技术领域technical field
本发明涉及涂料技术领域，特别涉及一种紫外光固化超支化星形聚合物涂料的制备方法、性能表征和应用前景，所述超支化星形聚合物涂料有希望应用于汽车和医疗等领域。The invention relates to the technical field of coatings, in particular to a preparation method, performance characterization and application prospect of a UV-cured hyperbranched star polymer coating. The hyperbranched star polymer coating is expected to be used in the fields of automobiles and medical treatment.
背景技术Background technique
紫外光固化涂料是一种于二十世纪六十年代发展起来的节能环保涂料，由于其固化速度快、溶剂含量少、能耗低且应用范围广等优点，近年来对紫外光固化涂料的研究和应用逐年增长。UV-curable coatings are energy-saving and environmentally friendly coatings developed in the 1960s. Due to their advantages such as fast curing speed, low solvent content, low energy consumption and wide application range, research on UV-curable coatings has been carried out in recent years. and applications are growing year by year.
紫外光固化涂料通常使用线性低聚物制备，多加入活性稀释剂以降低粘度，而活性稀释剂增加了涂料的毒性和污染性。近年来，超支化聚合物由于其独特的结构特点，使其成为光固化涂料的研究前沿(Prog.Org.Coat.2014,77,94；Prog.Org.Coat.2011,72,769；Macromolecules.2011,44,878；Polym.Chem.2013,4,3105)。超支化聚合物的粘度明显低于同分子量的线性低聚物，可以大大减少活性稀释剂的使用，有效降低挥发性有机化合物(VOC)排放；活性端基聚集在超支化聚合物的球形表面，大大提高了涂料的固化速率；超支化分子的分支结构能够减小固化收缩率，提高附着力。然而，超支化聚合物的球形结构一定程度上增大了交联位阻，导致未反应的富余官能团，未反应的活泼官能团会降低漆膜的稳定性和耐性，因此超支化聚合物涂料存在一定的局限性。UV-curable coatings are usually prepared using linear oligomers, and more reactive diluents are added to reduce the viscosity, while reactive diluents increase the toxicity and pollution of the coating. In recent years, due to its unique structural characteristics, hyperbranched polymers have become the research frontier of photocurable coatings (Prog.Org.Coat.2014,77,94; Prog.Org.Coat.2011,72,769; Macromolecules.2011, 44,878; Polym. Chem. 2013, 4, 3105). The viscosity of hyperbranched polymers is significantly lower than that of linear oligomers of the same molecular weight, which can greatly reduce the use of reactive diluents and effectively reduce the emission of volatile organic compounds (VOC); active end groups gather on the spherical surface of hyperbranched polymers, The curing rate of the coating is greatly improved; the branched structure of hyperbranched molecules can reduce the curing shrinkage and improve the adhesion. However, the spherical structure of hyperbranched polymers increases the crosslinking hindrance to a certain extent, resulting in unreacted redundant functional groups, and unreacted active functional groups will reduce the stability and resistance of the paint film. Therefore, hyperbranched polymer coatings have certain limitations.
发明内容Contents of the invention
本发明针对现有技术不足，提供一种紫外光固化超支化星形聚合物涂料。该超支化星形聚合物包括超支化聚合物内核和线性聚合物臂，能够结合超支化聚合物与线性聚合物的优点。超支化聚合物内核能够降低体系粘度、提供丰富的官能团和分支结构，线性聚合物臂能够降低体系的交联位阻，提高体系的交联度，减少未反应官能团，从而提高漆膜的稳定性和耐性。因此，为了突破线性聚合物涂料和超支化聚合物涂料的局限性，本发明构建了一种超支化星形聚合物，应用为紫外光固化涂料。Aiming at the deficiencies of the prior art, the invention provides an ultraviolet light curing hyperbranched star polymer coating. The hyperbranched star polymer includes a hyperbranched polymer core and linear polymer arms, and can combine the advantages of hyperbranched polymers and linear polymers. The hyperbranched polymer core can reduce the viscosity of the system and provide abundant functional groups and branched structures. The linear polymer arms can reduce the crosslinking hindrance of the system, increase the degree of crosslinking of the system, and reduce unreacted functional groups, thereby improving the stability of the paint film and patience. Therefore, in order to break through the limitations of linear polymer coatings and hyperbranched polymer coatings, the present invention constructs a hyperbranched star polymer, which is applied as a UV-curable coating.
本发明提供一种紫外光固化超支化星形聚合物涂料，以解决现有技术中线性聚合物粘度大、超支化聚合物交联位阻大且含有未反应官能团，最终污染环境或影响漆膜性能的技术性问题。The invention provides a UV-curable hyperbranched star-shaped polymer coating to solve the problem of high viscosity of linear polymers, large cross-linking steric hindrance of hyperbranched polymers and unreacted functional groups in the prior art, which will eventually pollute the environment or affect the paint film. Performance technical issues.
本发明还提供上述可紫外光固化的超支化星形聚合物的制备方法。The present invention also provides a preparation method of the above-mentioned ultraviolet curable hyperbranched star polymer.
本发明还提供上述紫外光固化超支化星形聚合物涂料的热稳定性、硬度、附着力、耐性和流平性等性能特点。The present invention also provides performance characteristics such as heat stability, hardness, adhesion, resistance and leveling of the above-mentioned UV-cured hyperbranched star polymer coating.
本发明还提供上述紫外光固化超支化星形聚合物涂料的聚合度对漆膜性能的影响。The present invention also provides the effect of the degree of polymerization of the above-mentioned UV-cured hyperbranched star polymer coating on the performance of the paint film.
本发明的目的是通过以下技术方案实现的：The purpose of the present invention is achieved through the following technical solutions:
第一方面，本发明提供了一种可紫外光固化的超支化星形聚合物，包括超支化聚合物内核与线性聚合物臂，所述超支化聚合物内核与线性聚合物臂通过化学键连接；所述超支化星形聚合物的端羟基修饰为含碳碳双键的基团。In a first aspect, the present invention provides a UV-curable hyperbranched star polymer, comprising a hyperbranched polymer core and a linear polymer arm, the hyperbranched polymer core and the linear polymer arm are connected by a chemical bond; The terminal hydroxyl group of the hyperbranched star polymer is modified as a group containing a carbon-carbon double bond.
优选地，所述超支化聚合物内核为超支化聚酯内核。Preferably, the hyperbranched polymer core is a hyperbranched polyester core.
更优选地，所述超支化聚合物内核为核为四代超支化聚酯内核，其平均每个分子含64个羟基，其理论分子量为7214g/mol。More preferably, the core of the hyperbranched polymer is a four-generation hyperbranched polyester core, which contains an average of 64 hydroxyl groups per molecule, and its theoretical molecular weight is 7214 g/mol.
优选地，所述线性聚合物臂为可生物降解的聚己内酯臂，其聚合度为15～25。所述的聚合度根据涂料实际应用需求进行调控。Preferably, the linear polymer arm is a biodegradable polycaprolactone arm with a degree of polymerization of 15-25. The degree of polymerization is regulated according to the actual application requirements of the coating.
更优选地，所述聚合度为20，其综合性能最优。More preferably, the degree of polymerization is 20, which has the best overall performance.
优选地，所述超支化星形聚合物的端羟基修饰为含碳碳双键的基团的方法为：将超支化星形聚合物与过量的封端剂反应，用甲基丙烯酸基封端，即可；所述封端剂为甲基丙烯酸酐。Preferably, the method for modifying the terminal hydroxyl group of the hyperbranched star-shaped polymer to a group containing a carbon-carbon double bond is: reacting the hyperbranched star-shaped polymer with an excessive amount of end-capping agent, and capping with a methacrylic acid group , That is, the end-capping agent is methacrylic anhydride.
第二方面，本发明提供了一种可紫外光固化的超支化星形聚合物的制备方法，包括以下步骤：In a second aspect, the present invention provides a method for preparing a UV-curable hyperbranched star polymer, comprising the following steps:
(1)将超支化聚酯与ε-己内酯在催化剂a作用下进行开环聚合反应，得到超支化星形聚合物一；(1) Carrying out ring-opening polymerization reaction of hyperbranched polyester and ε-caprolactone under the action of catalyst a to obtain hyperbranched star polymer one;
(2)超支化星形聚合物一与封端剂在催化剂b的作用下进行酯交换反应，封端聚合物，得到端基为含碳碳双键基团的超支化星形聚合物二，即所述的紫外光固化的超支化星形聚合物。(2) hyperbranched star polymer one and end-capping agent carry out transesterification reaction under the effect of catalyst b, end-cap polymer, obtain the hyperbranched star polymer two that end group is the group containing carbon-carbon double bond, That is, the hyperbranched star polymer cured by ultraviolet light.
优选地，步骤(1)中所述超支化聚酯所含羟基量与ε-己内酯的摩尔投料比为1:15～1:25；步骤(2)中，所述封端剂与步骤(1)所述的超支化聚酯所含羟基的摩尔投料比为2:1。Preferably, the molar ratio of the hydroxyl content of the hyperbranched polyester to ε-caprolactone in the step (1) is 1:15 to 1:25; in the step (2), the end-capping agent and the step (1) The molar feed ratio of the hydroxyl groups contained in the hyperbranched polyester is 2:1.
优选地，步骤(1)中所述催化剂a为Sn(Oct)2，催化剂a与超支化聚酯所含羟基的摩尔投料比为1:20；步骤(2)中所述催化剂b为三乙胺和4-二甲氨基吡啶，所述三乙胺与超支化聚酯所含羟基的摩尔投料比为3:1，所述4-二甲氨基吡啶与超支化聚酯所含羟基的摩尔投料比为1:2.5。Preferably, the catalyst a in the step (1) is Sn(Oct)2 , and the molar ratio of the catalyst a to the hydroxyl group contained in the hyperbranched polyester is 1:20; the catalyst b in the step (2) is triethyl Amine and 4-dimethylaminopyridine, the molar feeding ratio of the triethylamine and the hydroxyl group contained in the hyperbranched polyester is 3:1, the molar feeding ratio of the hydroxyl group contained in the 4-dimethylaminopyridine and the hyperbranched polyester The ratio is 1:2.5.
优选地，步骤(1)中所述的开环聚合为本体聚合，步骤(2)中所述的酯交换反应所用溶剂为二氯甲烷。Preferably, the ring-opening polymerization described in step (1) is bulk polymerization, and the solvent used in the transesterification reaction described in step (2) is dichloromethane.
优选地，步骤(1)中所述开环聚合反应温度为130℃，反应时间为5小时；步骤(2)中所述酯交换反应为冰浴下反应，反应时间为5小时。Preferably, the ring-opening polymerization reaction temperature in step (1) is 130° C., and the reaction time is 5 hours; the transesterification reaction in step (2) is a reaction under ice bath, and the reaction time is 5 hours.
优选地，步骤(1)中，所述反应前抽真空，并在氮气保护下反应，确保无水无氧的反应环境；所述ε-己内酯经减压蒸馏提纯后使用。Preferably, in step (1), vacuumize before the reaction, and react under nitrogen protection to ensure an anhydrous and oxygen-free reaction environment; the ε-caprolactone is used after being purified by vacuum distillation.
优选地，所述经步骤(1)的反应所得产物用冷甲醇：乙醚＝1:1的混合有机溶剂进行沉淀，之后抽滤，35℃烘干，得超支化星形聚合物一；Preferably, the product obtained through the reaction of step (1) is precipitated with a mixed organic solvent of cold methanol:ether=1:1, then suction filtered, and dried at 35°C to obtain a hyperbranched star polymer one;
所述经步骤(1)的反应所得产物用冷甲醇沉淀，之后抽滤，35℃烘干，得超支化星形聚合物二。The product obtained through the reaction of step (1) is precipitated with cold methanol, then suction-filtered, and dried at 35° C. to obtain hyperbranched star polymer II.
第三方面，本发明提供了一种可紫外光固化的超支化星形聚合物在制备紫外光固化涂料中的应用。其具有较好的流平性、固化速率、硬度、附着力和耐性等，有希望应用于汽车和医疗等领域。In a third aspect, the present invention provides an application of a UV-curable hyperbranched star polymer in the preparation of UV-curable coatings. It has good leveling, curing rate, hardness, adhesion and resistance, etc., and is expected to be used in automotive and medical fields.
第四方面，本发明提供了一种紫外光固化涂料的制备方法，包括采用前述的可紫外光固化的超支化星形聚合物与光引发剂混合，即得。In a fourth aspect, the present invention provides a method for preparing a UV-curable coating, comprising mixing the above-mentioned UV-curable hyperbranched star polymer with a photoinitiator.
所述紫外光固化涂料中，超支化星形聚合物的浓度为1.0～8.0mmol/L，或超支化星形聚合物的质量百分含量为10～80％。In the ultraviolet curing coating, the concentration of the hyperbranched star polymer is 1.0-8.0 mmol/L, or the mass percentage of the hyperbranched star polymer is 10-80%.
优选地，所述光引发剂为2-羟基-2-甲基苯丙酮，用量为3％质量分数。Preferably, the photoinitiator is 2-hydroxy-2-methylpropiophenone, and the dosage is 3% by mass fraction.
将前述的紫外光固化涂料进行涂布，在紫外光照下进行交联固化，得到光固化漆膜。所述紫外光照时间是5分钟；紫外光照灯的功率为300W；紫外光照波长为365nm。The aforementioned UV-curable paint is coated, and cross-linked and cured under UV light to obtain a photo-curable paint film. The ultraviolet light time is 5 minutes; the power of the ultraviolet light is 300W; the wavelength of the ultraviolet light is 365nm.
本发明所述超支化星形聚合物，能够在紫外光下快速固化，在线性聚合物臂聚合度适宜的情况下，超支化星形聚合物结合了超支化聚合物与线性聚合物的优点，涂料的流平性、固化速率、硬度、附着力和耐性等得到了提高。The hyperbranched star polymer of the present invention can be rapidly cured under ultraviolet light, and under the condition that the degree of polymerization of the linear polymer arms is suitable, the hyperbranched star polymer combines the advantages of the hyperbranched polymer and the linear polymer, The leveling, curing rate, hardness, adhesion and resistance of the coating are improved.
所述超支化聚合物由于其独特的三维球形结构，分子间几乎无链缠结，使得超支化聚合物的粘度明显低于同分子量的线性低聚物；且超支化聚合物的球形分子表面具有丰富的官能团，因此，所述的紫外光固化超支化星形聚合物涂料，其超支化聚酯内核显著降低了涂料的粘度，提高了涂料的流平性和固化速率。线性聚合物臂能够降低体系的交联位阻，提高体系的交联度，减少未反应官能团，因此，所述的紫外光固化超支化星形聚合物涂料，其聚己内酯臂提高了漆膜的稳定性和耐性。Due to its unique three-dimensional spherical structure, the hyperbranched polymer has almost no chain entanglement between molecules, so that the viscosity of the hyperbranched polymer is significantly lower than that of linear oligomers with the same molecular weight; and the spherical molecular surface of the hyperbranched polymer has Rich in functional groups, therefore, the hyperbranched polyester inner core of the UV-curable hyperbranched star polymer coating significantly reduces the viscosity of the coating and improves the leveling and curing rate of the coating. The linear polymer arm can reduce the cross-linking steric hindrance of the system, increase the cross-linking degree of the system, and reduce unreacted functional groups. Therefore, the polycaprolactone arm of the UV-curable hyperbranched star polymer coating improves the paint Membrane stability and durability.
与现有技术相比，本发明具有如下的有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、本发明的超支化星形聚合物，由于使用的超支化聚酯内核分子间几乎无链缠结，粘度明显低于同分子量的线性低聚物，能够有效减少活性稀释剂和溶剂的用量，因而有效降低了VOC的排放；1. The hyperbranched star polymer of the present invention has almost no chain entanglement between the hyperbranched polyester core molecules used, and the viscosity is significantly lower than that of linear oligomers with the same molecular weight, which can effectively reduce the consumption of reactive diluents and solvents , thus effectively reducing VOC emissions;
2、本发明的超支化星形聚合物，作为一种紫外光固化涂料，固化速度快，能量消耗明显少于加热干燥，可用于各种热敏材料的涂装；2. The hyperbranched star-shaped polymer of the present invention, as a UV-curable coating, has a fast curing speed and significantly less energy consumption than heating and drying, and can be used for coating various heat-sensitive materials;
3、本发明的紫外光固化超支化星形聚合物涂料，包括超支化聚合物内核与可生物降解的线性聚合物臂，两者之间通过化学键连接，用甲基丙烯酸酯基对超支化星形聚合物的端羟基进行修饰，能够结合超支化聚合物与线性聚合物的优点。超支化聚合物内核能够降低体系粘度、提供丰富的官能团和分支结构，线性聚合物臂能够降低体系的交联位阻，提高体系的交联度，减少未反应官能团，从而提高漆膜的稳定性和耐性。因此，本发明的超支化星形聚合物突破了线性聚合物涂料和超支化聚合物涂料的局限性，具有较好的流平性、固化速率、硬度、附着力和耐性等，并具有一定的生物降解性，有希望应用于汽车和医疗等领域；3. The UV-curable hyperbranched star polymer coating of the present invention comprises a hyperbranched polymer core and a biodegradable linear polymer arm, the two are connected by chemical bonds, and the hyperbranched star is linked with a methacrylate group. By modifying the terminal hydroxyl groups of polymers, the advantages of hyperbranched polymers and linear polymers can be combined. The hyperbranched polymer core can reduce the viscosity of the system and provide abundant functional groups and branched structures. The linear polymer arms can reduce the crosslinking hindrance of the system, increase the degree of crosslinking of the system, and reduce unreacted functional groups, thereby improving the stability of the paint film and patience. Therefore, the hyperbranched star polymer of the present invention breaks through the limitations of linear polymer coatings and hyperbranched polymer coatings, has good leveling properties, curing rate, hardness, adhesion and resistance, etc., and has a certain Biodegradability, promising applications in automotive and medical fields;
4、本发明的紫外光固化超支化星形聚合物涂料，探究了其综合性能最优时的聚合度，经过热性能和漆膜性能实验比较，当聚己内酯的聚合度为20时，既提高了涂料的流平性和固化速度，又保证了涂料的硬度、附着力和耐性；4. The UV-curable hyperbranched star-shaped polymer coating of the present invention explores the degree of polymerization when its comprehensive performance is optimal, and compares thermal performance and paint film performance experiments. When the degree of polymerization of polycaprolactone is 20, It not only improves the leveling and curing speed of the coating, but also ensures the hardness, adhesion and durability of the coating;
5、本发明中所使用的超支化聚酯是一种比较成熟且已经商业化的超支化聚合物，具有较好的性价比；接枝聚己内酯在提高漆膜性能的同时，也大大降低了涂料的成本；因而，本发明的紫外光固化超支化星形聚合物涂料具有较高的性价比，有希望应用到实际的工业生产中。5. The hyperbranched polyester used in the present invention is a relatively mature and commercialized hyperbranched polymer with good cost performance; grafted polycaprolactone improves the performance of the paint film while greatly reducing The cost of the coating is reduced; therefore, the UV-curable hyperbranched star polymer coating of the present invention has a higher cost performance, and is expected to be applied to actual industrial production.
附图说明Description of drawings
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：Other characteristics, objects and advantages of the present invention will become more apparent by reading the detailed description of non-limiting embodiments made with reference to the following drawings:
图1为实施例1合成接枝超支化聚合物的示意图；Fig. 1 is the schematic diagram of the synthetic graft hyperbranched polymer of embodiment 1;
图2为实施例1合成的接枝超支化聚合物H40-star-PCL20的1H NMR谱图；Fig. 2 is the1 H NMR spectrogram of the grafted hyperbranched polymer H40 -star-PCL20 synthesized in Example 1;
图3为实施例1合成的接枝超支化聚合物H40-star-PCL20的13C NMR谱图；Fig. 3 is the13 C NMR spectrogram of the grafted hyperbranched polymer H40 -star-PCL20 synthesized in Example 1;
图4为实施例1合成的甲基丙烯酸酯封端接枝超支化聚合物H40-star-PCL20-MAC的1H NMR谱图；Fig. 4 is the1 H NMR spectrogram of the methacrylate-terminated grafted hyperbranched polymer H40 -star-PCL20 -MAC synthesized in Example 1;
图5为实施例1合成的甲基丙烯酸酯封端接枝超支化聚合物H40-star-PCL20-MAC的13C NMR谱图；Fig. 5 is the13 C NMR spectrogram of the methacrylate-terminated grafted hyperbranched polymer H40 -star-PCL20 -MAC synthesized in Example 1;
图6为实施例1合成的接枝超支化聚合物H40-star-PCL20的DSC数据图；Fig. 6 is the DSC data graph of the grafted hyperbranched polymer H40 -star-PCL20 synthesized in Example 1;
图7为实施例1合成的H40、H40-star-PCL20、H40-MAC和H40-star-PCL20-MAC的热失重曲线。Fig. 7 is the thermogravimetric curves of H40 , H40 -star-PCL20 , H40 -MAC and H40 -star-PCL20 -MAC synthesized in Example 1.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变化和改进。这些都属于本发明的保护范围。The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make several changes and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
本发明中的超支化星形聚合物，包括超支化聚合物内核与可生物降解的线性聚合物臂，用甲基丙烯酸酐对超支化星形聚合物的端羟基进行修饰。本发明的超支化星形聚合物，具有紫外光下快速固化的能力，在线性聚合物臂聚合度适宜的情况下，超支化星形聚合物结合了超支化聚合物与线性聚合物的优点，提高了涂料的流平性、固化速率、硬度、附着力和耐性等。The hyperbranched star polymer in the present invention includes a hyperbranched polymer inner core and biodegradable linear polymer arms, and the terminal hydroxyl groups of the hyperbranched star polymer are modified with methacrylic anhydride. The hyperbranched star polymer of the present invention has the ability of rapid curing under ultraviolet light. Under the condition that the polymerization degree of the linear polymer arm is suitable, the hyperbranched star polymer combines the advantages of the hyperbranched polymer and the linear polymer, Improve the coating leveling, curing rate, hardness, adhesion and resistance.
且所述超支化聚合物由于其独特的三维球形结构，分子间几乎无链缠结，粘度明显低于同分子量的线性低聚物；且球形分子表面具有丰富的官能团，因此，所述的紫外光固化超支化星形聚合物涂料，其超支化聚酯内核显著降低了涂料的粘度，提高了涂料的流平性和固化速率。线性聚合物臂能够降低体系的交联位阻，提高体系的交联度，减少未反应官能团，因此，所述的紫外光固化超支化星形聚合物涂料，其聚己内酯臂提高了漆膜的稳定性和耐性。经过热性能和漆膜性能实验比较，当聚己内酯的聚合度为20时，其综合性能最优。And the hyperbranched polymer is due to its unique three-dimensional spherical structure, there is almost no chain entanglement between the molecules, and the viscosity is significantly lower than that of the linear oligomer with the same molecular weight; and the surface of the spherical molecule has abundant functional groups, therefore, the UV Photocurable hyperbranched star polymer coatings, whose hyperbranched polyester inner core significantly reduces the viscosity of the coating, and improves the leveling and curing rate of the coating. The linear polymer arm can reduce the cross-linking steric hindrance of the system, increase the cross-linking degree of the system, and reduce unreacted functional groups. Therefore, the polycaprolactone arm of the UV-curable hyperbranched star polymer coating improves the paint Membrane stability and durability. After thermal performance and paint film performance experiments, when the degree of polymerization of polycaprolactone is 20, its comprehensive performance is the best.
与现有技术相比，本发明所述的紫外光固化超支化星形聚合物涂料，突破了线性聚合物涂料和超支化聚合物涂料的局限性，解决了现有技术中线性聚合物粘度大、超支化聚合物交联位阻大且含有未反应官能团，最终污染环境或影响漆膜性能的技术性问题，并具有较好的流平性、固化速率、硬度、附着力和耐性等。Compared with the prior art, the UV-curable hyperbranched star polymer coating of the present invention breaks through the limitations of linear polymer coatings and hyperbranched polymer coatings, and solves the problem of high viscosity of linear polymers in the prior art. , Hyperbranched polymers have large cross-linking steric hindrance and contain unreacted functional groups, which will eventually pollute the environment or affect the technical problems of paint film performance, and have good leveling, curing rate, hardness, adhesion and resistance.
实施例1Example 1
本实施例的紫外光固化超支化星形聚合物涂料的制备方法包括如下步骤：The preparation method of the UV curing hyperbranched star polymer coating of the present embodiment comprises the steps:
(1)接枝超支化聚合物的制备：(1) Preparation of graft hyperbranched polymer:
以聚己内酯的聚合度为20时的制备方法为例。如图1所示，将四代超支化聚酯H40(0.800g，含7.10mmol羟基)和减压蒸馏提纯过的ε-己内酯(16.0g,142mmol)加到反应瓶中，在氮气氛围下，使H40完全溶解在ε-己内酯中，升温至130℃，加入催化剂Sn(Oct)2，催化剂与超支化聚酯所含羟基的摩尔投料比为1:20，引发开环聚合反应，搅拌，反应5小时，得到粘稠液体。冷却至室温后，向反应瓶中加四氢呋喃溶解，在400mL冷甲醇/乙醚(1:1)中沉淀，抽滤后得到白色固体颗粒，在35℃下干燥24小时，得到超支化星形聚合物一，标记为H40-star-PCL20(83.2％yield)。Take the preparation method when the degree of polymerization of polycaprolactone is 20 as an example. As shown in Figure 1, the four-generation hyperbranched polyester H40 (0.800g, containing 7.10mmol hydroxyl) and ε-caprolactone (16.0g, 142mmol) purified by vacuum distillation were added to the reaction flask, under nitrogen Under the atmosphere, completely dissolve H40 in ε-caprolactone, raise the temperature to 130°C, add the catalyst Sn(Oct)2 , the molar ratio of the catalyst to the hydroxyl group contained in the hyperbranched polyester is 1:20, and initiate ring opening Polymerization, stirring, and reacting for 5 hours, a viscous liquid was obtained. After cooling to room temperature, add tetrahydrofuran to the reaction flask to dissolve, precipitate in 400mL cold methanol/ether (1:1), obtain white solid particles after suction filtration, and dry at 35°C for 24 hours to obtain a hyperbranched star polymer One, labeled H40 -star-PCL20 (83.2% yield).
如图2所示，该聚合物的氢谱核磁结构确认数据如下：1H NMR(CDCl3,ppm):7.29,4.10-4.07,3.69-3.66,2.35-2.31,1.68-1.65,1.44-1.40,1.27。As shown in Figure 2, the H NMR structure confirmation data of the polymer are as follows:1 H NMR (CDCl3 , ppm): 7.29, 4.10-4.07, 3.69-3.66, 2.35-2.31, 1.68-1.65, 1.44-1.40, 1.27.
如图3所示，该聚合物的碳谱核磁结构确认数据如下：13C NMR(CDCl3,ppm):173.59,77.03,63.91,34.04,28.45,25.34,24.44。As shown in Figure 3, the carbon NMR structure confirmation data of the polymer are as follows:13 C NMR (CDCl3 , ppm): 173.59, 77.03, 63.91, 34.04, 28.45, 25.34, 24.44.
以同样方法制备聚合度为15(采用四代超支化聚酯H40(0.800g，含7.10mmol羟基)和减压蒸馏提纯过的ε-己内酯(12.0g,106.5mmol)进行反应)和25(采用四代超支化聚酯H40(0.800g，含7.10mmol羟基)和减压蒸馏提纯过的ε-己内酯(20g,177.5mmol)进行反应)的接枝超支化聚合物，标记为H40-star-PCL15和H40-star-PCL25。Prepared in the same way with a degree of polymerization of 15 (using four generations of hyperbranched polyester H40 (0.800g, containing 7.10mmol hydroxyl) and ε-caprolactone (12.0g, 106.5mmol) purified by vacuum distillation to react) and 25 (using four generations of hyperbranched polyester H40 (0.800g, containing 7.10mmol hydroxyl group) and ε-caprolactone (20g, 177.5mmol) purified by vacuum distillation to react) grafted hyperbranched polymer, labeled are H40 -star-PCL15 and H40 -star-PCL25 .
(2)甲基丙烯酸酯封端接枝超支化聚合物：(2) Methacrylate-terminated graft hyperbranched polymer:
以聚己内酯的聚合度为20时的制备方法为例。将制备得到的H40-star-PCL20(5.00g，含7.10mmol羟基)溶于15mL二氯甲烷中，在氮气氛围下，加入催化剂三乙胺(0.607g,6.00mmol)和4-二甲氨基吡啶(0.100g,0.82mmol)，三乙胺与超支化聚酯所含羟基的摩尔投料比为3:1，4-二甲氨基吡啶与超支化聚酯所含羟基的摩尔投料比为1:2.5。反应瓶上接入装有无水氯化钙的干燥球，反应在冰浴下进行。将稀释在3mL二氯甲烷中的甲基丙烯酸酐(0.617g,4.00mmol)逐滴加入反应瓶中，搅拌，反应3小时，得到淡黄色粘稠液体。向反应瓶中加入二氯甲烷稀释产物，在400mL冷甲醇中沉淀，抽滤，用冷超纯水洗涤3次后得到白色固体颗粒，在35℃下干燥24小时，得到超支化星形聚合物二，标记为H40-star-PCL20-MAC(87.6％yield)。Take the preparation method when the degree of polymerization of polycaprolactone is 20 as an example. The prepared H40 -star-PCL20 (5.00g, containing 7.10mmol hydroxyl group) was dissolved in 15mL of dichloromethane, and the catalyst triethylamine (0.607g, 6.00mmol) and 4-dimethyl Aminopyridine (0.100g, 0.82mmol), the molar feeding ratio of triethylamine and the hydroxyl group contained in the hyperbranched polyester is 3:1, and the molar feeding ratio of 4-dimethylaminopyridine and the hydroxyl group contained in the hyperbranched polyester is 1 :2.5. A dry bulb filled with anhydrous calcium chloride was connected to the reaction bottle, and the reaction was carried out under an ice bath. Methacrylic anhydride (0.617 g, 4.00 mmol) diluted in 3 mL of dichloromethane was added dropwise into the reaction flask, stirred, and reacted for 3 hours to obtain a light yellow viscous liquid. Add dichloromethane to the reaction flask to dilute the product, precipitate in 400mL of cold methanol, filter with suction, wash with cold ultrapure water for 3 times to obtain white solid particles, dry at 35°C for 24 hours to obtain a hyperbranched star polymer Two, labeled H40 -star-PCL20 -MAC (87.6% yield).
如图4所示，该聚合物的氢谱核磁结构确认数据如下：1H NMR(CDCl3,ppm):7.29,6.09,5.55,4.08-4.04,2.32-2.29,1.67-1.63,1.40-1.38,1.25。As shown in Figure 4, the H NMR structure confirmation data of the polymer are as follows:1 H NMR (CDCl3 , ppm): 7.29, 6.09, 5.55, 4.08-4.04, 2.32-2.29, 1.67-1.63, 1.40-1.38, 1.25.
如图5所示，该聚合物的碳谱核磁结构确认数据如下：13C NMR(CDCl3,ppm):173.81,125.53,77.59,77.27,64.38,34.33,28.55,25.73,24.78。As shown in Figure 5, the carbon NMR structure confirmation data of the polymer are as follows:13 C NMR (CDCl3 , ppm): 173.81, 125.53, 77.59, 77.27, 64.38, 34.33, 28.55, 25.73, 24.78.
以同样方法制备聚合度为15和25的甲基丙烯酸酯封端的接枝超支化聚合物，标记为H40-star-PCL15-MAC和H40-star-PCL25-MAC。The methacrylate-terminated grafted hyperbranched polymers with degrees of polymerization of 15 and 25 were prepared in the same way, labeled as H40 -star-PCL15 -MAC and H40 -star-PCL25 -MAC.
此外，为了体现接枝聚己内酯臂的特点并进行对比，同样合成H40-MAC，即直接用甲基丙烯酸酐修饰四代超支化聚酯H40的端羟基。In addition, in order to reflect the characteristics of grafted polycaprolactone arms and make comparisons, H40 -MAC was also synthesized, that is, the terminal hydroxyl groups of the fourth-generation hyperbranched polyester H40 were directly modified with methacrylic anhydride.
(3)等质量分数(以10％为例)的超支化星形聚合物紫外光固化漆膜制备：(3) Preparation of hyperbranched star polymer UV-curable paint film with equal mass fraction (taking 10% as an example):
取H40-star-PCLn(0.5g)溶于3mL二氯甲烷，加入3％质量分数的光引发剂2-羟基-2-甲基苯丙酮，用30μm厚的涂布棒将溶液涂于经过清洁处理的马口铁片，放置在功率300W、波长365nm的紫外灯下照射5分钟。共制备4种漆膜，即H40-MAC、H40-star-PCL15-MAC、H40-star-PCL20-MAC和H40-star-PCL25-MAC。Take H40 -star-PCLn (0.5g) and dissolve it in 3mL of dichloromethane, add 3% mass fraction of photoinitiator 2-hydroxyl-2-methylpropiophenone, and apply the solution to the The cleaned tinplate sheet is placed under a UV lamp with a power of 300W and a wavelength of 365nm for 5 minutes. Four paint films were prepared, namely H40 -MAC, H40 -star-PCL15 -MAC, H40 -star-PCL20 -MAC and H40 -star-PCL25 -MAC.
在等质量分数的情况下，聚己内酯臂的聚合度越小，体系中超支化聚酯的含量越高，能够凸显出超支化聚酯内核的特点。In the case of equal mass fractions, the smaller the degree of polymerization of polycaprolactone arms, the higher the content of hyperbranched polyester in the system, which can highlight the characteristics of the hyperbranched polyester core.
(4)等摩尔浓度(以1.0mmol/L为例)的超支化星形聚合物紫外光固化漆膜制备：(4) Preparation of hyperbranched star polymer UV-curable paint film with equimolar concentration (taking 1.0mmol/L as an example):
取H40-star-PCLn(3μmol)溶于3mL二氯甲烷，加入3％质量分数的光引发剂2-羟基-2-甲基苯丙酮，用30μm厚的涂布棒将溶液涂于经过清洁处理的马口铁片，放置在功率300W、波长365nm的紫外灯下照射5分钟。共制备4种漆膜，即H40-MAC、H40-star-PCL15-MAC、H40-star-PCL20-MAC和H40-star-PCL25-MAC。Take H40 -star-PCLn (3μmol) and dissolve it in 3mL of dichloromethane, add 3% mass fraction of photoinitiator 2-hydroxyl-2-methylpropiophenone, and apply the solution to the process with a 30μm thick coating rod The cleaned tinplate sheet is placed under an ultraviolet lamp with a power of 300W and a wavelength of 365nm for 5 minutes. Four paint films were prepared, namely H40 -MAC, H40 -star-PCL15 -MAC, H40 -star-PCL20 -MAC and H40 -star-PCL25 -MAC.
在等摩尔浓度的情况下，体系中超支化聚酯的含量相同，区别仅在于聚己内酯臂的长度，因而能够体现出接枝聚己内酯臂的特点。In the case of equimolar concentration, the content of the hyperbranched polyester in the system is the same, the difference is only the length of the polycaprolactone arm, so it can reflect the characteristics of the grafted polycaprolactone arm.
性能分析及效果验证：Performance analysis and effect verification:
1)对实施例1制备的超支化星形聚合物进行核磁、GPC、DSC和TGA测试，结果如下：1) NMR, GPC, DSC and TGA tests are carried out to the hyperbranched star polymer prepared by embodiment 1, and the results are as follows:
由氢谱核磁计算H40-star-PCL15、H40-star-PCL20和H40-star-PCL25中平均每个H40所含聚己内酯臂的个数以及聚己内酯臂的聚合度、分子量，具体数据列于表1。H40-star-PCLn的核磁谱图中，如图2所示，1.27ppm处的信号峰为超支化聚酯中的甲基质子峰，3.67ppm处的信号峰为与端羟基相邻的亚甲基的质子峰，2.34ppm处的信号峰为聚己内酯臂的重复单元中与酯基相邻的亚甲基的质子峰，通过比较前两者信号峰的积分面积，即可得到平均每个H40所含聚己内酯臂的个数，而后两者信号峰积分面积的比值为H40-star-PCLn的聚合度，结果显示计算聚合度与理论聚合度接近。H40 -star-PCL15 , H40 -star-PCL20 and H40 -star-PCL25 calculated the number of polycaprolactone arms and polycaprolactone arms contained in each H40 by H NMR The degree of polymerization, molecular weight, specific data are listed in Table 1. In the NMR spectrum of H40 -star-PCLn , as shown in Figure 2, the signal peak at 1.27ppm is the methyl proton peak in the hyperbranched polyester, and the signal peak at 3.67ppm is the proton peak adjacent to the terminal hydroxyl The proton peak of the methylene group, the signal peak at 2.34ppm is the proton peak of the methylene group adjacent to the ester group in the repeating unit of the polycaprolactone arm. By comparing the integral areas of the first two signal peaks, it can be obtained The number of polycaprolactone arms contained in each H40 is averaged, and the ratio of the integrated area of the signal peaks of the latter two is the degree of polymerization of H40 -star-PCLn . The results show that the calculated degree of polymerization is close to the theoretical degree of polymerization.
表1Table 1
对H40、H40-star-PCL15、H40-star-PCL20、H40-star-PCL25、H40-MAC、H40-star-PCL15-MAC、H40-star-PCL20-MAC和H40-star-PCL25-MAC进行DSC测试。称取约7mg样品，降温至-50℃，升温至150℃，稳定1分钟，以消除热历史，降温至-50℃，稳定1分钟，再升温至150℃，升温速率和降温速率均为10℃/min。H40-star-PCL20的DSC测试曲线如图6所示，所有样品的结晶度、熔融起点温度、熔点、玻璃化转变温度Tg列于表2。由于聚己内酯是一种半结晶的聚合物，因此随着聚己内酯聚合度的增加，超支化星形聚合物的结晶度增加，计算时以166.5J/g作为100％结晶度的熔融热；聚己内酯的熔点为60～63℃，Tg为-60℃，随着聚己内酯臂的增长，超支化星形聚合物的分子量增大、柔性提高，因此熔点增加、Tg降低；甲基丙烯酸酐改性超支化星形聚合物，支链末端引入酯基，端基极性下降，且分子中的柔性链段增加，因而Tg下降。For H40 , H40 -star-PCL15 , H40 -star-PCL20 , H40 -star-PCL25 , H40 -MAC, H40 -star-PCL15 -MAC, H40 -star-PCL20 -MAC and H40 -star-PCL25 -MAC for DSC testing. Weigh about 7 mg of sample, cool down to -50°C, heat up to 150°C, stabilize for 1 minute to eliminate thermal history, cool down to -50°C, stabilize for 1 minute, then raise the temperature to 150°C, the heating rate and cooling rate are both 10 °C/min. The DSC test curve of H40 -star-PCL20 is shown in Figure 6, and the crystallinity, melting onset temperature, melting point, and glass transition temperature Tg of all samples are listed in Table 2. Because polycaprolactone is a kind of semi-crystalline polymer, so along with the increase of polycaprolactone degree of polymerization, the degree of crystallinity of hyperbranched star-shaped polymer increases, when calculating with 166.5J/g as 100% degree of crystallinity Heat of fusion; the melting point of polycaprolactone is 60-63°C, and the Tg is -60°C. With the growth of polycaprolactone arms, the molecular weight and flexibility of hyperbranched star polymers increase, so the melting point increases, Tg decreased; methacrylic anhydride modified hyperbranched star polymers introduced ester groups at the end of branched chains, the polarity of the end groups decreased, and the flexible chain segment in the molecule increased, thus Tg decreased.
表2Table 2
对H40、H40-star-PCL15、H40-star-PCL20、H40-star-PCL25、H40-MAC、H40-star-PCL15-MAC、H40-star-PCL20-MAC和H40-star-PCL25-MAC进行TGA测试。样品质量约5mg，在氮气氛围下，以20℃/min的速率从50℃加热至600℃，测定样品的热稳定性。H40、H40-star-PCL20、H40-MAC和H40-star-PCL20-MAC的热失重曲线如图7所示，所有样品的热失重10％、50％和90％的温度列于表3，可知所有样品都有较好的热稳定性。接枝聚己内酯臂，超支化星形聚合物的热分解曲线表现为两段，即聚己内酯和超支化聚酯两段，侧面说明聚己内酯臂的成功接枝；用甲基丙烯酸酐对超支化星形聚合物端羟基改性后，热分解温度有较明显的提高，是因为改性后端基的甲基丙烯酸酯具有交联功能，受热过程中发生交联，且球形分子将较易分解的酯键包裹在分子内，因此，热稳定性提高。For H40 , H40 -star-PCL15 , H40 -star-PCL20 , H40 -star-PCL25 , H40 -MAC, H40 -star-PCL15 -MAC, H40 -star-PCL20 -MAC and H40 -star-PCL25 -MAC for TGA testing. The mass of the sample is about 5 mg, and it is heated from 50°C to 600°C at a rate of 20°C/min under a nitrogen atmosphere to measure the thermal stability of the sample. The thermogravimetric curves of H40 , H40 -star-PCL20 , H40 -MAC and H40 -star-PCL20 -MAC are shown in Fig. 7, the temperatures of 10%, 50% and 90% thermogravimetric loss of all samples Listed in Table 3, it can be seen that all samples have good thermal stability. Grafting polycaprolactone arms, the thermal decomposition curve of the hyperbranched star polymer is shown as two sections, namely polycaprolactone and hyperbranched polyester, which shows the successful grafting of polycaprolactone arms; After modification of terminal hydroxyl groups of hyperbranched star-shaped polymers with acrylic anhydride, the thermal decomposition temperature is significantly improved, because the methacrylates of the modified terminal groups have cross-linking functions, and cross-linking occurs during heating, and The spherical molecule wraps the easier-to-decompose ester bond in the molecule, so the thermal stability is improved.
表3table 3
2)对实施例1制备的超支化星形聚合物进行涂布、紫外光固化，并对漆膜进行性能测试，结果如下：2) the hyperbranched star polymer prepared in embodiment 1 is coated, cured by ultraviolet light, and the performance test is carried out to the paint film, the results are as follows:
制备等质量分数的H40-MAC、H40-star-PCL15-MAC、H40-star-PCL20-MAC和H40-star-PCL25-MAC四种漆膜。在等质量分数的情况下，聚己内酯臂的聚合度越小，体系中超支化聚酯的含量越高，能够凸显出超支化聚酯内核的特点。用30μm厚的涂布棒涂布，制备的漆膜厚度均为30μm。由于超支化聚合物低粘度的特点，本发明的涂料均不添加任何活性稀释剂。对四种超支化星形聚合物漆膜进行硬度、附着力、耐酸性、耐碱性、流平性和固化时间的测试分析，测试结果列于表4。硬度测定方法参考GB/T6739-2006，附着力测定方法参考GB/T 1720-79，耐酸碱性测定方法参考GB/T 1763-79。可以看出，聚己内酯臂越短，漆膜的硬度、附着力、流平性和固化速率性能越好，这是因为在等质量分数的情况下，聚己内酯臂越短，超支化聚酯的相对含量越高，体系的粘度越低，体系中的官能团含量越高，具有交联功能的甲基丙烯酸酯端基越多，因而交联密度越大，而且超支化聚酯的C＝C双键主要分布在球形分子表面，当进行紫外光固化时，超支化结构有利于交联反应的进行，使得固化速率提高，且容易形成致密的网状交联结构，故而超支化结构含量多的漆膜硬度、附着力、流平性和固化速率性能更好。但同时可以看出，聚己内酯臂越短，漆膜的耐酸性和耐碱性越差，这是因为含有过高含量的超支化结构，拥有富余的官能团，且球形分子间的交联位阻大于线性分子间的交联位阻，导致漆膜中含有未反应的富余C＝C双键，降低了漆膜的耐酸性和耐碱性。本实施例的漆膜性能测试实验充分体现了超支化结构的优点与缺点。Four paint films with equal mass fractions of H40 -MAC, H40 -star-PCL15 -MAC, H40 -star-PCL20 -MAC and H40 -star-PCL25 -MAC were prepared. In the case of equal mass fractions, the smaller the degree of polymerization of polycaprolactone arms, the higher the content of hyperbranched polyester in the system, which can highlight the characteristics of the hyperbranched polyester core. Coating with a 30 μm thick coating bar, the thickness of the prepared paint film is 30 μm. Due to the characteristics of low viscosity of the hyperbranched polymer, the coating of the present invention does not add any active diluent. The hardness, adhesion, acid resistance, alkali resistance, leveling and curing time of four hyperbranched star polymer paint films were tested and analyzed. The test results are listed in Table 4. The hardness test method refers to GB/T6739-2006, the adhesion test method refers to GB/T 1720-79, and the acid and alkali resistance test method refers to GB/T 1763-79. It can be seen that the shorter the polycaprolactone arm, the better the hardness, adhesion, leveling and curing rate properties of the paint film, because in the case of equal mass fraction, the shorter the polycaprolactone arm, the overrun The higher the relative content of polyester, the lower the viscosity of the system, the higher the content of functional groups in the system, the more methacrylate end groups with cross-linking function, and thus the greater the cross-linking density, and the hyperbranched polyester C=C double bonds are mainly distributed on the surface of spherical molecules. When UV curing is carried out, the hyperbranched structure is conducive to the progress of the crosslinking reaction, which increases the curing rate and easily forms a dense network crosslinked structure. Therefore, the hyperbranched structure The film hardness, adhesion, leveling and curing rate properties with higher content are better. But at the same time, it can be seen that the shorter the polycaprolactone arm, the worse the acid and alkali resistance of the paint film. The steric hindrance is greater than the crosslinking steric hindrance between linear molecules, resulting in unreacted redundant C=C double bonds in the paint film, which reduces the acid and alkali resistance of the paint film. The performance test experiment of the paint film in this embodiment fully reflects the advantages and disadvantages of the hyperbranched structure.
表4Table 4
表4中“流平性，耐酸性，耐碱性”均以10为最佳，数值越小表示性能越差。In Table 4, "leveling property, acid resistance and alkali resistance" are all taken as the best value of 10, and the smaller the value, the worse the performance.
制备等摩尔浓度的H40-MAC、H40-star-PCL15-MAC、H40-star-PCL20-MAC和H40-star-PCL25-MAC四种漆膜。在等摩尔浓度的情况下，体系中超支化聚酯的含量相同，区别仅在于聚己内酯臂的长度，因而能够体现出接枝聚己内酯臂的特点。用30μm厚的涂布棒涂布，由于质量分数不同，漆膜厚度均不相同，聚己内酯臂越长，质量分数越大，漆膜厚度越大。由于超支化聚合物低粘度的特点，本发明的涂料均不添加任何活性稀释剂。对四种超支化星形聚合物漆膜同样进行硬度、附着力、耐酸性、耐碱性、流平性和固化时间的测试分析，测试结果列于表5。可以看出，聚己内酯臂的聚合度越大，漆膜的硬度、附着力、耐酸性、耐碱性和固化速度性能越好，这是因为在等摩尔浓度的情况下，体系中的超支化聚酯含量相同，因而官能团含量相同，随着聚己内酯臂的增长，体系的质量分数增加，溶剂含量减少，同时柔性链段增加，大大降低了交联位阻，当进行紫外光固化时，聚己内酯臂提高了反应的交联度，提高了交联网络结构的密度，有效减少了体系中未反应的富余C＝C双键，故而聚己内酯臂长的漆膜硬度、附着力、耐酸性、耐碱性和固化速度性能更好。但同时可以看出，聚己内酯臂的聚合度越大，漆膜的流平性越差，这是因为聚合度越大，线性分子所占比例越大，分子量越大，体系的粘度越大，因而接枝聚己内酯臂导致漆膜的流平性有所损失。本实施例的漆膜性能测试实验充分体现了聚己内酯臂的优点与缺点。Four paint films of H40 -MAC, H40 -star-PCL15 -MAC, H40 -star-PCL20 -MAC and H40 -star-PCL25 -MAC were prepared at equimolar concentrations. In the case of equimolar concentration, the content of hyperbranched polyester in the system is the same, and the only difference is the length of the polycaprolactone arm, so it can reflect the characteristics of the grafted polycaprolactone arm. Coating with a 30μm thick coating rod, due to different mass fractions, the thickness of the paint film is not the same. The longer the polycaprolactone arm, the greater the mass fraction, and the greater the thickness of the paint film. Due to the characteristics of low viscosity of the hyperbranched polymer, the coating of the present invention does not add any active diluent. The hardness, adhesion, acid resistance, alkali resistance, leveling and curing time of the four hyperbranched star polymer paint films were also tested and analyzed. The test results are listed in Table 5. It can be seen that the greater the degree of polymerization of polycaprolactone arms, the better the hardness, adhesion, acid resistance, alkali resistance and curing speed of the paint film. This is because under the condition of equimolar concentration, the The content of hyperbranched polyester is the same, so the content of functional groups is the same. With the increase of polycaprolactone arm, the mass fraction of the system increases, the solvent content decreases, and the flexible chain segment increases, which greatly reduces the crosslinking hindrance. When curing, the polycaprolactone arms increase the crosslinking degree of the reaction, increase the density of the crosslinked network structure, and effectively reduce the unreacted excess C=C double bonds in the system, so the paint film with long polycaprolactone arms Hardness, adhesion, acid resistance, alkali resistance and curing speed are better. But at the same time, it can be seen that the greater the degree of polymerization of polycaprolactone arms, the worse the leveling property of the paint film is, because the greater the degree of polymerization, the larger the proportion of linear molecules, the larger the molecular weight, and the lower the viscosity of the system. Large, so the grafted polycaprolactone arms lead to loss of leveling of the paint film. The performance test experiment of the paint film in this embodiment fully reflects the advantages and disadvantages of the polycaprolactone arm.
表5table 5
表5中“流平性，耐酸性，耐碱性”均以10为最佳，数值越小表示性能越差。In Table 5, "leveling property, acid resistance and alkali resistance" are all set at 10 as the best value, and the smaller the value is, the worse the performance is.
表5中的结果显示，本发明制得的三种超支化星形聚合物涂料与H40相比，硬度、附着力、耐酸碱性均有提升。说明制备成星型结构之后，主要的优点在于降低了固化时的交联位阻，提高了交联反应程度，减少了多余的官能团，从而提高性能。The results in Table 5 show that compared withH40 , the three hyperbranched star polymer coatings prepared by the present invention have improved hardness, adhesion, and acid and alkali resistance. It shows that after the star structure is prepared, the main advantages are that the crosslinking hindrance during curing is reduced, the degree of crosslinking reaction is improved, and redundant functional groups are reduced, thereby improving performance.
表4中显示H40的性能更优，是由于在等质量分数的情况下，四组样品中的超支化聚酯含量差异过大，变量不唯一，因此主要体现了超支化聚酯的特点，很难体现PCL臂的特点。因此，在表5中，我们控制了样品中H40的含量相同，以体现PCL臂的特点。It is shown in Table 4 that the performance of H40 is better, because in the case of equal mass fractions, the content of hyperbranched polyester in the four groups of samples differs too much, and the variable is not unique, so it mainly reflects the characteristics of hyperbranched polyester, It is difficult to characterize the PCL arm. Therefore, in Table 5, we control the content ofH40 in the samples to be the same to reflect the characteristics of the PCL arm.
本实施例中的四种漆膜各有优势，有希望应用于不同的领域中。综合比较而言，当聚己内酯的聚合度为20时，H40-star-PCL20-MAC所制的漆膜具有最优的综合性能。The four paint films in this embodiment have their own advantages and are expected to be applied in different fields. In terms of comprehensive comparison, when the degree of polymerization of polycaprolactone is 20, the paint film prepared by H40 -star-PCL20 -MAC has the best comprehensive performance.
本发明中所使用的超支化聚酯H40是一种比较成熟且已经商业化的超支化聚合物，具有较好的性价比；接枝聚己内酯在提高漆膜性能的同时，也大大降低了涂料的成本；本发明的超支化星形聚合物涂料有效减少活性稀释剂和溶剂的用量，能够有效降低VOC的排放；因而，本发明的紫外光固化超支化星形聚合物涂料具有较高的性价比，有希望应用到实际的工业生产中。The hyperbranched polyester H40 used in the present invention is a relatively mature and commercialized hyperbranched polymer with good cost performance; while grafted polycaprolactone improves the performance of the paint film, it also greatly reduces reduce the cost of the coating; the hyperbranched star-shaped polymer coating of the present invention effectively reduces the consumption of reactive diluent and solvent, and can effectively reduce the discharge of VOC; It is expected to be applied to actual industrial production.
本发明创新的提供一类紫外光固化超支化星形聚合物涂料，超支化聚合物内核与线性聚合物臂通过化学键连接，用甲基丙烯酸酐对超支化星形聚合物的端羟基进行修饰，赋予其紫外光固化功能。本发明结合超支化聚合物和线性聚合物涂料的特点，利用超支化聚合物低粘度、官能团丰富和球形分支结构的优势，及利用线性聚合物柔性高和交联位阻小的优势，制备了能够紫外光下快速固化，且具有较好流平性、硬度、固化速率、附着力、耐酸性和耐碱性等性能超支化星形聚合物涂料，并探究了线性聚合物的聚合度对涂料性能的影响。基于其良好的附着力和生物降解性，以及较高的性价比，有希望应用于汽车和医疗等领域。The present invention innovatively provides a class of UV-curable hyperbranched star-shaped polymer coatings. The hyperbranched polymer core and linear polymer arms are connected by chemical bonds, and the terminal hydroxyl groups of the hyperbranched star-shaped polymer are modified with methacrylic anhydride. Give it UV curing function. The present invention combines the characteristics of hyperbranched polymers and linear polymer coatings, utilizes the advantages of hyperbranched polymers with low viscosity, rich functional groups and spherical branched structures, and utilizes the advantages of high flexibility and low crosslinking steric hindrance of linear polymers to prepare a It can be quickly cured under ultraviolet light, and has good leveling, hardness, curing rate, adhesion, acid resistance and alkali resistance. Hyperbranched star polymer coatings, and explored the effect of the degree of polymerization of linear polymers on coatings performance impact. Based on its good adhesion, biodegradability, and high cost performance, it is expected to be used in automotive and medical fields.
在本发明及上述实施例的教导下，本领域技术人员很容易预见到，本发明所列举或例举的各原料或其等同替换物、各加工方法或其等同替换物都能实现本发明，以及各原料和加工方法的参数上下限取值、区间值都能实现本发明，在此不一一列举实施例。Under the teaching of the present invention and the above-mentioned embodiments, those skilled in the art can easily foresee that each raw material or its equivalent replacements, each processing method or its equivalent replacements listed or exemplified in the present invention can realize the present invention, And the upper and lower limit values and interval values of the parameters of each raw material and processing method can realize the present invention, and the embodiments are not enumerated here one by one.
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变化或修改，这并不影响本发明的实质内容。在不冲突的情况下，本申请的实施例和实施例中的特征可以任意相互组合。Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art may make various changes or modifications within the scope of the claims, which do not affect the essence of the present invention. In the case of no conflict, the embodiments of the present application and the features in the embodiments can be combined with each other arbitrarily.
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