阅读说明：本技术 一种端基扩链聚醚衍生物的制备方法 (Preparation method of end-group chain-extended polyether derivative ) 是由 李桂妃 任绍志 潘生辉 詹锋 于 2019-09-20 设计创作，主要内容包括：本发明涉及一种端基扩链聚醚衍生物的制备方法。所述制备方法包括如下步骤：S1：聚醚多元醇与醇盐化试剂反应得醇盐化端基聚醚；S2：醇盐化端基聚醚和扩链剂反应得醇盐化端基扩链聚醚；所述扩链剂为带有两个卤素原子的烷烃、芳烃或环烷烃化合物；S3：醇盐化端基扩链聚醚和含卤素原子的硅烷偶联剂进行端基化反应,即得所述端基扩链聚醚衍生物。本发明首先通过将聚醚多元醇醇盐化后,选用特定的扩链剂进行扩链,既实现了聚醚多元醇分子量的加倍,又未在主链中导入其他基团,安全可靠,对其特性基本无影响；然后选用特定的硅烷偶联剂进行封端反应。本发明提供的制备方法步骤简单,合成工艺顺畅,符合环保要求,易于实现工业规模生产。(The invention relates to a preparation method of an end-group chain-extended polyether derivative. The preparation method comprises the following steps: s1: polyether glycol reacts with alcohol salinization reagent to obtain alcalinization end group polyether; s2: reacting the alkoxide end group polyether with a chain extender to obtain alkoxide end group chain extended polyether; the chain extender is an alkane, arene or cycloalkane compound with two halogen atoms; s3: and (3) carrying out a termination reaction on the alcohol-alkylated end-group chain-extended polyether and a silane coupling agent containing halogen atoms to obtain the end-group chain-extended polyether derivative. According to the method, firstly, after the polyether polyol is subjected to alcoholization, a specific chain extender is selected for chain extension, so that the molecular weight of the polyether polyol is doubled, other groups are not introduced into a main chain, the method is safe and reliable, and the characteristics of the polyether polyol are basically not influenced; then, a specific silane coupling agent is selected for carrying out end capping reaction. The preparation method provided by the invention has simple steps and smooth synthesis process, meets the environmental protection requirement, and is easy to realize industrial scale production.)

1. A preparation method of the end group chain extension polyether derivative is characterized by comprising the following steps:

s1: polyether glycol reacts with alcohol salinization reagent to obtain alcalinization end group polyether;

s2: reacting the alkoxide end group polyether with a chain extender to obtain alkoxide end group chain extended polyether; the chain extender is an alkane, arene or cycloalkane compound with two halogen atoms;

s3: and (3) carrying out a termination reaction on the alcohol-alkylated end-group chain-extended polyether and a silane coupling agent containing halogen atoms to obtain the end-group chain-extended polyether derivative.

2. The method of claim 1, wherein the polyether polyol of S1 has a molecular weight of 1000 to 10000 and a functionality of 2 to 3.

3. The method of claim 1, wherein the polyether polyol of S1 is dehydrated prior to reacting.

4. The method of claim 1, wherein the alcoholysis reagent of S1 is one or more selected from the group consisting of sodium metal, sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium metal, potassium methoxide, potassium ethoxide, potassium propoxide, and potassium hydroxide.

5. The method according to claim 1, wherein the molar ratio of the hydroxyl group contained in the polyether polyol to the alkali metal atom contained in the alkoxide at S1 is 1:1 to 1: 1.3.

6. The method according to claim 1, wherein the reaction temperature of S1 is 110-135 ℃ and the reaction time is 2 h.

7. The method of claim 1, wherein the reaction of S1 is performed under vacuum.

8. The method according to claim 1, wherein the chain extender in S2 is dichloromethane, 1, 2-dichloroethane, 1, 3-dichloropropane, dichlorobenzene, dichlorotoluene, dichlorocyclohexane, dibromomethane, 1, 2-dibromoethane, 1, 3-dibromopropane, dibromobenzene, dibromotoluene or dibromocyclohexane.

9. The method as claimed in claim 1, wherein the silane coupling agent containing halogen atom in S3 is one or more of gamma-chloropropyltrimethoxysilane or gamma-bromopropylmethyldiethoxysilane.

10. The method according to claim 1, wherein the molar ratio of the terminal group of the alkoxide terminated chain-extended polyether in S3 to the halogen atom in the silane coupling agent is 1:1 to 1: 1.5.

Technical Field

The invention belongs to the technical field of polyether chain extension and end group modification synthesis thereof, and particularly relates to a preparation method of an end group chain extension polyether derivative.

Background

Polyether polyols are important intermediate raw materials for the synthesis of polyurethanes, and are usually obtained by ring-opening polymerization of epoxides. The polyether polyol produced industrially in China is mainly prepared by adopting an anionic catalyst (such as KOH), and the polyether polyol has small molecular weight, wide molecular weight distribution, high unsaturation degree and small functionality degree, thereby influencing the physical and mechanical properties of a polyurethane material; the cationic catalyst (such as SnCl4) has higher activity, too violent reaction and difficult control, and more side reactions, so the cationic catalyst is not generally adopted when the polyether is industrially produced; the traditional catalytic system can not synthesize polyether polyol with higher molecular weight.

In order to solve The problem of synthesizing high molecular weight polyether, firstly, double metal cyanide complex (DMC) catalyst (4) The General wire & Rubber Corp, Method of making a double metal cyanide complex [ P ], US, US3278457, 1966-10-11) is developed abroad, and The catalyst is applied to ring-opening polymerization of alkylene oxide to successfully synthesize high-performance low-unsaturation high molecular weight polyether polyol. JP59267(1993) also reports the preparation of silicon modified polyethers using double metal cyanide complex catalysts to prepare high molecular weight polyethers followed by conversion of the terminal hydroxyl groups to terminal double bonds with allyl chloride followed by terminal double bonding with hydrolysable silyl groups. Despite the many unique advantages of DMC catalysts, they are not fully mature at present, but some suffer from problems such as easy deactivation of the catalyst and harsh storage conditions; the preparation process is complicated, the production period is long and the like. Domestic researchers have also studied DMC-catalyzed ring-opening polymerization of epoxy compounds ([5] yellow army, country Ror, Qianjin, etc., research on ring-opening polymerization of propylene oxide catalyzed by Fe-Zn double metal cyanide [ J ], published by Polymer, 2001, (2): 210-213), and some enterprises have begun to synthesize high molecular weight polyethers by DMC catalysis, but at present, domestic high-quality high molecular weight polyethers still depend on importation.

The high molecular weight polyether is an indispensable raw material for synthesizing materials such as MS glue, and the chain extension of the polyether with smaller molecular weight is an effective method for obtaining the polyether with high molecular weight. The chain extension of polyether polyol is carried out by taking dibasic acid or anhydride as a chain extender (Xujia, Chengping, Zhang Keliang and the like, and polyether modification research [ J ], proceedings of the Xian Petroleum institute, 2002,17(5), 47-49) is carried out by taking the dibasic acid as the chain extender, the chain extension mode is simple and convenient, but ester groups are introduced into a macromolecular chain, so that the method has certain influence on the properties of the chain extension polyether in the aspects of aging resistance, hydrolysis resistance and the like; the chain extension reaction is rapid and fast, but the strong polar bond of carbamate can be introduced into a macromolecular chain to bring great changes to the properties of the chain extension polyether.

From the above researches, to obtain high molecular weight polyether, besides the synthesis by using a novel catalyst, chain extension by using small molecular weight polyether is also a simple and effective method, but most of chain extenders bring groups such as ester groups and carbamate groups into the polyether main chain, which may adversely affect the properties of the chain extended polyether.

Disclosure of Invention

The invention aims to overcome the defects or shortcomings of the existing synthetic chain-extended polyether and provide a preparation method of an end-group chain-extended polyether derivative. According to the method, firstly, after the polyether polyol is subjected to alcoholization, a specific chain extender is selected for chain extension, so that the molecular weight of the polyether polyol is doubled, other groups are not introduced into a main chain, the method is safe and reliable, and the characteristics of the polyether polyol are basically not influenced; then, a specific silane coupling agent is selected for carrying out end capping reaction.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of the end-group chain-extended polyether derivative comprises the following steps:

s1: polyether glycol reacts with alcohol salinization reagent to obtain alcalinization end group polyether;

s2: reacting the alkoxide end group polyether with a chain extender to obtain alkoxide end group chain extended polyether; the chain extender is an alkane, arene or cycloalkane compound with two halogen atoms;

s3: and (3) carrying out a termination reaction on the alcohol-alkylated end-group chain-extended polyether and a silane coupling agent containing halogen atoms to obtain the end-group chain-extended polyether derivative.

The selection of the chain extender and the end capping agent is the key to obtain the end-group chain-extended polyether derivative with better performance.

According to the invention, firstly, after the polyether polyol is alcoholized, a specific chain extender is selected for chain extension, so that the molecular weight of the polyether polyol is doubled, other groups are not introduced into a main chain, the method is safe and reliable, and the characteristics of the polyether polyol are basically not influenced.

The preparation method provided by the invention has simple steps and smooth synthesis process, meets the environmental protection requirement, and is easy to realize industrial scale production.

The polyether polyol can be selected from polyether polyols for preparing the end-group chain-extending polyether derivative conventionally.

Preferably, the molecular weight of the polyether polyol in S1 is 1000-10000, and the functionality is 2-3.

Preferably, the polyether polyol in S1 is subjected to a dehydration treatment prior to the reaction.

The reaction of the polyether polyol with the alkoxylating agent may be carried out according to conventional conditions, as is conventional in the art.

Preferably, the alkoxide reagent in S1 is one or more of sodium metal, sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium metal, potassium methoxide, potassium ethoxide, potassium propoxide, and potassium hydroxide.

Taking sodium methoxide as an example, the reaction process of polyether polyol and sodium methoxide is as follows:

preferably, the molar ratio of the hydroxyl group contained in the polyether polyol to the alkali metal atom contained in the alkoxide in S1 is 1:1 to 1: 1.3.

Preferably, the reaction temperature of S1 is 110-135 ℃, and the reaction time is 2 h.

Preferably, the reaction of S1 is carried out under vacuum.

Preferably, the chain extender in S2 is dichloromethane, 1, 2-dichloroethane, 1, 3-dichloropropane, dichlorobenzene, dichlorotoluene, dichlorocyclohexane, dibromomethane, 1, 2-dibromoethane, 1, 3-dibromopropane, dibromobenzene, dibromotoluene or dibromocyclohexane.

The chain extension reaction is as follows (taking sodium methoxide and dichloromethane as examples):

preferably, the silane coupling agent containing halogen atoms in S3 is one or more of gamma-chloropropyltrimethoxysilane or gamma-bromopropylmethyldiethoxysilane.

The end-capping reaction in S3 may be carried out at normal temperature.

Preferably, the mole ratio of the end group of the alcohol-esterified end-group chain-extended polyether in S3 to the halogen atom in the silane coupling agent is 1: 1-1: 1.5.

Preferably, the method further comprises the steps of introducing dry carbon dioxide, desalting and purifying after the end-capping reaction in S3.

The pH value of the reaction system can be adjusted by introducing dry carbon dioxide into the reaction system, and meanwhile, the product is protected from being oxidized, thereby being beneficial to the purification post-treatment of the product.

Compared with the prior art, the invention has the following beneficial effects:

according to the method, firstly, after the polyether polyol is subjected to alcoholization, a specific chain extender is selected for chain extension, so that the molecular weight of the polyether polyol is doubled, other groups are not introduced into a main chain, the method is safe and reliable, and the characteristics of the polyether polyol are basically not influenced; then, a specific silane coupling agent is selected for carrying out end capping reaction.

The preparation method provided by the invention has simple steps and smooth synthesis process, meets the environmental protection requirement, and is easy to realize industrial scale production.

The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.

Example 1

This example provides an end-chain-extended polyether derivative, which is prepared as follows.

Feeding dehydrated polyether polyol with the molecular weight of 3000 and the functionality of 3 and a mixture of sodium methoxide and sodium hydroxide (the mass ratio of the sodium methoxide to the sodium hydroxide is 1:1) according to the proportion of 1:1.1, vacuumizing, reacting at the temperature of 110 ℃ for 2 hours to obtain alkoxide end group polyether, then reacting the alkoxide end group polyether and dibromomethane according to the proportion to obtain alkoxide end group chain extended polyether, then reacting with the alkoxide end group chain extended polyether according to the proportion by taking gamma-chloropropyl methyl dimethoxy silane as a capping reagent, introducing dried carbon dioxide, desalting and purifying to obtain the end methyl dimethoxy silane group chain extended polyether, wherein the average functionality of the product is 4, and the average molecular weight is 6300.