CN103421288B - A kind of method containing fluorine graft copolymer modified unsaturated polyester resin - Google Patents

本发明一种含氟接枝共聚物改性不饱和聚酯树脂的方法，属于高分子聚合领域。以活性聚合的方法合成含氟接枝共聚物，结构和分子量都可以控制；采用不饱和聚酯树脂在生产阶段和含氟接枝共聚物共混方法，易于在生产过程中实施；由于使用高热稳定性、高化学惰性和低表面能的含氟接枝共聚物，降低了不饱和聚酯树脂溶剂的挥发性，有利环境保护和保护施工人员的健康；含氟接枝共聚物使不饱和聚酯树脂固化后具有独特的表面性能。可广泛应用于工业、农业、交通以及一些特殊应用的场合。The invention relates to a method for modifying an unsaturated polyester resin with a fluorine-containing graft copolymer, which belongs to the field of polymer polymerization. The fluorine-containing graft copolymer is synthesized by living polymerization, and the structure and molecular weight can be controlled; the method of blending the unsaturated polyester resin with the fluorine-containing graft copolymer in the production stage is easy to implement in the production process; due to the use of high heat The fluorine-containing graft copolymer with high stability, high chemical inertness and low surface energy reduces the volatility of the unsaturated polyester resin solvent, which is beneficial to environmental protection and protects the health of construction workers; the fluorine-containing graft copolymer makes the unsaturated polyester resin Ester resins have unique surface properties after curing. It can be widely used in industry, agriculture, transportation and some special applications.

一种含氟接枝共聚物改性不饱和聚酯树脂的方法Method for modifying unsaturated polyester resin with fluorine-containing graft copolymer

技术领域：Technical field:

本发明属于高分子聚合领域，尤其涉及利用含氟接枝共聚物改性不饱和聚酯树脂的制备方法。 The invention belongs to the field of macromolecular polymerization, and in particular relates to a preparation method of unsaturated polyester resin modified by fluorine-containing graft copolymer.

背景技术：Background technique:

不饱和聚酯树脂(UPR)是由不饱和二元酸(马来酸酐)、饱和的二元酸、二元醇经缩聚反应而生成,由于树脂分子链中含有不饱和双键,因此可以与含双键的单体,如苯乙烯、甲基苯乙烯等发生共聚反应生成三维立体结构,形成不溶不熔的热固性塑料。它是近代塑料工业发展中的一个重要品种,在工业、农业、交通、建筑以及国防工业方面有广泛的应用。由于不饱和聚酯一般存在着韧性差,强度不高,容易燃烧,收缩率大等缺点,从而限制了其应用范围。为了扩大不饱和聚酯树脂应用范围,特别是为了满足一些特殊领域的要求,需要对不饱和聚酯进行改性,以提高UPR的性能。 Unsaturated polyester resin (UPR) is produced by polycondensation reaction of unsaturated dibasic acid (maleic anhydride), saturated dibasic acid and diol. Since the molecular chain of the resin contains unsaturated double bonds, it can be combined with Monomers containing double bonds, such as styrene and methyl styrene, undergo copolymerization reactions to form three-dimensional structures, forming insoluble and infusible thermosetting plastics. It is an important variety in the development of modern plastic industry, and it is widely used in industry, agriculture, transportation, construction and national defense industry. Unsaturated polyester generally has disadvantages such as poor toughness, low strength, easy burning, and large shrinkage, which limit its application range. In order to expand the application range of unsaturated polyester resin, especially to meet the requirements of some special fields, it is necessary to modify the unsaturated polyester to improve the performance of UPR.

含氟聚合物中由于C—F键的键能较大，比较稳定，F原子不但与C原子结合牢固，而且在碳链骨架外层排列十分紧密，有效地防止了C原子和C链的暴露，故含氟聚合物表现出卓越的化学稳定性、耐腐蚀、抗氧化等特性。由于一般的含氟均聚物不能溶解性较差，且容易固化过程中迁移到表面。因此采用一定比例的含氟单体与乙烯基单体用活性自由基聚合的方法合成接枝共聚物，制得的含氟接枝共聚物则可以溶于不饱和聚酯树脂体系中。含氟接枝共聚物兼具氟聚合物的高热稳定性、高化学惰性和低表面能等特性，可以降低不饱和聚酯树脂溶剂的挥发性，并使最终固化体系的表面性能得到改善。 In fluoropolymers, due to the large bond energy of the C—F bond, it is relatively stable, and the F atom is not only firmly combined with the C atom, but also arranged very closely in the outer layer of the carbon chain skeleton, effectively preventing the exposure of the C atom and the C chain. , so fluoropolymers exhibit excellent chemical stability, corrosion resistance, and oxidation resistance. Due to the poor solubility of general fluorine-containing homopolymers, it is easy to migrate to the surface during curing. Therefore, a certain proportion of fluorine-containing monomers and vinyl monomers are used to synthesize graft copolymers by living radical polymerization, and the prepared fluorine-containing graft copolymers can be dissolved in unsaturated polyester resin systems. Fluorine-containing graft copolymers have the characteristics of high thermal stability, high chemical inertness and low surface energy of fluoropolymers, which can reduce the volatility of unsaturated polyester resin solvents and improve the surface properties of the final curing system.

发明内容 Contents of the invention

其具体步骤如下： The specific steps are as follows:

本发明的目的是提供一种以共聚的方法合成含氟接枝共聚物为改性剂改性不饱和聚酯树脂的方法。 The purpose of the present invention is to provide a method for synthesizing a fluorine-containing graft copolymer as a modifier to modify an unsaturated polyester resin by a copolymerization method.

一种含氟接枝共聚物改性不饱和聚酯树脂的方法，按照下述步骤进行： A method for modifying unsaturated polyester resin with fluorine-containing graft copolymer, carried out according to the following steps:

一、含氟接枝共聚物的制备： 1. Preparation of fluorine-containing graft copolymer:

(1)将一定比例的乙烯基单体、含卤素乙烯基单体、引发剂以及溶剂，在磁力搅拌下置于80℃恒温油浴中反应24h；反应结束后，即得纯大分子引发剂； (1) Put a certain proportion of vinyl monomers, halogen-containing vinyl monomers, initiators and solvents in a constant temperature oil bath at 80°C under magnetic stirring for 24 hours; after the reaction, a pure macromolecular initiator is obtained ;

(2)将反应瓶预先经烘烤-真空脱气3次，充氩气冷却后，加入一定比例的有机卤代物催化剂、配体和大分子引发剂再抽真空充氩气，反复3次；然后加入溶剂和含氟单体，置于110℃油浴中反应；反应结束后，冷却至室温； (2) The reaction bottle is pre-baked-vacuum degassed 3 times, filled with argon and cooled, then adding a certain proportion of organic halide catalysts, ligands and macromolecular initiators, and then evacuated and filled with argon, repeated 3 times; Then add solvent and fluorine-containing monomer, and place it in an oil bath at 110°C for reaction; after the reaction, cool to room temperature;

(3)得到的产物除去溶剂及催化剂，得到含氟接枝共聚物； (3) The product obtained removes the solvent and the catalyst to obtain a fluorine-containing graft copolymer;

二、不饱和聚酯树脂预聚物的制备： 2. Preparation of unsaturated polyester resin prepolymer:

将不饱和二元酸、饱和二元酸和二元醇在催化剂的作用下采用熔融缩聚法，把二元醇和二元酸直接熔融缩聚，通氮气180℃缩合聚合3小时，后期粘度增大时用真空脱水，待酸值至20-60mgKOH/g冷却备用。 The unsaturated dibasic acid, saturated dibasic acid and dibasic alcohol are melted and polycondensed under the action of a catalyst, and the dibasic alcohol and dibasic acid are directly melted and polycondensed, and condensed and polymerized at 180°C for 3 hours under nitrogen gas. When the viscosity increases in the later stage Use vacuum dehydration, wait until the acid value reaches 20-60mgKOH/g, cool for later use.

所述的不饱和二元酸或酸酐为顺丁烯二酸酐、反丁烯二酸等带有双羧基的含有双键的有机化合物或聚合物；饱和二元酸为邻苯二甲酸酐、间苯二甲酸等；二元醇为乙二醇、丙二醇、丁二醇等有机含有双羟基的化合物或聚合物；催化剂为有机锡，如二丁基锡二月桂酸酯、辛酸亚锡、二(十二烷基硫)二丁基锡、二醋酸二丁基锡等；二元酸：二元醇：催化剂的摩尔比为1：1.01-1.10：0.001-0.05；二元酸中饱和二元酸和不饱和二元酸摩尔比为1：0-10。 The unsaturated dibasic acid or acid anhydride is an organic compound or polymer containing double bonds with dicarboxyl groups such as maleic anhydride and fumaric acid; the saturated dibasic acid is phthalic anhydride, m- Phthalic acid, etc.; dihydric alcohols are ethylene glycol, propylene glycol, butanediol and other organic compounds or polymers containing double hydroxyl groups; catalysts are organic tin, such as dibutyltin dilaurate, stannous octoate, di(dodecyl Alkyl sulfide) dibutyltin, dibutyltin diacetate, etc.; dibasic acid: dibasic alcohol: molar ratio of catalyst is 1: 1.01-1.10: 0.001-0.05; dibasic acid in saturated dibasic acid and unsaturated dibasic acid The molar ratio is 1:0-10.

三、改性不饱和聚酯树脂的制备： 3. Preparation of modified unsaturated polyester resin:

将合成的不饱和聚酯树脂预聚物加入总质量1-5%的含氟接枝共聚物，在50-80℃慢速搅拌混合，最后加入稀释剂苯乙烯、甲基丙烯酸甲酯等；最终制备改性不饱和聚酯树脂。 Add the synthesized unsaturated polyester resin prepolymer to the fluorine-containing graft copolymer with a total mass of 1-5%, stir and mix slowly at 50-80°C, and finally add diluents such as styrene and methyl methacrylate; Finally, the modified unsaturated polyester resin is prepared.

其中步骤一中(1)所述的乙烯基单体为苯乙烯，甲基丙烯酸甲酯等；含卤素乙烯基单体为对氯甲基苯乙烯等；引发剂为有机过氧化物，如过氧化二苯甲酰，过氧化苯甲酰叔丁酯等，或为偶氮化合物偶氮二异丁腈等；或是氧化-还原体系，如过氧化二苯甲酰和N,N-二甲基苯胺等；所提及的溶剂为甲苯，二甲苯等，溶剂用量为以体积计为单体用量的1-2倍；乙烯基单体：含卤素乙烯基单体：引发剂摩尔比为1-10：1：0.001-0.01。 Wherein the vinyl monomer described in step 1 (1) is styrene, methyl methacrylate etc.; The halogen-containing vinyl monomer is p-chloromethyl styrene etc.; Dibenzoyl oxide, benzoyl tert-butyl peroxide, etc., or azo compounds such as azobisisobutyronitrile; or oxidation-reduction systems, such as dibenzoyl peroxide and N,N-dimethyl base aniline, etc.; the solvent mentioned is toluene, xylene, etc., and the solvent consumption is 1-2 times of the monomer consumption by volume; vinyl monomer: halogen-containing vinyl monomer: initiator molar ratio is 1 -10:1:0.001-0.01.

其中步骤一(2)所述的有机卤代物催化剂为低价金属卤化物，如溴化亚铜；配体为2,2’-联二吡啶(bpy)；含氟单体为含有双键C=C以及-F功能基团，如：丙烯酸六氟丁酯(G01)、甲基丙烯酸六氟丁酯(G02)、甲基丙烯酸三氟乙酯(G03)、甲基丙烯酸十二庚酯(G04)等等；所述的溶剂为甲苯、环己酮；其中(2)所述含氟单体：大分子引发剂=10～220:1（摩尔比），有机卤代物催化剂：含氟单体=1～2：100(摩尔比)，低价金属卤化物催化剂：配体=1：3(摩尔比)，溶剂用量=体系质量的20%～35%；所述的溶剂为甲苯、环己酮。 Wherein the organic halide catalyst described in step one (2) is a low-valent metal halide, such as cuprous bromide; the ligand is 2,2'-bipyridine (bpy); =C and -F functional groups, such as: hexafluorobutyl acrylate (G01), hexafluorobutyl methacrylate (G02), trifluoroethyl methacrylate (G03), dodecyl heptyl methacrylate ( G04) etc.; the solvent is toluene, cyclohexanone; wherein (2) the fluorine-containing monomer: macromolecular initiator = 10 ~ 220:1 (molar ratio), organic halide catalyst: fluorine-containing monomer Body = 1 ~ 2: 100 (molar ratio), low-valent metal halide catalyst: ligand = 1: 3 (molar ratio), solvent dosage = 20% ~ 35% of the system quality; the solvent is toluene, ring Hexanone.

本发明的优点在于1：以活性聚合的方法合成含氟接枝共聚物，结构和分子量都可以控制；2：采用不饱和聚酯树脂在生产阶段和含氟接枝共聚物共混方法，易于在生产过程中实施；3：由于使用高热稳定性、高化学惰性和低表面能的含氟接枝共聚物，降低了不饱和聚酯树脂溶剂的挥发性，有利环境保护和保护施工人员的健康；4：含氟接枝共聚物使不饱和聚酯树脂固化后具有独特的表面性能。可广泛应用于工业、农业、交通以及一些特殊应用的场合。 The present invention has the advantages of 1: the fluorine-containing graft copolymer is synthesized by living polymerization, and the structure and molecular weight can be controlled; 2: the unsaturated polyester resin is used in the production stage to blend with the fluorine-containing graft copolymer, which is easy Implemented in the production process; 3: Due to the use of fluorine-containing graft copolymers with high thermal stability, high chemical inertness and low surface energy, the volatility of unsaturated polyester resin solvents is reduced, which is beneficial to environmental protection and the health of construction workers ; 4: The fluorine-containing graft copolymer makes the unsaturated polyester resin have unique surface properties after curing. It can be widely used in industry, agriculture, transportation and some special applications.

具体实施方式 detailed description

下面结合实例，对本发明作进一步的详细说明。 Below in conjunction with example, the present invention is described in further detail.

实施例1 Example 1

聚合步骤如下： The aggregation steps are as follows:

1、含氟接枝共聚物的制备 1. Preparation of fluorine-containing graft copolymer

(1)在带有机械搅拌器和冷凝管的三口烧瓶中加入20g苯乙烯、10g对氯甲基苯乙烯、0.1g过氧化二苯甲酰以及50g甲苯，通入30min氮气，在磁力搅拌下置于80℃恒温油浴中反应24h。反应结束后，45℃真空干燥即得纯大分子引发剂。 (1) Add 20g of styrene, 10g of p-chloromethylstyrene, 0.1g of dibenzoyl peroxide and 50g of toluene into a three-necked flask with a mechanical stirrer and a condenser, feed nitrogen gas for 30min, and stir under magnetic force Placed in a constant temperature oil bath at 80°C for 24 hours. After the reaction, vacuum-dry at 45°C to obtain the pure macromolecular initiator.

(2)将反应瓶预先经烘烤-真空脱气3次，充氩气冷却后，加入一定比例的溴化亚铜(CuBr)1g、2,2’-联二吡啶(bpy)3g和大分子引发剂1g再抽真空充氩气，反复3次。然后加入甲苯和甲基丙烯酸十二氟庚酯100g，置于110℃油浴中反应。反应结束后，冷却至室温，合成的共聚物以环己烷为溶剂，用索氏抽提器分别抽提48h，以除去未参与反应的大分子引发剂，60℃真空干燥至恒重。得到含氟接枝共聚物。 (2) The reaction bottle was pre-baked-vacuum degassed 3 times, filled with argon to cool, and a certain proportion of cuprous bromide (CuBr) 1g, 2,2'-bipyridine (bpy) 3g and large Molecular initiator 1g and then evacuated and filled with argon, repeated 3 times. Then add toluene and 100 g of dodecafluoroheptyl methacrylate, and place in an oil bath at 110° C. for reaction. After the reaction, cool down to room temperature, and use cyclohexane as a solvent to extract the synthesized copolymer for 48 hours with a Soxhlet extractor to remove macromolecular initiators that did not participate in the reaction, and vacuum-dry at 60°C to constant weight. A fluorine-containing graft copolymer is obtained.

2、不饱和聚酯树脂预聚物的制备 2. Preparation of unsaturated polyester resin prepolymer

丙二醇，167.4g；顺丁烯二酸酐98g；邻苯二甲酸酐148g通氮气180℃缩合聚合3小时，后期粘度增大时用真空脱水，待酸值至40mgKOH/g冷却备用。 Propylene glycol, 167.4g; maleic anhydride 98g; phthalic anhydride 148g, nitrogen gas, condensation polymerization at 180°C for 3 hours, vacuum dehydration when the viscosity increases in the later stage, and cool down for later use when the acid value reaches 40mgKOH/g.

3、改性不饱和聚酯树脂的制备 3. Preparation of modified unsaturated polyester resin

将合成的不饱和聚酯树脂预聚物100g加入总量3g的含氟接枝共聚物，在50℃温度下慢速搅拌混合，最后加入稀释剂60g苯乙烯。最终制备改性的不饱和聚酯树脂。 Add 100 g of the synthesized unsaturated polyester resin prepolymer to a total amount of 3 g of fluorine-containing graft copolymer, stir and mix slowly at a temperature of 50° C., and finally add 60 g of styrene diluent. Finally, a modified unsaturated polyester resin is prepared.

实施例2 Example 2

聚合步骤如下： The aggregation steps are as follows:

1、含氟接枝共聚物的制备 1. Preparation of fluorine-containing graft copolymer

(1)在带有机械搅拌器和冷凝管的三口烧瓶中加入20g苯乙烯、20g对氯甲基苯乙烯、0.1g过氧化二苯甲酰以及50g甲苯，通入30min氮气，在磁力搅拌下置于80℃恒温油浴中反应24h。反应结束后，45℃真空干燥即得纯大分子引发剂。 (1) Add 20g of styrene, 20g of p-chloromethylstyrene, 0.1g of dibenzoyl peroxide and 50g of toluene into a three-necked flask with a mechanical stirrer and a condenser, feed nitrogen gas for 30min, and stir under magnetic force Placed in a constant temperature oil bath at 80°C for 24 hours. After the reaction, vacuum-dry at 45°C to obtain the pure macromolecular initiator.

(2)将反应瓶预先经烘烤-真空脱气3次，充氩气冷却后，加入一定比例的溴化亚铜(CuBr)1g、2,2’-联二吡啶(bpy)3g和大分子引发剂1g再抽真空充氩气，反复3次。然后加入甲苯和甲基丙烯酸十二氟庚酯20g，置于110℃油浴中反应。反应结束后，冷却至室温，合成的共聚物以环己烷为溶剂，用索氏抽提器分别抽提48h，以除去未参与反应的大分子引发剂，60℃真空干燥至恒重。得到含氟接枝共聚物。 (2) The reaction bottle was pre-baked-vacuum degassed 3 times, filled with argon to cool, and a certain proportion of cuprous bromide (CuBr) 1g, 2,2'-bipyridine (bpy) 3g and large Molecular initiator 1g and then evacuated and filled with argon, repeated 3 times. Then add toluene and 20 g of dodecafluoroheptyl methacrylate, and place in an oil bath at 110° C. for reaction. After the reaction, cool down to room temperature, and use cyclohexane as a solvent to extract the synthesized copolymer for 48 hours with a Soxhlet extractor to remove macromolecular initiators that did not participate in the reaction, and vacuum-dry at 60°C to constant weight. A fluorine-containing graft copolymer is obtained.

2、不饱和聚酯树脂预聚物的制备 2. Preparation of unsaturated polyester resin prepolymer

丙二醇，146g；一缩二乙二醇28.6g；顺丁烯二酸酐98g；苯二甲酸酐148g通氮气180℃缩合聚合3小时，后期粘度增大时用真空脱水，待酸值至45mgKOH/g冷却备用。 Propylene glycol, 146g; Diethylene glycol condensate 28.6g; Maleic anhydride 98g; Phthalic anhydride 148g Condensation polymerization at 180°C for 3 hours with nitrogen gas, and vacuum dehydration when the viscosity increases in the later stage, until the acid value reaches 45mgKOH/g Let cool and set aside.

3、改性不饱和聚酯树脂的制备 3. Preparation of modified unsaturated polyester resin

将合成的不饱和聚酯树脂预聚物100g加入总量2g的含氟接枝共聚物，在50℃温度下慢速搅拌混合，最后加入质量比为1：1的稀释剂苯乙烯和甲基丙烯酸甲酯各40g。最终制备改性不饱和聚酯树脂。 Add 100 g of the synthesized unsaturated polyester resin prepolymer to a total amount of 2 g of fluorine-containing graft copolymer, stir and mix slowly at a temperature of 50 ° C, and finally add diluents styrene and methyl at a mass ratio of 1:1 Each 40g of methyl acrylate. Finally, the modified unsaturated polyester resin is prepared.

实施例3 Example 3

聚合步骤如下： The aggregation steps are as follows:

1、含氟接枝共聚物的制备 1. Preparation of fluorine-containing graft copolymer

(1)在带有机械搅拌器和冷凝管的三口烧瓶中加入20g苯乙烯、10g对氯甲基苯乙烯、0.1g偶氮二异丁腈以及50g甲苯，通入30min氮气，在磁力搅拌下置于50℃恒温油浴中反应24h。反应结束后，45℃真空干燥即得纯大分子引发剂。 (1) Add 20g of styrene, 10g of p-chloromethylstyrene, 0.1g of azobisisobutyronitrile and 50g of toluene into a three-necked flask with a mechanical stirrer and a condenser tube, feed nitrogen gas for 30min, and stir under magnetic force Placed in a constant temperature oil bath at 50°C for 24 hours. After the reaction, vacuum-dry at 45°C to obtain the pure macromolecular initiator.

(2)将反应瓶预先经烘烤-真空脱气3次，充氩气冷却后，加入一定比例的溴化亚铜(CuBr)1g、2,2’-联二吡啶(bpy)3g和大分子引发剂1g再抽真空充氩气，反复3次。然后加入甲苯和甲基丙烯酸十二氟庚酯100g，置于110℃油浴中反应。反应结束后，冷却至室温，合成的共聚物以环己烷为溶剂，用索氏抽提器分别抽提48h，以除去未参与反应的大分子引发剂，60℃真空干燥至恒重。得到含氟接枝共聚物。 (2) The reaction bottle was pre-baked-vacuum degassed 3 times, filled with argon to cool, and a certain proportion of cuprous bromide (CuBr) 1g, 2,2'-bipyridine (bpy) 3g and large Molecular initiator 1g and then evacuated and filled with argon, repeated 3 times. Then add toluene and 100 g of dodecafluoroheptyl methacrylate, and place in an oil bath at 110° C. for reaction. After the reaction, cool down to room temperature, and use cyclohexane as a solvent to extract the synthesized copolymer for 48 hours with a Soxhlet extractor to remove macromolecular initiators that did not participate in the reaction, and vacuum-dry at 60°C to constant weight. A fluorine-containing graft copolymer is obtained.

2、不饱和聚酯树脂预聚物的制备 2. Preparation of unsaturated polyester resin prepolymer

丙二醇，170g；一缩二乙二醇291.7g；顺丁烯二酸酐343.2g；苯二甲酸酐111g，己二酸109.6g。通氮气180℃缩合聚合3小时，后期粘度增大时用真空脱水，待酸值至55mgKOH/g冷却备用。 Propylene glycol, 170g; Diethylene glycol, 291.7g; Maleic anhydride, 343.2g; Phthalic anhydride, 111g, Adipic acid, 109.6g. Condensate and polymerize for 3 hours at 180°C with nitrogen gas, and vacuum dehydrate when the viscosity increases in the later stage, and cool down when the acid value reaches 55mgKOH/g for later use.

3、改性不饱和聚酯树脂的制备 3. Preparation of modified unsaturated polyester resin

将合成的不饱和聚酯树脂预聚物100g加入总量5g的含氟接枝共聚物，在50℃温度下慢速搅拌混合，最后加入稀释剂苯乙烯80g。最终制备改性不饱和聚酯树脂。 Add 100 g of the synthesized unsaturated polyester resin prepolymer to a total amount of 5 g of fluorine-containing graft copolymer, stir and mix slowly at a temperature of 50° C., and finally add 80 g of diluent styrene. Finally, the modified unsaturated polyester resin is prepared.

实施例4 Example 4

聚合步骤如下： The aggregation steps are as follows:

1、含氟接枝共聚物的制备 1. Preparation of fluorine-containing graft copolymer

(1)在带有机械搅拌器和冷凝管的三口烧瓶中加入40g苯乙烯、20g对氯甲基苯乙烯、0.1g过氧化二苯甲酰和0.05gN,N-二甲基苯胺以及50g甲苯，通入30min氮气，在磁力搅拌下置于40℃恒温油浴中反应24h。反应结束后，40℃真空干燥即得纯大分子引发剂。 (1) Add 40g of styrene, 20g of p-chloromethylstyrene, 0.1g of dibenzoyl peroxide, 0.05g of N,N-dimethylaniline and 50g of toluene into a three-necked flask with a mechanical stirrer and a condenser , nitrogen gas was introduced for 30 minutes, and placed in a constant temperature oil bath at 40° C. for 24 hours under magnetic stirring. After the reaction, vacuum-dry at 40°C to obtain the pure macromolecular initiator.

(2)将反应瓶预先经烘烤-真空脱气3次，充氩气冷却后，加入一定比例的溴化亚铜(CuBr)1g、2,2’-联二吡啶(bpy)3g和大分子引发剂1g再抽真空充氩气，反复3次。然后加入甲苯和甲基丙烯酸六氟丁酯50g，置于110℃油浴中反应。反应结束后，冷却至室温，合成的共聚物以环己烷为溶剂，用索氏抽提器分别抽提48h，以除去未参与反应的大分子引发剂，60℃真空干燥至恒重。得到含氟接枝共聚物。 (2) The reaction bottle was pre-baked-vacuum degassed 3 times, filled with argon to cool, and a certain proportion of cuprous bromide (CuBr) 1g, 2,2'-bipyridine (bpy) 3g and large Molecular initiator 1g and then evacuated and filled with argon, repeated 3 times. Then, toluene and 50 g of hexafluorobutyl methacrylate were added and reacted in an oil bath at 110°C. After the reaction, cool down to room temperature, and use cyclohexane as a solvent to extract the synthesized copolymer for 48 hours with a Soxhlet extractor to remove macromolecular initiators that did not participate in the reaction, and vacuum-dry at 60°C to constant weight. A fluorine-containing graft copolymer is obtained.

2、不饱和聚酯树脂预聚物的制备 2. Preparation of unsaturated polyester resin prepolymer

丙二醇，76g；一缩二乙二醇106g；顺丁烯二酸酐103g；苯二甲酸酐80g，四溴邻苯二甲酸酐111g。通氮气180℃缩合聚合3小时，后期粘度增大时用真空脱水，待酸值至43mgKOH/g冷却备用。 Propylene glycol, 76g; Diethylene glycol 106g; Maleic anhydride 103g; Phthalic anhydride 80g, Tetrabromophthalic anhydride 111g. Condensate and polymerize for 3 hours at 180°C with nitrogen gas, and vacuum dehydrate when the viscosity increases in the later stage, and cool down when the acid value reaches 43mgKOH/g for later use.

3、改性不饱和聚酯树脂的制备 3. Preparation of modified unsaturated polyester resin

将合成的不饱和聚酯树脂预聚物100g加入总量5%的含氟接枝共聚物，在50℃温度下慢速搅拌混合，最后加入稀释剂苯乙烯100g。最终制备改性不饱和聚酯树脂。 Add 100 g of the synthesized unsaturated polyester resin prepolymer to a total amount of 5% fluorine-containing graft copolymer, stir and mix slowly at a temperature of 50 ° C, and finally add 100 g of diluent styrene. Finally, the modified unsaturated polyester resin is prepared.

实施例5 Example 5

聚合步骤如下： The aggregation steps are as follows:

1、含氟接枝共聚物的制备 1. Preparation of fluorine-containing graft copolymer

(1)在带有机械搅拌器和冷凝管的三口烧瓶中加入20g苯乙烯、20g对氯乙基苯乙烯、0.1g过氧化二苯甲酰以及50g甲苯，通入30min氮气，在磁力搅拌下置于80℃恒温油浴中反应24h。反应结束后，40℃真空干燥即得纯大分子引发剂。 (1) Add 20g of styrene, 20g of p-chloroethylstyrene, 0.1g of dibenzoyl peroxide and 50g of toluene into a three-necked flask with a mechanical stirrer and a condenser, feed nitrogen gas for 30min, and stir under magnetic force Placed in a constant temperature oil bath at 80°C for 24 hours. After the reaction, vacuum-dry at 40°C to obtain the pure macromolecular initiator.

(2)将反应瓶预先经烘烤-真空脱气3次，充氩气冷却后，加入一定比例的溴化亚铜(CuBr)1g、2,2’-联二吡啶(bpy)3g和大分子引发剂1g再抽真空充氩气，反复3次。然后加入甲苯和甲基丙烯酸六氟丁酯100g，置于110℃油浴中反应。反应结束后，冷却至室温，合成的共聚物以环己烷为溶剂，用索氏抽提器分别抽提48h，以除去未参与反应的大分子引发剂，60℃真空干燥至恒重。得到含氟接枝共聚物。 (2) The reaction bottle was pre-baked-vacuum degassed 3 times, filled with argon to cool, and a certain proportion of cuprous bromide (CuBr) 1g, 2,2'-bipyridine (bpy) 3g and large Molecular initiator 1g and then evacuated and filled with argon, repeated 3 times. Then, toluene and 100 g of hexafluorobutyl methacrylate were added and reacted in an oil bath at 110°C. After the reaction, cool down to room temperature, and use cyclohexane as a solvent to extract the synthesized copolymer for 48 hours with a Soxhlet extractor to remove macromolecular initiators that did not participate in the reaction, and vacuum-dry at 60°C to constant weight. A fluorine-containing graft copolymer is obtained.

2、不饱和聚酯树脂预聚物的制备 2. Preparation of unsaturated polyester resin prepolymer

丙二醇，76g；一缩二乙二醇106g；顺丁烯二酸酐103g；苯二甲酸酐80g，四溴邻苯二甲酸酐111g。通氮气180℃缩合聚合3小时，后期粘度增大时用真空脱水，待酸值至43mgKOH/g冷却备用。 Propylene glycol, 76g; Diethylene glycol 106g; Maleic anhydride 103g; Phthalic anhydride 80g, Tetrabromophthalic anhydride 111g. Condensate and polymerize for 3 hours at 180°C with nitrogen gas, and vacuum dehydrate when the viscosity increases in the later stage, and cool down when the acid value reaches 43mgKOH/g for later use.

3、改性不饱和聚酯树脂的制备 3. Preparation of modified unsaturated polyester resin

将合成的不饱和聚酯树脂预聚物100g加入总量5g的含氟接枝共聚物，在50℃温度下慢速搅拌混合，最后加入稀释剂甲基丙酸甲酯100g。最终制备改性不饱和聚酯树脂。 Add 100 g of the synthesized unsaturated polyester resin prepolymer to a total amount of 5 g of fluorine-containing graft copolymer, stir and mix at a slow speed at a temperature of 50° C., and finally add 100 g of methyl methacrylate as a diluent. Finally, the modified unsaturated polyester resin is prepared.

固化体系的表面性能实验数据： Experimental data on the surface properties of the curing system:

将上述制备的未加入含氟接枝共聚物的不饱和聚酯树脂和加入含氟接枝共聚物和不饱和聚酯树脂加入固化剂后旋涂成膜，用接触角测试仪测试其水接触角并计算表面张力数据，结果如下： Spin-coat the unsaturated polyester resin prepared above without adding fluorine-containing graft copolymer and the unsaturated polyester resin with fluorine-containing graft copolymer and unsaturated polyester resin into a curing agent, and test its water contact with a contact angle tester. Angle and calculate the surface tension data, the results are as follows:

水接触角和表面张力数据(25℃) Water contact angle and surface tension data (25°C)

从表中可以明显看出，改性后不饱和聚酯树脂表面疏水性能得到明显改善。 It can be clearly seen from the table that the surface hydrophobicity of the modified unsaturated polyester resin has been significantly improved.