷,然后加热至128℃,在氮气保护和高速搅拌的条件下反应;待反应激活后逐步滴加剩余的92.4g环氧氯丙烷。环氧氯丙烷聚合完成以后,将反应釜内温度降至115℃,滴加17.6g环氧乙烷反应进行封端。反应完成后,真空脱出残留单体,精制得到平均相对分子质量为3264、平均羟基官能度为2的端羟基聚环氧氯丙烷醚多元醇。Embodiment 1. A kind of preparation method of highly active hydroxyl-terminated polyepichlorohydrin ether polyol. Add 15g 4,4-dihydroxydiphenylpropane, 0.099g double metal cyanide complex catalyst (DMC) in the pressure-resistant reactor, remove volatile components in vacuum, add 90g epichlorohydrin, and then heat To 128°C, react under nitrogen protection and high-speed stirring; after the reaction is activated, gradually add the remaining 92.4g of epichlorohydrin dropwise. After the polymerization of epichlorohydrin was completed, the temperature in the reactor was lowered to 115° C., and 17.6 g of ethylene oxide was added dropwise to react for capping. After the reaction is completed, the residual monomers are removed in vacuum, and the hydroxyl-terminated polyepichlorohydrin ether polyol with an average relative molecular mass of 3264 and an average hydroxyl functionality of 2 is obtained by refining.

实施例2.一种高活性端羟基聚环氧氯丙烷醚多元醇的制备方法。在耐压反应釜中加入15g 4,4-二羟基二苯基丙烷、0.132g DMC,真空脱出易挥发性组分,加入90g环氧氯丙烷,然后加热至128℃,在氮气保护和高速搅拌的条件下反应;待反应激活后逐步滴加剩余的224g环氧氯丙烷。环氧氯丙烷聚合完成以后,将反应釜内温度降至115℃,滴加17.6g环氧乙烷反应进行封端。反应完成后,真空脱出残留单体,精制得到平均相对分子质量为5264、平均羟基官能度为2的端羟基聚环氧氯丙烷醚多元醇。Embodiment 2. A kind of preparation method of highly active hydroxyl-terminated polyepichlorohydrin ether polyol. Add 15g of 4,4-dihydroxydiphenylpropane and 0.132g of DMC to the pressure-resistant reactor, remove the volatile components in vacuum, add 90g of epichlorohydrin, then heat to 128°C, under nitrogen protection and high-speed stirring Reaction under the condition; After the reaction is activated, gradually add the remaining 224g epichlorohydrin dropwise. After the polymerization of epichlorohydrin was completed, the temperature in the reactor was lowered to 115° C., and 17.6 g of ethylene oxide was added dropwise to react for capping. After the reaction is completed, the residual monomer is removed in vacuum, and the hydroxyl-terminated polyepichlorohydrin ether polyol with an average relative molecular weight of 5264 and an average hydroxyl functionality of 2 is obtained by refining.

实施例3.一种高活性端羟基聚环氧氯丙烷醚多元醇的制备方法。在耐压反应釜中加入15g 4,4-二羟基二苯基丙烷、0.099g DMC,真空脱出易挥发性组分,加入90g环氧氯丙烷,然后加热至128℃,在氮气保护和高速搅拌的条件下反应;待反应激活后逐步滴加剩余的92.4g环氧氯丙烷。环氧氯丙烷聚合完成以后,将反应釜内温度降至115℃,滴加23.2g环氧丙烷反应进行封端。反应完成后,真空脱出残留单体,精制得到平均相对分子质量为3348、平均羟基官能度为2的端羟基聚环氧氯丙烷醚多元醇。Embodiment 3. A kind of preparation method of highly active hydroxyl-terminated polyepichlorohydrin ether polyol. Add 15g of 4,4-dihydroxydiphenylpropane and 0.099g of DMC to the pressure-resistant reactor, remove the volatile components in vacuum, add 90g of epichlorohydrin, then heat to 128°C, under nitrogen protection and high-speed stirring Reaction under the conditions; After the reaction is activated, gradually add the remaining 92.4g epichlorohydrin dropwise. After the polymerization of epichlorohydrin is completed, the temperature in the reactor is lowered to 115° C., and 23.2 g of propylene oxide is added dropwise to react for capping. After the reaction is completed, the residual monomer is removed in a vacuum, and the hydroxyl-terminated polyepichlorohydrin ether polyol with an average relative molecular weight of 3348 and an average hydroxyl functionality of 2 is obtained by refining.

实施例4.一种高活性端羟基聚环氧氯丙烷醚多元醇的制备方法。在耐压反应釜中加入30g相对分子质量为400的两官能度聚醚多元醇、0.162g DMC,真空脱出易挥发性组分,加入60g环氧氯丙烷,然后加热至135℃,在氮气保护和高速搅拌的条件下反应;待反应激活后逐步滴加剩余的113g环氧氯丙烷。环氧氯丙烷聚合完成以后,将反应釜内温度降至115℃,滴加23g环氧丙烷反应进行封端。反应完成后,真空脱出残留单体,精制得到平均相对分子质量为3000、平均羟基官能度为2的端羟基聚环氧氯丙烷醚多元醇。Embodiment 4. A kind of preparation method of highly active hydroxyl-terminated polyepichlorohydrin ether polyol. Add 30g of bifunctional polyether polyol with a relative molecular mass of 400 and 0.162g of DMC into a pressure-resistant reactor, remove volatile components in vacuum, add 60g of epichlorohydrin, then heat to 135°C, React under the condition of high-speed stirring; After the reaction is activated, gradually add the remaining 113g epichlorohydrin dropwise. After the polymerization of epichlorohydrin is completed, the temperature in the reactor is lowered to 115° C., and 23 g of propylene oxide is added dropwise to react for capping. After the reaction is completed, the residual monomer is removed in a vacuum, and the hydroxyl-terminated polyepichlorohydrin ether polyol with an average relative molecular weight of 3000 and an average hydroxyl functionality of 2 is obtained by refining.

实施例5.一种高活性端羟基聚环氧氯丙烷醚多元醇的制备方法。在耐压反应釜中加入20g三羟乙基异氰尿酸酯、0.138g DMC,真空脱出易挥发性组分,加入80g环氧氯丙烷,然后加热至135℃,在氮气保护和高速搅拌的条件下反应;待反应激活后逐步滴加剩余的130g环氧氯丙烷。环氧氯丙烷聚合完成以后,将反应釜内温度降至115℃,滴加30.4g环氧乙烷反应进行封端。反应完成后,真空脱出残留单体,精制得到平均相对分子质量为3400、平均羟基官能度为3的端羟基聚环氧氯丙烷醚多元醇。Embodiment 5. A kind of preparation method of highly active hydroxyl-terminated polyepichlorohydrin ether polyol. Add 20g of trishydroxyethyl isocyanurate and 0.138g of DMC into a pressure-resistant reactor, remove the volatile components in vacuum, add 80g of epichlorohydrin, then heat to 135°C, under nitrogen protection and high-speed stirring Reaction under conditions; after the reaction is activated, gradually add the remaining 130g of epichlorohydrin dropwise. After the polymerization of epichlorohydrin is completed, the temperature in the reactor is lowered to 115° C., and 30.4 g of ethylene oxide is added dropwise to react for capping. After the reaction is completed, the residual monomer is removed in a vacuum, and the hydroxyl-terminated polyepichlorohydrin ether polyol with an average relative molecular mass of 3400 and an average hydroxyl functionality of 3 is obtained by refining.

实施例6.一种高活性端羟基聚环氧氯丙烷醚多元醇的制备方法。在耐压反应釜中加入20g三羟乙基异氰尿酸酯、0.138g DMC,真空脱出易挥发性组分,加入80g环氧氯丙烷,然后加热至135℃,在氮气保护和高速搅拌的条件下反应;待反应激活后逐步滴加剩余的130g环氧氯丙烷。环氧氯丙烷聚合完成以后,将反应釜内温度降至115℃,滴加40g环氧丙烷反应进行封端。反应完成后,真空脱出残留单体,精制得到平均相对分子质量为3500、平均羟基官能度为3的端羟基聚环氧氯丙烷醚多元醇。Embodiment 6. A kind of preparation method of highly active hydroxyl-terminated polyepichlorohydrin ether polyol. Add 20g of trishydroxyethyl isocyanurate and 0.138g of DMC into a pressure-resistant reactor, remove the volatile components in vacuum, add 80g of epichlorohydrin, then heat to 135°C, under nitrogen protection and high-speed stirring Reaction under conditions; after the reaction is activated, gradually add the remaining 130g of epichlorohydrin dropwise. After the polymerization of epichlorohydrin is completed, the temperature in the reactor is lowered to 115° C., and 40 g of propylene oxide is added dropwise to react for capping. After the reaction is completed, the residual monomer is removed in a vacuum, and the hydroxyl-terminated polyepichlorohydrin ether polyol with an average relative molecular weight of 3500 and an average hydroxyl functionality of 3 is obtained by refining.

实施例7.一种高活性端羟基聚环氧氯丙烷醚多元醇的制备方法。在耐压反应釜中加入20g三羟乙基异氰尿酸酯、0.153g DMC、真空脱出易挥发性组分,加入80g环氧氯丙烷,然后加热至128℃,在氮气保护和高速搅拌的条件下反应;待反应激活后逐步滴加剩余的296.4g环氧氯丙烷。环氧氯丙烷聚合完成以后,将反应釜内温度降至115℃,滴加40g环氧丙烷反应进行封端。反应完成后,真空脱出残留单体,精制得到平均相对分子质量为4500、平均羟基官能度为3的端羟基聚环氧氯丙烷醚多元醇。Embodiment 7. A kind of preparation method of highly active hydroxyl-terminated polyepichlorohydrin ether polyol. Add 20g of trishydroxyethyl isocyanurate, 0.153g of DMC, vacuum out the volatile components in a pressure-resistant reactor, add 80g of epichlorohydrin, then heat to 128°C, under nitrogen protection and high-speed stirring Reaction under conditions; after the reaction is activated, gradually add the remaining 296.4g of epichlorohydrin dropwise. After the polymerization of epichlorohydrin is completed, the temperature in the reactor is lowered to 115° C., and 40 g of propylene oxide is added dropwise to react for capping. After the reaction is completed, the residual monomers are removed in a vacuum, and the hydroxyl-terminated polyepichlorohydrin ether polyol with an average relative molecular weight of 4500 and an average hydroxyl functionality of 3 is obtained by refining.

实施例8.一种高活性端羟基聚环氧氯丙烷醚多元醇的制备方法。在耐压反应釜中加入20g三羟乙基异氰尿酸酯、0.192g DMC,真空脱出易挥发性组分,加入80g环氧氯丙烷,然后加热至128℃,在氮气保护和高速搅拌的条件下反应;待反应激活后逐步滴加剩余的283.1g环氧氯丙烷。环氧氯丙烷聚合完成以后,将反应釜内温度降至115℃,滴加30.4g环氧丙烷反应进行封端。反应完成后,真空脱出残留单体,精制得到平均相对分子质量为5400、平均羟基官能度为3的端羟基聚环氧氯丙烷醚多元醇。Embodiment 8. A kind of preparation method of highly active hydroxyl-terminated polyepichlorohydrin ether polyol. Add 20g of trishydroxyethyl isocyanurate and 0.192g of DMC into a pressure-resistant reactor, remove volatile components in a vacuum, add 80g of epichlorohydrin, then heat to 128°C, under nitrogen protection and high-speed stirring Reaction under conditions; after the reaction is activated, gradually add the remaining 283.1g of epichlorohydrin dropwise. After the polymerization of epichlorohydrin is completed, the temperature in the reactor is lowered to 115° C., and 30.4 g of propylene oxide is added dropwise to react for capping. After the reaction is completed, the residual monomer is removed in a vacuum, and the hydroxyl-terminated polyepichlorohydrin ether polyol with an average relative molecular weight of 5400 and an average hydroxyl functionality of 3 is obtained by refining.

实施例9.一种高活性端羟基聚环氧氯丙烷醚多元醇的制备方法。在耐压反应釜中加入20g三羟乙基异氰尿酸酯、0.192g DMC,真空脱出易挥发性组分,加入80g环氧氯丙烷,然后加热至128℃,在氮气保护和高速搅拌的条件下反应;待反应激活后逐步滴加剩余的283.1g环氧氯丙烷。环氧氯丙烷聚合完成以后,将反应釜内温度降至115℃,滴加40g环氧丙烷反应进行封端。反应完成后,真空脱出残留单体,精制得到平均相对分子质量为5500、平均羟基官能度为3的端羟基聚环氧氯丙烷醚多元醇。Embodiment 9. A kind of preparation method of highly active hydroxyl-terminated polyepichlorohydrin ether polyol. Add 20g of trishydroxyethyl isocyanurate and 0.192g of DMC into a pressure-resistant reactor, remove volatile components in a vacuum, add 80g of epichlorohydrin, then heat to 128°C, under nitrogen protection and high-speed stirring Reaction under conditions; after the reaction is activated, gradually add the remaining 283.1g of epichlorohydrin dropwise. After the polymerization of epichlorohydrin is completed, the temperature in the reactor is lowered to 115° C., and 40 g of propylene oxide is added dropwise to react for capping. After the reaction is completed, the residual monomer is removed in a vacuum, and the hydroxyl-terminated polyepichlorohydrin ether polyol with an average relative molecular weight of 5500 and an average hydroxyl functionality of 3 is obtained by refining.

实施例10.一种高活性端羟基聚环氧氯丙烷醚多元醇的制备方法。在耐压反应釜中加入20g相对分子质量为700的三官能度聚醚多元醇、0.114g DMC,真空脱出易挥发性组分,加入60g环氧氯丙烷,然后加热至135℃,在氮气保护和高速搅拌的条件下反应;待反应激活后逐步滴加剩余的63g环氧氯丙烷。环氧氯丙烷聚合完成以后,将反应釜内温度降至115℃,滴加40g环氧丙烷反应进行封端。反应完成后,真空脱出残留单体,精制得到平均相对分子质量为5500、平均羟基官能度为3的端羟基聚环氧氯丙烷醚多元醇。Embodiment 10. A preparation method of highly active hydroxyl-terminated polyepichlorohydrin ether polyol. Add 20g of trifunctional polyether polyol with a relative molecular mass of 700 and 0.114g of DMC into a pressure-resistant reactor, remove volatile components in vacuum, add 60g of epichlorohydrin, then heat to 135°C, React under the condition of high-speed stirring; After the reaction is activated, gradually add the remaining 63g of epichlorohydrin dropwise. After the polymerization of epichlorohydrin is completed, the temperature in the reactor is lowered to 115° C., and 40 g of propylene oxide is added dropwise to react for capping. After the reaction is completed, the residual monomer is removed in a vacuum, and the hydroxyl-terminated polyepichlorohydrin ether polyol with an average relative molecular weight of 5500 and an average hydroxyl functionality of 3 is obtained by refining.

实施例11.一种高活性端羟基聚环氧氯丙烷醚多元醇的制备方法。在耐压反应釜中加入15g三羟乙基异氰尿酸酯、0.230g DMC,真空脱出易挥发性组分,加入80g环氧氯丙烷,然后加热至128℃,在氮气保护和高速搅拌的条件下反应;待反应激活后逐步滴加剩余的365g环氧氯丙烷。环氧氯丙烷聚合完成以后,将反应釜内温度降至115℃,滴加40g环氧丙烷反应进行封端。反应完成后,真空脱出残留单体,精制得到平均相对分子质量为8500、平均羟基官能度为3的端羟基聚环氧氯丙烷醚多元醇。Embodiment 11. A preparation method of highly active hydroxyl-terminated polyepichlorohydrin ether polyol. Add 15g of trishydroxyethyl isocyanurate and 0.230g of DMC into a pressure-resistant reactor, remove the volatile components in vacuum, add 80g of epichlorohydrin, then heat to 128°C, under nitrogen protection and high-speed stirring Reaction under conditions; After the reaction is activated, gradually add the remaining 365g of epichlorohydrin dropwise. After the polymerization of epichlorohydrin is completed, the temperature in the reactor is lowered to 115° C., and 40 g of propylene oxide is added dropwise to react for capping. After the reaction is completed, the residual monomer is removed in a vacuum, and the hydroxyl-terminated polyepichlorohydrin ether polyol with an average relative molecular weight of 8500 and an average hydroxyl functionality of 3 is obtained by refining.

Claims (10)

1. high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol, it is characterized in that its molecular structure be have a large amount of METHYLENE CHLORIDE side groups with oxyethane or the end capped end hydroxy polyether polyvalent alcohol of propylene oxide, average molecular mass 500~9000, the average hydroxy functionality is between 2~3.
2. according to the described high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol of claim 1, it is characterized in that described terminal hydroxy group Hydrin ethoxylated polyhydric alcohol is that a kind of end group is the telechelic polymer of primary hydroxyl or secondary hydroxyl.
3. according to the described high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol of claim 1, it is characterized in that described terminal hydroxy group Hydrin ethoxylated polyhydric alcohol is to adopt bimetallic cyanide complex catalyst catalysis synthetic.
4. the preparation method as the described high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol of above-mentioned each claim is characterized in that comprising the steps:
(1) in withstand voltage reactor, adds small molecular weight initiator, bimetallic cyanide complex catalyst, vacuum is deviate from volatile component, add the part epoxy chloropropane, be heated to 100~140 ℃ then, under the condition of nitrogen protection and high-speed stirring, react; Progressively drip the residual epoxide chloropropane behind the reacting activation;
After the epoxy chloropropane polymerization is finished in (2) (1) steps, reactor temperature is reduced to 90~120 ℃, drip propylene oxide or oxyethane again and carry out end-blocking, reaction finishes, vacuum is deviate from residual monomer, obtain average molecular mass 500~9000, the average hydroxy functionality is at 2~3 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
5. the preparation method of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol according to claim 4, it is characterized in that the small molecular weight initiator in the described step (1) is 4,4-dihydroxy-diphenyl propane, 1,4-butyleneglycol, relative molecular mass are that 400 two functionality polyether glycols, trihydroxyethyl isocyanuric ester, relative molecular mass are that 250 three-functionality-degree polyether glycol, relative molecular mass are one or more the mixture in 700 the three-functionality-degree polyether glycol.
6. the preparation method of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol according to claim 4, the mass ratio that it is characterized in that a part of epoxy chloropropane in the described step (1) and remainder epoxy chloropropane is between 100:0~1:99; The mol ratio of small molecular weight initiator and epoxy chloropropane is between 1:4~1:100 in the described step (1).
7. the preparation method of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol according to claim 4 is characterized in that bimetallic cyanide complex catalyst in the described step (1) is that the trimethyl carbinol is that the bimetallic cyanide complex catalyst of one of part is a disperse phase, the oligomer polyol that contains reactive hydrogen is the emulsion form bimetallic cyanide complex catalyst of external phase.Wherein the bimetallic cyanide complex catalyst consumption accounts for 300~800ppm. of institute's synthetic polyether glycol quality
8. the preparation method of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol according to claim 4 is characterized in that bimetallic cyanide complex catalyst is that potassium hexacyanocobaltate and zinc salt prepare through operations such as complexing reaction, washing, dryings in the described step (1) in the presence of water, the trimethyl carbinol, polyether glycol.
9. the preparation method of bimetallic cyanide complex catalyst according to claim 8, it is characterized in that described zinc salt is one or more the mixture in zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, zinc phosphate, zinc carbonate, the zinc oxalate, the mol ratio of zinc salt and Cobalt Potassium Cyanide is between 1.5:1~20:1, and wherein the mol ratio of zinc bromide and Cobalt Potassium Cyanide is between 1.8:1~15:1.
10. the preparation method of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol according to claim 4, the mol ratio that it is characterized in that Hydrin ether and oxyethane or propylene oxide in the described step (2) is between 1:1~1:3.
CNA2008101877053A 2008-12-31 2008-12-31 High activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol and preparation thereof Pending CN101497691A (en)

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CN102174185A (en) * 2011-01-31 2011-09-07 武汉工程大学 Synthesis technology of hydroxyl terminated polyepichlorohydrin
CN101701063B (en) * 2009-11-18 2012-01-11 武汉工程大学 Preparation method of polyepichlorohydrin
CN102391494A (en) * 2011-08-24 2012-03-28 山东蓝星东大化工有限责任公司 Method for synthesizing high-activity high molecular weight polyether polyol
CN102040731B (en) * 2009-10-23 2012-07-25 中国石油化工集团公司 Method for preparing polyether polyol
CN103709392A (en) * 2013-11-28 2014-04-09 山东蓝星东大化工有限责任公司 Preparation method of polyether polyol for automobile sealant
CN103848984A (en) * 2012-11-30 2014-06-11 天津中油渤星工程科技有限公司 Shale inhibitor polyether polyol for drilling fluids, and preparation and application thereof
CN103937467A (en) * 2013-01-21 2014-07-23 中国石油化工股份有限公司 Thickened-oil hydrothermal catalytic viscosity reducer, preparation method thereof, transition metal complex and ligand of complex
CN103987811A (en) * 2011-10-09 2014-08-13 溴化合物有限公司 Flame retardants, their preparation and their use in polyurethane and polyisocyanurate foams
CN105019243A (en) * 2015-06-29 2015-11-04 江苏百护纺织科技有限公司 Preparation method and application of epoxy-terminated brominated polyether fabric flame-retardation finishing agent
CN105111429A (en) * 2015-09-06 2015-12-02 江阴职业技术学院 Preparation method and application of brominated flame-retardant polyether glycol
CN105504257A (en) * 2015-12-28 2016-04-20 广东工业大学 Preparation method of poly(propylidene carbonate)polyol including chlorine on side chain
CN107722257A (en) * 2017-09-28 2018-02-23 句容宁武高新技术发展有限公司 One kind is applied to high water-content crude oil demulsifier and preparation method thereof
CN108070068A (en) * 2016-11-15 2018-05-25 中国科学院青岛生物能源与过程研究所 A kind of high anti-microbial property method for preparing polyurethane elastic body of low cost
CN108070067A (en) * 2016-11-15 2018-05-25 中国科学院青岛生物能源与过程研究所 A kind of preparation method of Cross-linkable coating antibacterial polyurethane
CN108368230A (en) * 2015-12-21 2018-08-03 国际壳牌研究有限公司 Method for manufacturing polyurethane foam
CN109897361A (en) * 2018-12-29 2019-06-18 肇庆市珈旺环境技术研究院 Modified polyurethane foam and preparation method and application thereof
CN111087600A (en) * 2018-10-23 2020-05-01 中国石油化工股份有限公司 Polyurethane elastomer resin and preparation method thereof
CN111171268A (en) * 2020-01-22 2020-05-19 黎明化工研究设计院有限责任公司 Heat-resistant polyurethane soft foam and preparation method thereof
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CN102040731B (en) * 2009-10-23 2012-07-25 中国石油化工集团公司 Method for preparing polyether polyol
CN101701063B (en) * 2009-11-18 2012-01-11 武汉工程大学 Preparation method of polyepichlorohydrin
CN102174185B (en) * 2011-01-31 2012-10-10 武汉工程大学 Synthetic Technology of Hydroxyl-terminated Polyepichlorohydrin
CN102174185A (en) * 2011-01-31 2011-09-07 武汉工程大学 Synthesis technology of hydroxyl terminated polyepichlorohydrin
CN102391494A (en) * 2011-08-24 2012-03-28 山东蓝星东大化工有限责任公司 Method for synthesizing high-activity high molecular weight polyether polyol
CN103987811A (en) * 2011-10-09 2014-08-13 溴化合物有限公司 Flame retardants, their preparation and their use in polyurethane and polyisocyanurate foams
CN103987811B (en) * 2011-10-09 2016-08-24 溴化合物有限公司 Fire retardant, its preparation method and its purposes in polyurethane and polyisocyanurate foam
CN103848984A (en) * 2012-11-30 2014-06-11 天津中油渤星工程科技有限公司 Shale inhibitor polyether polyol for drilling fluids, and preparation and application thereof
CN103937467A (en) * 2013-01-21 2014-07-23 中国石油化工股份有限公司 Thickened-oil hydrothermal catalytic viscosity reducer, preparation method thereof, transition metal complex and ligand of complex
CN103937467B (en) * 2013-01-21 2016-08-03 中国石油化工股份有限公司 Thick oil hydrothermal catalytic thinner and preparation method thereof and transient metal complex and part
CN103709392B (en) * 2013-11-28 2016-01-20 山东蓝星东大化工有限责任公司 The preparation method of polyether polyol for automobile sealant
CN103709392A (en) * 2013-11-28 2014-04-09 山东蓝星东大化工有限责任公司 Preparation method of polyether polyol for automobile sealant
CN105019243A (en) * 2015-06-29 2015-11-04 江苏百护纺织科技有限公司 Preparation method and application of epoxy-terminated brominated polyether fabric flame-retardation finishing agent
CN105111429A (en) * 2015-09-06 2015-12-02 江阴职业技术学院 Preparation method and application of brominated flame-retardant polyether glycol
CN108368230A (en) * 2015-12-21 2018-08-03 国际壳牌研究有限公司 Method for manufacturing polyurethane foam
CN108368230B (en) * 2015-12-21 2021-08-20 国际壳牌研究有限公司 Method for making polyurethane foam
US11814467B2 (en) 2015-12-21 2023-11-14 Shell Usa, Inc. Process for the production of polyurethane foams
CN105504257A (en) * 2015-12-28 2016-04-20 广东工业大学 Preparation method of poly(propylidene carbonate)polyol including chlorine on side chain
CN108070068A (en) * 2016-11-15 2018-05-25 中国科学院青岛生物能源与过程研究所 A kind of high anti-microbial property method for preparing polyurethane elastic body of low cost
CN108070067A (en) * 2016-11-15 2018-05-25 中国科学院青岛生物能源与过程研究所 A kind of preparation method of Cross-linkable coating antibacterial polyurethane
CN107722257A (en) * 2017-09-28 2018-02-23 句容宁武高新技术发展有限公司 One kind is applied to high water-content crude oil demulsifier and preparation method thereof
CN111087600A (en) * 2018-10-23 2020-05-01 中国石油化工股份有限公司 Polyurethane elastomer resin and preparation method thereof
CN109897361A (en) * 2018-12-29 2019-06-18 肇庆市珈旺环境技术研究院 Modified polyurethane foam and preparation method and application thereof
CN111171268A (en) * 2020-01-22 2020-05-19 黎明化工研究设计院有限责任公司 Heat-resistant polyurethane soft foam and preparation method thereof
CN111171268B (en) * 2020-01-22 2022-03-08 黎明化工研究设计院有限责任公司 Heat-resistant polyurethane soft foam and preparation method thereof
CN117264161A (en) * 2023-11-17 2023-12-22 江苏瑞洋安泰新材料科技有限公司 Preparation method of bio-based blocked isocyanate cross-linking agent

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