阅读说明：本技术 一种端烯丙氧基羧酸单体及其制备方法和用途 (Terminal alkene propoxy carboxylic acid monomer and preparation method and application thereof ) 是由 唐聪 方舟 向英 王春林 方翌立 颜邦民 兰剑平 张丹 蒋小琴 于 2021-08-30 设计创作，主要内容包括：一种端烯丙氧基羧酸单体,其具有端烯丙氧基、酯基及端羧基结构,酯基及氧的存在赋予端烯基良好的聚合活性,易于不饱和基团实现共聚,也易于-SH发生加成反应,使得端环羧基封端改性过程变得简单,单体分子链柔性好,端羧基具有反应性,与大分子链的结合能力强,与环氧树脂、聚酯、PA等材料枝接、共混,为后续材料进一步改性提供可能。(A terminal allyl propoxy carboxylic acid monomer has terminal allyl propoxy, ester group and terminal carboxyl structure, the existence of the ester group and oxygen endows the terminal alkenyl with good polymerization activity, unsaturated groups are easy to realize copolymerization, and-SH is easy to generate addition reaction, so that the terminal carboxyl end capping modification process becomes simple, the flexibility of a monomer molecular chain is good, the terminal carboxyl has reactivity and strong binding capacity with a macromolecular chain, and the terminal allyl propoxy carboxylic acid monomer is grafted and blended with materials such as epoxy resin, polyester, PA and the like, thereby providing possibility for further modification of subsequent materials.)

1. A terminal allyl propoxy carboxylic acid monomer is characterized in that the structural formula is as follows:

wherein R is₁Is straight chain- (CH)₂)_nN is 2 to 6, or branchedR₂Is straight-Chain (CH)₂)_m-, m is 2 to 8, or branched

2. The method of preparing a terminally allyloxycarboxylic acid monomer of claim 1, comprising the steps of:

1) get and haveAllyloxy alcohols of structure and havingReacting diacid or anhydride thereof with a structure at 40-150 ℃, removing generated water during reaction, removing residual allyloxy alcohol after the reaction is finished, and filtering to obtain clear liquid;

2) adding into the above clear liquidCarrying out ester exchange reaction on diacid or anhydride thereof with a structure at the temperature of 80-150 ℃ by taking an organic tin compound as a catalyst until the reaction is finished to obtain a target product.

3. The method of claim 2 wherein the allyloxy alcohol of step 1) is present in a molar ratio of 1: 1-2.5, and the reaction time is 1-5 h.

4. The process according to claim 2 or 3, wherein the catalyst A is added in step 1), the amount of the catalyst A is 0 to 2 wt% of the diacid or the anhydride thereof, and the catalyst A is pyridine and/or 4-dimethylaminopyridine.

5. The method of claim 2, wherein in step 1) the water produced is removed by evaporation and the balance of allyloxy alcohol is removed by distillation.

6. The method of claim 1 wherein the molar ratio of additional diacid or anhydride from step 2) to allyloxy alcohol from step 1) is 0.1 to 2: 1.

7. The preparation method of claim 1, wherein the organic tin compound in step 2) is added in an amount of 0.5 to 2 wt% based on the additional diacid or anhydride thereof in step 2), and the organic tin compound is dibutyltin oxide and/or butyltin trichloride.

8. The preparation method of claim 1, wherein the allyl propoxy end carboxylic acid monomer is obtained by filtering, washing, extracting and separating after the reaction of step 2).

9. Use of the terminal allyloxy carboxylic acid monomer of claim 1 as an additive in a polymerization system.

10. Use according to claim 9, characterized in that the additives are compatibilizers and dispersants.

Technical Field

The invention relates to the field of chemical industry, and particularly relates to a terminal allyl propoxy carboxylic acid monomer and a preparation method and application thereof.

Background

The terminal allyloxy carboxylic acid has a terminal alkenyl group and a terminal carboxyl group. The terminal allyl propyl group endows the monomer with good polymerization activity and can participate in polymerization of polymerization systems such as polyolefin rubber, tetrafluoroethylene and the like; the carboxyl end groups provide excellent dispersibility and reactivity to such polymers, and may provide good dispersion in emulsion polymers/waterborne polymers. The allyl propoxy carboxylic acid can be applied to industries such as liquid fluororubber, epoxy resin modification, carboxyl end capping, plastic alloy compatilizer, inorganic substance filled elastomer coupling agent and the like, and has a lot of reports in the fields of synthesizing biodegradable elastomers, hydrogel, adhesives, photosensitive materials and the like.

The long-chain compounds with terminal alkenyl and carboxyl groups currently on the market are mainly undecylenic acid, 3-allyloxypropionic acid. The polymerization activity of the undecylenic acid is poor, the 3-allyloxy propionic acid is harmful to water, the discharge pollutes underground water and water channels, and the use has certain limitation.

Therefore, the development of a terminal allyloxy carboxylic acid with good polymerization activity has positive practical significance.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a terminal allyl propoxy carboxylic acid monomer and a preparation method thereof, wherein the terminal allyl propoxy carboxylic acid monomer has a terminal allyl propoxy structure, an ester group and a terminal carboxyl structure, the existence of the ester group and oxygen endows the terminal alkenyl with good polymerization activity, unsaturated groups are easy to copolymerize, and-SH is easy to perform addition reaction, so that the terminal end-terminated modification process of the terminal carboxyl becomes simple, the flexibility of a monomer molecular chain is good, the terminal carboxyl has reactivity, the binding capacity with a macromolecular chain is strong, and the terminal allyl propoxy carboxylic acid monomer is grafted and blended with materials such as epoxy resin, polyester, PA and the like, so that the possibility is provided for further modification of subsequent materials.

The technical scheme of the invention is as follows: a terminal allyloxy carboxylic acid monomer having the formula:

wherein R is₁Is straight chain- (CH)₂)_nN is 2 to 6, or branchedR₂Is straight-Chain (CH)₂)_m-, m is 2 to 8, or branched

The preparation method of the terminal allyl propoxy carboxylic acid monomer comprises the following steps:

1) get and haveAllyloxy alcohols of structure and havingReacting diacid or anhydride thereof with a structure at 40-150 ℃, removing generated water during reaction, removing residual allyloxy alcohol after the reaction is finished, and filtering to obtain clear liquid;

2) adding into the above clear liquidCarrying out ester exchange reaction on diacid or anhydride thereof with a structure at the temperature of 80-150 ℃ by taking an organic tin compound as a catalyst until the reaction is finished to obtain a target product.

Step 1) the molar ratio of allyloxy alcohol to diacid or anhydride thereof is 1: 1-2.5, and the reaction time is 1-5 h.

The catalyst A is added in the step 1), the addition amount of the catalyst A is 0-2 wt% of diacid or anhydride thereof, and the catalyst A is pyridine and/or 4-dimethylamino pyridine.

Step 1) removing generated water by adopting an evaporation mode, and removing the rest allyl-oxy alcohol by adopting a distillation mode.

The molar ratio of the additional diacid or anhydride of the step 2) to the allyloxy alcohol of the step 1) is 0.1-2: 1.

The adding amount of the organic tin compound in the step 2) is 0.5-2 wt% of the added diacid or the acid anhydride thereof in the step 2), and the organic tin compound is dibutyltin oxide and/or butyltin trichloride.

And 2) after the reaction is finished, filtering, washing, extracting and separating to obtain the end-alkene propoxy carboxylic acid monomer.

The invention also provides the application of the terminal allyl propoxy carboxylic acid monomer as an additive in a polymerization system.

Further, the additives are a compatibilizer and a dispersant.

Adopt above-mentioned technical scheme to have following beneficial effect:

1. the terminal allyl propoxy carboxylic acid monomer provided by the invention has a terminal allyl propoxy structure, has strong monomer activity, is easy to realize copolymerization with unsaturated groups, and is also easy to generate addition reaction with-SiH/-SH, so that the modification of terminal groups becomes simple, for example, the terminal groups can be used for reaction with liquid polysulfide rubber to prepare carboxyl-terminated polysulfide rubber, eliminate the odor of the polysulfide rubber, and can also be used for blending modification to enrich the using method of the polysulfide rubber.

2. The end-allyl propoxy carboxylic acid monomer provided by the invention has a carboxyl end structure, has excellent dispersibility and reactivity, and can provide good dispersion effect in emulsion polymer/water-based polymer, for example, the dispersibility of pigment can be improved by adding 1-10% of the end-allyl propoxy carboxylic acid monomer in PFEVE emulsion polymerization.

3. Through two-step reaction, the oily diacid-producing diester is also converted into a product, the yield of the allyloxy alcohol is improved to 95 percent, and the method is economical and environment-friendly.

4. The preparation method of the monomer of the invention utilizesAllyloxy alcohols of structure and havingThe diacid or anhydride with the structure is used as raw material. The diacid/anhydride has carboxyl structure at both ends and can react with the hydroxyl of allyloxy alcohol: the ratio of diacid/anhydride is 1: 1-2.5, and the excessive diacid or anhydride can reduce the generation of a byproduct, namely diacid diester; the reaction time can be greatly shortened by the catalytic promotion reaction of dimethylaminopyridine, pyridine and the like, and the reaction temperature is not suitable to be too high, so that the side reaction process is accelerated by the too high temperature; for R₂The diacid or anhydride with longer molecular chain has relatively poor selectivity for generating the target product, so the diacid or anhydride is supplemented, and the content of the target product of the end-alkene propoxy carboxylic acid can be effectively improved by carrying out the ester exchange reaction under the catalyst of metal tin.

The following is a further description with reference to specific embodiments.

Detailed Description

In the invention, the following materials are used:

example 1

Synthesis of 4- (2- (allyloxy) ethoxy) -4-oxobutyric acid and application thereof in end-capped polysulfide rubber

Ethylene glycol monoallyl ether: succinic acid is 90 g: 110g of the mixed solution is added into a 500mL three-neck flask,and (3) building a reduced pressure distillation device, starting stirring, heating to 120 ℃ for reaction for 2.5h, distilling off excessive ethylene glycol monoallyl ether, filtering to obtain clear liquid, and supplementing 20g of succinic acid and 0.8g of dibutyltin oxide for reaction for 2h at 90 ℃. The mixture was cooled to 0 ℃ in an ice-water bath, a white solid was filtered off, the clear solution was washed three times with a 5% sodium hydrogensulfate solution, and water was removed with anhydrous magnesium sulfate to obtain 174g of a yellowish transparent oily liquid, i.e., 4- (2- (allyloxy) ethoxy) -4-oxobutanoic acid. 256g of dimercapto-terminated liquid polysulfide rubber (relative molecular mass 1000, mercapto content 6.6%) was mixed with 60g of 4- (2- (allyloxy) ethoxy) -4-oxobutyric acid at room temperature, 0.1g of ABIN was added, and the mixture was reacted at 50 ℃ for 3 hours, followed by addition of 45g of 4- (2- (allyloxy) ethoxy) -4-oxobutyric acid and heat preservation for 3 hours. After the reaction is stopped, 200ml of absolute ethyl alcohol is used for washing for 3 times, and the light yellow carboxyl terminated polysulfide polymer can be obtained. The carboxyl-terminated polysulfide polymer has obviously reduced viscosity and odor, and the terminal carboxyl has reactivity, so that the carboxyl-terminated polysulfide polymer can be widely applied to blending modification of materials such as nylon, polyester and the like without adding a compatilizer. The prepared carboxyl-terminated polysulfide polymer and nylon 6 are subjected to twin-screw melt extrusion at 250 ℃ to prepare a novel reinforced and toughened nylon material, the novel reinforced and toughened nylon material is dried and then is injected into a standard sample for measurement, and the impact strength of the novel reinforced and toughened nylon material is measured by using a standard sample injection mold, wherein the impact strength of the novel reinforced and toughened nylon material is 20Kj/m²The tensile shear strength is increased from 75MPa to 82MPa, and the elongation at break is increased from 50 to 55 percent. The tensile shear strength was measured in accordance with GB/T7124-. The impact strength was measured according to GB/T2567 + 2008 "test method for Properties of resin cast body". )

Example 2

Application of water-based fluorine coating

Taking 32g of ethyl vinyl ether, 21g of isobutyl vinyl ether, 56g of ethylene glycol monoallyl ether, 2.5g of 4- (2- (allyloxy) ethoxy) -4-oxobutyric acid prepared in example 1, 6.5g of ammonium persulfate, an anionic emulsifier sodium dodecyl sulfate and a nonionic emulsifier nonylphenol polyoxyethylene ether composite emulsifier, 2.4g of an initiator and 200g of deionized water, adding the deionized water into a 1L high-pressure reaction kettle, pre-emulsifying at normal temperature for 30 minutes, introducing nitrogen to discharge air in the kettle, injecting 128g of liquid chlorotrifluoroethylene monomer, introducing nitrogen again to discharge air in the kettle, heating to 60 ℃, stirring and reacting under the pressure of 0.8MPa for 20 hours, then cooling, decompressing and discharging to obtain the PFEVE fluorocarbon resin emulsion. The acid value of the emulsion is 10-15 mgKOH/g (calculated by solid resin), the prepared emulsion is coated on the surface of a test steel plate which is subjected to polishing, cleaning, drying and other procedures in advance, the coating thickness is 100 mu m, the surface of a cured paint film is flat, high in transmittance, good in gloss and free of paint film morbidity, the pencil hardness (GB/T6739-1996) is grade B, the adhesive force is determined according to the standard GB 9286 plus 1998, and the adhesive force is grade 1 by adopting a cross-hatch method. The corresponding emulsion formed without adding 4- (2- (allyloxy) ethoxy) -4-oxobutyric acid has poor hydrophilicity, poor surface flatness of a cured paint film, 3-grade adhesive force, and about 20 percent of stripping area by a grid marking method.

Example 3

Synthesis of 4- (4- (allyloxy) butoxy) -4-oxobutyric acid and synthesis of allyl-terminated functional capped polyethylene glycol

Butanediol monoallyl ether: succinic acid 100 g: adding 100g of pyridine into a 1000mL three-neck flask, adding 1g of pyridine, building a reduced pressure distillation device, starting stirring, reacting at a low temperature of 40 ℃ for 3 hours, distilling off excessive butanediol monoallyl ether, filtering to obtain a clear solution, and adding 60g of succinic acid and 1g of dibutyltin oxide to react at a temperature of 90 ℃ for 2 hours. The mixture was cooled to 0 ℃ in an ice-water bath, a white solid was filtered off, the clear solution was washed three times with a 5% sodium hydrogensulfate solution, and water was removed with anhydrous magnesium sulfate to obtain 185g of a yellowish transparent oily liquid, i.e., 4- (4- (allyloxy) butoxy) -4-oxobutanoic acid. Dissolving 30g of polyethylene glycol (with a relative molecular weight of 3000) into 100ml of dichloromethane, adding 4g of pyridine, slowly dropwise adding 15.5g of 4- (4- (allyloxy) butoxy) -4-oxobutyric acid at 0 ℃ in an ice water bath, reacting at room temperature for 24 hours, adding 250g of diethyl ether after the reaction is finished, standing, and collecting white precipitate, namely the allyl-terminated polyethylene glycol. The capped polyethylene glycol reacts with a compound with much-SH/-NH to prepare polyethylene glycol hydrogel, and the polyethylene glycol hydrogel is further applied to industries such as medicine.