CN107337746B - Chain-transferring agent of epoxy group and the preparation method and application thereof is contained in a kind of end - Google Patents

Abstract

The present invention relates to a chain transfer agent containing an epoxy group at the end and its preparation method and application. The chemical structural formula of the chain transfer agent is: Wherein, A is C ₁ - _{C 20} linear, branched or cyclic saturated or unsaturated hydrocarbons, said unsaturated hydrocarbons include alkenes, alkynes, aromatics or heterocyclic hydrocarbons containing N and O; B is _C2 - _C20 linear, branched or cyclic saturated aliphatic alkane; the preparation method is to use dibasic alcohol and epichlorohydrin as raw materials, prepare dibasic alcohol monoglycidyl ether by phase transfer catalyst, and then Glycidyl alcohol monoglycidyl ether and mercapto carboxylic acid are raw materials, and under the action of a catalyst, a chain transfer agent containing an epoxy group at the end is prepared; the chain transfer agent is used to prepare benzene with a relative molecular weight of 2000-10000 Ethylene-maleic anhydride alternating copolymer. Compared with the prior art, the chain transfer agent of the invention has high activity, can effectively control the molecular weight of polymerization products, and can prevent the occurrence of destructive free radical chain reactions, and has good application prospects.

Description

A chain transfer agent containing epoxy groups at the end and its preparation method and application

technical field

The invention belongs to the field of polymer material synthesis and application, and relates to a chain transfer agent with an epoxy group at the end, a preparation method and application thereof.

Background technique

Free radical polymerization is the earliest and most thoroughly studied polymerization reaction developed by human beings. It has the advantages of wide source of monomers, simple production process, various preparation methods and low industrialization cost. It has become one of the most important polymer synthesis methods. Such as low-density polyethylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, styrene-butadiene rubber, nitrile rubber, neoprene, etc. In the free radical polymerization process, adding a chain transfer agent to the polymerization reaction system can effectively adjust the degree of polymerization of the polymer. The introduction of the chain transfer agent can react with free radicals to generate new free radicals, thereby forming new polymer molecular chains, and can effectively control the molecular weight of the polymer when the polymerization rate remains unchanged.

Low molecular weight styrene-maleic anhydride resin has excellent emulsifying and dispersing properties due to its hydrophilic styrene group and lipophilic anhydride group, and is widely used in textiles, coatings, printing and dyeing, papermaking and chemical industries. Chain transfer agents are also widely used in the preparation of low molecular weight styrene-maleic anhydride resins to adjust the molecular weight of the resin. The most widely used chain transfer agents are mercaptans.

Xiao Cuiling et al. (Petrochemical Industry, 2000, 18 (1): 15-18) have reported a method for the synthesis of low molecular weight styrene-maleic anhydride resins by a solution method, which involves the regulation of styrene-maleic anhydride by 3-mercaptopropionic acid. The application of acid anhydride molecular weight has obtained the styrene-maleic anhydride resin with molecular weight between 2000-10000.

Tan Hongliang et al. (Petrochemical Industry, 1994, (11): 706-710) reported a method for the synthesis of styrene-maleic anhydride resin by precipitation polymerization, using dodecyl mercaptan as a chain transfer agent, successfully prepared Low molecular weight styrene-maleic anhydride alternating copolymer.

The Chinese patent application publication number CN102653578A discloses a method for synthesizing styrene-maleic anhydride polymers by precipitation method, comprising the following steps: (1) maleic anhydride and initiator are added to dissolve in a solvent of 70ml-90ml; ( 2) Dissolve styrene in 70ml-90ml solvent, stir and heat to 65°C-80°C and keep warm; (3) Mix inhibitor with 30ml-50ml solvent, stir while heating to 65°C-80°C and keep warm; (4) When the solution obtained in step (1) is heated to 65°C-80°C, while adding the solution obtained in step (2) dropwise, add the solution obtained in step (3) dropwise, after the dropwise addition, heat to 75°C-90°C and keep warm React for 1.8h-3h to obtain a low-molecular-weight styrene-maleic anhydride polymer dispersion system; (5) suction filter and vacuum-dry at 60°C-80°C to obtain a low-molecular-weight-maleic anhydride copolymer, and the number-average molecular weight of the copolymer It is 5000-10000. The polymerization inhibitor (being chain transfer agent) that adopts in this patent is mercaptans, such as dodecyl mercaptan, ethanethiol, propylene mercaptan, 1-butanethiol and p-chlorobenzene mercaptan, obtained number average Styrene-maleic anhydride copolymer with molecular weight between 5000-10000.

Contents of the invention

The object of the present invention is to provide a chain transfer agent containing epoxy groups at the end and its preparation method and application in order to overcome the above-mentioned defects in the prior art.

The purpose of the present invention can be achieved through the following technical solutions:

A chain transfer agent containing epoxy groups at the end, the chemical structural formula of the chain transfer agent is:

Wherein, A is C ₁ -C ₂₀ linear, branched or cyclic saturated or unsaturated hydrocarbons, said unsaturated hydrocarbons include alkenes, alkynes, aromatics or heterocyclic hydrocarbons containing N and O; B is C ₂ -C ₂₀ straight chain, branched or cyclic saturated aliphatic alkane.

In the chemical structural formula, A is a C ₁ -C ₅ linear saturated aliphatic alkane.

In the chemical structural formula, B is a C ₂ -C ₆ linear saturated aliphatic alkane.

In the chemical structural formula, B is a C ₆ -C ₁₀ cyclic or branched saturated aliphatic alkane.

As a preferred technical scheme, A is C ₂ straight chain saturated aliphatic alkane, B is C ₂ -C ₆ straight chain saturated aliphatic alkane, and its reaction process is as follows:

A kind of preparation method of the chain transfer agent that contains epoxy group at the end, this method specifically comprises the following steps:

(1) Add dibasic alcohol, alkali and phase transfer catalyst into the mixed solution of organic solvent and water, stir evenly, heat to a suitable temperature, then slowly add an appropriate amount of epichlorohydrin for reaction, after the reaction is finished, Rotary evaporation to remove the organic solvent, followed by washing and extraction to obtain diol monoglycidyl ether;

(2) Add diol monoglycidyl ether, mercapto carboxylic acid, and catalyst into the organic solvent, heat up and reflux for dehydration, wash after the reaction is over, dry the organic phase, and remove the solvent to obtain a compound containing epoxy groups at the end. chain transfer agent.

In the step (1), the molar ratio of dihydric alcohol, alkali and phase transfer catalyst is 1:1-6:0.01-0.1.

The volume ratio of the organic solvent to water in the mixed solution described in step (1) is 1:1, and the mass concentration of the alkali in the mixed solution is 0.05-0.2 g/ml.

The molar ratio of glycol monoglycidyl ether, mercaptocarboxylic acid and catalyst described in step (2) is 1:0.5-1.5:0.01-0.1.

The phase transfer catalyst described in the step (1) comprises tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium bisulfate, tetrabutylammonium chloride, dodecyltrimethylammonium chloride 1. One or more of cetyl ammonium bromide or benzyl triethyl ammonium chloride, the alkali is sodium hydroxide, and the organic solvent is toluene;

The catalyst described in step (2) includes one of concentrated sulfuric acid, p-toluenesulfonic acid or acidic ion exchange resin, and the mercaptocarboxylic acid is 3-mercaptopropionic acid.

The application of a chain transfer agent containing epoxy groups at the end, the chain transfer agent is used to prepare styrene-maleic anhydride alternating copolymers with a relative molecular weight of 2000-10000.

Compared with the prior art, the chain transfer agent containing epoxy groups at the end of the present invention can be used to prepare low molecular weight styrene-maleic anhydride resins, and obtain the styrene maleic anhydride resins modified with epoxy groups at the end groups, as Its modification research provides a broader space. The preparation method of the invention is simple, the reaction conditions are well controllable, the yield is high, and the prepared chain transfer agent containing epoxy groups at the end has high activity, which can effectively control the molecular weight of the polymerization product, and can prevent destructive free radical chain formation The occurrence of the reaction is suitable for large-scale industrial production, has good economic benefits, and has good application prospects.

Detailed ways

The present invention will be described in detail below in conjunction with specific embodiments.

In the examples of the present invention, GC is used to determine the purity of the compound, and HPLC-MS and ¹ HNMR are used to determine the structure of the compound.

The invention uses a gel chromatograph to measure the weight-average molecular weight, number-average molecular weight and molecular weight distribution of the styrene-maleic anhydride copolymer by using tetrahydrofuran (THF) as the mobile phase.

The preparation of embodiment 1 ethylene glycol monoglycidyl ether

In a four-necked flask equipped with a reflux condenser, a constant pressure dropping funnel, a stirrer and a thermometer, add 9.31g (0.15mol) of ethylene glycol, 6.00g (0.15mol) of NaOH, 0.5g of tetrabutyl bromide Ammonium and toluene (30ml)/water (30ml), stirred evenly, raised to 40°C, slowly added 9.25g (0.1mol) epichlorohydrin dropwise, and continued the reaction for 6h. After the reaction, the organic solvent was removed by rotary evaporation, the resulting aqueous solution was washed with an appropriate amount of cyclohexane, the aqueous phase was extracted with an appropriate amount of dichloromethane, and the solvent was removed to obtain ethylene glycol monoglycidyl ether with a yield of 54% and a GC purity of 97.4 %.

¹ H NMR (CDCl ₃ , 400MHz), δ: 3.72～3.66(m,1H), 3.56～3.47(m,1H), 3.35～3.28(m,1H), 3.02～2.89(m,1H), 2.44～ 2.25(m,1H).

ESI-MS (35eV), m/z: 119.24 (M+H), 141.27 (M+Na).

Example 2 Preparation of 1,4-butanediol monoglycidyl ether

In a four-necked flask equipped with a reflux condenser, a constant pressure dropping funnel, a stirrer and a thermometer, 13.52g (0.15mol) of 1,4-butanediol, 6.00g (0.15mol) of NaOH, 0.5g of tetra Butylammonium bromide and toluene (30ml)/water (30ml), stirred evenly and raised to 40°C, slowly added 9.25g (0.1mol) epichlorohydrin dropwise, and continued the reaction for 6h. After the reaction, the organic solvent was removed by rotary evaporation, the resulting aqueous solution was washed with an appropriate amount of cyclohexane, the aqueous phase was extracted with an appropriate amount of dichloromethane, and the solvent was removed to obtain 1,4-butanediol monoglycidyl ether with a yield of 65%. , GC purity 98.6%.

¹ HNMR (CDCl ₃ , 400MHz), δ: 3.74～3.76, 3.37～3.40(m, 2H); 3.62～3.65(m, 2H); 3.50～3.58(m, 2H); 2.80～2.81, 2.61～2.62( m, 2H); 2.77～2.79(m, 1H); 1.63～1.70(m, 4H);

ESI-MS (35eV), m/z: 147.17 (M+H), 169.09 (M+Na).

Example 3 Preparation of 1,6-hexanediol monoglycidyl ether

In a four-neck flask equipped with a reflux condenser, a constant pressure dropping funnel, a stirrer and a thermometer, 17.73g (0.15mol) of 1,6-hexanediol, 6.00g (0.15mol) of NaOH, 0.5g of tetra Butylammonium bromide and toluene (30ml)/water (30ml), stirred evenly and raised to 40°C, slowly added 9.25g (0.1mol) epichlorohydrin dropwise, and continued the reaction for 6h. After the reaction, the organic solvent was removed by rotary evaporation, the resulting aqueous solution was washed with an appropriate amount of cyclohexane, the aqueous phase was extracted with an appropriate amount of dichloromethane, and the solvent was removed to obtain 1,6-hexanediol monoglycidyl ether with a yield of 63%. , GC purity 97.8%.

¹ HNMR (CDCl ₃ , 400MHz), δ: 3.49～3.64(m, 3H); 3.28～3.36(m, 3H); 2.91～3.02(m, 1H); 2.25～2.44(m, 2H); 1.43～1.64 (m, 8H);

ESI-MS (35eV), m/z: 175.34 (M+H), 197.14 (M+Na).

Example 4 Preparation of 3-mercaptopropionate hydroxyethyl glycidyl ether

In the four-necked flask equipped with reflux condenser, constant pressure dropping funnel, stirrer and water separator, add 11.81g (0.10mol) ethylene glycol monoglycidyl ether, 2.0g ion exchange resin and 50ml toluene successively, Stir evenly and heat up to reflux, slowly add 3-mercaptopropionic acid dropwise, and at the same time separate the water generated by the reaction, and continue the reaction for 1 hour until no water is released. After the reaction, the reaction solution was washed three times with 20 ml of water, the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was removed by rotary evaporation to obtain 3-mercaptopropionate hydroxyethyl glycidyl ether with a yield of 86% and a GC purity of 97.2%.

¹ HNMR (CDCl ₃ , 400MHz), δ: 4.16～4.24(t, 2H); 3.49～3.65(m, 3H); 3.29～3.37(m, 1H); 2.91～3.10(m, 3H); 2.30～2.55 (m, 4H);

ESI-MS (35eV), m/z: 207.45 (M+H), 239.07 (M+Na).

Example 5 Preparation of 3-mercaptopropionate hydroxybutyl glycidyl ether

In the four-neck flask equipped with reflux condenser, constant pressure dropping funnel, stirrer and water separator, add 14.62g (0.10mol) butanediol monoglycidyl ether, 2.0g ion exchange resin and 50ml toluene successively, Stir evenly and heat up to reflux, slowly add 3-mercaptopropionic acid dropwise, and at the same time separate the water generated by the reaction, and continue the reaction for 1 hour until no water is released. After the reaction, the reaction solution was washed three times with 20 ml of water, the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was removed by rotary evaporation to obtain 3-mercaptopropionate hydroxybutyl glycidyl ether with a yield of 84% and a GC purity of 97.6%.

¹ HNMR (CDCl ₃ , 400MHz), δ: 4.10～4.15(t, 2H); 3.48～3.56(m, 1H); 3.27～3.36(m, 3H); 2.90～3.08(m, 3H); 2.29～2.54 (m, 4H); 1.50～1.73(m, 4H);

ESI-MS (35eV), m/z: 235.32 (M+H), 257.22 (M+Na).

Example 6 Preparation of 3-mercaptopropionate hydroxyhexyl glycidyl ether

In the four-neck flask equipped with reflux condenser, constant pressure dropping funnel, stirrer and water separator, add 17.42g (0.10mol) hexanediol monoglycidyl ether, 2.0g ion exchange resin and 50ml toluene successively, Stir evenly and heat up to reflux, slowly add 3-mercaptopropionic acid dropwise, and at the same time separate the water generated by the reaction, and continue the reaction for 1 hour until no water is released. After the reaction, the reaction solution was washed three times with 20 ml of water, the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was removed by rotary evaporation to obtain 3-mercaptopropionate hydroxybutyl glycidyl ether with a yield of 82% and a GC purity of 97.8%.

¹ HNMR (CDCl ₃ , 400MHz), δ: 4.01～4.16(t, 2H); 3.49～3.56(m, 1H); 3.29～3.38(m, 3H); 2.91～3.07(m, 3H); 2.30～2.54 (m, 4H); 1.36～1.68(m, 8H);

ESI-MS (35eV), m/z: 263.35 (M+H), 285.60 (M+Na).

Embodiment 7-10 styrene-maleic anhydride alternate copolymerization

Embodiment 7 blank experiment

_N Under protection, in a four-necked flask equipped with a magnetic stirrer, a reflux condenser, a thermometer and a constant pressure dropping funnel, add 4.903g (50.0mmol) maleic anhydride and 70ml of butyl acetate and n-heptane mixed solvent (1:3), stir to dissolve. Raise the temperature to 80°C, add 0.506g (3.1mmol) azobisisobutyronitrile, dropwise add 5.207g (50.0mmol) styrene within 1h, continue the reaction for 3h, cool down to room temperature, filter with suction, and wash the filter cake with absolute ethanol , dried to constant weight to obtain a white solid with a yield of 96.8% and a number average molecular weight of 11051.

Example 8 3-Mercaptopropionate-Hydroxyethyl Glycidyl Ether (CTA-1) as Chain Transfer Agent

_N Under protection, in a four-necked flask equipped with a magnetic stirrer, a reflux condenser, a thermometer and a constant pressure dropping funnel, add 4.903g (50.0mmol) maleic anhydride and 70ml of butyl acetate and n-heptane mixed solvent (1:3), stir to dissolve. Raise the temperature to 80°C, add 0.506g (3.1mmol) of azobisisobutyronitrile and 0.303g of CTA-1, dropwise add 5.207g (50.0mmol) of styrene within 1h, continue the reaction for 3h, cool down to room temperature, suction filter, filter The cake was washed with absolute ethanol and dried to constant weight to obtain a white solid with a yield of 95.1% and a number average molecular weight of 5749.

Example 9 3-mercaptopropionate-hydroxybutyl glycidyl ether (CTA-2) used as chain transfer agent

_N Under protection, in a four-necked flask equipped with a magnetic stirrer, a reflux condenser, a thermometer and a constant pressure dropping funnel, add 4.903g (50.0mmol) maleic anhydride and 70ml of butyl acetate and n-heptane mixed solvent (1:3), stir to dissolve. Raise the temperature to 80°C, add 0.506g (3.1mmol) of azobisisobutyronitrile and 0.303g of CTA-2, dropwise add 5.207g (50.0mmol) of styrene within 1h, continue the reaction for 3h, cool down to room temperature, suction filter, filter The cake was washed with absolute ethanol and dried to constant weight to obtain a white solid with a yield of 94.3% and a number average molecular weight of 3279.

Example 10 3-Mercaptopropionate-Hydroxyhexyl Glycidyl Ether (CTA-3) as Chain Transfer Agent

_N Under protection, in a four-necked flask equipped with a magnetic stirrer, a reflux condenser, a thermometer and a constant pressure dropping funnel, add 4.903g (50.0mmol) maleic anhydride and 70ml of butyl acetate and n-heptane mixed solvent (1:3), stir to dissolve. Raise the temperature to 80°C, add 0.506g (3.1mmol) of azobisisobutyronitrile and 0.303g of CTA-3, dropwise add 5.207g (50.0mmol) of styrene within 1h, continue the reaction for 3h, cool down to room temperature, suction filter, filter The cake was washed with absolute ethanol and dried to constant weight to obtain a white solid with a yield of 94.8% and a number average molecular weight of 3127.

Table 1 is blank experiment and each chain transfer agent used in the experimental data of low molecular weight styrene-maleic anhydride copolymer in the embodiment:

Table 1

As can be seen from the experimental data in Table 1, the chain transfer agent in the present invention has played an obvious regulatory role to the molecular weight of styrene-maleic anhydride resin, adding a certain amount of chain transfer agent CTA-1, CTA-2, CTA-3 The number average molecular weight of the polymer can be reduced from 11051 to 5749, 3279 and 3127 respectively.

The above descriptions of the embodiments are for those of ordinary skill in the art to understand and use the invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described here to other embodiments without creative efforts. Therefore, the present invention is not limited to the above-mentioned embodiments. Improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should fall within the protection scope of the present invention.

Claims (10)

1. the chain-transferring agent of epoxy group is contained in a kind of end, which is characterized in that the chemical structural formula of the chain-transferring agent is：

Wherein, A C₁-C₂₀Straight chain, branched or cricoid saturated hydrocarbons or unsaturated hydrocarbons, the unsaturated hydrocarbons include alkene, Alkynes, aromatic hydrocarbon or the heterocyclic hydrocarbon containing N and O；B is C₂-C₂₀Straight chain, branched or cricoid Saturated alkane.

2. the chain-transferring agent of epoxy group is contained in a kind of end according to claim 1, which is characterized in that the chemistry In structural formula, A C₁-C₅Straight chain Saturated alkane.

3. the chain-transferring agent of epoxy group is contained in a kind of end according to claim 1, which is characterized in that the chemistry In structural formula, B C₂-C₆Straight chain Saturated alkane.

4. the chain-transferring agent of epoxy group is contained in a kind of end according to claim 1, which is characterized in that the chemistry In structural formula, B C₆-C₁₀Cyclic annular or branched Saturated alkane.

5. special as the preparation method of the chain-transferring agent of epoxy group is contained in a kind of end of Claims 1-4 any one of them Sign is that this method specifically includes following steps：

(1) dihydric alcohol, alkali and phase transfer catalyst are added in the mixed solution of organic solvent and water, are stirred evenly, heated To preference temperature, then suitable epoxychloropropane being slowly added dropwise and is reacted, waits for after reaction, revolving removes organic solvent, By washing, extraction, dihydric alcohol monoglycidyl ether is made；

(2) dihydric alcohol monoglycidyl ether and mercaptan carboxylic acid, catalyst are added in organic solvent, temperature rising reflux dehydration waits for After reaction, it washs, organic phase drying removes solvent, obtains the chain-transferring agent that epoxy group is contained in end.

6. the preparation method of the chain-transferring agent of epoxy group is contained in a kind of end according to claim 5, which is characterized in that The molar ratio of dihydric alcohol, alkali and phase transfer catalyst is 1 in step (1):1-6:0.01-0.1.

7. the preparation method of the chain-transferring agent of epoxy group is contained in a kind of end according to claim 5, which is characterized in that The volume ratio of organic solvent and water is 1 in mixed solution described in step (1):1, quality of the alkali in mixed solution A concentration of 0.05-0.2g/mL.

8. the preparation method of the chain-transferring agent of epoxy group is contained in a kind of end according to claim 5, which is characterized in that The molar ratio of dihydric alcohol monoglycidyl ether and mercaptan carboxylic acid, catalyst described in step (2) is 1:0.5-1.5:0.01- 0.1。

9. the preparation method of the chain-transferring agent of epoxy group is contained in a kind of end according to claim 5, which is characterized in that Phase transfer catalyst described in step (1) includes tetraethylammonium bromide, tetrabutylammonium bromide, 4-butyl ammonium hydrogen sulfate, four fourths It is one or more in ammonium chloride, dodecyl trimethyl ammonium chloride, cetyl ammonium bromide or benzyltriethylammoinium chloride, The alkali is sodium hydroxide, and the organic solvent is toluene；

Catalyst described in step (2) includes one kind in the concentrated sulfuric acid, p-methyl benzenesulfonic acid or acid-exchange resin, described Mercaptan carboxylic acid be 3- mercaptopropionic acids.

10. as the application of the chain-transferring agent of epoxy group, feature are contained in a kind of end of Claims 1-4 any one of them It is, the chain-transferring agent is used to prepare the alternate styrene-maleic anhydride copolymer that relative molecular weight is 2000-10000.