WO2015100517A1

WO2015100517A1 - Substance containing multiple epoxy functional groups, preparation method therefor, terpolymer of same, carbon dioxide and epoxy propane, and copolymerization method therefor

Info

Publication number: WO2015100517A1
Application number: PCT/CN2013/001669
Authority: WO
Inventors: 刘埃林; 王克智; 高文焕; 李训刚; 张光军; 陈有业; 毛晨曦; 李向阳; 海山; 李成军; 王四海; 刘金融; 张光东; 李彦斌
Original assignee: 内蒙古蒙西高新技术集团有限公司; 山西省化工研究院（有限公司）
Priority date: 2013-12-31
Filing date: 2013-12-31
Publication date: 2015-07-09

Abstract

The present invention provides a substance containing multiple epoxy functional groups, copolymerized by the following monomers in parts by weight: 10-90 parts of styrene monomer; 10-90 parts of glycidyl (methyl)acrylate monomer, wherein 'the multiple' means each molecule averagely contains 3-100 epoxy functional groups. The present invention also provides a preparation method for the substance containing multiple epoxy functional groups. Also disclosed is a terpolymer of the substance containing multiple epoxy functional groups, carbon dioxide and epoxy propane and a preparation method therefor. The yield of the terpolymer prepared by the method of the present invention is greatly improved, hot processing temperature is substantially improved, and the prepared terpolymer can be used alone like common plastics.

Description

Material containing a plurality of epoxy functional groups, preparation method thereof, terpolymer thereof with carbon dioxide and propylene oxide, and copolymerization method

The invention belongs to the field of preparation of epoxy compounds, and belongs to the technical field of industrial production of carbon dioxide copolymers.

Background technique

Carbon dioxide copolymer is a polymer material obtained by copolymerization of carbon dioxide and an epoxy compound. It has complete biodegradability and plays an important role in solving the "white pollution" caused by ordinary plastics. At the same time, carbon dioxide and epoxide copolymerization can effectively use carbon dioxide, which reduces greenhouse gas emissions and makes it a new carbon source. Therefore, carbon dioxide copolymers have a dual role of environmental protection and resources. The industrial production of carbon dioxide copolymers has been pursued by chemical experts and entrepreneurs. Inner Mongolia Mengxi High-tech Group Co., Ltd. cooperated with the Changchun Institute of Applied Chemistry of the Chinese Academy of Sciences. In 2002, it was the first to realize the industrial production of carbon dioxide and propylene oxide polymerization (CN 1844189A, CN1895775A, CN2865843Y), and successfully obtained polypropylene carbonate ( PPC) product.

Polypropylene carbonate (PPC) products obtained by polymerizing carbon dioxide and propylene oxide are amorphous polymers, which have high temperature and low viscosity agglomeration, and have a low thermal decomposition temperature and a hot working temperature of only 140. Around C, affecting the processing performance of materials, while the cost is relatively high, there are certain difficulties in marketing. In order to improve the performance of PPC and reduce the cost, the patents CN101045814A, CN101089044A, CN101857668A, CN101851409A, CN102964801A, etc. adopt PPC and other biodegradable plastic blending modification methods, and the obtained blends have better performance. However, the amount of PPC is small and the cost is not reduced, which is not conducive to PPC. Market-oriented promotion, and PPC is less compatible with other biodegradable plastics. Physical blending does not fundamentally solve the problem of poor PPC performance. Patent CN101319035A uses peroxide to crosslink PPC. After cross-linking, the performance of PPC is improved, but the process is complicated, the cost is increased, the performance of PPC is not fundamentally improved, and it is not conducive to market promotion.

In order to improve the overall performance of PPC, the patent CN1775828A uses an epoxy compound containing a double bond as a third monomer copolymerized with carbon dioxide and propylene oxide, and the obtained terpolymer is then treated by radiation or a crosslinking agent. Linked, performance has been greatly improved. However, when a third monomer (i.e., an epoxy compound containing a double bond) is added in a large amount, the yield of the copolymer is affected, and the crosslinking process is complicated, which is not suitable for industrial production.

At present, there are reports on the use of a third monomer to copolymerize carbon dioxide and propylene oxide to improve the performance of PPC (Chinese patent CN 102329421A ; Donald J. Darensbourg et a l. Macromo lecules , 2242-2248 , 2012) Dona ld J. Darensbourg et a l. J ACS, 18610-18613, 2011; Chen Shaoyun et al, University Chemistry, 12, 2011, etc.). However, the third monomer selected is a mono-epoxy functional substance, the performance of the copolymer is not sufficiently improved, and the cost of the product is improved, which is not suitable for industrial production.

The use of a material containing two epoxy functional groups as a third monomer to copolymerize with carbon dioxide and propylene oxide can double the molecular weight of PPC and improve the performance of PPC (Youhua Tao et al., Polymer, 7368- 7373, 2006). However, the chemical bond between the two epoxy functional groups in this paper is an ether bond, which does not improve the heat resistance of the copolymer, and the price of the material containing two epoxy functional groups is relatively high, and the yield of the terpolymer is high. It is also significantly reduced, so it is not suitable for industrial production. Another applicant's patent application (Application No. 201310681493. 5) uses an ADR-4370S epoxy functionalized chain extender produced by BASF and contains 9 epoxy functional groups, and is produced by Shanxi Chemical Industry Research Institute. The epoxy functionalized 4370 epoxy functional chain extender is copolymerized with carbon dioxide and propylene oxide, and the yield and thermal processing temperature of the terpolymer are significantly improved. However, these two epoxy functional chain extenders are all chain extenders used in the process of biodegradable plastics. The three problems of carbon dioxide and propylene oxide copolymerization have the following problems: First, the structure of the chain extender is not suitable. The catalytic system of the terpolymerization, the polymerization process and the binary copolymerization conditions of carbon dioxide and propylene oxide have different process conditions, and the optimum conditions of the ternary copolymerization are not achieved. Second, the structure of the chain extender has been determined. The ternary copolymerization of carbon dioxide and propylene oxide cannot reflect the improvement of the molecular chain composition and improve the performance of the terpolymer. Third, the number of epoxy functional groups of the chain extender has been determined, and the ring cannot be increased or decreased according to requirements. The number of oxygen functional groups is used for the ternary copolymerization of carbon dioxide and propylene oxide. The addition amount is less than the purpose of increasing the degree of crosslinking. When the amount of addition is large, although the degree of crosslinking is increased, the molecular chain structure of the copolymer cannot be improved. the goal of.

Therefore, there is an urgent need in the art to design and synthesize other materials containing a plurality of epoxy functional groups according to the final properties and cost requirements of carbon dioxide copolymers, so as to use these epoxy-containing materials for carbon dioxide and propylene oxide. The ternary polymerization to improve the performance of the terpolymer, so as to reduce the cost of the terpolymer and improve its performance, the performance and cost of the carbon dioxide copolymer is close to that of ordinary plastic, and can be used alone as ordinary plastic.

The present invention solves the above problems.

Summary of invention

In a first aspect, the invention relates to a material comprising a plurality of epoxy functional groups which are prepared by copolymerization of the following monomers in the following parts by weight: Styrene monomer: 10-90;

(methyl) glycidyl acrylate monomer: 10-90;

Wherein said plurality means an average of from 3 to 100 epoxy functional groups per molecule.

In a second aspect, the invention relates to a method of preparing a material comprising a plurality of epoxy functional groups, comprising the steps of:

a. The styrene monomer, the glycidyl (meth) acrylate monomer, the initiator, and the solvent are mixed in the following parts by weight to obtain a mixture:

Styrene monomer: 10-90

(methyl) glycidyl acrylate monomer: 1 0-90;

Initiator: 2-12;

Solvent: 150-200

b. raising the mixture to 110-120 ° C and refluxing at this temperature for 2-5 hours to initiate copolymerization;

c The solvent is optionally removed to obtain the material containing a plurality of epoxy functional groups.

In a third aspect, the present invention relates to a material comprising a plurality of epoxy functional groups, a cyclopropane-carbon dioxide terpolymer, which is obtained by copolymerizing the following monomers in the following proportions:

Propylene oxide: 1 part by weight;

The plurality of epoxy functional group-containing materials according to the first aspect of the present invention: 0. 0001 parts by weight to the weight corresponding to the saturated concentration of the propylene oxide;

Carbon dioxide: 0. 5 - 0. 7 parts by weight.

In a fourth aspect, the present invention relates to a propylene oxide-carbon dioxide ternary copolymerization method comprising a plurality of epoxy functional groups, comprising polymerizing carbon dioxide and propylene oxide Initially, the plurality of epoxy functional group-containing substances according to the first aspect of the invention are added, wherein the plurality of epoxy functional group-containing substances are added in an amount of 0.01% by weight of the propylene oxide to the plurality of epoxy functional groups. The saturated concentration of the substance in propylene oxide.

BRIEF DESCRIPTION OF THE DRAWINGS

No

Detailed ways

The multi-epoxy functional group-containing substance of the present invention is actually a copolymer of two types of monomers, one type of monomer is a phenelzine monomer, and the other type is a (fluorenyl) glycidyl acrylate monomer. body. The above two monomers are copolymerized in the following parts by weight to obtain the plurality of epoxy functional groups.

Styrene monomer: 10-90 parts by weight;

(fluorenyl) glycidyl acrylate monomer: 10-90 parts by weight; wherein the plurality refers to an average of 3 to 100 epoxy functional groups per molecule, preferably 3 to 96, for example, may be 3- 8, or 10-19, or 21 - 96.

The term "glycidyl (meth)acrylate" is a common expression by those skilled in the art and refers to glycidyl acrylate or glycidyl methacrylate.

Wherein the styrenic monomer is selected from the group consisting of styrene, o-divinylbenzene, m-divinylbenzene or p-divinylbenzene; wherein the (mercapto)acrylic acid glycidyl ester monomer is selected From glycidyl acrylate or glycidyl methacrylate.

The preparation method of the above-mentioned substance containing a plurality of epoxy functional groups is as follows:

a. The styrene monomer, the glycidyl (meth)acrylate monomer, the initiator, and the solvent are mixed in the following parts by weight to obtain a mixture: Styrene monomer: 10-90

(fluorenyl) glycidyl acrylate monomer: 10-90;

Initiator: 2-12;

Solvent: 150-200;

b. The mixture is warmed to 110-120. C and reflux at this temperature for 2-5 hours to initiate copolymerization;

c Optionally, the solvent is removed to obtain the plurality of epoxy functional groups.

The obtained material having a plurality of epoxy functional groups can also be granulated as needed to obtain a product which is easy to transport and use.

The above reaction can be carried out in any reactor equipped with heating, stirring and reflux equipment.

Wherein the styrenic monomer is selected from the group consisting of styrene, o-divinylbenzene, m-divinylbenzene or p-divinylbenzene; wherein the (mercapto)acrylic acid glycidyl ester monomer is selected From glycidyl acrylate or glycidyl methacrylate. Wherein the initiator is selected from the group consisting of peroxides, preferably benzoyl peroxide; wherein the solvent is selected from the group consisting of toluene, xylene or mixtures thereof.

The above-mentioned substance containing a plurality of epoxy functional groups can be used for ternary copolymerization with carbon dioxide and propylene oxide to obtain a terpolymer of three, which has excellent properties.

Accordingly, the present invention also relates to a propylene oxide-carbon dioxide terpolymer containing a plurality of epoxy functional groups which are copolymerized from the following monomers in the following proportions:

Propylene oxide: 1 part by weight;

The foregoing material having a plurality of epoxy functional groups: 0.0001 parts by weight to the epoxy group thereof The weight corresponding to the saturation concentration in propane;

Carbon dioxide: 0. 5 - 0. 7 parts by weight.

The propylene oxide in the present invention may be industrial grade propylene oxide.

The purity of the carbon dioxide in the present invention is required to be 99.9% or more.

The propylene oxide-carbon dioxide ternary copolymerization method of the plurality of epoxy functional group-containing materials of the present invention comprises adding a plurality of epoxy functional group-containing substances according to the first aspect of the invention at the beginning of polymerization of carbon dioxide and propylene oxide. The amount of the propylene oxide-containing substance is from 0.01% by weight to the saturated concentration of the epoxy-containing substance in propylene oxide. Regarding the polymerization conditions of carbon dioxide and propylene oxide, reference may be made to the relevant literature, for example, the conditions described in Chinese Patent No. CN1306021A, CN101003619A.

The above copolymerization reaction can also be carried out in a two-stage copolymerization process. The process conditions of the first stage are pressures of 3. 5-4. 0 MPa, temperature 70-90 ° C, time 4-20 hours, the second stage process conditions are pressure 3. 0-3. 6 MPa, temperature 60- 80 ° C, time 4-20 hours; or the first stage process conditions are pressure 3. 0-3. 6 MPa, temperature 60-80 ° C 4- 20 hours, time 4-20 hours, the second stage process conditions are Pressure 3. 5-4. 0 MPa, temperature 70-90 ° C, time 4-20 hours.

Of course, the above copolymerization reaction can also be carried out by a three-stage copolymerization or a more stage co-polymerization process. Benefiting from the teachings of the present invention, those skilled in the art will be able to design or experimentally explore the process parameters for each stage, depending on the particular situation.

The beneficial effects of the present invention are that the yield of the terpolymer of the present invention is increased by 5-100% compared with the yield without adding the epoxy functional group-containing substance according to the different addition amount of the substance containing a plurality of epoxy functional groups. The above; the hot working temperature of the terpolymer of the present invention is increased by 10-80 as compared with the binary polymer obtained by copolymerizing only propylene oxide and carbon dioxide at the same propylene oxide/carbon dioxide ratio. C, the increase in hot working temperature is beneficial to the use of the terpolymer more easily downstream The household is industrialized. The terpolymer of the present invention can be used alone as a normal plastic. It can be seen that the present invention not only greatly reduces the production cost of the carbon dioxide copolymer, but also improves the performance of the carbon dioxide copolymer, so that the above terpolymer can be used alone, and is very suitable for industrial production. The invention solves the problems of high cost and low hot processing temperature of the carbon dioxide copolymer which has been plagued for many years, and opens up a new way for the industrialization and market promotion of the carbon dioxide copolymer.

Example

The invention is illustrated by the following examples, which are merely illustrative and not restrictive.

Embodiment 1

(1) Preparation of a substance containing a plurality of epoxy functional groups

The parts by weight of each substance in the reaction mixture are as follows:

Styrene monomer: 10

Glycidyl acrylate monomer: 90;

Initiator: 10;

Preparation process: 500 ml of toluene, 50 g of styrene, 450 g of glycidyl methacrylate, 50 g of benzoyl peroxide were added to a 5000 ml three-necked flask, and the temperature was raised to 110 ° C for 5 h. After the reaction, the solvent was recovered and the material was discharged. A substance containing a plurality of epoxy functional groups. The average number of functional groups per molecule was 95. 9, and the weight average molecular weight was 24,399.

(2) Substance containing multiple epoxy functional groups - Carbon dioxide-propylene oxide ternary copolymerization

Ternary copolymerization experiment 1 :

25%, according to the weight ratio of the epoxy-containing compound to the propylene oxide is 0. 25%, according to Example 1 of Patent CN1306021A was subjected to a terpolymerization reaction. The polymerization time is 10 hours, the pressure in the first 5 hours is 3.5-4. OMPa, and the temperature is 70-90. C; The pressure after the 5 hours is 3.0-3.6 MPa, and the temperature is 60-80'C. The yield of the obtained terpolymer is 51.5 g, which is about 38% higher than that of the polymer containing no epoxy functional group, and the hot working temperature of the terpolymer is about 161'C. The epoxy functional polymer was increased by about 21 °C.

Ternary copolymerization experiment 2:

A substance having an epoxy functional group number of 95.9 was dissolved in propylene oxide, wherein a weight ratio of a substance having a plurality of epoxy functional groups to propylene oxide was 0.5%, and a ternary copolymerization reaction was carried out in accordance with Example 1 of the patent CN101003619A. The polymerization time was 30 hours, the pressure in the first 15 hours was 3.5-4.0 MPa, and the temperature was 70-90. C; The pressure after the 15 hours is 3.0-3.6MPa, and the temperature is 60-80. C. The yield of the obtained terpolymer was 61.4 g, which was about 63% higher than that of the polymer containing no epoxy functional group, and the hot working temperature of the terpolymer was about 170 ° C. The polymer of the plurality of epoxy functional shields was increased by about 30 °C.

Ternary copolymerization experiment 3:

The physical shield having an epoxy functional group number of 95.9 was dissolved in propylene oxide, and the weight ratio of the plurality of epoxy functional group shields to propylene oxide was 0.75%, and the ternary copolymerization was carried out according to Example 5 of Patent CN1306021A. reaction. The polymerization time is 10 hours, the pressure in the first 5 hours is 3.0-3.6 MPa, and the temperature is 60-80. C; After 5 hours, the pressure is 3.5-4. OMPa, and the temperature is 70-90 °C. The yield of the obtained terpolymer was 79.6 g, which was about 98% higher than that of the polymer containing no epoxy functional group, and the thermal processing temperature of the terpolymer was 184. Around C, it is about 44'C higher than that of a polymer which does not contain a substance having a plurality of epoxy functional groups.

Embodiment 2

(1) Preparation of a substance containing a plurality of epoxy functional groups The parts by weight of each substance in the reaction mixture are as follows:

Styrene monomer: 30

Glycidyl acrylate monomer: 70;

Initiator: 10;

Preparation process: 500ml of benzene, 150g of styrene, 350g of glycidyl methacrylate, 50g of benzoyl peroxide, heated to 115 'C, kept for 5h, the solvent was recovered, and the discharge was obtained. An epoxy functional substance. The average number of functional groups contained in each molecule was 78. 9, and the weight average molecular weight was 17302.

Ternary copolymerization experiment 1:

The 5%, according to the embodiment 1 of the patent CN1306021A, the material having a plurality of epoxy functional groups of 78. 9 is dissolved in the propylene oxide, wherein the weight ratio of the substance having a plurality of epoxy functional groups to the propylene oxide is 0.5%. Ternary copolymerization. The polymerization time is 10 hours, and the pressure in the first 5 hours is 3. 5-4. 0 MPa, and the temperature is 70-90. C; After 5 hours, the pressure is 3. 0-3. 6 MPa, and the temperature is 60-80 °C. The yield of the obtained terpolymer was 49.9 g, which was about 34% higher than that of the polymer without a plurality of epoxy functional groups, and the thermal processing temperature of the terpolymer was 158. Around C, about 18 'C is increased compared to the addition of a polymer containing a plurality of epoxy functional groups.

Ternary copolymerization experiment 2:

5%, according to the embodiment of the patent CN101003619A, the weight ratio of the substance having a plurality of epoxy functional groups to the propylene oxide is 0.75%, according to the embodiment of the patent CN101003619A. The ternary copolymerization reaction was carried out. The polymerization time is 30 hours, the pressure in the first 15 hours is 3. 5-4. 0 MPa, the temperature is 70-90 . C; The pressure after the 15 hours is 3, 0-3.6 MPa, and the temperature is 60-80 °C. The yield of the obtained terpolymer is 58.5 g, which is about 55% higher than that of the polymer containing no epoxy functional group, and the hot working temperature of the terpolymer is about 169'C. The polymer of the epoxy functional material was increased by about 29 °C.

Ternary copolymerization experiment 3:

A material having a plurality of epoxy functional groups of 78.9 is dissolved in propylene oxide, and the weight ratio of the plurality of epoxy functional groups to propylene oxide is 1.0%, and ternary according to Example 5 of Patent CN1306021A Copolymerization reaction. The polymerization time is 10 hours, the pressure in the first 5 hours is 3.0-3.6 MPa, the temperature is 60-80 °C; the pressure in the last 5 hours is 3.5-4.0 MPa, and the temperature is 70-90 'C. The yield of the obtained terpolymer was 58.6 g, which was about 87% higher than that of the polymer containing no epoxy functional group, and the thermal processing temperature of the terpolymer was 181. C is about 41 higher than that of a polymer which does not contain a substance having a plurality of epoxy functional groups. C.

Embodiment 3

The parts by weight of each substance in the reaction mixture are as follows:

Styrene monomer: 45

Glycidyl acrylate monomer: 55;

Initiator: 10;

Preparation: 500 ml of toluene, 225 g of styrene, 275 g of glycidyl methacrylate, 50 g of benzoyl peroxide were added to a 5000 ml three-necked flask, and the temperature was raised to 110. C, kept for 5h, recovering the solvent, and discharging the material containing a plurality of epoxy functional groups. The average number of functional groups contained in each molecule was 64.3 and the weight average molecular weight was 19,508. (2) A substance containing a plurality of epoxy functional groups - carbon dioxide - propylene oxide terpolymer

Ternary copolymerization experiment 1 :

The 5%, according to the embodiment 1 of the patent CN1306021A, wherein the propylene oxide is a compound having a plurality of epoxy functional groups of 6.4. Ternary copolymerization. The polymerization time is 10 hours, the pressure in the first 5 hours is 3. 5-4. 0 MPa, the temperature is 70-90 'C; the pressure after 5 hours is 3. 0-3. 6 MPa, and the temperature is 60-80. C. The yield of the obtained terpolymer is 49.9 g, which is about 31% higher than that of the polymer without a plurality of epoxy functional groups, and the hot working temperature of the terpolymer is about 157 ° C. The epoxy functional polymer is increased by about 17 compared to the polymer. C.

Ternary copolymerization experiment 2:

The material having a plurality of epoxy functional groups of 64.3 is dissolved in propylene oxide, wherein the weight ratio of the substance containing a plurality of epoxy functional groups to propylene oxide is 1%, and is carried out according to the embodiment 1 of the patent CN101003619A. Copolymerization reaction. The polymerization time is 30 hours, the pressure in the first 15 hours is 3. 5- 4. 0 MPa, the temperature is 70-90 'C; the pressure in the last 15 hours is 3. 0-3. 6 MPa, the temperature is 60-80 ° (. The yield of the obtained terpolymer is 56.2 g, which is about 49% higher than that of the shield without the addition of a plurality of epoxy functional groups, and the hot working temperature of the terpolymer is about 168 ° C, and is not added. The polymer of a material containing a plurality of epoxy functional groups is increased by about 29 C.

Ternary copolymerization experiment 3:

The 5%, according to the embodiment 5 of the patent CN1306021A, the weight ratio of the epoxide-containing substance to the propylene oxide is 1.5%. The ternary copolymerization reaction was carried out. The temperature is 60-80 ° C. The temperature is 60-80 ° C for the first 5 hours, and the pressure is 3. 5-4. 0 MPa, the temperature is 70-90. C. The resulting ternary copolymer The amount of the polymer is 68. lg, which is about 80% higher than that of the material without the addition of a plurality of epoxy functional groups. The thermal processing temperature of the terpolymer is about 180 ° C, and no epoxy functional group is added. The polymer of the substance is increased by about 40'C.

Embodiment 4

(1) Preparation of materials containing multiple epoxy functional groups

The parts by weight of each substance in the reaction mixture are as follows:

Styrene monomer: 55

Glycidyl acrylate monomer: 45;

Initiator: 10;

Preparation process: 500ml of benzene, 275g of divinylbenzene, 225g of glycidyl acrylate, 50g of benzoyl peroxide, heated to 120'C for 5h, recovering solvent, and discharging more An epoxy functional substance. The average number of functional groups per molecule was 40. 4 and the weight average molecular weight was 13179.

(2) A substance containing a plurality of epoxy functional groups - carbon dioxide - propylene oxide ternary copolymerization

Ternary copolymerization experiment 1:

The 5%, according to the embodiment 1 of the patent CN1306021A, the material having a plurality of epoxy functional groups of 40.4 is dissolved in the propylene oxide, wherein the weight ratio of the substance having a plurality of epoxy functional groups to the propylene oxide is 0.5%. Ternary copolymerization. The polymerization time is 10 hours, the pressure in the first 5 hours is 3. 5-4. 0 MPa, the temperature is 70-90 ° C; the pressure in the last 5 hours is 3. 0-3. 6 MPa, the temperature is 60-80 ° (. The yield of the obtained terpolymer is 51.6 g, which is about 28% higher than that of the polymer without a plurality of epoxy functional groups, and the hot working temperature of the terpolymer is about 155 ° C. The epoxy functional polymer is about 15 'C higher than that of the polymer. Ternary copolymerization experiment 2:

The material having a plurality of epoxy functional groups of 40.4 is dissolved in propylene oxide, wherein the weight ratio of the physical shield containing a plurality of epoxy functional groups to propylene oxide is 2%, according to the embodiment 1 of the patent CN101003619A. Ternary copolymerization. The polymerization time is 30 hours, the pressure in the first 15 hours is 3, 5-4. 0 MPa, the temperature is 70-90 ° C; the pressure in the last 15 hours is 3. 0-3. 6 MPa, the temperature is 60-80 ° (. The yield of the obtained terpolymer is 52.8 g, which is about 40% higher than that of the polymer without the addition of a plurality of epoxy functional groups, and the hot working temperature of the terpolymer is about 168 ° C, with or without The polymer of the plurality of epoxy functional materials is increased by about 28 C.

Ternary copolymerization experiment 3:

The 5%, according to the embodiment 5 of the patent CN1306021A, the weight ratio of the epoxide-containing material to the propylene oxide is 3.5%. Ternary copolymerization. The polymerization time is 10 hours, the pressure in the first 5 hours is 3. 0-3. 6 MPa, the temperature is 60-80 °C; the pressure in the last 5 hours is 3. 5-4. 0 MPa, and the temperature is 70-90'C. The yield of the obtained terpolymer was 62. 8 g, which was about 66% higher than that of the material containing no epoxy functional group, and the thermal processing temperature of the terpolymer was 182. Around C, it is about 42 higher than that of a polymer which does not contain a substance having a plurality of epoxy functional groups. C.

Embodiment 5

The parts by weight of each substance in the reaction mixture are as follows:

Styrene monomer: 70

Glycidyl acrylate monomer: 30;

Initiator: 10;

Preparation process: Add 500ml of benzene, 350g of two to 500ml three-necked bottle Alkenylbenzene, 150 g of glycidyl methacrylate, 50 g of benzoyl peroxide, heated to 115. C, kept for 5h, recovering the solvent, and discharging the material containing a plurality of epoxy functional groups. The average number of functional groups per molecule is 19.8, and the weight average molecular weight is 28,121.

Ternary copolymerization experiment 1 :

0重量进行进行实施例3的实施例3的实施例3的实施例3的实施例3 Ternary copolymerization. The polymerization time is 32 hours, the pressure in the first 16 hours is 3. 5-4. 0 MPa, the temperature is 70-90'C; the pressure in the last 16 hours is 3, 0-3. 6 MPa, and the temperature is 60-80 °C. The yield of the obtained terpolymer is 73. 4g, which is about 53% higher than that of the polymer without adding a plurality of epoxy functional substances, and the thermal processing temperature of the terpolymer is about 185 °C, and the polymerization is not added to 4370. The object has increased by about 45 'C.

Ternary copolymerization experiment 2:

The material having a plurality of epoxy functional groups of 19.8 is dissolved in propylene oxide, wherein the weight ratio of the physical shield containing a plurality of epoxy functional groups to propylene oxide is 3%, according to the third embodiment of the patent CN1306021A. Ternary copolymerization. The polymerization time is 14 hours, the pressure in the first 7 hours is 3. 5-4. 0 MPa, the temperature is 70-90'C; the pressure in the last 7 hours is 3. 0-3. 6 MPa, and the temperature is 60-80. C. The yield of the obtained terpolymer is 84.0 g, which is about 78% higher than that of the polymer containing no epoxy functional group, and the hot working temperature of the terpolymer is about 196 °C. The polymer of the plurality of epoxy functional materials is increased by about 56. C.

Ternary copolymerization experiment 3:

a substance having a plurality of epoxy functional groups of 19.8 is dissolved in propylene oxide, The weight ratio of the substance having a plurality of epoxy functional groups of 95.9 to propylene oxide was 5%, and the ternary copolymerization reaction was carried out according to Example 5 of Patent CN1306021A. The polymerization time is 10 hours, the pressure in the first 5 hours is 3, 0-3. 6 MPa, the temperature is 60-80 ° C; the pressure in the last 5 hours is 3. 5-4. 0 MPa, the temperature is 70-90 ° (. The yield of the obtained terpolymer is 74. 4g, which is about 97% higher than the yield of the polymer without adding a plurality of epoxy functional groups, and the hot working temperature of the terpolymer is about 210'C, and is not added. The polymer of the material with multiple epoxy functional groups is increased by about 70%.

Embodiment 6

(1) Preparation of a physical shield containing multiple epoxy functional groups

The parts by weight of each substance in the reaction mixture are as follows:

Styrene monomer: 90

Glycidyl acrylate monomer: 10;

Initiator: 10;

Preparation: 500 ml of toluene, 450 g of divinyl benzene, 50 g of glycidyl acrylate, 50 g of benzoyl peroxide were added to a 5000 ml three-necked flask, and the temperature was raised to 110. C, hold for 5h, recover the solvent, and discharge to obtain a substance containing a plurality of epoxy functional groups. The average number of functional groups per molecule was 3. 2 and the weight average molecular weight was 14710.

Ternary copolymerization experiment 1:

The material having an epoxy functional group number of 3.2 is dissolved in propylene oxide, wherein a weight ratio of a plurality of epoxy functional groups to propylene oxide is 2%, and the ternary copolymerization reaction is carried out according to Example 1 of Patent CN1306021A. . Polymerization time 10 The pressure in the first 5 hours is 3. 5-4. O MPa , the temperature is 70-90 ° C; the pressure in the last 5 hours is 3. 0- 3. 6 MPa, and the temperature is 60-80 ° C. The yield of the obtained terpolymer was 50.8 g, which was about 26% higher than that of the polymer without the addition of a plurality of epoxy functional groups, and the thermal processing temperature of the terpolymer was 156. Around C, about 16 is increased compared to the addition of a polymer containing a plurality of epoxy functional groups. C.

Ternary copolymerization experiment 2:

The material having an epoxy functional group number of 3.2 is dissolved in propylene oxide, wherein the weight ratio of the substance containing a plurality of epoxy functional groups to propylene oxide is 6%, and the ternary copolymerization is carried out according to Example 1 of the patent CN101003619A. reaction. The polymerization time is 30 hours, the pressure in the first 15 hours is 3. 5- 4. 0 MPa, the temperature is 70-90 'C; the pressure in the last 15 hours is 3. 0-3. 6 MPa, the temperature is 60-80 °C; . The yield of the obtained terpolymer was 60.4 g, which was about 60% higher than that of the material containing no epoxy functional group, and the thermal processing temperature of the terpolymer was 187. Around C, it is about 47 °C higher than that of a polymer which does not contain a substance having a plurality of epoxy functional groups.

Ternary copolymerization experiment 3:

The material having an epoxy functional group number of 3.2 is dissolved in propylene oxide, and the weight ratio of the plurality of epoxy functional groups to propylene oxide is 10%, and the ternary copolymerization is carried out according to Example 5 of Patent CN1306021A. reaction. The polymerization time is 10 hours, the pressure in the first 5 hours is 3. 0-3. 6 MPa, the temperature is 60-80 ° C; the pressure in the last 5 hours is 3. 5-4. 0 MPa, and the temperature is 70-90. C. The yield of the obtained terpolymer is 68.0 g, which is about 80% higher than that of the material without adding a plurality of epoxy functional groups, and the hot working temperature of the terpolymer is about 215 ,, with or without The polymer of the multiple epoxy functional shields was increased by about 75. C.

As can be seen from the results of the above examples, the addition of a trace amount of a substance containing a plurality of or more epoxy functional groups allows the yield of the obtained terpolymer to be improved as compared with the case where a substance containing a plurality of epoxy functional groups is not added. 5-about 100%; and make hot plus The working temperature is increased by 10-80 ° C compared to the binary polymer obtained by copolymerizing only propylene oxide and carbon dioxide at the same propylene oxide / carbon dioxide ratio, which is difficult for a person skilled in the art to advance. Expected.

More importantly, the preparation method of the present invention containing a plurality of epoxy functional groups can select different starting materials according to the final performance and cost requirements of the carbon dioxide copolymer, and design and synthesize different numbers per molecule. A series of epoxy functional groups containing a plurality of epoxy functional groups, for example, in embodiments, may contain from about 3 to about 96 epoxy functional groups per molecule. Then, the series of materials containing a plurality of epoxy functional groups are respectively used for the terpolymerization of carbon dioxide and propylene oxide to improve the performance and cost of the carbon dioxide terpolymer, so that the carbon dioxide terpolymer can be like ordinary plastic. Used alone, and the cost is close to ordinary plastic. The problem of high cost and low thermal processing temperature of carbon dioxide copolymers that have been plagued for many years has been solved, and breakthroughs have been made, opening up new avenues for the industrialization and marketization of carbon dioxide copolymers. The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not intended to be limited to the embodiments shown herein, but is to be accorded to the broadest scope of the principles and novel features disclosed herein.

Claims

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What is claimed is: 1. A material comprising a plurality of epoxy functional groups which are prepared by copolymerization of the following monomers in the following parts by weight:

Styrene monomer: 1 0-90;

(methyl) glycidyl acrylate monomer: 10-90;

Wherein said plurality means an average of 3-1 00 epoxy functional groups per molecule.

2. The plurality of epoxy functional group-containing materials according to claim 1, wherein the styrenic monomer is selected from the group consisting of styrene, o-divinylbenzene, m-diethyl benzene or p-divinyl benzene; Wherein the (mercapto) styrene glycidyl ester monomer is selected from the group consisting of glycidyl propionate or glycidyl methacrylate.

3. A method of preparing a material comprising a plurality of epoxy functional groups, comprising the steps of:

a. The styrene monomer, the glycidyl (meth)acrylate monomer, the initiator, and the solvent are mixed in the following parts by weight to obtain a mixture:

Styrene monomer: 1 0-90

(Methyl) glycidyl acrylate monomer: 10-90

Initiator: 2-12

Solvent: 150-200;

b. heating the mixture to 110-120 ° C and refluxing at this temperature for 2-5 hours to initiate copolymerization;

c. Optionally removing the solvent to obtain the plurality of epoxy functional groups.

4. The method of claim 3 wherein said styrenic monomer is selected from the group consisting of styrene An alkene, o-divinylbenzene, m-divinylbenzene or p-divinylbenzene; wherein the glycidyl (meth)acrylate monomer is selected from glycidyl acrylate or glycidyl methacrylate Wherein the initiator is selected from the group consisting of peroxides; wherein the solvent is selected from the group consisting of toluene, dinonylbenzene or mixtures thereof.

5. The method of claim 3 wherein said peroxide is a benzoyl peroxide.

6. A propylene oxide-carbon dioxide terpolymer containing a plurality of epoxy functional groups, which is copolymerized from the following monomers in the following proportions:

Propylene oxide: 1 part by weight;

The phenolic functional group-containing material of claim 1 : 0. 0001 by weight to the weight corresponding to the saturated concentration of propylene oxide;

Carbon dioxide: 0. 5 - 0. 7 parts by weight.

The terpolymer of claim 6 wherein the hot working temperature is increased by 10-80 ° C compared to the binary polymer obtained by copolymerizing only propylene oxide and carbon dioxide at the same propylene oxide / carbon dioxide ratio.

8. A propylene oxide-carbon dioxide ternary copolymerization method comprising a plurality of epoxy functional groups, comprising: adding a plurality of epoxy functional groups according to claim 1 at the beginning of polymerization of carbon dioxide and propylene oxide; The amount of the propylene oxide-containing substance is from 0.01% by weight to the saturated concentration of the epoxy-containing substance in propylene oxide.

The ternary copolymerization process of claim 8 is a two-stage copolymerization process, wherein the first stage process conditions are a pressure of 3.5-4. O MPa , a temperature of 70-90 ° C, a time of 4-20 hours, The process conditions of the second stage are 3. 0-3. 6 MPa, temperature 60-80 ° C, time 4-20 hours; or the first stage process conditions are pressure 3. 0-3. 6 MPa, temperature 60-80 ° C 4-20 hours, time 4-20 hours, second The stage process conditions are a pressure of ^3.5 - ⁴ .0 MPa, a temperature of 70-90 ° C, and a time of 4-20 hours.