CN101177485A - Low surface energy fluorosiloxane oligomer containing double parallel main chain structure and its synthesis method - Google Patents

Abstract

Translated fromChinese

本发明属于功能性材料技术领域，公开了一种通过自由基溶液聚合与溶胶－凝胶法复合的合成方法，采用丙烯酸含氟烷基酯和乙烯基硅烷合成了氟硅氧烷共聚物，再采用硅烷为无机相前驱体，通过溶胶－凝胶法将氟硅氧烷聚合物溶液和硅烷共水解和缩聚，在同一种有机共溶剂存在的条件下，直接制备了一种分子级复合、分别以碳碳链和硅氧网络结构为并行双主链结构、侧链引入一定浓度的CF₃基团的新型氟硅氧烷聚合物材料及其合成方法。本发明制备的材料既吸收了CF₃基团的超低表面能特性，又与基底材料以共价键方式结合，有很好的结合强度，同时通过无机硅网络结构的构建提高了杂化材料的涂敷厚度及耐久性，可以极大的扩展氟硅氧烷聚合物材料的应用领域。The invention belongs to the technical field of functional materials, and discloses a compound synthesis method through free radical solution polymerization and sol-gel method. Fluorosiloxane copolymer is synthesized by using fluorine-containing alkyl acrylic acid and vinyl silane, and then Using silane as the precursor of the inorganic phase, the fluorosiloxane polymer solution and silane were co-hydrolyzed and polycondensed by the sol-gel method, and a molecular-level composite, respectively, was directly prepared in the presence of the same organic co-solvent. A new type of fluorosiloxane polymer material with a carbon-carbon chain and a silicon-oxygen network structure as a parallel double main chain structure, and a certain concentration of CF₃ groups introduced into the side chain, and a synthesis method thereof. The material prepared by the present invention not only absorbs the ultra-low surface energy characteristics of the_CF3 group, but also combines with the base material in a covalent bond, which has good bonding strength. At the same time, the construction of the inorganic silicon network structure improves the hybrid material Excellent coating thickness and durability can greatly expand the application field of fluorosilicone polymer materials.

Description

Translated fromChinese

含双平行主链结构低表面能氟硅氧烷低聚物及其合成方法Low surface energy fluorosiloxane oligomer containing double parallel main chain structure and its synthesis method

技术领域technical field

本发明属于功能性材料技术领域，涉及新的聚合组合物及该聚合物的合成方法。特别涉及一种分子级复合、分别以碳碳链和硅氧网络结构为并行双主链结构、侧链引入一定浓度的CF₃基团的高耐久性低表面能氟硅氧烷低聚物材料。The invention belongs to the technical field of functional materials, and relates to a new polymer composition and a synthesis method of the polymer. In particular, it relates to a molecular-level composite, a carbon-carbon chain and a silicon-oxygen network structure as a parallel double main chain structure, and a high-durability low-surface-energy fluorosiloxane oligomer material with a certain concentration of_CF3 groups introduced into the side chain .

背景技术Background technique

低表面自由能材料具有许多独特的性能，在印刷、不粘锅、汽车玻璃、纺织以及防污垢等方面得到了广泛的应用。材料的表面自由能取决于材料表面最外层的化学组成，最外层化学组成为紧密有序排列的CF₃的固体表面具有最低的表面自由能。含氟材料一般为长链碳氟化合物，碳氟键的键能较大，比较稳定，氟原子不但与碳原子结合牢固，而且在碳骨架外层排列十分紧密，有效地防止了碳原子和碳链的暴露，故碳氟化合物表现出卓越的低表面能、化学稳定性、耐候性、耐腐蚀性、抗氧化性等性能。但由于本身热塑性有限，在照顾玻璃化温度的同时易造成耐污性变差；而且它的线性分子上缺少交联点，难以形成三维交联网状涂膜，低温时易龟裂、粉化，而且耐刮伤性、硬度低。要想拓宽碳氟化合物的应用领域和综合性能，必须根据需要对其进行改性。Low surface free energy materials have many unique properties and have been widely used in printing, non-stick pans, automotive glass, textiles, and anti-fouling. The surface free energy of the material depends on the chemical composition of the outermost layer of the material surface, and the solid surface with the outermost chemical composition of CF₃ arranged in close order has the lowest surface free energy. Fluorine-containing materials are generally long-chain fluorocarbons. The bond energy of the carbon-fluorine bond is relatively large and relatively stable. The fluorine atoms are not only firmly bonded to the carbon atoms, but also arranged very closely on the outer layer of the carbon skeleton, effectively preventing the carbon atoms and carbon Chain exposure, so fluorocarbons exhibit excellent low surface energy, chemical stability, weather resistance, corrosion resistance, oxidation resistance and other properties. However, due to its limited thermoplasticity, it is easy to cause poor stain resistance while taking care of the glass transition temperature; and its linear molecules lack cross-linking points, making it difficult to form a three-dimensional cross-network coating film, and it is easy to crack and pulverize at low temperatures. Moreover, it has low scratch resistance and low hardness. In order to broaden the application fields and comprehensive properties of fluorocarbons, they must be modified as required.

目前报道的相关氟硅氧烷聚合物材料以硅氧链为主链，在侧链中引入一定浓度的CF₃基团，该基团由于其极大的表面活性将严格取向于表面，整个大分子既保持了线形聚硅氧烷的高弹性及高流动性，又吸收了CF₃基团的超低表面能特性，同时，通过共价键与基底材料结合，杂化材料具有很好的结合力。其结合了有机硅与有机氟聚合物的优点，成为聚合物材料领域的一个新热点，目前在织物、纸张、皮革整理剂，涂料，脱模剂及润滑剂等方面都有广泛的应用前景。参见中国专利申请号97106780.5、00108172.1、02124034.5、200510101356.5、200610122270.5、美国专利号US6265515B1等。The related fluorosiloxane polymer materials reported so far have a silicon chain as the main chain, and a certain concentration of CF₃ groups are introduced into the side chains. Due to their great surface activity, the groups will be strictly oriented on the surface, and the entire large The molecule not only maintains the high elasticity and high fluidity of linear polysiloxane, but also absorbs the ultra-low surface energy characteristics of CF₃ groups. At the same time, it combines with the base material through covalent bonds, and the hybrid material has a good combination force. It combines the advantages of organosilicon and organic fluoropolymers, and has become a new hot spot in the field of polymer materials. At present, it has broad application prospects in fabrics, paper, leather finishing agents, coatings, release agents and lubricants. See Chinese patent application numbers 97106780.5, 00108172.1, 02124034.5, 200510101356.5, 200610122270.5, US patent number US6265515B1, etc.

合成氟硅聚合物的常用含氟单体主要有(甲基)丙烯酸氟烷基酯类、氟烷基乙烯基醚类和氟烯烃等单体。含硅化合物主要有含硅烷基丙烯酸酯类、乙烯基硅烷类、环硅氧烷类等单体。合成工艺一般通过自由基聚合，采用乳液聚合、溶液聚合、本体聚合等传统聚合方法实施，可以达到引入碳氟键(C-F)不多却具较好性能的目的。所用引发剂大多数是水溶性引发剂，如过硫酸铵((NH₃)₂S₂O₈)、过硫酸钾(K₂S₂O₈)、过硫酸钠(Na₂S₂O₈)和过硫酸钠-亚硫酸氢钠(Na₂S₂O₈-NaHSO₃)；也可用油溶性引发剂，如偶氮二异丁腈(AIBN)、过氧化二苯甲酰(BPO)；或用偶氮大分子作为引发剂。Commonly used fluorine-containing monomers for the synthesis of fluorosilicon polymers mainly include fluoroalkyl (meth)acrylates, fluoroalkyl vinyl ethers, and fluoroolefins. Silicon-containing compounds mainly include monomers such as silyl-containing acrylates, vinyl silanes, and cyclosiloxanes. The synthesis process is generally carried out by free radical polymerization, using traditional polymerization methods such as emulsion polymerization, solution polymerization, and bulk polymerization, which can achieve the purpose of introducing few carbon-fluorine bonds (CF) but having better performance. Most of the initiators used are water-soluble initiators, such as ammonium persulfate ((NH₃ )₂ S₂ O₈ ), potassium persulfate (K₂ S₂ O₈ ), sodium persulfate (Na₂ S₂ O₈ ) And sodium persulfate-sodium bisulfite (Na₂ S₂ O₈ -NaHSO₃ ); oil-soluble initiators such as azobisisobutyronitrile (AIBN), dibenzoyl peroxide (BPO) can also be used; or Azo macromolecules are used as initiators.

但是上述的氟烷基硅烷低表面能材料以单层硅氧链为主链，在侧链中引入一定浓度的CF₃基团，其形成的杂化材料涂敷厚度较薄，耐久性能差。同时，由于含氟侧链与分子中其它的基团具有不相容性，导致含有全氟烷基侧链的化合物能够自发地形成层状结构。多次涂敷后其结合力较差，易分层、龟裂，无法通过多次涂敷提高其厚度及耐久性。耐久性能差的问题限制了其在一些特殊环境下应用。通过合适的工艺提高氟硅氧烷聚合物材料的耐久性能，可以极大的提高其综合性能和促进氟硅氧烷聚合物材料在多领域的实际应用，如大型桥梁和高层建筑防腐、海军舰船防污、防雾汽车玻璃、织物和皮革的整理剂等。However, the above-mentioned fluoroalkylsilane low surface energy materials have a single-layer silicon-oxygen chain as the main chain, and a certain concentration of_CF3 groups are introduced into the side chains. The resulting hybrid material has a thin coating thickness and poor durability. At the same time, due to the incompatibility of fluorine-containing side chains with other groups in the molecule, compounds containing perfluoroalkyl side chains can spontaneously form a layered structure. After multiple coatings, its bonding force is poor, and it is easy to delaminate and crack, and its thickness and durability cannot be improved through multiple coatings. The problem of poor durability limits its application in some special environments. Improving the durability of fluorosilicone polymer materials through a suitable process can greatly improve its comprehensive performance and promote the practical application of fluorosilicone polymer materials in many fields, such as large bridges and high-rise building anticorrosion, naval ships Boat anti-fouling, anti-fog automotive glass, finishing agent for fabric and leather, etc.

发明内容Contents of the invention

本发明目的是提供一种对各种基材有优异的结合力、涂敷厚度厚、耐久性能强、表面修饰以含氟侧链的低表面能氟硅氧烷聚合物材料。The purpose of the present invention is to provide a low surface energy fluorosiloxane polymer material with excellent binding force to various substrates, thick coating thickness, strong durability, and surface modification with fluorine-containing side chains.

本发明的另一个目的是提供上述氟硅氧烷聚合物材料的合成方法。该方法一步完成、产物为分子间复合、工艺简单、产物不需要提纯、加水或有机溶剂稀释到需要浓度可直接使用。Another object of the present invention is to provide a method for synthesizing the above-mentioned fluorosilicone polymer material. The method is completed in one step, the product is intermolecular complex, the process is simple, the product does not need to be purified, and can be directly used after adding water or an organic solvent to dilute to the required concentration.

本发明的技术方案如下：Technical scheme of the present invention is as follows:

本发明提供的上述氟硅氧烷聚合物乳液的合成方法为自由基乳液聚合和溶胶-凝胶法复合。采用甲基丙烯酸含氟烷基酯或丙烯酸含氟烷基酯和乙烯基硅烷自由基乳液聚合合成了氟硅氧烷共聚物，再采用硅烷为无机相前驱体，通过溶胶-凝胶法将氟硅氧烷聚合物溶液和硅烷共水解和缩聚直接制备了一种分子级复合、分别以碳碳链和硅氧网络结构为并行双主链结构、侧链引入一定浓度的CF₃基团的氟硅氧烷聚合物乳液材料。The synthesis method of the above-mentioned fluorosilicone polymer emulsion provided by the present invention is free radical emulsion polymerization and sol-gel compounding. Fluorosiloxane copolymers were synthesized by free radical emulsion polymerization of fluorine-containing alkyl methacrylate or fluorine-containing alkyl acrylate and vinyl silane, and then silane was used as the precursor of the inorganic phase, and fluorine was synthesized by sol-gel method. Cohydrolysis and polycondensation of siloxane polymer solution and silane directly prepared a molecular-level compound, with carbon-carbon chain and silicon-oxygen network structure as parallel double main chain structure, and a certain concentration of CF₃ groups introduced into the side chain of fluorine Silicone polymer emulsion material.

本发明的合成方法包括以下步骤：Synthetic method of the present invention comprises the following steps:

a)采用自由基溶液共聚制备氟硅氧烷共聚物，其中含氟单体为含有甲基丙烯酸含氟烷基酯或丙烯酸含氟烷基酯，含硅氧烷单体为乙烯基硅氧烷，其基本结构式为：a) Preparation of fluorosilicone copolymer by free radical solution copolymerization, wherein the fluorine-containing monomer contains fluorine-containing alkyl methacrylate or fluorine-containing alkyl acrylate, and the siloxane-containing monomer is vinyl siloxane , its basic structure is:

其中，in,

m，n＞1；m,n>1;

R为H或CH₃；R is H or_CH3 ;

Rf为C_1-12烷基中的氢原子被氟原子部分或全部置换的多氟烷基；Rf is a polyfluoroalkyl group in which the hydrogen atoms in the_C1-12 alkyl group are partially or fully replaced by fluorine atoms;

D为CH₃或C₂H₅D is CH₃ or C₂ H₅

b)采用溶胶-凝胶工艺将上述氟硅氧烷共聚物溶液与无机硅前驱体共水解缩聚制备底层为硅网络结构的氟硅氧烷低聚物，其基本结构式为：b) Using the sol-gel process to co-hydrolyze and polycondense the above-mentioned fluorosilicone copolymer solution and the inorganic silicon precursor to prepare a fluorosilicone oligomer with a silicon network structure as the bottom layer, the basic structural formula of which is:

Rf为C_1-12烷基中的氢原子被氟原子部分或全部置换的多氟烷基；Rf is a polyfluoroalkyl group in which the hydrogen atoms in the_C1-12 alkyl group are partially or fully replaced by fluorine atoms;

R为H或CH₃；R is H or_CH3 ;

m，n＞1；m,n>1;

x≥1x≥1

具体合成工艺是，首先将甲基丙烯酸含氟烷基酯或丙烯酸含氟烷基酯和乙烯基硅氧烷溶于有机共溶剂中，缓慢滴加引发剂在带冷却回流装置的三口烧瓶中，恒温60℃强力搅拌聚合反应3小时，形成氟烷基硅烷聚合溶液。再加入无机硅前驱体、H₂O及适量酸调节pH在3.5左右，持续搅拌水解反应4小时，得到透明的氟硅氧烷杂化材料胶体溶液。具体反应过程如下所示。The specific synthesis process is as follows: first, dissolve fluorine-containing alkyl methacrylate or fluorine-containing alkyl acrylate and vinyl siloxane in an organic co-solvent, slowly add the initiator dropwise in a three-necked flask with a cooling reflux device, The polymerization reaction was vigorously stirred at a constant temperature of 60° C. for 3 hours to form a fluoroalkylsilane polymerization solution. Adding an inorganic silicon precursor, H₂ O and an appropriate amount of acid to adjust the pH to about 3.5, and continuing to stir for 4 hours for hydrolysis reaction to obtain a transparent fluorosilicone hybrid material colloidal solution. The specific reaction process is as follows.

其中，in,

m，n＞1；m,n>1;

x≥1；x≥1;

R为H或CH₃；R is H or_CH3 ;

D为CH₃或C₂H₅；D is_CH3 or_C2H5;

Rf为C_1-12烷基中的氢原子被氟原子部分或全部置换的多氟烷基；Rf is a polyfluoroalkyl group in which the hydrogen atoms in the_C1-12 alkyl group are partially or fully replaced by fluorine atoms;

A为具有至少一个碳原子的烷基或亚烷基；A is an alkyl or alkylene group having at least one carbon atom;

B为-O-Si-B is -O-Si-

各组份按摩尔比的投料量为：The charging amount of each component by molar ratio is:

有机共溶剂                                30.00～75.00Organic co-solvent 30.00～75.00

甲基丙烯酸含氟烷基酯或丙烯酸含氟烷基酯    0.5～2Fluorine-containing alkyl methacrylate or fluorine-containing alkyl acrylate 0.5～2

乙烯基硅氧烷                              0.5～2Vinyl siloxane 0.5～2

无机硅先驱液                              0.5～60Inorganic silicon precursor fluid 0.5～60

去离子水                                  1～120Deionized water 1～120

引发剂                                    0.005～0.01Initiator 0.005～0.01

催化剂                                    0.025～3Catalyst 0.025～3

在上述技术方案中，In the above technical scheme,

甲基丙烯酸含氟烷基酯或丙烯酸含氟烷基酯是如下通式：Fluorine-containing alkyl methacrylate or fluorine-containing alkyl acrylate has the following general formula:

式中：In the formula:

R＝H或CH₃；R=H or_CH3 ;

Rf为C_1-12烷基中的氢原子被氟原子部分或全部置换的多氟烷基。Rf is a polyfluoroalkyl group in which the hydrogen atoms in the_C1-12 alkyl group are partially or completely replaced by fluorine atoms.

乙烯基硅氧烷是指常用的乙烯基硅烷偶联剂，如CH₂＝CHSi(OCH₃)₃，CH₂＝C(CH₃)Si(OCH₃)₃，CH₂＝CHSi(OC₂H₅)₃等。Vinyl siloxane refers to commonly used vinyl silane coupling agents, such as CH₂ =CHSi(OCH₃ )₃ , CH₂ =C(CH₃ )Si(OCH₃ )₃ , CH₂ =CHSi(OC₂ H₅ )₃ etc.

无机硅先驱液是指正硅酸乙酯(Si(OC₂H₅)₄，TEOS)或正硅酸甲酯(Si(OCH₃)₄，TMOS)。The inorganic silicon precursor refers to ethyl orthosilicate (Si(OC₂ H₅ )₄ , TEOS) or methyl orthosilicate (Si(OCH₃ )₄ , TMOS).

引发剂为水溶性过硫酸盐，如K₂S₂O₈ Na₂S₂O₈(NH₄)₂S₂O₈等；或偶氮类引发剂，如AIBN等；或有机过氧类引发剂，如BPO等。The initiator is a water-soluble persulfate, such as K₂ S₂ O₈ Na₂ S₂ O₈ (NH₄ )₂ S₂ O₈ , etc.; or an azo initiator, such as AIBN; or an organic peroxy initiator agents, such as BPO, etc.

有机共溶剂没有特殊限制，如苯、甲苯、二甲苯等芳香烃类；四氢呋喃、醋酸乙酯、乙醇、丁醇、三氯乙烯或甲基乙基酮等。Organic co-solvents are not particularly limited, such as aromatic hydrocarbons such as benzene, toluene, and xylene; tetrahydrofuran, ethyl acetate, ethanol, butanol, trichloroethylene, or methyl ethyl ketone, etc.

水解催化剂为醋酸、盐酸或硝酸等酸性催化剂。The hydrolysis catalyst is an acidic catalyst such as acetic acid, hydrochloric acid or nitric acid.

本发明的效果和益处是通过自由基溶液聚合和溶胶一凝胶法复合采用同一种有机共溶剂直接制备了一种分子级复合、分别以碳碳链和硅氧网络结构为并行双主链结构、侧链引入一定浓度的CF₃基团的氟硅氧烷聚合物材料。合成的氟硅氧烷聚合物材料既吸收了CF₃基团的超低表面能特性，又与基底材料以共价键方式结合，有很好的结合强度，同时通过底层无机硅网络结构的构建提高了杂化材料的涂敷厚度及耐久性，可以极大的扩展氟硅氧烷聚合物材料的应用领域。The effect and benefit of the present invention is that a molecular-level compound is directly prepared by using the same organic co-solvent through radical solution polymerization and sol-gel compounding, with carbon-carbon chains and silicon-oxygen network structures as parallel double main chain structures. 1. Fluorosilicone polymer material with a certain concentration of CF₃ groups introduced into the side chain. The synthesized fluorosiloxane polymer material not only absorbs the ultra-low surface energy characteristics of the CF₃ group, but also combines with the substrate material in a covalent bond, which has good bonding strength. At the same time, through the construction of the underlying inorganic silicon network structure The coating thickness and durability of the hybrid material are improved, and the application field of the fluorosiloxane polymer material can be greatly expanded.

本发明合成工艺一步完成，产物为分子间复合，工艺简单，产物不需要提纯，可直接使用。The synthesis process of the invention is completed in one step, the product is intermolecular compound, the process is simple, the product does not need to be purified, and can be used directly.

具体实施方式Detailed ways

下面列举部分具体实施例对本发明进行说明，有必要在此指出下述实施例仅用来进一步说明本发明，而不是将本发明具体限制在实施例所说明的方式和应用领域。相关领域的技术人员会理解包括本发明实施例内容及以外不背离本发明实质和范围的修改和完善。Some specific examples are listed below to illustrate the present invention. It is necessary to point out that the following examples are only used to further illustrate the present invention, rather than to limit the present invention specifically to the methods and application fields described in the examples. Those skilled in the relevant fields will understand the modifications and perfections including the contents of the embodiments of the present invention and other modifications that do not depart from the spirit and scope of the present invention.

实施例1：Example 1:

首先将甲基丙烯酸十二氟庚酯(FA)和乙烯基三乙氧基硅烷(VTES)溶于四氢呋喃(THF)溶剂中，缓慢滴加引发剂过氧化二苯甲酰(BPO)在带冷却回流装置的三口烧瓶中，恒温60℃强力搅拌聚合反应3小时，形成氟烷基硅烷聚合溶液。再加入正硅酸乙酯(TEOS)、H₂O及适量盐酸调节pH在3.5左右，持续搅拌水解反应4小时，得到透明的氟硅氧烷杂化材料胶体溶液。具体组成(摩尔比)为FA∶VTES∶THF∶BPO∶TEOS∶H₂O∶HCl＝1∶1∶60∶0.01∶1∶6∶0.05。聚合溶液的各项性能测定结果见表1。First, dodecafluoroheptyl methacrylate (FA) and vinyltriethoxysilane (VTES) were dissolved in tetrahydrofuran (THF) solvent, and the initiator dibenzoyl peroxide (BPO) was slowly added dropwise in the belt cooling In the three-necked flask of the reflux device, the polymerization reaction was vigorously stirred at a constant temperature of 60° C. for 3 hours to form a fluoroalkylsilane polymerization solution. Then, tetraethyl orthosilicate (TEOS), H₂ O and appropriate amount of hydrochloric acid were added to adjust the pH to about 3.5, and the hydrolysis reaction was continuously stirred for 4 hours to obtain a transparent fluorosilicone hybrid material colloidal solution. The specific composition (molar ratio) is FA:VTES:THF:BPO:TEOS:H₂ O:HCl=1:1:60:0.01:1:6:0.05. The performance measurement results of the polymerization solution are shown in Table 1.

实施例2：Example 2:

首先将甲基丙烯酸十二氟庚酯(FA)和乙烯基三乙氧基硅烷(VTES)溶于乙醇(ETOH)溶剂中，缓慢滴加引发剂过氧化二苯甲酰(BPO)在带冷却回流装置的三口烧瓶中，恒温60℃强力搅拌聚合反应3小时，形成氟烷基硅烷聚合溶液。再加入正硅酸乙酯(TEOS)、H₂O及适量硝酸调节pH在3.5左右，持续搅拌水解反应4小时，得到透明的氟硅氧烷杂化材料胶体溶液。具体组成(摩尔比)为FA∶VTES∶ETOH∶BPO∶TEOS∶H₂O∶HNO₃＝1∶1∶60∶0.01∶1∶6∶0.05。聚合溶液的各项性能测定结果见表1。First, dodecafluoroheptyl methacrylate (FA) and vinyltriethoxysilane (VTES) were dissolved in ethanol (ETOH) solvent, and the initiator dibenzoyl peroxide (BPO) was slowly added dropwise in the belt cooling In the three-necked flask of the reflux device, the polymerization reaction was vigorously stirred at a constant temperature of 60° C. for 3 hours to form a fluoroalkylsilane polymerization solution. Then, tetraethyl orthosilicate (TEOS), H₂ O and an appropriate amount of nitric acid were added to adjust the pH to about 3.5, and the hydrolysis reaction was continuously stirred for 4 hours to obtain a transparent fluorosilicone hybrid material colloidal solution. The specific composition (molar ratio) is FA:VTES:ETOH:BPO:TEOS_{:H 2} O:HNO₃ =1:1:60:0.01:1:6:0.05. The performance measurement results of the polymerization solution are shown in Table 1.

实施例3：Example 3:

首先将甲基丙烯酸十二氟庚酯(FA)和乙烯基三乙氧基硅烷(VTES)溶于正丁醇(Butanol)溶剂中，缓慢滴加引发剂过硫酸钾(K₂S₂O₈)在带冷却回流装置的三口烧瓶中，恒温60℃强力搅拌聚合反应3小时，形成氟烷基硅烷聚合溶液。再加入正硅酸乙酯(TEOS)、H₂O及适量盐酸调节pH在3.5左右，持续搅拌水解反应4小时，得到透明的氟硅氧烷杂化材料胶体溶液。具体组成(摩尔比)为FA∶VTES∶Butanol∶K₂S₂O₈∶TEOS∶H₂O∶HCl＝1∶1∶60∶0.01∶1∶6∶0.05。聚合溶液的各项性能测定结果见表1。First, dodecafluoroheptyl methacrylate (FA) and vinyltriethoxysilane (VTES) were dissolved in n-butanol (Butanol) solvent, and the initiator potassium persulfate (K₂ S₂ O₈ ) In a three-necked flask with a cooling reflux device, the polymerization reaction was vigorously stirred at a constant temperature of 60° C. for 3 hours to form a fluoroalkylsilane polymerization solution. Then, tetraethyl orthosilicate (TEOS), H₂ O and appropriate amount of hydrochloric acid were added to adjust the pH to about 3.5, and the hydrolysis reaction was continuously stirred for 4 hours to obtain a transparent fluorosilicone hybrid material colloidal solution. The specific composition (molar ratio) is FA:VTES:Butanol:_{K 2} S₂ O₈ :TEOS:H₂ O:HCl=1:1:60:0.01:1:6:0.05. The performance measurement results of the polymerization solution are shown in Table 1.

实施例4：Example 4:

首先将甲基丙烯酸十二氟庚酯(FA)和乙烯基三甲氧基硅烷(VTMS)溶于四氢呋喃(THF)溶剂中，缓慢滴加引发剂过氧化二苯甲酰(BPO)在带冷却回流装置的三口烧瓶中，恒温60℃强力搅拌聚合反应3小时，形成氟烷基硅烷聚合溶液。再加入正硅酸乙酯(TMOS)、H₂O及适量盐酸调节pH在3.5左右，持续搅拌水解反应4小时，得到透明的氟硅氧烷杂化材料胶体溶液。具体组成(摩尔比)为FA∶VTMS∶THF∶BPO∶TMOS∶H₂O∶HCl＝1∶1∶60∶0.01∶1∶6∶0.05。聚合溶液的各项性能测定结果见表1。First, dodecafluoroheptyl methacrylate (FA) and vinyltrimethoxysilane (VTMS) were dissolved in tetrahydrofuran (THF) solvent, and the initiator dibenzoyl peroxide (BPO) was slowly added dropwise at reflux with cooling. In the three-necked flask of the device, the polymerization reaction was vigorously stirred at a constant temperature of 60° C. for 3 hours to form a fluoroalkylsilane polymerization solution. Tetraethyl silicate (TMOS), H₂ O and an appropriate amount of hydrochloric acid were added to adjust the pH to about 3.5, and the hydrolysis reaction was continuously stirred for 4 hours to obtain a transparent fluorosilicone hybrid material colloidal solution. The specific composition (molar ratio) is FA:VTMS:THF:BPO:TMOS:H₂ O:HCl=1:1:60:0.01:1:6:0.05. The performance measurement results of the polymerization solution are shown in Table 1.

实施例5：Example 5:

首先将甲基丙烯酸十二氟庚酯(FA)和乙烯基三乙氧基硅烷(VTES)溶于四氢呋喃(THF)溶剂中，缓慢滴加引发剂过氧化二苯甲酰(BPO)在带冷却回流装置的三口烧瓶中，恒温60℃强力搅拌聚合反应3小时，形成氟烷基硅烷聚合溶液。再加入正硅酸乙酯(TEOS)、H₂O及适量盐酸调节pH在3.5左右，持续搅拌水解反应4小时，得到透明的氟硅氧烷杂化材料胶体溶液。具体组成(摩尔比)为FA∶VTES∶THF∶BPO∶TEOS∶H₂O∶HCl＝1∶1∶60∶0.01∶4∶12∶0.1。聚合溶液的各项性能测定结果见表1。First, dodecafluoroheptyl methacrylate (FA) and vinyltriethoxysilane (VTES) were dissolved in tetrahydrofuran (THF) solvent, and the initiator dibenzoyl peroxide (BPO) was slowly added dropwise in the belt cooling In the three-necked flask of the reflux device, the polymerization reaction was vigorously stirred at a constant temperature of 60° C. for 3 hours to form a fluoroalkylsilane polymerization solution. Then, tetraethyl orthosilicate (TEOS), H₂ O and appropriate amount of hydrochloric acid were added to adjust the pH to about 3.5, and the hydrolysis reaction was continuously stirred for 4 hours to obtain a transparent fluorosilicone hybrid material colloidal solution. The specific composition (molar ratio) is FA:VTES:THF:BPO:TEOS:H₂ O:HCl=1:1:60:0.01:4:12:0.1. The performance measurement results of the polymerization solution are shown in Table 1.

实施例6：Embodiment 6:

首先将甲基丙烯酸十二氟庚酯(FA)和乙烯基三乙氧基硅烷(VTES)溶于四氢呋喃(THF)溶剂中，缓慢滴加引发剂过氧化二苯甲酰(BPO)在带冷却回流装置的三口烧瓶中，恒温60℃强力搅拌聚合反应3小时，形成氟烷基硅烷聚合溶液。再加入正硅酸乙酯(TEOS)、H₂O及适量盐酸调节pH在3.5左右，持续搅拌水解反应4小时，得到透明的氟硅氧烷杂化材料胶体溶液。具体组成(摩尔比)为FA∶VTES∶THF∶BPO∶TEOS∶H₂O∶HCl＝1∶1∶60∶0.01∶12∶72∶0.6。聚合溶液的各项性能测定结果见表1。First, dodecafluoroheptyl methacrylate (FA) and vinyltriethoxysilane (VTES) were dissolved in tetrahydrofuran (THF) solvent, and the initiator dibenzoyl peroxide (BPO) was slowly added dropwise in the belt cooling In the three-necked flask of the reflux device, the polymerization reaction was vigorously stirred at a constant temperature of 60° C. for 3 hours to form a fluoroalkylsilane polymerization solution. Then, tetraethyl orthosilicate (TEOS), H₂ O and appropriate amount of hydrochloric acid were added to adjust the pH to about 3.5, and the hydrolysis reaction was continuously stirred for 4 hours to obtain a transparent fluorosilicone hybrid material colloidal solution. The specific composition (molar ratio) is FA:VTES:THF:BPO:TEOS:H₂ O:HCl=1:1:60:0.01:12:72:0.6. The performance measurement results of the polymerization solution are shown in Table 1.

实施例7：Embodiment 7:

实施例1～6聚合物溶液制备的低表面能涂层的物理性能。Examples 1-6 Physical properties of low surface energy coatings prepared from polymer solutions.

将所得实施例1～6聚合物溶液采用拉膜法在抛光如镜面并超声波清洗后的铝合金表面涂覆氟硅氧烷聚合物涂层。首先将铝基底材料浸泡在结果溶液中10分钟，再以10cm/min的速率拉膜。将涂有涂层的铝金属片在室温下风干，然后再在烘箱中以0.25℃/min的升温速率升温到140℃干燥固化处理。以上涂敷步骤分别重复五次。耐腐蚀性能采用动电位阳极极化曲线测定，用Tafel法计算腐蚀电流I_corr、腐蚀速率V_corr并根据金属耐蚀性通用十级标准评定耐蚀等级。The obtained polymer solutions of Examples 1-6 were coated with a fluorosiloxane polymer coating on the surface of the aluminum alloy after polishing such as a mirror surface and ultrasonic cleaning by using the film drawing method. First, the aluminum base material was soaked in the resulting solution for 10 minutes, and then the film was pulled at a rate of 10 cm/min. The coated aluminum metal sheet was air-dried at room temperature, and then dried and cured in an oven at a rate of 0.25°C/min to 140°C. The above coating steps were repeated five times respectively. Corrosion resistance is measured by potentiodynamic anodic polarization curve, and the corrosion current I_corr and corrosion rate V_corr are calculated by Tafel method, and the corrosion resistance grade is evaluated according to the general ten-grade standard for metal corrosion resistance.

表1实施例1～6所得聚合物溶液特性Table 1 embodiment 1～6 gained polymer solution characteristic

  特性characteristics    实施例Example  1 1  2 2  33  44  55  66  黏度(cp)Viscosity (cp)  0.70.7  1.551.55  2.652.65  0.670.67  0.840.84  1.111.11  分子量molecular weight  76597659  79817981  65376537  71237123  95249524  1122511225  溶液表观solution appearance  澄清clarify  澄清clarify  微浑浊slightly turbid  澄清clarify  澄清clarify  澄清clarify

表2实施例1～6涂敷后各项性能测定结果Table 2 Example 1～6 performance measurement results after coating

特性characteristic    实施例Example  1 1  2 2  33  44  55  66涂层外观Coating Appearance  光滑无缺陷smooth and flawless  光滑无缺陷smooth and flawless  光滑无缺陷smooth and flawless  光滑无缺陷smooth and flawless  光滑无缺陷smooth and flawless  光滑无缺陷smooth and flawless耐蚀等级Corrosion resistance grade  一级，完全耐蚀Level 1, fully corrosion-resistant  一级，完全耐蚀Level 1, fully corrosion-resistant  一级，完全耐蚀Level 1, fully corrosion-resistant  一级，完全耐蚀Level 1, fully corrosion-resistant  一级，完全耐蚀Level 1, fully corrosion-resistant  一级，完全耐蚀Level 1, fully corrosion-resistant单位面积增重(mg/cm²)Weight gain per unit area (mg/cm² )  0.35830.3583  0.52250.5225  0.34010.3401  0.35120.3512  0.71870.7187  0.88370.8837表面能(mJ/m²)Surface energy (mJ/m² )  12.0112.01  12.7312.73  13.6413.64  12.1112.11  15.8415.84  17.5617.56

Claims (9)

Translated fromChinese

1.含双平行主链结构低表面能氟硅氧烷低聚物及其合成方法，其特征在于一种分子级复合、分别以碳碳链和硅氧网络结构为并行双主链结构、侧链引入一定浓度的CF₃基团的低表面能氟硅氧烷低聚物材料的制备方法，该方法包括以下步骤：1. A low surface energy fluorosiloxane oligomer containing a double parallel main chain structure and a synthesis method thereof, characterized in that it is a molecular-level composite, with a carbon-carbon chain and a silicon-oxygen network structure as a parallel double main chain structure, side A method for preparing a low surface energy fluorosiloxane oligomer material with a certain concentration of CF_groups introduced into the chain, the method comprising the following steps:a)采用自由基溶液共聚制备氟硅氧烷共聚物，其中含氟单体为含有甲基丙烯酸含氟烷基酯或丙烯酸含氟烷基酯，含硅氧烷单体为乙烯基硅氧烷，其基本结构式为：a) Preparation of fluorosilicone copolymer by free radical solution copolymerization, wherein the fluorine-containing monomer contains fluorine-containing alkyl methacrylate or fluorine-containing alkyl acrylate, and the siloxane-containing monomer is vinyl siloxane , its basic structure is:

其中，in,m，n＞1；m,n>1;R为H或CH₃；R is H or_CH3 ;Rf为C_1-12烷基中的氢原子被氟原子部分或全部置换的多氟烷基；Rf is a polyfluoroalkyl group in which the hydrogen atoms in the_C1-12 alkyl group are partially or fully replaced by fluorine atoms;D为CH₃或C₂H₅D is CH₃ or C₂ H₅b)采用溶胶-凝胶工艺将上述氟硅氧烷共聚物溶液与无机硅前驱体共水解缩聚制备底层为硅网络结构的氟硅氧烷低聚物，其基本结构式为：b) Using the sol-gel process to co-hydrolyze and polycondense the above-mentioned fluorosilicone copolymer solution and the inorganic silicon precursor to prepare a fluorosilicone oligomer with a silicon network structure as the bottom layer, the basic structural formula of which is:Rf为C_1-12烷基中的氢原子被氟原子部分或全部置换的多氟烷基；Rf is a polyfluoroalkyl group in which the hydrogen atoms in the_C1-12 alkyl group are partially or fully replaced by fluorine atoms;R为H或CH₃；R is H or_CH3 ;m，n＞1；m,n>1;x≥1x≥12.按照权利要求1所述的方法，其特征在于：所述的甲基丙烯酸含氟烷基酯或丙烯酸含氟烷基酯通式如下：2. according to the described method of claim 1, it is characterized in that: described fluorine-containing alkyl methacrylate or fluorine-containing alkyl acrylate general formula is as follows:

式中In the formulaR＝H或CH₃；R=H or_CH3 ;Rf为C_1-12烷基中的氢原子被氟原子部分或全部置换的多氟烷基。Rf is a polyfluoroalkyl group in which the hydrogen atoms in the_C1-12 alkyl group are partially or completely replaced by fluorine atoms.3.按照权利要求1所述的方法，其特征在于：所述的乙烯基硅氧烷是指乙烯基硅烷偶联剂，如CH₂＝CHSi(OCH₃)₃，CH₂＝CHSi(OC₂H₅)₃等。3. The method according to claim 1, characterized in that: said vinyl siloxane refers to a vinyl silane coupling agent, such as CH₂ =CHSi(OCH₃ )₃ , CH₂ =CHSi(OC₂ H₅ )₃ etc.4.按照权利要求1所述的方法，其特征在于：所述的无机硅前驱体是指正硅酸乙酯或正硅酸甲酯。4. The method according to claim 1, wherein the inorganic silicon precursor refers to ethyl orthosilicate or methyl orthosilicate.5.按照权利要求1所述的方法，其特征在于：所述的引发剂为水溶性过硫酸盐，如K₂S₂O₈、Na₂S₂O₈、或(NH₄)₂S₂O₈等；或偶氮类引发剂，如AIBN等；或有机过氧类引发剂，如BPO等。5. The method according to claim 1, characterized in that: the initiator is a water-soluble persulfate, such as K₂ S₂ O₈ , Na₂ S₂ O₈ , or (NH₄ )₂ S₂ O₈ , etc.; or azo initiators, such as AIBN, etc.; or organic peroxy initiators, such as BPO, etc.6.按照权利要求1所述的方法，其特征在于：所述的合成工艺中自由基溶液聚合和溶胶-凝胶法采用的有机溶剂为同一种溶剂；所述的有机共溶剂没有特殊限制，如苯、甲苯、二甲苯等芳香烃类；四氢呋喃、醋酸乙酯、乙醇、丁醇、三氯乙烯或甲基乙基酮等。6. according to the described method of claim 1, it is characterized in that: the organic solvent that free radical solution polymerization and sol-gel method adopts in the described synthetic technique is the same solvent; Described organic co-solvent has no special restriction, Such as benzene, toluene, xylene and other aromatic hydrocarbons; tetrahydrofuran, ethyl acetate, ethanol, butanol, trichloroethylene or methyl ethyl ketone, etc.7.按照权利要求1所述的方法，其特征在于：所述的水解催化剂为醋酸、盐酸或硝酸等酸性催化剂。7. according to the described method of claim 1, it is characterized in that: described hydrolysis catalyst is acidic catalysts such as acetic acid, hydrochloric acid or nitric acid.8.按照权利要求1所述的方法，其特征在于：所述的合成方法为自由基溶液聚合和溶胶凝胶法复合。8. The method according to claim 1, characterized in that: the synthesis method is free radical solution polymerization and sol-gel compounding.9.按照权利要求1所述的方法，其特征在于：所述的聚合物的结构特征为以碳碳链和硅氧网络结构为并行双主链结构、侧链引入一定浓度的CF₃基团。9. according to the described method of claim 1, it is characterized in that: the structural feature of described polymkeric substance is that take carbon-carbon chain and silicon-oxygen network structure as parallel double main chain structure, side chain introduces certain concentration_CF3 group .