Epoxy-terminated vinyl ether monomer and preparation method and application thereof
阅读说明：本技术 一种端环氧基乙烯基醚单体及其制备方法和用途 (Epoxy-terminated vinyl ether monomer and preparation method and application thereof ) 是由 向英 唐聪 龙星昕 王剑宇 兰剑平 王娟 张丹 于 2020-07-16 设计创作，主要内容包括：本发明涉及一种端环氧基乙烯基醚单体,以及该醚单体的制备方法,包括如下步骤制备,1)取分子结构式为<Image he="69" wi="377" file="DDA0002587159100000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>的端羟基烯醚、分子结构式为<Image he="87" wi="241" file="DDA0002587159100000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>的端环氧基氯代烷作为原料待用,其中,R<Sub>1</Sub>为H或-(CH<Sub>2</Sub>)<Sub>n</Sub>-,n为1-5,R<Sub>2</Sub>为直链-(CH<Sub>2</Sub>)<Sub>n</Sub>-,n为2-7,或为带有支链的烷基,R<Sub>3</Sub>为-(CH<Sub>2</Sub>)<Sub>n</Sub>-,n为1-4；2)在封闭环境下,加入步骤1)的原料、强碱、起始剂、相转移催化剂,反应得到目标产品。本发明提供的醚单体具有端环氧基和端乙烯基结构,单体活性较强,易于不饱和基团实现共聚,也易于-SiH/-SH/-OH发生加成反应,使得端环氧基封端改性过程变得简单,使用本发明单体改性后的材料具有端环氧基,可以轻易与环氧树脂嵌段、枝接,为后续材料进一步改性提供可能。(The invention relates to an epoxy-terminated vinyl ether monomer and a preparation method thereof, and the preparation method comprises the following steps of 1) taking a molecular structural formula as The terminal hydroxyl vinyl ether has a molecular structural formula of Using the epoxy-terminated chloroalkane as a raw material for standby, wherein R 1 Is H or- (CH) 2 ) n N is 1-5, R 2 Is straight chain- (CH) 2 ) n N is 2 to 7, orAlkyl with a branched chain, R 3 Is- (CH) 2 ) n -n is 1 to 4; 2) under a closed environment, adding the raw material, strong base, initiator and phase transfer catalyst in the step 1) to react to obtain a target product. The ether monomer provided by the invention has a terminal epoxy group and terminal vinyl structure, has stronger monomer activity, is easy to realize copolymerization of unsaturated groups, and is also easy to carry out addition reaction of-SiH/-SH/-OH, so that the terminal epoxy group terminal modification process becomes simple.)
1. An epoxy-terminated vinyl ether monomer is characterized by having the following molecular structural formula,
wherein R is1Is H or- (CH)2)nN is 1-5, R2Is straight chain- (CH)2)nN is 2-7 or is alkyl with a branch, R3Is- (CH)2)nAnd n is 1 to 4.
2. The epoxy-terminated vinyl ether monomer of claim 1, wherein R is2Is composed of
3. The process for producing an epoxy-terminated vinyl ether monomer according to claim 1 or 2, which comprises the steps of,
1) taking a molecular structural formula asThe terminal hydroxyl vinyl ether has a molecular structural formula ofUsing the epoxy-terminated chloroalkane as a raw material for standby, wherein R1Is H or- (CH)2)nN is 1-5, R2Is straight chain- (CH)2)nN is 2-8 or is alkyl with a branch, R3Is- (CH)2)n-n is 1 to 4;
2) under a closed environment, adding the raw material, strong base, initiator and phase transfer catalyst in the step 1) to react to obtain a target product.
4. The method according to claim 3, wherein the molar ratio of the hydroxyl-terminated vinyl ether, the epoxy-terminated chloroalkane, and the strong base in step 2) is 1: 1-1.5: 1-4, the strong base is sodium hydroxide and/or potassium hydroxide, the phase transfer agent catalyst is tetrabutylammonium bromide and/or benzyltriethylammonium chloride, and the dosage of the phase transfer catalyst is 0.5-5 wt% of the hydroxyl-terminated vinyl ether.
5. The method according to claim 3, wherein the initiator in step 2) is sodium alkoxide and/or sodium hydride, and the amount of sodium hydride is 0.5-2 wt% of the hydroxyl terminated vinyl ether.
6. The process according to claim 5, wherein the sodium alkoxide is sodium methoxide and/or sodium ethoxide, and the sodium methoxide and/or sodium ethoxide is used in an amount of 0.5 to 2 wt% based on the hydroxy-terminated vinyl ether.
7. The method according to claim 5, wherein the sodium alkoxide is a sodium alkoxide corresponding to a terminal hydroxy alkenyl ether, and is used in an amount of 0.5 to 5 wt% based on the terminal hydroxy alkenyl ether.
8. The preparation method according to claim 3, wherein the reaction in the step 2) is carried out by rapidly stirring after feeding to initiate the reaction, self-heating to a stable temperature by utilizing the heat release of the reaction system, rapidly heating to 105-150 ℃ until the pressure is stable, preserving the heat for 3-6h, then cooling to 50-80 ℃, preserving the heat for 3-6h, and discharging.
9. The method of claim 3, wherein hydroquinone is added in the step 2) in an amount of 0.2-3 wt% of the hydroxyl-terminated vinyl ether, and preferably polyethylene glycol is added in an amount of 0-1 wt% of the hydroxyl-terminated vinyl ether.
10. Use of an epoxy-terminated vinyl ether monomer according to claim 1 or 2 for epoxy termination, preferably the epoxy termination is a polysiloxane or polysulfide rubber epoxy termination.
Technical Field
The invention relates to the field of chemical industry, in particular to an epoxy-terminated vinyl ether monomer and a preparation method and application thereof.
Background
With the continuous development of polymer material technology, the requirements on the performance of polymer materials are higher and higher. The modification of the terminal epoxy group is a common resin modification method, the epoxy group is connected, the original characteristics of the material can be kept, the characteristics of low viscosity, good flexibility and the like are achieved, the chemical activity of the epoxy group enables the epoxy group to be capable of reacting with all compounds containing active hydrogen, the possibility is provided for the modification of other compounds, and the development and application of the product in different fields are expanded.
The strong yellow world and the like in the literature mention that the epoxy-terminated modified organosilicon softener can endow fabrics with excellent smoothness and softness, improve the washability, the hydrophilicity and the antistatic property of the fabrics, and prevent yellowing at high temperature; the Caochuan and the like use epoxy-terminated polysulfide polymer as a toughening agent to carry out toughening modification research on epoxy resin adhesives, and the results show that the addition of the epoxy-terminated polysulfide polymer improves the curing speed of the room-temperature fast-curing epoxy adhesive at normal temperature and low temperature, the mechanical property of a cured product is also obviously improved, and the oil resistance of the cured product is improved; wanhongju et al use waterborne polyurethane with epoxy end capping to modify gelatin, not only improve the defects of hard and brittle gelatin material and poor water resistance, but also retain the advantages of good elasticity, strong covering power, excellent weather resistance and wear resistance, good corrosion resistance, high adhesion, good bending resistance and the like of polyurethane.
Currently, the epoxy-terminated technology is mainly terminated by using epoxy-terminated allyl alcohol polyether, and the method generally needs to perform three steps: firstly, unsaturated alcohol is used for reacting with silicon hydride/mercaptan on the main chain, then ethylene oxide is used for reacting with alcoholic hydroxyl to generate condensed ether, and finally epoxy group is used for ring closure. The method has long process flow, the quantity of polyether can not be accurately controlled, and the material becomes brittle and the dielectric constant is increased due to the growth of ether bonds. Epoxy terminal materials can also be synthesized by using epoxy resin and silicon hydride/mercaptan, but the reaction rate of the silicon hydride/mercaptan and epoxy groups is very slow, and the common organic amine catalysts tend to cause gel, so that stable liquid resins cannot be obtained. The synthesis by the solvent method can inhibit the branching reaction, but is not economical and environment-friendly, and the catalyst is still remained in the resin finally, which is not beneficial to the long-term storage of the resin.
Therefore, the development of an epoxy-terminated vinyl ether monomer for epoxy capping has positive practical significance.
Disclosure of Invention
One of the purposes of the present invention is to provide an epoxy-terminated vinyl ether monomer, which has a structure of an epoxy-terminated vinyl ether and a structure of a vinyl-terminated vinyl ether, has strong monomer activity, is easy to realize copolymerization of unsaturated groups, and is easy to generate addition reaction of-SiH/-SH/-OH, so that the modification process of the end-terminated epoxy group becomes simple.
The technical scheme for realizing one purpose of the invention is as follows: an epoxy-terminated vinyl ether monomer has the following molecular structural formula,
wherein R is1Is H or- (CH)2)nN is 1-5, R2Is straight chain- (CH)2)nN is 2 to 7, or is an alkyl group with a branched chain,R3is- (CH)2)nAnd n is 1 to 4.
The R is2Is composed ofOr is that
The invention also aims to provide the preparation method of the monomer, the preparation process is simple and convenient, the energy consumption is low, and the carbon chain of the monomer can be adjusted according to actual requirements, so that the actual requirements can be effectively met.
The second technical scheme for realizing the aim of the invention is as follows:
the preparation method of the epoxy-terminated vinyl ether monomer comprises the following steps,
1) taking a molecular structural formula asThe terminal hydroxyl vinyl ether has a molecular structural formula ofUsing the epoxy-terminated chloroalkane as a raw material for standby, wherein R1Is H or- (CH)2)nN is 1-5, R2Is straight chain- (CH)2)nN is 2-7 or is alkyl with a branch, R3Is- (CH)2)n-n is 1 to 4;
2) under a closed environment, adding the raw material, strong base, initiator and phase transfer catalyst in the step 1) to react to obtain a target product.
The mol ratio of the hydroxyl-terminated vinyl ether, the epoxy-terminated chloroalkane and the strong base in the step 2) is 1: 1-1.5: 1-4, the strong base is sodium hydroxide and/or potassium hydroxide, the phase transfer agent catalyst is tetrabutylammonium bromide and/or benzyltriethylammonium chloride, and the dosage of the phase transfer catalyst is 0.5-5 wt% of the hydroxyl-terminated vinyl ether.
The initiator in the step 2) is sodium alkoxide and/or sodium hydride, and the dosage of the sodium hydride is 0.5-2 wt% of the hydroxyl-terminated vinyl ether.
The sodium alkoxide is sodium methoxide and/or sodium ethoxide, and the dosage of the sodium methoxide and/or sodium ethoxide is 0.5-2 wt% of the hydroxyl-terminated vinyl ether.
The sodium alkoxide is corresponding to the terminal hydroxyl vinyl ether, and the using amount of the sodium alkoxide is 0.5-5 wt% of the terminal hydroxyl vinyl ether.
And 2) carrying out the reaction, namely, quickly stirring after feeding to initiate the reaction, automatically heating to a stable temperature by utilizing the heat release of a reaction system, quickly heating to 105-150 ℃, keeping the temperature for 3-6h after the pressure is stable, then cooling to 50-80 ℃, keeping the temperature for 3-6h, and discharging.
In the step 2), hydroquinone is also added, the dosage of the hydroquinone is 0.2-3 wt% of the hydroxyl-terminated vinyl ether, preferably, polyethylene glycol can also be added, and the dosage of the polyethylene glycol is 0-1 wt% of the hydroxyl-terminated vinyl ether.
The invention also claims the use of the above-described epoxy-terminated vinyl ether monomers for epoxy termination. Especially in polysiloxane or polysulfide rubber epoxy end-capping.
Adopt above-mentioned technical scheme to have following beneficial effect:
1. the epoxy-terminated vinyl ether monomer provided by the invention has strong activity, is easy to perform addition reaction with-SiH/-SH/-OH, and can be widely used for modification of polysiloxane/polysulfide rubber.
2. The invention provides an epoxy-terminated vinyl ether monomer, which is prepared by controlling R1The carbon chain length of (1) to (5) to maintain good polymerization activity of vinyl, and if the polymerization degree is more than 5, the vinyl activity is reduced; by controlling R2The carbon chain length of the epoxy resin is 2-7, the raw material hydroxyl-terminated vinyl ether is easy to synthesize, when the carbon chain length is 1 and is more than 7, the raw material hydroxyl-terminated vinyl ether is difficult to synthesize, and when the carbon chain length is more than 7, the molecular weight is increased, and the viscosity of the system is increased when the carbon chain length is used for epoxy modification; by controlling R3The carbon chain length of (2) is 1-4, mainly considering the availability of raw materials, such as R3The epoxy-terminated chloroalkanes having carbon greater than 4 are difficult to purchase.
3. The preparation method of the invention is realized by using a catalyst containingHydroxy-terminated alkenyl ethers of the structure and compositions havingThe epoxy-terminated chloroalkane with the structure is prepared by closed reaction under the strong alkaline condition. The reaction mainly comprises 3 steps: taking sodium alkoxide/sodium hydride as initiator to removeProduction of H on the hydroxyl groupInitiating a reaction; ② the rapid reaction, the violent heat release,
4. the invention controls the mol ratio of the hydroxyl-terminated vinyl ether, the epoxy-terminated chloroalkane and the strong base to be 1: 1-1.5: 1-4, the strong base and the epoxy-terminated chloroalkane are in proper excess to ensure higher reaction conversion rate, and if other types of bases are adopted, the cationic polymerization of raw materials can be initiated due to larger cationic charge amount; the dosage of the phase transfer agent catalyst is 0.5-5 wt% of the hydroxyl-terminated vinyl ether, if the dosage is less than 0.5%, the catalytic effect is poor, and if the dosage is more than 5%, the phase transfer catalyst is wasted and the impurities are increased; the amount of the initiator is 0.5-2 wt% of the hydroxyl-terminated vinyl ether, if the amount is less than 0.5%, the initiator will fail to react with a small amount of water in the raw material, and if the amount is more than 2%, the initial reaction rate is too fast, and a large amount of heat is released, so that the reaction is difficult to control.
5. The method carries out the reaction in a closed environment, firstly utilizes the reaction system to release heat for self-heating, and quickly heats the reaction system to 105-150 ℃ after the temperature of the system is stable, namely, the reaction heat can not further raise the temperature of the reaction system, so that the reaction heat of the reaction system can be effectively utilized; the closed environment is beneficial to maintaining the pressure at a higher stable level, quickens the reaction progress, reduces the heat required by heat preservation, and can effectively reduce the energy consumption of the reaction.
The following is a further description with reference to specific examples.
Detailed Description
In the invention, the used ethylene glycol monovinyl ether is provided by Chongqing chemical research institute Co., Ltd, and the purity is more than or equal to 99 percent; the hydroxybutyl vinyl ether is provided by chemical research institute of Chongqing city, and the purity is more than or equal to 98.5 percent; epichlorohydrin (AR, metropolis chemicals ltd); sodium hydroxide (AR, tokyo chemical agents ltd); potassium hydroxide (AR, tokyo chemical agents ltd); tetrabutylammonium bromide (AR, tokyo chemical agents ltd); benzyltriethylammonium chloride (AR, tokyo chemical agents ltd); hydroquinone (AR, tokyo chemical agents ltd); a double mercapto group-terminated liquid polysulfide rubber (6.6% mercapto group content, relative molecular mass 1000, from east-li polysulfide japan); hydrogen-terminated silicone oil (self-made, average relative molecular mass 1000); ABIN (AR, Yongda Chemicals Co., Tianjin); chloroplatinic acid (hexahydrate, AR, tokyo chemical agents ltd.).