CN103113566A - Organic silicon modified hydroxyl-terminated hyperbranched polyester resin, and preparation method and application thereof - Google Patents

本发明公开了有机硅改性端羟基超支化聚酯树脂及具制备方法与应用，该方法由以下步骤组成：将三元醇和间苯二甲酸混合均匀后加热至70～90℃，加入端氨基硅油和二甲苯；在180～210℃下加热1～3h后，升温至220～240℃，加热1～3h后；降温至90℃，加入有机溶剂，有机硅低聚物和1～5％的交联催化剂；加热至110～120℃，加热2～3h；降温至90℃，最后加入有机溶剂调整固含量为60～70％。该方法将在合成聚酯时加入端氨基硅油，提高聚酯的耐热性能和柔韧性；将有机硅低聚物和聚酯进行交联反应，提高聚酯的耐热性能。本发明所述方法制备的树脂可以用于制备耐高温涂料。

The invention discloses organosilicon-modified hydroxyl-terminated hyperbranched polyester resin and its preparation method and application. The method consists of the following steps: mixing trihydric alcohol and isophthalic acid evenly, heating to 70-90°C, adding terminal amino groups Silicone oil and xylene; after heating at 180-210°C for 1-3 hours, raise the temperature to 220-240°C, heat for 1-3 hours; cool down to 90°C, add organic solvent, silicone oligomer and 1-5% Cross-linking catalyst; heating to 110-120°C for 2-3 hours; cooling to 90°C, and finally adding an organic solvent to adjust the solid content to 60-70%. In the method, the amino-terminated silicone oil is added when synthesizing the polyester to improve the heat resistance and flexibility of the polyester; the silicone oligomer and the polyester are subjected to a crosslinking reaction to improve the heat resistance of the polyester. The resin prepared by the method of the invention can be used to prepare high temperature resistant coatings.

有机硅改性端羟基超支化聚酯树脂及其制备方法与应用Organosilicon-modified hydroxyl-terminated hyperbranched polyester resin and its preparation method and application

技术领域technical field

本发明涉及超支化聚酯树脂，特别是涉及一种有机硅改性端羟基超支化聚酯树脂及其制备方法与应用，属于有机高分子化合物领域。The invention relates to a hyperbranched polyester resin, in particular to an organosilicon-modified hydroxyl-terminated hyperbranched polyester resin and a preparation method and application thereof, belonging to the field of organic polymer compounds.

背景技术Background technique

聚酯树脂具有优异的金属附着力，硬度高等良好的物理机械性能以及较好的耐化学腐蚀性能，在涂料行业中得到广泛应用。但是聚酯树脂存在耐热性能差，耐水性能低和耐候性能差的缺点，限制其在耐高温涂料中的应用。为了提高聚酯树脂的耐高温性能，常用其他树脂对其进行化学改性。有机硅树脂是一种有机-无机杂化材料，具有优异的耐热性、耐候性、耐水性和较低的表面张力。使用有机硅树脂对聚酯树脂进行改性，可以提高聚酯树脂的耐热性能、耐水性能和耐化学品性能。例如姚江柳等(高功能性改性的端羟基超支化聚酯树脂的研究，上海涂料，2007，45(7)，4～6)设计合成了有机硅改性多羟基聚酯树脂，将该树脂和聚氨酯固化剂HDI缩二脲和HDI三聚体配制两组分涂料。该涂料具有优异的耐候性，良好的附着力和弹性，但是该改性聚酯必须和聚氨酯固化剂配合使用，存在使用不方便快捷的缺点。马艺闻等(马艺闻等，硅醇改性聚酯树脂的制备，电镀与涂饰，2011，02期)中利用饱和羟基硅烷为改性剂、以1，2-丙二醇与己二酸进行缩聚反应，制备了改性醇酸型聚酯树脂，该改性聚酯树脂的附着力1级，冲击强度4.5Mpa，硬度2H；但是存在耐热性的缺点。李华恭等(李华恭等，有机硅改性端羟基聚酯的合成，合成树脂及塑料，2012，29(2)：20～23)采用有机硅预聚体改性端羟基聚酯，提高了聚酯的耐热性能和耐盐水性能。Polyester resin has excellent metal adhesion, good physical and mechanical properties such as high hardness and good chemical corrosion resistance, and is widely used in the coating industry. However, polyester resin has the disadvantages of poor heat resistance, low water resistance and poor weather resistance, which limit its application in high temperature resistant coatings. In order to improve the high temperature resistance of polyester resin, other resins are often used to chemically modify it. Silicone resin is an organic-inorganic hybrid material with excellent heat resistance, weather resistance, water resistance and low surface tension. Using silicone resin to modify polyester resin can improve the heat resistance, water resistance and chemical resistance of polyester resin. For example, Yao Jiangliu et al. (Research on highly functionally modified hydroxyl-terminated hyperbranched polyester resins, Shanghai Paint, 2007, 45 (7), 4-6) designed and synthesized organosilicon-modified polyhydroxy polyester resins. Prepare two-component coatings with polyurethane curing agents HDI biuret and HDI trimer. The coating has excellent weather resistance, good adhesion and elasticity, but the modified polyester must be used in conjunction with a polyurethane curing agent, which has the disadvantage of being inconvenient and quick to use. Ma Yiwen et al. (Ma Yiwen et al., Preparation of Silanol Modified Polyester Resin, Electroplating and Finishing, 2011, Issue 02) used saturated hydroxysilane as a modifier, and carried out the process with 1,2-propanediol and adipic acid. Polycondensation reaction, prepared modified alkyd type polyester resin, the adhesion of the modified polyester resin level 1, impact strength 4.5Mpa, hardness 2H; but there are shortcomings of heat resistance. Li Huagong et al. (Li Huagong et al., Synthesis of organosilicon-modified hydroxyl-terminated polyesters, Synthetic Resins and Plastics, 2012, 29(2): 20-23) used organosilicon prepolymers to modify hydroxyl-terminated polyesters to improve polyester Excellent heat resistance and salt water resistance.

超支化聚合物具有高度支化的结构和大量的端基活性基团，具有高溶解性、低粘度以及较高的化学反应活性等，广泛应用在涂料领域。低粘度使得超支化聚合物适合应用于高固体组分涂料，可与线形聚合物涂料共混降低体系粘度，改善体系流动性；高的溶解性可以减少溶剂的用量，降低成本，减少有害气体排放；高度支化结构使得超支化聚合物分子链间缠结较少，不易结晶，使涂料具有良好的成膜性能；众多的端基官能团使得超支化聚合物涂料具有很强的可改性能力，能制备适合多种用途的涂料。例如公开号为CN102504271A的发明专利申请采用端羟基超支化聚酯所制的改性有机硅树脂，显著提高了有机硅树脂的机械性能、耐化学品性能和耐水性能，但是柔韧性差，高低温交变条件下会开裂，限制了其应用。Hyperbranched polymers have a highly branched structure and a large number of terminal active groups, have high solubility, low viscosity and high chemical reactivity, etc., and are widely used in the field of coatings. Low viscosity makes hyperbranched polymers suitable for high-solid coatings, and can be blended with linear polymer coatings to reduce system viscosity and improve system fluidity; high solubility can reduce the amount of solvents, reduce costs, and reduce harmful gas emissions ; The highly branched structure makes the hyperbranched polymer molecular chain less entangled, not easy to crystallize, so that the coating has good film-forming properties; the numerous terminal functional groups make the hyperbranched polymer coating have a strong ability to modify, Coatings suitable for a variety of purposes can be prepared. For example, the invention patent application with the publication number CN102504271A uses a modified silicone resin made of hydroxyl-terminated hyperbranched polyester, which significantly improves the mechanical properties, chemical resistance and water resistance of the silicone resin. It will crack under changing conditions, which limits its application.

发明内容Contents of the invention

本发明解决的技术问题是提供一种耐热性能和柔韧性好的有机硅改性端羟基超支化聚酯树脂。The technical problem solved by the invention is to provide a silicone-modified hydroxyl-terminated hyperbranched polyester resin with good heat resistance and flexibility.

本发明第二个所要解决的技术问题是提供有机硅改性端羟基超支化聚酯树脂的制备方法。The second technical problem to be solved by the present invention is to provide a preparation method of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin.

本发明所要解决的第三个问题是提供含有该有机硅改性端羟基超支化聚酯树脂的涂料。The third problem to be solved by the present invention is to provide a coating containing the organosilicon-modified hydroxyl-terminated hyperbranched polyester resin.

为解决上述技术问题，本发明采用的技术方案是：In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

一种有机硅改性端羟基超支化聚酯树脂的制备方法，该方法由以下步骤组成：A preparation method of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin, the method is composed of the following steps:

将三元醇和三元醇摩尔数0.5～1.0倍的间苯二甲酸混合均匀后加热至70～90℃，加入三元醇重量0.05～0.1倍的端氨基硅油和三元醇重量0.02～0.1倍的二甲苯；在180～210℃下加热1～3h后，升温至220～240℃，加热1～3h后；降温至90℃，加入三元醇重量1.0～1.5倍的有机溶剂，三元醇重量1.5～2.5倍的有机硅低聚物和三元醇重量的1～5％的交联催化剂；加热至110～120℃，加热2～3h；降温至90℃，最后加入有机溶剂调整固含量为60～70％。Mix trihydric alcohol and isophthalic acid with 0.5 to 1.0 times the molar number of trihydric alcohol and heat it to 70~90°C, add amino-terminated silicone oil with 0.05 to 0.1 times the weight of trihydric alcohol and 0.02 to 0.1 times the weight of trihydric alcohol xylene; after heating at 180-210°C for 1-3 hours, raise the temperature to 220-240°C, and heat for 1-3 hours; cool down to 90°C, add an organic solvent 1.0-1.5 times the weight of the triol, triol 1.5 to 2.5 times the weight of silicone oligomers and 1 to 5% of the weight of the trihydric alcohol crosslinking catalyst; heating to 110 to 120 ° C, heating for 2 to 3 hours; cooling to 90 ° C, and finally adding an organic solvent to adjust the solid content 60-70%.

本发明所述的三元醇是三羟甲基乙烷和三羟甲基丙烷其中一种或者两种。The trihydric alcohol described in the present invention is one or both of trimethylolethane and trimethylolpropane.

所述的端氨基硅油的重均分子量为300～1000，且含有0.1～2w％的氨基；The weight-average molecular weight of the amino-terminated silicone oil is 300-1000, and contains 0.1-2w% amino groups;

所述的有机硅低聚物的重均分子量为800～2000，且含有2.5～15w％的甲氧基或乙氧基和3～20w％的羟基；The weight average molecular weight of the silicone oligomer is 800-2000, and contains 2.5-15w% methoxyl or ethoxyl and 3-20w% hydroxyl;

所述的交联催化剂是钛酸四丁酯或者钛酸四异丁酯；The crosslinking catalyst is tetrabutyl titanate or tetraisobutyl titanate;

所述的有机溶剂为丁醇、丙二醇甲醚醋酸酯、二丙二醇甲醚醋酸酯和二丙二醇丁醚醋酸酯中的一种或两种以上。The organic solvent is one or more of butanol, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate and dipropylene glycol butyl ether acetate.

上述制备方法，所述的端氨基硅油可以由以下方法制备得到：Above-mentioned preparation method, described amino-terminated silicone oil can be prepared by following method:

将八甲基环四硅氧烷、八甲基环四硅氧烷重量0.01％的四甲基二硅氧烷，八甲基环四硅氧烷重量0.02～0.08％的氢氧化四甲基铵，八甲基环四硅氧烷重量1～10％的氨基硅烷偶联剂加入反应器中，升温至120℃，氮气保护下反应2～3h；减压蒸馏除去低沸物，得到端氨基硅油；其中所述的氨基硅烷偶联剂是氨丙基三乙氧基硅烷，氨丙基三甲氧基硅烷，N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷，N-β-氨乙基-γ-氨丙基甲基二乙氧基硅烷其中一种或者两种以上。Octamethylcyclotetrasiloxane, tetramethyldisiloxane of 0.01% by weight of octamethylcyclotetrasiloxane, tetramethylammonium hydroxide of 0.02-0.08% by weight of octamethylcyclotetrasiloxane Add aminosilane coupling agent of 1-10% by weight of octamethylcyclotetrasiloxane into the reactor, raise the temperature to 120°C, and react for 2-3 hours under the protection of nitrogen; remove the low boilers by distillation under reduced pressure to obtain amino-terminated silicone oil ; Wherein the aminosilane coupling agent is aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N -One or more of β-aminoethyl-γ-aminopropylmethyldiethoxysilanes.

上述制备方法，其中所述的有机硅低聚物可以由一甲基三乙氧基硅烷、二甲基二乙氧基硅烷和一苯基三乙氧基等硅氧烷一种或多种进行水解缩合反应得到，也可以由一甲基三甲氧基硅烷、二甲基二甲氧基硅烷和一苯基三甲氧基等硅氧烷一种或多种进行水解缩合反应得到。其中，所述的硅氧烷进行水解缩合反应是本领域常用的硅氧烷进行水解缩合反应，其工艺和反应条件是本领域技术人员应掌握的常规技术。The above preparation method, wherein the organosilicon oligomer can be made of one or more siloxanes such as monomethyltriethoxysilane, dimethyldiethoxysilane and onephenyltriethoxy It can be obtained by hydrolysis and condensation reaction, and can also be obtained by hydrolysis and condensation reaction of one or more siloxanes such as monomethyltrimethoxysilane, dimethyldimethoxysilane and phenyltrimethoxy. Wherein, the hydrolysis and condensation reaction of siloxane is the hydrolysis and condensation reaction of siloxane commonly used in the field, and the process and reaction conditions are conventional techniques that should be mastered by those skilled in the art.

上述制备方法，其中所述的有机硅低聚物还可以是信越公司的KR211、信越公司的KR212、信越公司的KR214、信越公司的KR216、瓦克公司的IC836、信越公司的KR213、信越公司的KR9218、信越公司的KR217、道康宁公司的233、道康宁公司的249、道康宁公司的Z-6108、道康宁公司的3074、道康宁公司的3037中的一种或者两种以上。The above preparation method, wherein the organosilicon oligomer can also be Shin-Etsu KR211, Shin-Etsu KR212, Shin-Etsu KR214, Shin-Etsu KR216, Wacker IC836, Shin-Etsu KR213, Shin-Etsu KR213, Shin-Etsu One or more of KR9218, Shin-Etsu KR217, Dow Corning 233, Dow Corning 249, Dow Corning Z-6108, Dow Corning 3074, Dow Corning 3037.

上述制备方法，其中，其中交联催化剂是钛酸四丁酯。所述的端氨基硅油的重均分子量较好为300～800，且含有0.5～1w％的氨基。The above preparation method, wherein, wherein the crosslinking catalyst is tetrabutyl titanate. The weight-average molecular weight of the amino-terminated silicone oil is preferably 300-800, and contains 0.5-1w% of amino groups.

本发明所述的方法制备的有机硅改性端羟基超支化聚酯，具有以下优点：The organosilicon-modified hydroxyl-terminated hyperbranched polyester prepared by the method of the present invention has the following advantages:

首先将三元醇、间苯二甲酸和端氨基硅油进行反应制备端羟基超支化聚酯树脂，其中三元醇上的羟基和间苯二甲酸上的羧基进行酯化反应，同时间苯二甲酸上的羧基和端氨基硅油上的氨基发生反应，将柔性有机硅链段嵌入超支化聚酯中，提高聚酯的耐热性能，柔韧性和涂膜抗冷热变化性能。First, the trihydric alcohol, isophthalic acid and amino-terminated silicone oil are reacted to prepare a hydroxyl-terminated hyperbranched polyester resin, wherein the hydroxyl group on the trihydric alcohol and the carboxyl group on the isophthalic acid undergo esterification reaction, and at the same time, the phthalic acid The carboxyl group on the silicone oil reacts with the amino group on the amino-terminated silicone oil, and the flexible silicone segment is embedded in the hyperbranched polyester to improve the heat resistance, flexibility and thermal change resistance of the coating film.

然后将端羟基超支化聚酯树脂和有机硅低聚物反应制备有机硅改性端羟基超支化聚酯树脂，其中端羟基超支化聚酯树脂上的羟基，在交联催化剂作用下可以和有机硅低聚物上的烷氧基或者硅羟基发生交联反应，提高聚酯树脂的耐热性能。Then react the hydroxyl-terminated hyperbranched polyester resin with the organosilicon oligomer to prepare the organosilicon-modified hydroxyl-terminated hyperbranched polyester resin, wherein the hydroxyl group on the hydroxyl-terminated hyperbranched polyester resin can be combined with the organic silicon under the action of the crosslinking catalyst The alkoxy group or silicon hydroxyl group on the silicon oligomer undergoes a crosslinking reaction to improve the heat resistance of the polyester resin.

本发明所述的有机硅改性端羟基超支化聚酯可以应用在制备耐高温低表面能涂料，该涂料具有良好的耐热性能和柔韧性。The organosilicon-modified hydroxyl-terminated hyperbranched polyester of the invention can be used in the preparation of high-temperature-resistant low-surface-energy coatings, and the coatings have good heat resistance and flexibility.

本发明所述的涂料，该涂料含有60～80w％上述有机硅改性端羟基超支化聚酯、10～20w％耐高温填料和5～20w％高沸点溶剂，其中，The coating of the present invention, the coating contains 60-80w% of the above-mentioned organosilicon-modified hydroxyl-terminated hyperbranched polyester, 10-20w% of high-temperature-resistant fillers and 5-20w% of high-boiling point solvents, wherein,

所述的高沸点溶剂是二价酸酯混合物、乙二醇乙醚醋酸酯、二乙二醇丁醚醋酸酯、异丁酸异丁酯、丙酸-3-乙醚乙酯和甲基异戊基酮中的一种或者两种以上；Described high boiling point solvent is divalent ester mixture, ethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, isobutyl isobutyrate, propionate-3-ethyl ether ethyl ester and methyl isoamyl One or more of ketones;

所述的填料为本领域常用的耐高温填料，可以是二氧化钛、二氧化硅或碳化硅。The filler is a high temperature resistant filler commonly used in this field, which may be titanium dioxide, silicon dioxide or silicon carbide.

上述涂料中还可加入本领域常用的耐高温颜料，所述耐高温颜料可以是碳黑、铁红等无机耐高温颜料，也可以是酞青蓝等有机耐高温颜料。High-temperature-resistant pigments commonly used in the field can also be added to the above-mentioned coatings. The high-temperature-resistant pigments can be inorganic high-temperature-resistant pigments such as carbon black and iron red, or organic high-temperature-resistant pigments such as phthalocyanine blue.

上述涂料中还可以加入本领域常用的有机硅助剂，如，起到流平、消泡、颜料润湿、粘度调节等作用。上述有机硅助剂还可以是硅油、聚醚改性有机硅助剂，如，迈图高新材料有限公司的CoatOSiI系列聚醚改性有机硅助剂。本领域的技术人员可以依据要求确定有机硅助剂的种类和用量，本发明人推荐的用量为1～5w％。Silicone additives commonly used in the field can also be added to the above coatings, for example, to play the roles of leveling, defoaming, pigment wetting, viscosity adjustment, etc. The silicone additives mentioned above can also be silicone oil, polyether modified silicone additives, such as CoatOSiI series polyether modified silicone additives of Momentive High-tech Materials Co., Ltd. Those skilled in the art can determine the type and dosage of the silicone additive according to requirements, and the dosage recommended by the inventors is 1-5w%.

上述的涂料的制备方法是本领域常用的制备方法，即将有机硅改性端羟基超支化聚酯、颜料、填料、有机硅助剂和高沸点溶剂混合得到。The preparation method of the above-mentioned coating is a commonly used preparation method in the field, that is, it is obtained by mixing organosilicon-modified hydroxyl-terminated hyperbranched polyester, pigments, fillers, organosilicon additives and high-boiling point solvents.

由于本发明所述的涂料采用上述有机硅改性端羟基超支化聚酯制备，因此具有高耐热性能和良好的柔韧性。Since the coating of the present invention is prepared by using the above-mentioned organosilicon-modified hydroxyl-terminated hyperbranched polyester, it has high heat resistance and good flexibility.

相对于现有技术，本发明具有如下优点和有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:

1)本发明将三元醇、间苯二甲酸和端氨基硅油进行反应制备端羟基超支化聚酯树脂，其中三元醇上的羟基和间苯二甲酸上的羧基进行酯化反应，同时间苯二甲酸上的羧基和端氨基硅油上的氨基发生反应，将柔性有机硅链段嵌入超支化聚酯中，提高聚酯的耐热性能，柔韧性和涂膜抗冷热变化性能。1) The present invention reacts trihydric alcohol, isophthalic acid and amino-terminated silicone oil to prepare hydroxyl-terminated hyperbranched polyester resin, wherein the hydroxyl group on the trihydric alcohol and the carboxyl group on the isophthalic acid carry out esterification reaction, and at the same time The carboxyl group on the phthalic acid reacts with the amino group on the amino-terminated silicone oil to embed the flexible silicone segment into the hyperbranched polyester to improve the heat resistance, flexibility and thermal change resistance of the coating film.

2)本发明将端羟基超支化聚酯树脂和有机硅低聚物反应制备有机硅改性端羟基超支化聚酯树脂，其中端羟基超支化聚酯树脂上的羟基，在交联催化剂作用下可以和有机硅低聚物上的烷氧基或者硅羟基发生交联反应，提高聚酯树脂的耐热性能。2) The present invention reacts the hydroxyl-terminated hyperbranched polyester resin and the organosilicon oligomer to prepare the organosilicon-modified hydroxyl-terminated hyperbranched polyester resin, wherein the hydroxyl groups on the hydroxyl-terminated hyperbranched polyester resin, under the action of a crosslinking catalyst It can have a cross-linking reaction with the alkoxy group or silanol group on the organosilicon oligomer to improve the heat resistance of the polyester resin.

3)本发明所述的涂料采用上述有机硅改性端羟基超支化聚酯制备，因此具有高耐热性能和良好的柔韧性。所述的有机硅改性端羟基超支化聚酯可以应用在制备耐高温低表面能涂料，该涂料具有良好的耐热性能和柔韧性。3) The coating of the present invention is prepared by using the above-mentioned organosilicon-modified hydroxyl-terminated hyperbranched polyester, so it has high heat resistance and good flexibility. The organosilicon-modified hydroxyl-terminated hyperbranched polyester can be used in the preparation of high-temperature-resistant and low-surface-energy coatings, and the coatings have good heat resistance and flexibility.

附图说明Description of drawings

图1为实施例1所得有机硅改性端羟基超支化聚酯树脂的红外图谱。Fig. 1 is the infrared spectrum of the silicone-modified hydroxyl-terminated hyperbranched polyester resin obtained in Example 1.

具体实施方式Detailed ways

实施例1：Example 1:

1)端氨基硅油的制备1) Preparation of amino-terminated silicone oil

在装有冷凝管、温度计和搅拌器的反应器中按配比依次加入八甲基环四硅氧烷200g，四甲基二硅氧烷0.02g、氢氧化四甲基铵0.04g、甲苯20g和氨基硅烷偶联剂N-6-氨乙基-γ-氨丙基甲基二乙氧基硅烷2g后，氮气保护升温至100℃，反应7h；减压蒸馏除去低沸物和溶剂，得到端氨基硅油。端氨基硅油的重均分子量采用凝胶渗透色谱法检测，结果为1002；端氨基硅油的氨值采用酸碱滴定法测定，其具体步骤如下：先准确称取约1.5g的氨基硅油于锥形瓶中，加入20mL四氢呋喃和甲苯，搅拌使其完全溶解；再加入3～4滴甲基橙指示剂，以浓度为0.2mol/L的盐酸滴定，颜色由黄色变为浅橘红色时即为滴定终点。氨值按下式计算Add octamethylcyclotetrasiloxane 200g, tetramethyldisiloxane 0.02g, tetramethylammonium hydroxide 0.04g, toluene 20g and After 2 g of aminosilane coupling agent N-6-aminoethyl-γ-aminopropylmethyldiethoxysilane, the temperature was raised to 100 ° C under nitrogen protection, and the reaction was carried out for 7 hours; the low boilers and solvent were removed by distillation under reduced pressure to obtain terminal Amino silicone oil. The weight-average molecular weight of the amino-terminated silicone oil is detected by gel permeation chromatography, and the result is 1002; the ammonia value of the amino-terminated silicone oil is determined by acid-base titration, and the specific steps are as follows: first accurately weigh about 1.5g of amino-silicone oil in a conical Add 20mL tetrahydrofuran and toluene to the bottle, stir to dissolve completely; then add 3 to 4 drops of methyl orange indicator, titrate with hydrochloric acid with a concentration of 0.2mol/L, the titration is when the color changes from yellow to light orange end. The ammonia value is calculated according to the formula

A＝(V-V₀)*c*1.5/mA＝(VV ₀ )*c*1.5/m

A：氨值w％每克氨基硅油含有的氨基重量A: Ammonia value w% Amino weight per gram of amino silicone oil

V：氨基硅油消耗盐酸标准溶液的体积，mLV: Amino silicone oil consumed volume of hydrochloric acid standard solution, mL

V₀：空白样消耗盐酸标准溶液的体积，mLV ₀ : the volume of hydrochloric acid standard solution consumed by the blank sample, mL

c：盐酸浓度，mol/L；c: concentration of hydrochloric acid, mol/L;

m：氨基硅油的重量，gm: weight of amino silicone oil, g

上述制备的氨基硅油的氨值为0.102w％。(这表示1g氨基硅油含有氨基0.102％g)The ammonia value of the amino silicone oil prepared above is 0.102w%. (This means that 1g of amino silicone oil contains 0.102% of amino groups)

2)有机硅改性端羟基超支化聚酯树脂的制备2) Preparation of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

将三元醇三羟甲基丙烷134g(1.0mol)和间苯二甲酸107.9g(0.65mol)混合均匀后加热至80℃，加入端氨基硅油6.7g和二甲苯2.74g；在180℃下加热1h后，升温至240℃，加热1h后；降温至90℃，加入三元醇重量的1.0倍的有机溶剂丙二醇甲醚醋酸酯134g，信越有机硅树脂KR150的有机硅低聚物229g和交联催化剂钛酸四正丁酯2.5g；加热至110℃，加热2h；降温至90℃，最后加入剩余有机溶剂丙二醇甲醚醋酸酯176g，控制固含量为60％，这样就得到了有机硅改性端羟基超支化聚酯。相对于端羟基超支化聚酯，加入端氨基硅油和有机硅低聚物反应改性则得到了含有有机硅链段的端羟基超支化聚酯。如附图1中红外光谱显示：3100～3600cm^-1处宽峰为-OH和-NH-吸收峰，2950cm^-1处为-CH₃吸收峰，1730cm^-1处为-COO-的吸收峰，1120cm^-1处为Si-O-Si吸收峰，1250cm^-1和800cm^-1处为Si-CH₃吸收峰。羟基峰和酯基峰证明了主体树脂的聚酯结构，硅氧峰和硅甲基峰则证明了树脂成功经过硅油的改性。下面实施例中有关有机硅改性端羟基超支化聚酯树脂的红外图谱与图1基本相同，不一一提供。Mix 134g (1.0mol) of trihydric alcohol trimethylolpropane and 107.9g (0.65mol) of isophthalic acid evenly and heat to 80°C, add 6.7g of amino-terminated silicone oil and 2.74g of xylene; heat at 180°C After 1 hour, heat up to 240°C, after heating for 1 hour; cool down to 90°C, add 134g of organic solvent propylene glycol methyl ether acetate which is 1.0 times the weight of trihydric alcohol, 229g of silicone oligomer of Shin-Etsu Silicone Resin KR150 and crosslinking Catalyst tetra-n-butyl titanate 2.5g; heat to 110°C, heat for 2h; cool down to 90°C, and finally add 176g of the remaining organic solvent propylene glycol methyl ether acetate, and control the solid content to 60%, thus obtaining the organosilicon modified Hydroxyl-terminated hyperbranched polyester. Compared with the hydroxyl-terminated hyperbranched polyester, the hydroxyl-terminated hyperbranched polyester containing silicone chain segments is obtained by adding amino-terminated silicone oil and organosilicon oligomers for reaction modification. As shown in the infrared spectrum in Figure 1: the broad peaks at 3100 to 3600cm ^-1 are the absorption peaks of -OH and -NH-, the absorption peaks of -CH at _2950cm ^-1 , and the absorption peaks of -COO- at 1730cm ^-1 . The Si-O-Si absorption peak is at 1120cm ^-1 , and the Si- _CH3 absorption peak is at 1250cm ^-1 and 800cm ^-1 . The hydroxyl peak and ester peak prove the polyester structure of the main resin, and the siloxane and silyl methyl peaks prove that the resin has been successfully modified with silicone oil. In the following examples, the infrared spectrum of the silicone-modified hydroxyl-terminated hyperbranched polyester resin is basically the same as that of Figure 1, and will not be provided one by one.

有机硅改性端羟基超支化聚酯树脂性能检测情况如表1所示。可以看到：有机硅改性端羟基超支化聚酯树脂在硬度、附着力和柔韧性都具有优异的性能，尤其是耐热可以到390℃，柔韧性1mm。有机硅改性端羟基超支化聚酯树脂相比聚酯树脂在耐热性能上的提升可以证明有机硅链段已经引入到超支化聚酯树脂基体上。The performance testing of silicone-modified hydroxyl-terminated hyperbranched polyester resin is shown in Table 1. It can be seen that the silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in terms of hardness, adhesion and flexibility, especially the heat resistance can reach 390°C, and the flexibility is 1mm. The improvement of heat resistance of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin compared with polyester resin can prove that the organosilicon segment has been introduced into the hyperbranched polyester resin matrix.

表1有机硅改性端羟基超支化聚酯树脂的综合性能Table 1 Comprehensive properties of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

1^*耐溶剂性能检测方法：在25℃下，使用丁酮来同擦拭100次。1 ^* Solvent resistance test method: at 25°C, use methyl ethyl ketone to wipe 100 times.

2^*耐热性能检测方法：将试片于180℃烘烤2h后，放入电位差计核对的恒温箱式电炉中，按5℃/min升高温度，随炉温到实验要求温度开始计时，试样经过持续高温后，取出，冷至室温(25℃)，用放大镜观察涂层表面状况，如无龟裂、脱落现象，即说明涂层耐热性能良好。2 ^* Heat resistance test method: After the test piece is baked at 180°C for 2 hours, put it into a constant temperature box-type electric furnace checked by a potentiometer, increase the temperature at 5°C/min, and start timing as the furnace temperature reaches the experimental temperature , After the sample has been subjected to continuous high temperature, take it out, cool it to room temperature (25°C), and observe the surface condition of the coating with a magnifying glass. If there is no cracking or falling off, it means that the coating has good heat resistance.

3)含有有机硅改性端羟基超支化聚酯树脂的涂料的制备3) Preparation of coatings containing organosilicon-modified hydroxyl-terminated hyperbranched polyester resins

将颜料碳黑40g、填料二氧化钛20g、有机硅改性端羟基超支化聚酯树脂100g、硅油

/350cst的有机硅助剂8g、二价酸酯混合物(DBE)的高沸点溶剂5g混合均匀，加入研磨机中研磨到所需要粒径，既得。经测试，制备的涂料性能如表2所示。可以看到：有机硅改性端羟基超支化聚酯树脂配制的涂料在硬度、附着力、冷热交变性和柔韧性都具有优异的性能，尤其是耐热可以到490℃，柔韧性2mm，耐冷热交变性58次。Pigment carbon black 40g, filler titanium dioxide 20g, organosilicon modified terminal hydroxyl hyperbranched polyester resin 100g, silicone oil

/350cst silicone additive 8g, dibasic ester mixture (DBE) high boiling point solvent 5g, mix evenly, put into the grinder and grind to the required particle size, it is obtained. After testing, the properties of the prepared coatings are shown in Table 2. It can be seen that the coating prepared by silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion, alternating temperature and flexibility, especially the heat resistance can reach 490°C, and the flexibility is 2mm. Resistance to alternating cold and heat 58 times.

表2涂料的性能指标The performance index of table 2 coating

1*：耐溶剂性能检测方法：在25℃下，使用丁酮来同擦拭100次。1*: Solvent resistance test method: at 25°C, use methyl ethyl ketone to wipe 100 times.

2*：耐热性能检测方法：将试片于180℃烘烤2h后，放入电位差计核对的恒温箱式电炉中，按5℃/min升高温度，随炉温到实验要求温度开始计时，试样经过持续高温后，取出，冷至室温(25℃)，用放大镜观察涂层表面状况，如无龟裂、脱落现象，即说明涂层耐热性能良好。2*: Heat resistance test method: After the test piece is baked at 180°C for 2 hours, put it into a thermostatic box-type electric furnace checked by a potentiometer, increase the temperature at 5°C/min, and start with the furnace temperature reaching the required temperature for the experiment Timing, take out the sample after continuous high temperature, cool to room temperature (25°C), observe the surface condition of the coating with a magnifying glass, if there is no cracking or falling off, it means that the coating has good heat resistance.

实施例2：Example 2:

1)端氨基硅油的制备：1) Preparation of amino-terminated silicone oil:

在装有冷凝管、温度计和搅拌器的反应器中按配比依次加入八甲基环四硅氧烷，四甲基二硅氧烷、氢氧化四甲基铵、氨基硅烷偶联剂和甲苯后，氮气保护升温至90℃，反应9h；减压蒸馏除去低沸物和溶剂，得到端氨基硅油。其中八甲基环四硅氧烷200g、氢氧化四甲基铵0.04g、四甲基二硅氧烷0.01g、氨基硅烷偶联剂N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷11g、甲苯10g。After adding octamethylcyclotetrasiloxane, tetramethyldisiloxane, tetramethylammonium hydroxide, aminosilane coupling agent and toluene in sequence in proportion to the reactor equipped with condenser tube, thermometer and stirrer , heated to 90° C. under nitrogen protection, and reacted for 9 hours; low boilers and solvents were removed by distillation under reduced pressure to obtain amino-terminated silicone oil. Among them, octamethylcyclotetrasiloxane 200g, tetramethylammonium hydroxide 0.04g, tetramethyldisiloxane 0.01g, aminosilane coupling agent N-β-aminoethyl-γ-aminopropylmethyl 11 g of dimethoxysilane, 10 g of toluene.

端氨基硅油的重均分子量采用凝胶渗透色谱法检测，结果为310；端氨基硅油的氨值采用酸碱滴定法测定，氨值为0.12wt％。The weight-average molecular weight of the amino-terminated silicone oil was detected by gel permeation chromatography, and the result was 310; the ammonia value of the amino-terminated silicone oil was determined by acid-base titration, and the ammonia value was 0.12 wt%.

2)有机硅改性端羟基超支化聚酯树脂的制备2) Preparation of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

将三羟甲基丙烷134g和间苯二甲酸83g混合均匀后加热至80℃，加入上述制备的端氨基硅油13.4g和二甲苯13.4g；在200℃下加热3h后，升温至220℃，加热2h后；降温至90℃，加入丙二醇甲醚醋酸酯141g，信越有机硅树脂KR150100g，信越公司的KR212101g和钛酸四正丁酯6.7g；加热至115℃，加热3h；降温至90℃，最后加入丁醇34g。控制固含量为60％，这样就得到了有机硅改性端羟基超支化聚酯。相对于端羟基超支化聚酯，加入端氨基硅油和有机硅低聚物改性反应则得到了含有有机硅链段的端羟基超支化聚酯。Mix 134g of trimethylolpropane and 83g of isophthalic acid and heat to 80°C, add 13.4g of amino-terminated silicone oil and 13.4g of xylene prepared above; heat at 200°C for 3 hours, then raise the temperature to 220°C, heat After 2 hours; cool down to 90°C, add 141g of propylene glycol methyl ether acetate, Shin-Etsu silicone resin KR150100g, Shin-Etsu KR212101g and tetra-n-butyl titanate 6.7g; heat to 115°C for 3h; cool down to 90°C, and finally Add 34 g of butanol. The solid content is controlled to be 60%, so that the organosilicon-modified hydroxyl-terminated hyperbranched polyester is obtained. Compared with the hydroxyl-terminated hyperbranched polyester, the hydroxyl-terminated hyperbranched polyester containing silicone chain segments is obtained by adding amino-terminated silicone oil and organosilicon oligomers for modification reaction.

有机硅改性端羟基超支化聚酯树脂的性能检测列于表3。可以看到：有机硅改性端羟基超支化聚酯树脂在硬度、附着力和柔韧性都具有优异的性能，尤其是耐热可以到390℃，柔韧性1mm。The performance testing of silicone-modified hydroxyl-terminated hyperbranched polyester resin is listed in Table 3. It can be seen that the silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in terms of hardness, adhesion and flexibility, especially the heat resistance can reach 390°C, and the flexibility is 1mm.

表3有机硅改性端羟基超支化聚酯树脂的综合性能Table 3 Comprehensive properties of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

3)涂料3) paint

组成：上述制备的有机硅改性端羟基超支化聚酯树脂160g；二氧化钛10g；二氧化硅8g；碳黑8g；硅油

/350cst1g；乙二醇乙醚醋酸酯10g。Composition: 160g of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin prepared above; 10g of titanium dioxide; 8g of silicon dioxide; 8g of carbon black; silicone oil

/350cst1g; Ethylene glycol ether acetate 10g.

制备工艺：将颜料、填料、有机硅改性端羟基超支化聚酯树脂、高沸点溶剂、助剂混合均匀，加入研磨机中研磨到所需要粒径，既得。涂膜性能列于表4。可以看到：有机硅改性端羟基超支化聚酯树脂配制的涂料在硬度、附着力、冷热交变性和柔韧性都具有优异的性能，尤其是耐热可以到510℃，柔韧性2mm，耐冷热交变性57次。Preparation process: Mix pigments, fillers, organosilicon-modified hydroxyl-terminated hyperbranched polyester resins, high-boiling point solvents, and additives evenly, add them to a grinder, and grind them to the required particle size. The coating properties are listed in Table 4. It can be seen that the coating prepared by silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion, alternating temperature and flexibility, especially the heat resistance can reach 510°C, and the flexibility is 2mm. Resistance to alternating cold and heat 57 times.

表4涂料的性能指标The performance index of table 4 coating

实施例3：Example 3:

1)端氨基硅油的制备1) Preparation of amino-terminated silicone oil

在装有冷凝管、温度计和搅拌器的反应器中按配比依次加入八甲基环四硅氧烷，四甲基二硅氧烷、氢氧化四甲基铵、甲苯和氨基硅烷偶联剂后，氮气保护升温至95℃，反应8h；减压蒸馏除去低沸物和溶剂，得到端氨基硅油。其中物质用量情况：八甲基环四硅氧烷200g、氢氧化四甲基铵0.06g、四甲基二硅氧烷0.015g、N-β-氨乙基-γ-氨丙基甲基二乙氧基硅烷3g、甲苯15g。After adding octamethylcyclotetrasiloxane, tetramethyldisiloxane, tetramethylammonium hydroxide, toluene and aminosilane coupling agent sequentially in the reactor equipped with condenser tube, thermometer and stirrer , heated to 95° C. under nitrogen protection, and reacted for 8 hours; low boilers and solvents were distilled off under reduced pressure to obtain amino-terminated silicone oil. The amount of substances used: octamethylcyclotetrasiloxane 200g, tetramethylammonium hydroxide 0.06g, tetramethyldisiloxane 0.015g, N-β-aminoethyl-γ-aminopropylmethyl di Ethoxysilane 3g, toluene 15g.

端氨基硅油的重均分子量采用凝胶渗透色谱法检测，结果为499；端氨基硅油的氨值采用酸碱滴定法测定，氨值为1.14w％。The weight-average molecular weight of the amino-terminated silicone oil was detected by gel permeation chromatography, and the result was 499; the ammonia value of the amino-terminated silicone oil was determined by acid-base titration, and the ammonia value was 1.14w%.

2)有机硅低聚物的制备2) Preparation of silicone oligomers

在装有冷凝管、温度计、滴液漏斗和搅拌器的反应器中按配比依次加入42.0g一甲基三甲氧基硅烷，18.7g二甲基二甲氧基硅烷，123.0g一苯基三甲氧基硅烷和4.5mmol盐酸后，开始搅拌并升温，升温到60℃后保持温度恒定，在搅拌下滴加31.7g蒸馏水，滴加完毕后，再恒温反应3h后，开始减压蒸馏，压力控制在0.06MPa，蒸去反应过程中产生的小分子，冷却到室温，调整固含量为60％，得到有机硅低聚物290g。Add 42.0g monomethyltrimethoxysilane, 18.7g dimethyldimethoxysilane, 123.0g monophenyltrimethoxysilane to the reactor equipped with condenser tube, thermometer, dropping funnel and stirrer After the base silane and 4.5mmol hydrochloric acid, start to stir and raise the temperature, keep the temperature constant after raising the temperature to 60°C, add 31.7g of distilled water dropwise under stirring, after the dropwise addition is completed, after constant temperature reaction for 3h, start vacuum distillation, the pressure is controlled at 0.06 MPa, evaporate small molecules generated during the reaction, cool to room temperature, adjust the solid content to 60%, and obtain 290 g of organosilicon oligomers.

有机硅低聚物的重均分子量采用凝胶渗透色谱法检测，结果为802；有机硅低聚物的羟基含量采用乙酸酐法测定，结果为10.6w％；有机硅低聚物的甲氧基含量采用高氯酸乙酰法测定，结果为7.4w％；R/Si＝1.14；ph/Me＝1.04。The weight average molecular weight of organosilicon oligomer is detected by gel permeation chromatography, and the result is 802; the hydroxyl content of organosilicon oligomer is measured by acetic anhydride method, and the result is 10.6w%; the methoxy group of organosilicon oligomer The content was determined by the perchloric acid acetyl method, and the result was 7.4w%; R/Si=1.14; ph/Me=1.04.

3)有机硅改性端羟基超支化聚酯树脂的制备3) Preparation of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

将120g三羟甲基乙烷和166g间苯二甲酸混合均匀后加热至85℃，加入9.6g上述制备的端氨基硅油和8.7g二甲苯；在210℃下加热2.5h后，升温至235℃，加热3h后；降温至90℃，加入180g二丙二醇甲醚醋酸酯，200g上述制备的有机硅低聚物，110g道康宁公司的249，2.5g钛酸异丁酯和3.5g钛酸正丁酯交联催化剂；加热至120℃，加热2.5h；降温至90℃，最后加入70g二丙二醇丁醚醋酸酯。控制固含量为60％，这样就得到了有机硅改性端羟基超支化聚酯。相对于端羟基超支化聚酯，加入端氨基硅油和有机硅低聚物改性反应则得到了含有有机硅链段的端羟基超支化聚酯。Mix 120g of trimethylolethane and 166g of isophthalic acid evenly and heat to 85°C, add 9.6g of amino-terminated silicone oil prepared above and 8.7g of xylene; heat at 210°C for 2.5h, then raise the temperature to 235°C , after heating for 3 hours; cool down to 90°C, add 180g of dipropylene glycol methyl ether acetate, 200g of the silicone oligomer prepared above, 110g of Dow Corning 249, 2.5g of isobutyl titanate and 3.5g of n-butyl titanate Cross-linking catalyst; heat to 120°C for 2.5h; cool down to 90°C, and finally add 70g of dipropylene glycol butyl ether acetate. The solid content is controlled to be 60%, so that the organosilicon-modified hydroxyl-terminated hyperbranched polyester is obtained. Compared with the hydroxyl-terminated hyperbranched polyester, the hydroxyl-terminated hyperbranched polyester containing silicone chain segments is obtained by adding amino-terminated silicone oil and organosilicon oligomers for modification reaction.

树脂性能检测列于表5。可以看到：有机硅改性端羟基超支化聚酯树脂在硬度、附着力和柔韧性都具有优异的性能，尤其是耐热可以到400℃，柔韧性2mm。Resin performance testing is listed in Table 5. It can be seen that the silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion and flexibility, especially the heat resistance can reach 400°C, and the flexibility is 2mm.

表5有机硅改性端羟基超支化聚酯树脂的综合性能Table 5 Comprehensive properties of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

4)涂料4) paint

组成：100g步骤3制备的有机硅改性端羟基超支化聚酯树脂；20g二氧化硅；10g二氧化钛；5g酞青蓝；2g铁红；4g CoatOSiI7001；6g硅油/350cst；5g二乙二醇丁醚醋酸酯；5g醋酸丁酯。Composition: 100g silicone-modified hydroxyl-terminated hyperbranched polyester resin prepared in step 3; 20g silicon dioxide; 10g titanium dioxide; 5g phthalocyanine blue; 2g iron red; 4g CoatOSiI7001; 6g silicone oil /350cst; 5g diethylene glycol butyl ether acetate; 5g butyl acetate.

制备工艺：将颜料、填料、有机硅改性端羟基超支化聚酯树脂、有机硅助剂、高沸点溶剂混合均匀，加入研磨机中研磨到所需要粒径，既得。可以看到：有机硅改性端羟基超支化聚酯树脂配制的涂料在硬度、附着力、冷热交变性和柔韧性都具有优异的性能，尤其是耐热可以到510℃，柔韧性3mm，耐冷热交变性60次。Preparation process: Mix pigments, fillers, organosilicon-modified hydroxyl-terminated hyperbranched polyester resin, organosilicon additives, and high-boiling point solvents evenly, add them to a grinder and grind them to the required particle size, and the product is obtained. It can be seen that the coating prepared with silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion, alternating temperature and flexibility, especially the heat resistance can reach 510°C, and the flexibility is 3mm. Resistance to alternating cold and heat 60 times.

表6涂料的性能指标The performance index of table 6 coating

实施例4：Example 4:

1)端氨基硅油的制备1) Preparation of amino-terminated silicone oil

在装有冷凝管、温度计和搅拌器的反应器中按配比依次加入八甲基环四硅氧烷，四甲基二硅氧烷、氢氧化四甲基铵、甲苯和氨基硅烷偶联剂后，氮气保护升温至90℃，反应9h；减压蒸馏除去低沸物和溶剂，得到端氨基硅油。其中物质用量情况：八甲基环四硅氧烷200g、氢氧化四甲基铵0.1g、四甲基二硅氧烷0.02g、丙基三乙氧基硅烷4g，氨丙基三甲氧基硅烷6g，N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷3g，N-β-氨乙基-γ-氨丙基甲基二乙氧基硅烷7g、甲苯20g。After adding octamethylcyclotetrasiloxane, tetramethyldisiloxane, tetramethylammonium hydroxide, toluene and aminosilane coupling agent sequentially in the reactor equipped with condenser tube, thermometer and stirrer , heated to 90° C. under nitrogen protection, and reacted for 9 hours; low boilers and solvents were removed by distillation under reduced pressure to obtain amino-terminated silicone oil. The amount of substances used: octamethylcyclotetrasiloxane 200g, tetramethylammonium hydroxide 0.1g, tetramethyldisiloxane 0.02g, propyltriethoxysilane 4g, aminopropyltrimethoxysilane 6g, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane 3g, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane 7g, toluene 20g.

端氨基硅油的重均分子量采用凝胶渗透色谱法检测，结果为712；端氨基硅油的氨值采用酸碱滴定法测定，氨值为1.4w％。The weight-average molecular weight of the amino-terminated silicone oil was detected by gel permeation chromatography, and the result was 712; the ammonia value of the amino-terminated silicone oil was determined by acid-base titration, and the ammonia value was 1.4w%.

2)有机硅改性端羟基超支化聚酯树脂的制备2) Preparation of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

将67g三羟甲基丙烷，60g三羟甲基乙烷和86g间苯二甲酸混合均匀后加热至80℃，加入6.4g上述制备的端氨基硅油和2.6g二甲苯；在220℃下加热2.5h后，升温至230℃，加热2.5h后；降温至90℃，加入27g丙二醇甲醚醋酸酯，100g丁醇，54g道康宁公司的3074、50g道康宁公司的3037，120g信越公司的KR9218，30g信越公司的KR217和2.7g钛酸四正丁酯；加热至110℃，加热3h；降温至70℃，最后加入30g二丙二醇甲醚醋酸酯和40g二丙二醇丁醚醋酸酯。控制固含量为60％，这样就得到了有机硅改性端羟基超支化聚酯。相对于端羟基超支化聚酯，加入端氨基硅油和有机硅低聚物反应改性则得到了含有有机硅链段的端羟基超支化聚酯。Mix 67g of trimethylolpropane, 60g of trimethylolethane and 86g of isophthalic acid and heat to 80°C, add 6.4g of amino-terminated silicone oil prepared above and 2.6g of xylene; heat at 220°C for 2.5 After h, heat up to 230°C, heat for 2.5h; cool down to 90°C, add 27g propylene glycol methyl ether acetate, 100g butanol, 54g Dow Corning 3074, 50g Dow Corning 3037, 120g Shin-Etsu KR9218, 30g Shin-Etsu The company's KR217 and 2.7g tetra-n-butyl titanate; heated to 110°C, heated for 3h; cooled to 70°C, and finally added 30g dipropylene glycol methyl ether acetate and 40g dipropylene glycol butyl ether acetate. The solid content is controlled to be 60%, so that the organosilicon-modified hydroxyl-terminated hyperbranched polyester is obtained. Compared with the hydroxyl-terminated hyperbranched polyester, the hydroxyl-terminated hyperbranched polyester containing silicone chain segments is obtained by adding amino-terminated silicone oil and organosilicon oligomers for reaction modification.

树脂性能检测列于表7。可以看到：有机硅改性端羟基超支化聚酯树脂在硬度、附着力和柔韧性都具有优异的性能，尤其是耐热可以到400℃，柔韧性1mm。Resin performance testing is listed in Table 7. It can be seen that the silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in terms of hardness, adhesion and flexibility, especially the heat resistance can reach 400°C, and the flexibility is 1mm.

表7有机硅改性端羟基超支化聚酯树脂的综合性能Table 7 Comprehensive performance of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

3)涂料3) paint

组成：120g步骤2制备的有机硅改性端羟基超支化聚酯树脂的综合性能；10g碳化硅；10g二氧化硅；5g二氧化钛；4g CoatOSiI3500；4g硅油

β50cst；20g丙酸-3-乙醚乙酯(EEP)。Composition: 120g comprehensive properties of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin prepared in step 2; 10g silicon carbide; 10g silicon dioxide; 5g titanium dioxide; 4g CoatOSiI3500; 4g silicone oil

β50cst; 20g 3-ethyl ether ethyl propionate (EEP).

制备工艺：将填料、有机硅改性端羟基超支化聚酯树脂的综合性能、有机硅助剂、高沸点溶剂混合均匀，加入研磨机中研磨到所需要粒径，既得。涂膜性能列于表8。可以看到：有机硅改性端羟基超支化聚酯树脂配制的涂料在硬度、附着力、冷热交变性和柔韧性都具有优异的性能，尤其是耐热可以到500℃，柔韧性2mm，耐冷热交变性59次。Preparation process: Mix the filler, the comprehensive properties of silicone-modified hydroxyl-terminated hyperbranched polyester resin, silicone additives, and high-boiling point solvents, add them into a grinder, and grind them to the required particle size. The coating properties are listed in Table 8. It can be seen that the coating prepared by silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion, alternating temperature and flexibility, especially the heat resistance can reach 500°C, and the flexibility is 2mm. Resistance to alternating cold and heat 59 times.

表8涂料的性能指标The performance index of table 8 coating

实施例5Example 5

1)端氨基硅油的制备1) Preparation of amino-terminated silicone oil

在装有冷凝管、温度计和搅拌器的反应器中按配比依次加入八甲基环四硅氧烷，四甲基二硅氧烷、氢氧化四甲基铵、甲苯和氨基硅烷偶联剂后，氮气保护升温至90℃，反应9h；减压蒸馏除去低沸物和溶剂，得到端氨基硅油。其中物质用量情况：八甲基环四硅氧烷200g、氢氧化四甲基铵0.08g、四甲基二硅氧烷0.02g、氨丙基三甲氧基硅烷6g，N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷4g，N-β-氨乙基-γ-氨丙基甲基二乙氧基硅烷6g甲苯20g。After adding octamethylcyclotetrasiloxane, tetramethyldisiloxane, tetramethylammonium hydroxide, toluene and aminosilane coupling agent sequentially in the reactor equipped with condenser tube, thermometer and stirrer , heated to 90° C. under nitrogen protection, and reacted for 9 hours; low boilers and solvents were removed by distillation under reduced pressure to obtain amino-terminated silicone oil. The amount of substances used: octamethylcyclotetrasiloxane 200g, tetramethylammonium hydroxide 0.08g, tetramethyldisiloxane 0.02g, aminopropyltrimethoxysilane 6g, N-β-aminoethyl - 4 g of γ-aminopropylmethyldimethoxysilane, 6 g of N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, 20 g of toluene.

端氨基硅油的重均分子量采用凝胶渗透色谱法检测，结果为507；端氨基硅油的氨值采用酸碱滴定法测定，氨值为0.94w％。The weight-average molecular weight of the amino-terminated silicone oil was detected by gel permeation chromatography, and the result was 507; the ammonia value of the amino-terminated silicone oil was determined by acid-base titration, and the ammonia value was 0.94w%.

2)有机硅改性端羟基超支化聚酯树脂的制备2) Preparation of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

将134g三羟甲基丙烷和132.8g间苯二甲酸混合均匀后加热至80℃，加入9.38g上述制备的端环氧基硅油和8.0g二甲苯；在190℃下加热3h后，升温至220℃，加热2h后；降温至90℃，加入201g丙二醇甲醚醋酸酯，28.0g道康宁公司的233，70g道康宁公司的249，40g道康宁公司的Z-6108，50g瓦克公司的IC836，20g信越公司的KR213，30g信越公司的KR9218，55g信越公司的KR217和4.3g钛酸四正丁酯；加热至115℃，加热3h；降温至90℃，最后加入74g丁醇。控制固含量为60％，这样就得到了有机硅改性端羟基超支化聚酯。相对于端羟基超支化聚酯，加入端氨基硅油和有机硅低聚物反应改性则得到了含有有机硅链段的端羟基超支化聚酯。Mix 134g of trimethylolpropane and 132.8g of isophthalic acid evenly and heat to 80°C, add 9.38g of epoxy-terminated silicone oil prepared above and 8.0g of xylene; heat at 190°C for 3h, then raise the temperature to 220°C ℃, after heating for 2 hours; cool down to 90 ℃, add 201g propylene glycol methyl ether acetate, 28.0g Dow Corning 233, 70g Dow Corning 249, 40g Dow Corning Z-6108, 50g Wacker IC836, 20g Shin-Etsu KR213, 30g Shin-Etsu KR9218, 55g Shin-Etsu KR217 and 4.3g tetra-n-butyl titanate; heated to 115°C for 3h; cooled to 90°C, and finally added 74g butanol. The solid content is controlled to be 60%, so that the organosilicon-modified hydroxyl-terminated hyperbranched polyester is obtained. Compared with the hydroxyl-terminated hyperbranched polyester, the hydroxyl-terminated hyperbranched polyester containing silicone chain segments is obtained by adding amino-terminated silicone oil and organosilicon oligomers for reaction modification.

树脂性能检测列于表9。可以看到：有机硅改性端羟基超支化聚酯树脂在硬度、附着力和柔韧性都具有优异的性能，尤其是耐热可以到390℃，柔韧性1mm。Resin performance testing is listed in Table 9. It can be seen that the silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in terms of hardness, adhesion and flexibility, especially the heat resistance can reach 390°C, and the flexibility is 1mm.

表9有机硅改性端羟基超支化聚酯树脂的综合性能Table 9 Comprehensive properties of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

3)涂料3) paint

组成：140g步骤2制备的有机硅改性端羟基超支化聚酯树脂；20g二氧化硅；14g二氧化硅；4g CoatOSiI3500；2g CoatOSiI7650；2g甲基异戊基酮(MIAK)；4g异丁酸异丁酯。Composition: 140g silicone-modified hydroxyl-terminated hyperbranched polyester resin prepared in step 2; 20g silica; 14g silica; 4g CoatOSiI3500; 2g CoatOSiI7650; 2g methyl isoamyl ketone (MIAK); 4g isobutyric acid isobutyl ester.

制备工艺：将填料、有机硅改性端羟基超支化聚酯树脂、有机硅助剂、高沸点溶剂混合均匀，加入研磨机中研磨到所需要粒径，既得。涂膜性能列于表10。可以看到：有机硅改性端羟基超支化聚酯树脂配制的涂料在硬度、附着力、冷热交变性和柔韧性都具有优异的性能，尤其是耐热可以到490℃，柔韧性2mm，耐冷热交变性61次。Preparation process: Mix the filler, organosilicon-modified hydroxyl-terminated hyperbranched polyester resin, organosilicon additives, and high-boiling point solvent evenly, add it into a grinder, and grind it to the required particle size. The coating properties are listed in Table 10. It can be seen that the coating prepared by silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion, alternating temperature and flexibility, especially the heat resistance can reach 490°C, and the flexibility is 2mm. Resistance to alternating cold and heat 61 times.

表10涂料的性能指标The performance index of table 10 coating

实施例6Example 6

1)端氨基硅油的制备1) Preparation of amino-terminated silicone oil

在装有冷凝管、温度计和搅拌器的反应器中按配比依次加入八甲基环四硅氧烷，四甲基二硅氧烷、氢氧化四甲基铵、甲苯和氨基硅烷偶联剂后，氮气保护升温至90℃，反应9h；减压蒸馏除去低沸物和溶剂，得到端氨基硅油。其中物质用量情况：八甲基环四硅氧烷200g、氢氧化四甲基铵0.12g、四甲基二硅氧烷0.02g、氨丙基三乙氧基硅烷5g、甲苯20g。After adding octamethylcyclotetrasiloxane, tetramethyldisiloxane, tetramethylammonium hydroxide, toluene and aminosilane coupling agent sequentially in the reactor equipped with condenser tube, thermometer and stirrer , heated to 90° C. under nitrogen protection, and reacted for 9 hours; low boilers and solvents were removed by distillation under reduced pressure to obtain amino-terminated silicone oil. Wherein the amount of substances used: octamethylcyclotetrasiloxane 200g, tetramethylammonium hydroxide 0.12g, tetramethyldisiloxane 0.02g, aminopropyltriethoxysilane 5g, toluene 20g.

端氨基硅油的重均分子量采用凝胶渗透色谱法检测，结果为845；端氨基硅油的氨值采用酸碱滴定法测定，氨值为0.23w％。The weight-average molecular weight of the amino-terminated silicone oil was detected by gel permeation chromatography, and the result was 845; the ammonia value of the amino-terminated silicone oil was determined by acid-base titration, and the ammonia value was 0.23w%.

2)有机硅改性端羟基超支化聚酯树脂的制备2) Preparation of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

将120g三羟甲基乙烷和99.6g间苯二甲酸混合均匀后加热至70℃，加入8.7g步骤1制备的端氨基硅油和4.二甲苯；在210℃下加热1h后，升温至220℃，加热3h后；降温至90℃，加入190g丙二醇甲醚醋酸酯，27g信越有机硅树脂KR150，30g信越公司的KR211，40g信越公司的KR212，60g信越公司的KR214，60g信越公司的KR216和3.6g钛酸四正丁酯；加热至120℃，加热3h；最后加入50g二丙二醇甲醚醋酸酯和40g二丙二醇丁醚醋酸酯。控制固含量为60％，这样就得到了有机硅改性端羟基超支化聚酯。相对于端羟基超支化聚酯，加入端氨基硅油和有机硅低聚物反应改性则得到了含有有机硅链段的端羟基超支化聚酯。Mix 120g of trimethylolethane and 99.6g of isophthalic acid evenly and heat to 70°C, add 8.7g of the amino-terminated silicone oil prepared in step 1 and 4.xylene; heat at 210°C for 1 hour, then raise the temperature to 220°C ℃, after heating for 3 hours; cool down to 90 ℃, add 190g propylene glycol methyl ether acetate, 27g Shin-Etsu silicone resin KR150, 30g Shin-Etsu KR211, 40g Shin-Etsu KR212, 60g Shin-Etsu KR214, 60g Shin-Etsu KR216 and 3.6g tetra-n-butyl titanate; heat to 120°C for 3h; finally add 50g dipropylene glycol methyl ether acetate and 40g dipropylene glycol butyl ether acetate. The solid content is controlled to be 60%, so that the organosilicon-modified hydroxyl-terminated hyperbranched polyester is obtained. Compared with the hydroxyl-terminated hyperbranched polyester, the hydroxyl-terminated hyperbranched polyester containing silicone chain segments is obtained by adding amino-terminated silicone oil and organosilicon oligomers for reaction modification.

树脂性能测试列于表11。可以看到：有机硅改性端羟基超支化聚酯树脂在硬度、附着力和柔韧性都具有优异的性能，尤其是耐热可以到400℃，柔韧性1mm。Resin performance tests are listed in Table 11. It can be seen that the silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in terms of hardness, adhesion and flexibility, especially the heat resistance can reach 400°C, and the flexibility is 1mm.

表11有机硅改性端羟基超支化聚酯树脂的综合性能Table 11 Comprehensive performance of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

3)涂料3) paint

组成：120g步骤2制备的有机硅改性端羟基超支化聚酯树脂；15g二氧化硅；15g二氧化钛；4g CoatOSiI3500；2g CoatOSiI7510；4g硅油

/350cst；12g丙酸-3-乙醚乙酯。Composition: 120g silicone-modified hydroxyl-terminated hyperbranched polyester resin prepared in step 2; 15g silicon dioxide; 15g titanium dioxide; 4g CoatOSiI3500; 2g CoatOSiI7510; 4g silicone oil

/350cst; 12g 3-ethyl ether propionate.

制备工艺：将填料、有机硅改性端羟基超支化聚酯树脂、有机硅助剂、高沸点溶剂混合均匀，加入研磨机中研磨到所需要粒径，既得。涂膜性能列于表12。可以看到：有机硅改性端羟基超支化聚酯树脂配制的涂料在硬度、附着力、冷热交变性和柔韧性都具有优异的性能，尤其是耐热可以到510℃，柔韧性2mm，耐冷热交变性60次。Preparation process: Mix the filler, organosilicon-modified hydroxyl-terminated hyperbranched polyester resin, organosilicon additives, and high-boiling point solvent evenly, add it into a grinder, and grind it to the required particle size. The coating properties are listed in Table 12. It can be seen that the coating prepared by silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion, alternating temperature and flexibility, especially the heat resistance can reach 510°C, and the flexibility is 2mm. Resistance to alternating cold and heat 60 times.

表12涂料的性能指标The performance index of table 12 coating

实施例7Example 7

1)端氨基硅油的制备1) Preparation of amino-terminated silicone oil

在装有冷凝管、温度计和搅拌器的反应器中按配比依次加入八甲基环四硅氧烷，四甲基二硅氧烷、氢氧化四甲基铵、甲苯和氨基硅烷偶联剂后，氮气保护升温至90℃，反应9h；减压蒸馏除去低沸物和溶剂，得到端氨基硅油。其中物质用量情况：八甲基环四硅氧烷200g、氢氧化四甲基铵0.09g、四甲基二硅氧烷0.02g、氨丙基三乙氧基硅烷4g氨丙基三甲氧基硅烷4g、甲苯20g。After adding octamethylcyclotetrasiloxane, tetramethyldisiloxane, tetramethylammonium hydroxide, toluene and aminosilane coupling agent sequentially in the reactor equipped with condenser tube, thermometer and stirrer , heated to 90° C. under nitrogen protection, and reacted for 9 hours; low boilers and solvents were distilled off under reduced pressure to obtain amino-terminated silicone oil. The amount of substances used: octamethylcyclotetrasiloxane 200g, tetramethylammonium hydroxide 0.09g, tetramethyldisiloxane 0.02g, aminopropyltriethoxysilane 4g aminopropyltrimethoxysilane 4g, toluene 20g.

端氨基硅油的重均分子量采用凝胶渗透色谱法检测，结果为661；端氨基硅油的氨值采用酸碱滴定法测定，氨值为1.54w％。The weight-average molecular weight of the amino-terminated silicone oil was detected by gel permeation chromatography, and the result was 661; the ammonia value of the amino-terminated silicone oil was determined by acid-base titration, and the ammonia value was 1.54w%.

2)有机硅改性端羟基超支化聚酯树脂的制备2) Preparation of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

将134g三羟甲基丙烷和116.2g间苯二甲酸混合均匀后加热至75℃，加入10.6g步骤1制备的端氨基硅油和12g二甲苯；在180℃下加热1h后，升温至240℃，加热1h后；降温至90℃，加入丙二醇甲醚醋酸酯，168g信越有机硅树脂KR150，100g瓦克公司的IC836和5.2g钛酸四正丁酯；加热至110℃，加热2h；最后加入55g丁醇。控制固含量为60％，这样就得到了有机硅改性端羟基超支化聚酯。相对于端羟基超支化聚酯，加入端氨基硅油和有机硅低聚物反应改性则得到了含有有机硅链段的端羟基超支化聚酯。Mix 134g of trimethylolpropane and 116.2g of isophthalic acid evenly and heat to 75°C, add 10.6g of amino-terminated silicone oil prepared in step 1 and 12g of xylene; heat at 180°C for 1 hour, then raise the temperature to 240°C, After heating for 1 hour; cool down to 90°C, add propylene glycol methyl ether acetate, 168g Shin-Etsu silicone resin KR150, 100g Wacker IC836 and 5.2g tetra-n-butyl titanate; heat to 110°C, heat for 2h; finally add 55g butanol. The solid content is controlled to be 60%, so that the organosilicon-modified hydroxyl-terminated hyperbranched polyester is obtained. Compared with the hydroxyl-terminated hyperbranched polyester, the hydroxyl-terminated hyperbranched polyester containing silicone chain segments is obtained by adding amino-terminated silicone oil and organosilicon oligomers for reaction modification.

树脂性能测试列于表13。可以看到：有机硅改性端羟基超支化聚酯树脂在硬度、附着力和柔韧性都具有优异的性能，尤其是耐热可以到400℃，柔韧性1mm。The resin performance tests are listed in Table 13. It can be seen that the silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in terms of hardness, adhesion and flexibility, especially the heat resistance can reach 400°C, and the flexibility is 1mm.

表13有机硅改性端羟基超支化聚酯树脂的综合性能Table 13 Comprehensive performance of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

3)涂料3) paint

组成：110g步骤2制备的有机硅改性端羟基超支化聚酯树脂；5g二氧化硅；25g碳化硅；异丁酸异丁酯60g。Composition: 110g of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin prepared in step 2; 5g of silicon dioxide; 25g of silicon carbide; 60g of isobutyl isobutyrate.

制备工艺：将填料、有机硅改性端羟基超支化聚酯树脂、高沸点溶剂混合均匀，加入研磨机中研磨到所需要粒径，既得。涂膜性能列于表14。可以看到：有机硅改性端羟基超支化聚酯树脂配制的涂料在硬度、附着力、冷热交变性和柔韧性都具有优异的性能，尤其是耐热可以到510℃，柔韧性2mm，耐冷热交变性58次。Preparation process: Mix the filler, organosilicon-modified hydroxyl-terminated hyperbranched polyester resin, and high-boiling point solvent evenly, add to a grinder and grind to the required particle size, and the product is obtained. The coating properties are listed in Table 14. It can be seen that the coating prepared by silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion, alternating temperature and flexibility, especially the heat resistance can reach 510°C, and the flexibility is 2mm. Resistance to alternating cold and heat 58 times.

表14涂料的性能指标The performance index of table 14 coating

实施例8Example 8

1)端氨基硅油的制备1) Preparation of amino-terminated silicone oil

在装有冷凝管、温度计和搅拌器的反应器中按配比依次加入八甲基环四硅氧烷，四甲基二硅氧烷、氢氧化四甲基铵、甲苯和氨基硅烷偶联剂后，氮气保护升温至90℃，反应9h；减压蒸馏除去低沸物和溶剂，得到端氨基硅油。其中物质用量情况：八甲基环四硅氧烷200g、氢氧化四甲基铵0.11g、四甲基二硅氧烷0.02g、氨丙基三乙氧基硅烷12g、甲苯20g。After adding octamethylcyclotetrasiloxane, tetramethyldisiloxane, tetramethylammonium hydroxide, toluene and aminosilane coupling agent sequentially in the reactor equipped with condenser tube, thermometer and stirrer , heated to 90° C. under nitrogen protection, and reacted for 9 hours; low boilers and solvents were removed by distillation under reduced pressure to obtain amino-terminated silicone oil. Wherein the amount of substances used: octamethylcyclotetrasiloxane 200g, tetramethylammonium hydroxide 0.11g, tetramethyldisiloxane 0.02g, aminopropyltriethoxysilane 12g, toluene 20g.

端氨基硅油的重均分子量采用凝胶渗透色谱法检测，结果为297；端氨基硅油的氨值采用酸碱滴定法测定，氨值为2.01w％。The weight-average molecular weight of the amino-terminated silicone oil was detected by gel permeation chromatography, and the result was 297; the ammonia value of the amino-terminated silicone oil was determined by acid-base titration, and the ammonia value was 2.01w%.

2)有机硅低聚物的制备2) Preparation of silicone oligomers

在装有冷凝管、温度计、滴液漏斗和搅拌器的反应器中按配比依次加入44.5g一甲基三乙氧基硅烷，50.3g二甲基二乙氧基硅烷，98.4g一苯基三乙氧基硅烷和7.0mmol盐酸后，开始搅拌并升温，升温到70℃后保持温度恒定，在搅拌下滴加43.1g蒸馏水，滴加完毕后，再恒温反应3h后，开始减压蒸馏，压力控制在0.06MPa，蒸去反应过程中产生的小分子，冷却到室温，调整固含量为80％，得到有机硅低聚物230g。Add 44.5g of monomethyltriethoxysilane, 50.3g of dimethyldiethoxysilane, 98.4g of phenyltriethoxysilane to the reactor equipped with condenser tube, thermometer, dropping funnel and stirrer After ethoxysilane and 7.0mmol hydrochloric acid, start to stir and heat up. After heating up to 70°C, keep the temperature constant. Add 43.1g of distilled water dropwise under stirring. Controlled at 0.06MPa, evaporated small molecules generated during the reaction, cooled to room temperature, adjusted the solid content to 80%, and obtained 230g of organosilicon oligomer.

有机硅低聚物的重均分子量采用凝胶渗透色谱法检测，结果为1986；有机硅低聚物的羟基含量采用乙酸酐法测定，结果为15w％；有机硅低聚物的乙氧基含量采用高氯酸乙酰法测定，结果为3w％；R/Si＝1.34；ph/Me＝0.44。The weight-average molecular weight of the silicone oligomer was detected by gel permeation chromatography, and the result was 1986; the hydroxyl content of the silicone oligomer was measured by the acetic anhydride method, and the result was 15w%; the ethoxyl content of the silicone oligomer Measured by the acetyl perchloric acid method, the result is 3w%; R/Si=1.34; ph/Me=0.44.

3)有机硅改性端羟基超支化聚酯树脂的制备3) Preparation of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

将134g三羟甲基丙烷和107.9g间苯二甲酸混合均匀后加热至90℃，加入6.5g步骤1制备的端氨基硅油和6.7g二甲苯；在180℃下加热1h后，升温至240℃，加热1h后；降温至90℃，加入134g丙二醇甲醚醋酸酯，228g步骤2制备有机硅低聚物和3.1g钛酸四正丁酯；加热至110℃，加热2h；最后加入146g丙二醇甲醚醋酸酯。控制固含量为60％，这样就得到了有机硅改性端羟基超支化聚酯。相对于端羟基超支化聚酯，加入端氨基硅油和有机硅低聚物反应改性则得到了含有有机硅链段的端羟基超支化聚酯。Mix 134g of trimethylolpropane and 107.9g of isophthalic acid evenly and heat to 90°C, add 6.5g of amino-terminated silicone oil prepared in step 1 and 6.7g of xylene; heat at 180°C for 1 hour, then raise the temperature to 240°C , after heating for 1 hour; cool down to 90°C, add 134g propylene glycol methyl ether acetate, 228g step 2 prepared silicone oligomer and 3.1g tetra-n-butyl titanate; heat to 110°C, heat for 2h; finally add 146g propylene glycol methyl ether acetate. The solid content is controlled to be 60%, so that the organosilicon-modified hydroxyl-terminated hyperbranched polyester is obtained. Compared with the hydroxyl-terminated hyperbranched polyester, the hydroxyl-terminated hyperbranched polyester containing silicone chain segments is obtained by adding amino-terminated silicone oil and organosilicon oligomers for reaction modification.

树脂性能检测列于表15。可以看到：有机硅改性端羟基超支化聚酯树脂在硬度、附着力和柔韧性都具有优异的性能，尤其是耐热可以到400℃，柔韧性2mm。Resin performance tests are listed in Table 15. It can be seen that the silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion and flexibility, especially the heat resistance can reach 400°C, and the flexibility is 2mm.

表15有机硅改性端羟基超支化聚酯树脂的综合性能Table 15 Comprehensive properties of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

4)涂料4) paint

组成：150g步骤3制备的有机硅改性端羟基超支化聚酯树脂；15g二氧化硅；5g二氧化钛；5g CoatOSiI3500；5g硅油

/350cst；10g甲基异戊基酮Composition: 150g of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin prepared in step 3; 15g of silicon dioxide; 5g of titanium dioxide; 5g of CoatOSiI3500; 5g of silicone oil

/350cst; 10g methyl isoamyl ketone

制备工艺：将填料、有机硅改性端羟基超支化聚酯树脂、有机硅助剂、高沸点溶剂混合均匀，加入研磨机中研磨到所需要粒径，既得。涂膜性能列于表16。可以看到：有机硅改性端羟基超支化聚酯树脂配制的涂料在硬度、附着力、冷热交变性和柔韧性都具有优异的性能，尤其是耐热可以到500℃，柔韧性3mm，耐冷热交变性59次。Preparation process: Mix the filler, organosilicon-modified hydroxyl-terminated hyperbranched polyester resin, organosilicon additives, and high-boiling point solvent evenly, add it into a grinder, and grind it to the required particle size. The film properties are listed in Table 16. It can be seen that the coating prepared by silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion, alternating temperature and flexibility, especially the heat resistance can reach 500°C, and the flexibility is 3mm. Resistance to alternating cold and heat 59 times.

表16涂料的性能指标Table 16 Performance indicators of coatings

实施例9Example 9

1)端氨基硅油的制备1) Preparation of amino-terminated silicone oil

在装有冷凝管、温度计和搅拌器的反应器中按配比依次加入八甲基环四硅氧烷，四甲基二硅氧烷、氢氧化四甲基铵、甲苯和氨基硅烷偶联剂后，氮气保护升温至90℃，反应9h；减压蒸馏除去低沸物和溶剂，得到端氨基硅油。其中物质用量情况：八甲基环四硅氧烷200g、氢氧化四甲基铵0.14g、四甲基二硅氧烷0.02g、氨丙基三乙氧基硅烷9g、N-β-氨乙基-γ-氨丙基甲基二乙氧基硅烷9g、甲苯20g。After adding octamethylcyclotetrasiloxane, tetramethyldisiloxane, tetramethylammonium hydroxide, toluene and aminosilane coupling agent sequentially in the reactor equipped with condenser tube, thermometer and stirrer , heated to 90° C. under nitrogen protection, and reacted for 9 hours; low boilers and solvents were removed by distillation under reduced pressure to obtain amino-terminated silicone oil. The amount of substances used: octamethylcyclotetrasiloxane 200g, tetramethylammonium hydroxide 0.14g, tetramethyldisiloxane 0.02g, aminopropyltriethoxysilane 9g, N-β-aminoethyl Base-γ-aminopropylmethyldiethoxysilane 9g, toluene 20g.

端氨基硅油的重均分子量采用凝胶渗透色谱法检测，结果为985；端氨基硅油的氨值采用酸碱滴定法测定，氨值为0.17w％。The weight-average molecular weight of the amino-terminated silicone oil was detected by gel permeation chromatography, and the result was 985; the ammonia value of the amino-terminated silicone oil was determined by acid-base titration, and the ammonia value was 0.17w%.

2)有机硅低聚物2) Silicone oligomer

在装有冷凝管、温度计、滴液漏斗和搅拌器的反应器中按配比依次加入69.1g一甲基三乙氧基硅烷，34.0g二甲基二乙氧基硅烷，109.24g一苯基三乙氧基硅烷和5.5mmol盐酸后，开始搅拌并升温，升温到70℃后保持温度恒定，在搅拌下滴加42.7g蒸馏水，滴加完毕后，再恒温反应3h后，开始减压蒸馏，压力控制在0.06MPa，蒸去反应过程中产生的小分子，冷却到室温，调整固含量为60％，得到有机硅低聚物322g。Add 69.1g of monomethyltriethoxysilane, 34.0g of dimethyldiethoxysilane, 109.24g of phenyltriethoxysilane in the reactor equipped with condenser tube, thermometer, dropping funnel and stirrer After ethoxysilane and 5.5mmol hydrochloric acid, start to stir and heat up. After heating up to 70°C, keep the temperature constant. Add 42.7g of distilled water dropwise under stirring. Controlled at 0.06MPa, distilled off the small molecules produced during the reaction, cooled to room temperature, adjusted the solid content to 60%, and obtained 322g of organosilicon oligomer.

有机硅低聚物的重均分子量采用凝胶渗透色谱法检测，结果为1808；有机硅低聚物的羟基含量采用乙酸酐法测定，结果为20w％；有机硅低聚物的乙氧基含量采用高氯酸乙酰法测定，结果为2.5w％；R/Si＝1.21；ph/Me＝0.55。The weight-average molecular weight of the silicone oligomer is detected by gel permeation chromatography, and the result is 1808; the hydroxyl content of the silicone oligomer is measured by the acetic anhydride method, and the result is 20w%; the ethoxyl content of the silicone oligomer Measured by perchloric acid acetyl method, the result is 2.5w%; R/Si=1.21; ph/Me=0.55.

3)有机硅改性端羟基超支化聚酯树脂的制备3) Preparation of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

将134g三羟甲基丙烷醇和116.2g间苯二甲酸混合均匀后加热至80℃，加入9g步骤1制备的端氨基硅油和7.2g二甲苯；在190℃下加热1.5h后，升温至230℃，加热2h后；降温至90℃，加入160g丙二醇甲醚醋酸酯，120g信越有机硅树脂KR150，41g步骤2制备的有机硅低聚物，80g瓦克公司的IC836和5.4g钛酸四正丁酯；加热至120℃，加热2h；降温到90℃，最后加入70g丙二醇丁醚醋酸酯。控制固含量为60％，这样就得到了有机硅改性端羟基超支化聚酯。相对于端羟基超支化聚酯，加入端氨基硅油和有机硅低聚物反应改性则得到了含有有机硅链段的端羟基超支化聚酯。Mix 134g of trimethylolpropanol and 116.2g of isophthalic acid evenly and heat to 80°C, add 9g of amino-terminated silicone oil prepared in step 1 and 7.2g of xylene; heat at 190°C for 1.5h, then heat up to 230°C , after heating for 2 hours; cool down to 90°C, add 160g propylene glycol methyl ether acetate, 120g Shin-Etsu silicone resin KR150, 41g silicone oligomer prepared in step 2, 80g Wacker IC836 and 5.4g tetra-n-butyl titanate Esters; heated to 120°C, heated for 2h; cooled to 90°C, and finally added 70g of propylene glycol butyl ether acetate. The solid content is controlled to be 60%, so that the organosilicon-modified hydroxyl-terminated hyperbranched polyester is obtained. Compared with the hydroxyl-terminated hyperbranched polyester, the hydroxyl-terminated hyperbranched polyester containing silicone chain segments is obtained by adding amino-terminated silicone oil and organosilicon oligomers for reaction modification.

树脂性能检测列于表17。可以看到：有机硅改性端羟基超支化聚酯树脂在硬度、附着力和柔韧性都具有优异的性能，尤其是耐热可以到400℃，柔韧性1mm。Resin performance tests are listed in Table 17. It can be seen that the silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in terms of hardness, adhesion and flexibility, especially the heat resistance can reach 400°C, and the flexibility is 1mm.

表17有机硅改性端羟基超支化聚酯树脂的综合性能Table 17 Comprehensive performance of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

4)涂料4) paint

组成：150g步骤3制备的有机硅改性端羟基超支化聚酯树脂；40g二氧化钛；8gCoatOSiI7510；2g异丁酸异丁酯。Composition: 150g of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin prepared in step 3; 40g of titanium dioxide; 8g of CoatOSiI7510; 2g of isobutyl isobutyrate.

制备工艺：将填料、有机硅改性端羟基超支化聚酯树脂、有机硅助剂、高沸点溶剂混合均匀，加入研磨机中研磨到所需要粒径，既得。涂膜性能列于表18。可以看到：有机硅改性端羟基超支化聚酯树脂配制的涂料在硬度、附着力、冷热交变性和柔韧性都具有优异的性能，尤其是耐热可以到500℃，柔韧性2mm，耐冷热交变性61次。Preparation process: Mix the filler, organosilicon-modified hydroxyl-terminated hyperbranched polyester resin, organosilicon additives, and high-boiling point solvent evenly, add it into a grinder, and grind it to the required particle size. The film properties are listed in Table 18. It can be seen that the coating prepared by silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion, alternating temperature and flexibility, especially the heat resistance can reach 500°C, and the flexibility is 2mm. Resistance to alternating cold and heat 61 times.

表18涂料的性能指标Table 18 Performance Index of Coatings

实施例10Example 10

1)端氨基硅油的制备1) Preparation of amino-terminated silicone oil

在装有冷凝管、温度计和搅拌器的反应器中按配比依次加入八甲基环四硅氧烷，四甲基二硅氧烷、氢氧化四甲基铵、甲苯和氨基硅烷偶联剂后，氮气保护升温至90℃，反应9h；减压蒸馏除去低沸物和溶剂，得到端氨基硅油。其中物质用量情况：八甲基环四硅氧烷200g、氢氧化四甲基铵0.1g、四甲基二硅氧烷0.02g、N-β-氨乙基-γ-氨丙基甲基二乙氧基硅烷20g、甲苯20g。After adding octamethylcyclotetrasiloxane, tetramethyldisiloxane, tetramethylammonium hydroxide, toluene and aminosilane coupling agent sequentially in the reactor equipped with condenser tube, thermometer and stirrer , heated to 90° C. under nitrogen protection, and reacted for 9 hours; low boilers and solvents were distilled off under reduced pressure to obtain amino-terminated silicone oil. The amount of substances used: octamethylcyclotetrasiloxane 200g, tetramethylammonium hydroxide 0.1g, tetramethyldisiloxane 0.02g, N-β-aminoethyl-γ-aminopropylmethyl di Ethoxysilane 20g, toluene 20g.

端氨基硅油的重均分子量采用凝胶渗透色谱法检测，结果为603；端氨基硅油的氨值采用酸碱滴定法测定，氨值为1.07w％。The weight-average molecular weight of the amino-terminated silicone oil was detected by gel permeation chromatography, and the result was 603; the ammonia value of the amino-terminated silicone oil was determined by acid-base titration, and the ammonia value was 1.07w%.

2)有机硅低聚物2) Silicone oligomer

在装有冷凝管、温度计、滴液漏斗和搅拌器的反应器中按配比依次加入42.0g一甲基三甲氧基硅烷，18.7g二甲基二甲氧基硅烷，123.0g一苯基三甲氧基硅烷和4.5mmol盐酸后，开始搅拌并升温，升温到60℃后保持温度恒定，在搅拌下滴加31.7g蒸馏水，滴加完毕后，再恒温反应3h后，开始减压蒸馏，压力控制在0.06MPa，蒸去反应过程中产生的小分子，冷却到室温，调整固含量为60％，得到有机硅低聚物290g。Add 42.0g monomethyltrimethoxysilane, 18.7g dimethyldimethoxysilane, 123.0g monophenyltrimethoxysilane to the reactor equipped with condenser tube, thermometer, dropping funnel and stirrer After the base silane and 4.5mmol hydrochloric acid, start to stir and raise the temperature, keep the temperature constant after raising the temperature to 60°C, add 31.7g of distilled water dropwise under stirring, after the dropwise addition is completed, after constant temperature reaction for 3h, start vacuum distillation, the pressure is controlled at 0.06 MPa, evaporate small molecules generated during the reaction, cool to room temperature, adjust the solid content to 60%, and obtain 290 g of organosilicon oligomers.

有机硅低聚物的重均分子量采用凝胶渗透色谱法检测，结果为802；有机硅低聚物的羟基含量采用乙酸酐法测定，结果为10.6w％；有机硅低聚物的甲氧基含量采用高氯酸乙酰法测定，结果为7.4w％；R/Si＝1.14；ph/Me＝1.04。The weight average molecular weight of organosilicon oligomer is detected by gel permeation chromatography, and the result is 802; the hydroxyl content of organosilicon oligomer is measured by acetic anhydride method, and the result is 10.6w%; the methoxy group of organosilicon oligomer The content was determined by the perchloric acid acetyl method, and the result was 7.4w%; R/Si=1.14; ph/Me=1.04.

3)有机硅改性端羟基超支化聚酯树脂的制备3) Preparation of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

将134g三羟甲基丙烷和149.4g间苯二甲酸混合均匀后加热至90℃，加入11.8g步骤1制备的端氨基硅油和13.2g二甲苯；在190℃下加热3h后，升温至230℃，加热3h后；降温至90℃，加入134g丙二醇甲醚醋酸酯，110g信越公司的KR212，120g步骤2制备的有机硅低聚物和3.9g钛酸四正丁酯；加热至115℃，加热3h；降温至80℃，最后加入146g丙二醇甲醚醋酸酯。控制固含量为60％，这样就得到了有机硅改性端羟基超支化聚酯。相对于端羟基超支化聚酯，加入端氨基硅油和有机硅低聚物反应改性则得到了含有有机硅链段的端羟基超支化聚酯。Mix 134g of trimethylolpropane and 149.4g of isophthalic acid evenly and heat to 90°C, add 11.8g of amino-terminated silicone oil prepared in step 1 and 13.2g of xylene; heat at 190°C for 3 hours, then heat up to 230°C , after heating for 3 hours; cool down to 90°C, add 134g propylene glycol methyl ether acetate, 110g KR212 of Shin-Etsu Company, 120g silicone oligomer prepared in step 2 and 3.9g tetra-n-butyl titanate; heat to 115°C, heat 3h; cool down to 80°C, and finally add 146g of propylene glycol methyl ether acetate. The solid content is controlled to be 60%, so that the organosilicon-modified hydroxyl-terminated hyperbranched polyester is obtained. Compared with the hydroxyl-terminated hyperbranched polyester, the hydroxyl-terminated hyperbranched polyester containing silicone chain segments is obtained by adding amino-terminated silicone oil and organosilicon oligomers for reaction modification.

有机硅改性端羟基超支化聚酯树脂性能列于表19。可以看到：有机硅改性端羟基超支化聚酯树脂配制的涂料在硬度、附着力和柔韧性都具有优异的性能，尤其是耐热可以到400℃，柔韧性2mm。The properties of silicone-modified hydroxyl-terminated hyperbranched polyester resin are listed in Table 19. It can be seen that the coating prepared with silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion and flexibility, especially the heat resistance can reach 400°C, and the flexibility is 2mm.

表19有机硅改性端羟基超支化聚酯树脂的综合性能Table 19 Comprehensive performance of organosilicon-modified hydroxyl-terminated hyperbranched polyester resin

4)涂料4) paint

组成：120g步骤3制备的有机硅改性端羟基超支化聚酯树脂；40g二氧化钛；20g二氧化硅；5g铁红；2g CoatOSiI7510：18g异丁酸异丁酯。Composition: 120g silicone-modified hydroxyl-terminated hyperbranched polyester resin prepared in step 3; 40g titanium dioxide; 20g silicon dioxide; 5g iron red; 2g CoatOSiI7510: 18g isobutyl isobutyrate.

制备工艺：将颜料、填料、有机硅改性端羟基超支化聚酯树脂、有机硅助剂、高沸点溶剂混合均匀，加入研磨机中研磨到所需要粒径，既得。涂膜性能列于表20。可以看到：有机硅改性端羟基超支化聚酯树脂配制的涂料在硬度、附着力、冷热交变性和柔韧性都具有优异的性能，尤其是耐热可以到510℃，柔韧性3mm，耐冷热交变性61次。Preparation process: Mix pigments, fillers, organosilicon-modified hydroxyl-terminated hyperbranched polyester resin, organosilicon additives, and high-boiling point solvents evenly, add them to a grinder and grind them to the required particle size, and the product is obtained. The film properties are listed in Table 20. It can be seen that the coating prepared with silicone-modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesion, alternating temperature and flexibility, especially the heat resistance can reach 510°C, and the flexibility is 3mm. Resistance to alternating cold and heat 61 times.

表20涂料的性能指标Table 20 Performance indicators of coatings

对比实施例comparative example

对比涂料1参考文献(马艺闻等，端氨基硅油改性聚酯树脂的制备，电镀与涂饰，2011，02期)配制；对比涂料2参考文献(李华恭等，有机硅改性端羟基聚酯的合成，合成树脂及塑料，2012，29(2)：20～23)配制；对比涂料3参考文献(CN102504271A)配制。对比涂料的性能测试情况见表21。表中耐热性依据方法1*检测；柔韧性依据GB/T1731-1993检测；冷热交变性依据方法2*检测。Comparative coating 1 reference (Ma Yiwen et al., Preparation of amino-terminated silicone oil modified polyester resin, electroplating and finishing, 2011, 02 issue) preparation; comparative coating 2 reference (Li Huagong et al., Silicone modified hydroxyl-terminated polyester Synthesis of Synthetic Resins and Plastics, 2012, 29(2): 20-23); preparation of comparative coating 3 reference (CN102504271A). The performance tests of the comparative coatings are shown in Table 21. In the table, heat resistance is tested according to method 1*; flexibility is tested according to GB/T1731-1993; cold and heat alternation is tested according to method 2*.

表21涂料的性能指标Table 21 Performance indicators of coatings

对比涂料1中的聚酯是由1，6-己二酸、1，3-丙二醇和羟基硅油反应制备得到，该有机硅改性聚酯的柔韧性达到4mm，冷热交变性达到35次，但是仅仅采用少量硅油在制备树脂过程中进行改性，没有使用有机硅中间体对聚酯进行改性，导致制备的改性聚酯耐热性才280℃，其耐热性能远远差于本发明所述的涂料。The polyester in comparative coating 1 is prepared by the reaction of 1,6-adipic acid, 1,3-propanediol and hydroxyl silicone oil. The flexibility of the silicone-modified polyester reaches 4mm, and the alternating temperature and temperature reach 35 times. However, only a small amount of silicone oil is used to modify the resin during the preparation of the resin, and no silicone intermediates are used to modify the polyester, resulting in the heat resistance of the prepared modified polyester being only 280°C, which is far worse than that of the original resin. Invention of the described coatings.

对比涂料2中的树脂是采用有机硅中间体对多羟基聚酯树脂进行改性，该树脂具有良好的耐热性能，其耐热温度达到350℃。但是在采用的多羟基聚酯没有使用硅醇改性，导致其柔韧性较差，仅仅6mm，耐冷热交变性才19次。The resin in the comparative coating 2 is a polyhydroxy polyester resin modified with a silicone intermediate. This resin has good heat resistance, and its heat resistance temperature reaches 350°C. However, the polyhydroxy polyester used is not modified with silanol, resulting in poor flexibility, only 6mm, and only 19 times of alternating cold and heat resistance.

对比涂料3中的树脂是采用有机硅中间体对端羟基超支化聚酯树脂进行改性，该树脂具有良好的耐热性能，其耐热温度达到350℃。但是在制备端羟基超支化聚酯过程中仅仅采用对苯二甲酸、间苯二甲酸、己二酸和丁二酸等二元酸与三羟甲基乙烷、1，3，5-苯三醇和1，2，4-苯三醇等三元醇反应，未添加低分子量硅油，导致涂膜柔韧性较差，仅仅6mm。The resin in comparative coating 3 is modified by the use of organic silicon intermediates to modify the hydroxyl-terminated hyperbranched polyester resin. The resin has good heat resistance, and its heat resistance temperature can reach 350°C. However, only dibasic acids such as terephthalic acid, isophthalic acid, adipic acid and succinic acid and trimethylolethane, 1,3,5-benzenetribenzoic acid are used in the process of preparing hydroxyl-terminated hyperbranched polyesters. Alcohol and 1,2,4-benzenetriol and other trihydric alcohols react without adding low-molecular-weight silicone oil, resulting in poor flexibility of the coating film, which is only 6mm.

本发明所述的树脂制备的涂料耐热性能达到490℃以上，柔韧性达到3mm。其耐热性能和柔韧性远远好于对比涂料1，对比涂料2和对比涂料3。The heat resistance of the paint prepared by the resin of the invention reaches above 490 DEG C, and the flexibility reaches 3mm. Its heat resistance and flexibility are far better than those of Comparative Paint 1, Comparative Paint 2 and Comparative Paint 3.