WO2017066905A1 - 含氟(甲基)丙烯酸酯聚合物及其制备方法 - Google Patents

含氟(甲基)丙烯酸酯聚合物及其制备方法 Download PDF

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WO2017066905A1
WO2017066905A1 PCT/CN2015/092166 CN2015092166W WO2017066905A1 WO 2017066905 A1 WO2017066905 A1 WO 2017066905A1 CN 2015092166 W CN2015092166 W CN 2015092166W WO 2017066905 A1 WO2017066905 A1 WO 2017066905A1
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acrylate
meth
methacrylate
fluorine
mixture
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PCT/CN2015/092166
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English (en)
French (fr)
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郝健
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台州国汇新型材料有限公司
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Publication of WO2017066905A1 publication Critical patent/WO2017066905A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09J133/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate

Definitions

  • the present application belongs to the field of polymer materials, and relates to a fluorine-containing (meth) acrylate polymer and a preparation method thereof.
  • Synthetic adhesives can be roughly classified into epoxy adhesives, polyurethane adhesives, phenolic resin adhesives, acrylic adhesives, etc., which have their own advantages and disadvantages.
  • Epoxy adhesives are corrosion resistant and have good dielectric properties, strong adhesion, low shrinkage, and good compatibility with various organic and inorganic materials. However, when not toughened, the cured products are generally brittle. It is resistant to peeling, cracking and impact resistance. It has low adhesion to materials with low polarity. It must be surface-activated before use. Some raw materials have different degrees of toxicity and irritation.
  • Polyurethane adhesive has the advantages of soft hardness, low temperature resistance, good flexibility and high bonding strength. It can bond a variety of materials such as metal and non-metal. It is widely used, but it is easy to use in high temperature and high humidity environment. The hydrolysis is such that the adhesive strength is lowered, the curing speed is slow, the temperature and weather resistance are poor, and the adhesion to the metal is small.
  • Phenolic resin adhesive has high polarity, strong adhesive force, high rigidity, high heat resistance, good aging resistance, excellent insulation performance, easy modification, and can be modified, manufactured easily, and widely used.
  • the brittleness is large and the peeling strength is low; as time goes by, the color of the rubber layer is deeper and deeper, and it needs to be cured under high temperature and high pressure for a long time, and the shrinkage rate is large; the glue has certain toxicity, and the smell is large when solidified. It is easy to crack and the moisture content of the veneer is strict.
  • (Methyl) acrylate adhesive has light color, good water resistance, environmental corrosion resistance, good discoloration resistance, easy adjustment of performance, high bonding strength, high strength, impact resistance, easy to use, but its heat resistance and weather resistance Sexuality is not ideal.
  • Acrylic or methacrylic acid has certain corrosive problems. It is not suitable for most non-metallic materials such as plastic substrates. The working gap, air and other factors have a great influence on the curing, and the curing reaction is intense, which is not suitable for bonding and potting of large gaps. The packaging and storage requirements are relatively high, the monomer has a pungent odor and has certain toxicity.
  • the fluorine-containing (meth) acrylate adhesive of the invention can not only make up for most of the defects of the above adhesive, but also has more excellent water resistance, corrosion resistance, weather resistance, impact resistance, peel resistance, Performance such as stretchability. In addition, it has excellent flexibility, adjustable toughness, good transparency and a wide range of bonding (for metal and non-metal)
  • the metal has good bonding strength), has high bonding strength, and has strong adhesion to materials with low polarity (such as fluoroplastics), and the bonded surface does not need special treatment and has strong adaptability.
  • PTFE polytetrafluoroethylene materials are resistant to acids and alkalis and to various organic solvents, and are hardly soluble in all solvents.
  • PTFE also has the characteristics of high temperature resistance, and the friction coefficient is extremely low, so it can be used as a kind of easy-to-clean material.
  • the fatal disadvantage of PTFE is that it is difficult to bond.
  • the treatment methods for this problem are sodium-naphthalene complex chemical treatment, high-temperature melting method, radiation grafting method, low-temperature plasma technology, and laser treatment, but both More complicated.
  • the fluorine-containing (meth)acrylate adhesive of the present invention is excellent in performance, particularly excellent in weather resistance, and has been filled. The gap between the two areas.
  • a primary object of the present invention is to provide a fluorine-containing (meth) acrylate polymer which is adhesive to polytetrafluoroethylene.
  • Another object of the present invention is to provide a process for preparing a fluorine-containing (meth) acrylate polymer which is excellent in performance and specific in nature.
  • Still another object of the present invention is to provide an adhesive use of a fluorine-containing (meth) acrylate polymer in glass, plastic, ceramics, wood, rubber, textiles, leather, metal, building materials and the like.
  • the fluorine-containing (meth) acrylate polymer contains the structure shown in the following formula 1:
  • a, b, c, d, and e are integers of 0-40, respectively;
  • R F1 , R F2 , R F3 , R F4 may be -(CF 2 ) m -CFH 2 or -(CF 2 ) m -CF 2 H, respectively, wherein m and n are each an integer from 1 to 15; preferably An integer of 1-10;
  • R 1 , R 2 , R 3 , R 4 , R 5 may be H or methyl respectively;
  • R may be a C1-C20 alkyl group which is unsubstituted or substituted by a hydroxy group, a 3-7 membered heterocyclic group; a C3-C10 cycloalkyl group; a C5-C10 bridged ring group; a 3-7 membered heterocyclic group;
  • R may be a C1-C18 alkyl group; a hydroxy-substituted C1-C10 alkyl group; an isobornyl group; a glycidyl group;
  • the polymer has a number average molecular weight of 10,000 to 18,000.
  • the fluorine-containing (meth) acrylate polymer of the present invention can be obtained, for example, by a bulk polymerization method, but the invention is not limited thereto.
  • a fluorine-containing (meth) acrylate, a (meth) acrylate, a plasticizer, and an initiator are mixed under conditions and pre-polymerized for a while, and polymerization is continued to obtain a final product.
  • the preparation method of the fluorine-containing (meth) acrylate polymer is achieved by the following steps, by weight,
  • the obtained fluorine-containing (meth) acrylate polymer is cooled in a hose to obtain a fluorine-containing (meth) acrylate adhesive.
  • Adhesive solid When heated to soften, it is extrusion coated on the surface of the object to be bonded, and a little pressure is applied after bonding to make the adhesive fully contact with the surface. Maintain the pressure until the adhesive is cured for 3 hours to achieve the best results.
  • the fluorine-containing (meth) acrylate monomer is selected from the group consisting of trifluoroethyl acrylate, hexafluorobutyl acrylate, dodecafluoroheptyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, At least one of hexafluorobutyl methacrylate, octafluoropentyl methacrylate, decafluorohexyl methacrylate, and dodecafluoroheptyl methacrylate.
  • the (meth) acrylate monomer is selected from the group consisting of ethyl acrylate, isobornyl acrylate, glycidyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate. At least one of octadecyl methacrylate.
  • the initiator is at least one selected from the group consisting of lauroyl peroxide, methyl ethyl ketone peroxide, dibenzoyl peroxide, and azobisisoheptanenitrile.
  • the plasticizer is selected from the group consisting of butyl benzyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, di-n-octyl phthalate, diisononyl phthalate. At least one of them.
  • the invention fills the blank in the domestic market that no adhesive can bond polytetrafluoroethylene and polytetrafluoroethylene, polytetrafluoroethylene and metal, polytetrafluoroethylene and glass, and passes the experiment from the level of 100 grams. Enlarged to a ton of industrial scale, its technical parameters are stable.
  • the polymer according to the present invention has good adhesion to various materials such as glass, metal, ceramic, wood, plastic, etc., especially the fluorine-containing (meth) acrylate adhesive of the present invention.
  • Fluorine has good adhesion and excellent weather resistance, corrosion resistance, stain resistance, chemical resistance, hydrophobicity and insulation.
  • the fluorine-containing (meth) acrylate polymer of the present invention has the following characteristics as compared with the prior art materials:
  • the fluorine-containing (meth) acrylate polymer produced is a high-performance material with high adhesion, strong acid and alkali resistance, waterproof and antifouling.
  • the produced fluorine-containing (meth) acrylate polymer has adhesion to polytetrafluoroethylene.
  • the fluorine-containing (meth) acrylate polymer produced can bond special anti-interference materials with metal surfaces.
  • Examples 1-9 are exemplified by preparing a raw material input amount of 100 g of a fluorine-containing (meth) acrylate adhesive, and the raw and auxiliary materials are mixed in parts by weight, for example.
  • Liquid B after uniformly mixing, was heated to 120 ° C, reacted for 15 min, and then cooled to 80 ° C for 7 h to obtain a fluorine-containing (meth) acrylate adhesive having a structure represented by the following formula 1-1.
  • a, b, c, d, and e range from 4 to 20.
  • the product had a number average molecular weight of 15,000, a density of 1.53 g/cm 3 and a glass transition temperature of 84 °C.
  • a, b, and e range from 4 to 18.
  • the number average of the products was 12,000, the density was 1.32 g/cm 3 , and the glass transition temperature was 77 °C.
  • a, b, and e range from 7 to 25.
  • the product had a number average molecular weight of 14,000, a density of 1.48 g/cm 3 and a glass transition temperature of 82 °C.
  • a fluorine-containing (meth) acrylate adhesive having a structure represented by the following formula 4-1.
  • a, b, and e range from 8 to 30.
  • the product had a number average molecular weight of 13,000, a density of 1.29 g/cm 3 and a glass transition temperature of 79 °C.
  • a and e range from 8-35.
  • the product had a number average molecular weight of 13,000, a density of 1.59 g/cm 3 and a glass transition temperature of 80 °C.
  • a and e range from 12 to 35.
  • the product had a number average molecular weight of 12,500, a density of 1.53 g/cm 3 and a glass transition temperature of 79 °C.
  • a and e range from 10 to 30.
  • the product had a number average molecular weight of 1,1,500, a density of 1.47 g/cm 3 and a glass transition temperature of 76 ° C.
  • a and e range from 8-35.
  • the product had a number average molecular weight of 1,1,500, a density of 1.39 g/cm 3 and a glass transition temperature of 76 ° C.
  • a and e range from 8-30.
  • the product had a number average molecular weight of 11,000, a density of 1.62 g/cm 3 and a glass transition temperature of 76 °C.
  • a, b, and e range from 4 to 25.
  • the product had a number average molecular weight of 14,000, a density of 1.43 g/cm 3 and a glass transition temperature of 82 °C.
  • a, b, c, and e range from 7-14.
  • the product had a number average molecular weight of 15,000, a density of 1.54 g/cm 3 and a glass transition temperature of 85 °C.
  • a, b, c, and e range from 7 to 15.
  • the product had a number average molecular weight of 16,000, a density of 1.56 g/cm 3 and a glass transition temperature of 85 °C.
  • the properties of the fluorine-containing (meth) acrylate polymer prepared in Examples 1-12 were tested below.
  • the instruments used in the following tests are the universal material testing machines produced by Trusta Instruments (Shanghai) Co., Ltd., model XD-121.
  • the shear strength test is based on GB/T 7124-2008 and the carrier is stainless steel.
  • the peel strength test is based on GB/T 2790-1995 and the carrier is stainless steel-aluminum alloy.
  • Example 1 the overall performance of Example 1 is optimal, and the effects of the products produced by the examples 10, 11, and 12 are magnified. Stable quality, mature technology and easy production.
  • the fluorine-containing (meth) acrylate polymer of the present invention also has a good adhesive effect on polytetrafluoroethylene, and the test results are shown in Table 5.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明公开了一种包含如下式1所示结构的含氟(甲基)丙烯酸酯聚合物及其制备方法。所述含氟(甲基)丙烯酸酯聚合物是通过将含氟(甲基)丙烯酸酯和(甲基)丙烯酸酯在一定条件下聚合得到。本发明的聚合物对例如玻璃、金属、陶瓷、木材、塑料等材料均有较好的粘附力，尤其是对聚四氟乙烯有良好的胶粘作用。

Description

含氟(甲基)丙烯酸酯聚合物及其制备方法 技术领域
本申请属于高分子材料领域，涉及一种含氟(甲基)丙烯酸酯聚合物及其制备方法。
背景技术
在我们日常生活和工业生产中，经常会涉及到物体的粘接问题，我们所熟知的一些天然胶粘剂，如皮胶、骨胶、淀粉、糊精、松香、天然橡胶、沥青等。另一大类是合成胶粘剂。合成胶粘剂大体可分为环氧胶黏剂、聚氨酯胶黏剂、酚醛树脂胶黏剂、丙烯酸胶黏剂等等，它们有各自的优缺点。
环氧胶黏剂耐腐蚀并且介电性能好，粘附力强，收缩性低，与多种有机物、无机物有很好的相容性，但是在不增韧时，固化物一般偏脆，抗剥离、抗开裂、抗冲击性能差，对极性小的材料粘接力小，使用前必须进行表面活化处理，部分原料有不同程度的毒性和刺激性。
聚氨酯胶黏剂具有软硬度可调节、耐低温、柔韧性好、粘接强度大等优点,能粘接金属、非金属等多种材料，用途很广，但是它在高温高湿环境下易水解以致降低粘合强度，且固化速度慢，耐温耐候性差，对金属附着力小。
酚醛树脂胶黏剂极性大、粘接力强、刚性大，耐热性高、耐老化性能好，绝缘性能优良，本身易改性，也能够对其它进行改性，制造容易，应用广，但是脆性大、剥离强度低；随着时间推移，胶层颜色越来越深，且使用时需要高温高压下较长时间固化，收缩率较大；胶液有一定的毒性，固化时气味较大，易龟裂，单板含水率要求严格。
(甲基)丙烯酸酯类胶黏剂色泽清浅，耐水、耐环境侵蚀、抗变色性好，性能易于调节，粘接强度高，高强度、耐冲击，使用方便，但是它的耐热、耐候性还不够理想，丙烯酸或甲基丙烯酸对产品有一定的腐蚀性的问题，不适用于塑料基材等大部分非金属材料。工作的间隙、空气等因素对固化影响很大，固化反应放热激烈，不适合大间隙的粘接和灌封。包装和贮存要求比较高，单体具有刺激性气味以及具有一定的毒性。
本发明的含氟(甲基)丙烯酸酯胶黏剂不仅可以弥补上述胶黏剂的大部分缺陷，同时还具有更加优异的耐水性、耐腐蚀性、耐候性、耐冲击性、抗剥离性、可伸展性等性能。另外它还具备优异的柔韧特性，韧性可调节且透明性好，粘接范围广(对金属和非 金属具有较好的粘接强度)，粘结强度高，对极性小的材料(如氟塑料等)粘接力大，且被粘结表面不必要求特殊处理，适应性强。
众所周知，聚四氟乙烯材料具有抗酸抗碱、抗各种有机溶剂的特点，几乎不溶于所有的溶剂。同时，聚四氟乙烯还具有耐高温的特点，摩擦系数极低，所以可作润滑作用之余，亦是一种易清洁材料。但聚四氟乙烯的致命缺点是难以粘接，目前对于此问题的处理方法有钠—萘络合物化学处理、高温熔融法、辐射接枝法、低温等离子体技术、激光处理法，但是都较为复杂。另外，军工领域一直缺乏一种可以将特种抗干扰材料与金属表面粘接在一起的胶黏剂，而且在氟化工领域中，业内专家普遍认为以氟碳树脂掺杂在丙烯酸等树脂中能提高它的耐酸碱以及防水等机械性能，但是在加入这些材料后会降低它的粘结性能，虽也有少数企业尝试在粘结剂中掺杂微量的氟碳树脂，但效果甚微，而本发明反其道而行之，大量增加含氟树脂，取得了预料不到的成果，本发明的含氟(甲基)丙烯酸酯胶黏剂性能优异，特别是有极佳的耐候性，填补了该两个领域的空白。
发明内容
本发明的首要目的在于提供一种对聚四氟乙烯有胶粘作用的含氟(甲基)丙烯酸酯聚合物。
本发明的另一目的在于提供一种性能优异、性质特殊的含氟(甲基)丙烯酸酯聚合物的制备方法。
本发明的又一目的在于提供含氟(甲基)丙烯酸酯聚合物在玻璃、塑料、陶瓷、木材、橡胶、纺织品、皮革、金属、建筑材料等的胶黏用途。
本发明的目的通过以下技术方案实现：
含氟(甲基)丙烯酸酯聚合物包含如下式1所示的结构：
[式1]
Figure PCTCN2015092166-appb-000001
其中，a、b、c、d、e分别为0-40的整数；
RF1、RF2、RF3、RF4可分别为-(CF2)m-CFH2或-(CF2)m-CF2H，其中，m和n分别为1-15的整数；优选为1-10的整数；
R1、R2、R3、R4、R5可分别为H或甲基；
R可为未取代或由羟基、3-7元杂环基取代的C1-C20烷基；C3-C10环烷基；C5-C10桥环基；3-7元杂环基；
优选地，R可为C1-C18烷基；羟基取代的C1-C10烷基；异冰片基；环氧丙基；
所述聚合物的数均分子量为10000-18000。
可以使用例如本体聚合方法来得到本发明的含氟(甲基)丙烯酸酯聚合物，但本发明不限于此。例如，将含氟(甲基)丙烯酸酯、(甲基)丙烯酸酯、增塑剂、引发剂按条件混合后预聚合一段时间，再继续聚合，得到最终产品。
含氟(甲基)丙烯酸酯聚合物的制备方法，通过以下步骤实现，按重量份计，
先取引发剂共0.2-2份，并加入乙酸乙酯1.5-5份预混在一起，静止20-30min，得到混合液A；取增塑剂共5-15份，预混在一起，静止20-30min，得到混合液B；
将含氟(甲基)丙烯酸酯60-80份加入到反应容器中，加热至45-60℃，开启搅拌，升温至70-85℃时，向其中加入(甲基)丙烯酸酯2-15份，搅拌15-25min后，加入混合液A，继续搅拌4-8min后，加入混合液B，边搅拌边升温至90-125℃，反应15-60min；然后降温到70-85℃，反应5-8h，得到含氟(甲基)丙烯酸酯聚合物。
将得到的含氟(甲基)丙烯酸酯聚合物装入软管冷却得到含氟(甲基)丙烯酸酯胶 黏剂固体。使用时加热至软化后挤出涂覆于需要粘接物体的表面，粘合后施加少许压力使胶黏剂与表面充分接触。保持压力待胶黏剂固化3h后达到最佳效果。
所述含氟(甲基)丙烯酸酯单体为选自丙烯酸三氟乙酯、丙烯酸六氟丁酯、丙烯酸十二氟庚酯、甲基丙烯酸三氟乙酯、甲基丙烯酸四氟丙酯、甲基丙烯酸六氟丁酯、甲基丙烯酸八氟戊酯、甲基丙烯酸十氟己酯、甲基丙烯酸十二氟庚酯中的至少一种。
所述(甲基)丙烯酸酯单体为选自丙烯酸乙酯、丙烯酸异冰片酯、甲基丙烯酸环氧丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟丁酯、甲基丙烯酸十八烷基酯中的至少一种。
所述引发剂为选自过氧化月桂酰、过氧化甲乙酮、过氧化二苯甲酰、偶氮二异庚腈中的至少一种。
所述增塑剂为选自邻苯二甲酸丁苄酯、邻苯二甲酸二环己酯、邻苯二甲酸二丁酯、邻苯二甲酸二正辛酯、邻苯二甲酸二异壬酯中的至少一种。
本发明填补了国内市场上仍无胶黏剂能粘合聚四氟乙烯与聚四氟乙烯、聚四氟乙烯与金属、聚四氟乙烯与玻璃的空白，并经过从一百克级别的实验放大到一吨的工业化规模，其技术参数稳定。
根据本发明的聚合物对各种材料如玻璃、金属、陶瓷、木材、塑料等均有较好的粘附力，尤其是本发明的含氟(甲基)丙烯酸酯类胶黏剂对聚四氟乙烯有良好的胶粘作用，且具有优异的耐候性、防腐蚀性、耐沾污性、耐药品性、疏水性及绝缘性。
本发明的含氟(甲基)丙烯酸酯聚合物相较于现有材料具有以下特点：
(1)使用酸催化法进行本体聚合，产品纯净，后处理简单，而且生产能力大，易于连续化生产。
(2)所生产的含氟(甲基)丙烯酸酯聚合物是一种有高附着力，耐强酸强碱，防水防污的高性能材料。
(3)所生产的含氟(甲基)丙烯酸酯聚合物对聚四氟乙烯具有粘附力。
(4)所生产的含氟(甲基)丙烯酸酯聚合物可以粘接特种抗干扰材料与金属表面。
具体实施方式
以下，用实施例对本发明作更详细的描述。这些实施例仅仅是对本发明最佳实施方 式的描述，并不对本发明的范围有任何限制。
实施例1-9以制备100g含氟(甲基)丙烯酸酯胶黏剂的原料投入量为例，其原辅材料按重量份数配比如下。
实施例1
取甲基丙烯酸十三氟辛酯25g、甲基丙烯酸十二氟庚酯23g、甲基丙烯酸八氟戊酯17g、甲基丙烯酸六氟丁酯21g；甲基丙烯酸羟丁酯4.40g。
取引发剂过氧化甲乙酮0.43g、过氧化二苯甲酰0.20g、过氧化月桂酰0.15g，并加入乙酸乙酯2g预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸二丁酯2.02g、邻苯二甲酸二正辛酯4.80g，预混在一起，静止20min待用，标为混合液B。
按下列顺序将甲基丙烯酸六氟丁酯、甲基丙烯酸十二氟庚酯、甲基丙烯酸八氟戊酯、甲基丙烯酸十三氟辛酯加入到耐温玻璃杯中，油浴加热至50℃时开启搅拌，转速100r/min，当杯中温度升至80℃时加入甲基丙烯酸羟丁酯，继续搅拌，转速100r/min，20min后，加入混合液A，继续搅拌5min后，加入混合液B，混合均匀后升温至120℃，反应15min，然后降温至80℃反应7h，得到包含如下式1-1所示结构的含氟(甲基)丙烯酸酯胶黏剂。
[式1-1]
Figure PCTCN2015092166-appb-000002
其中，a、b、c、d、e范围为4-20。
产品的数均分子量为15000，密度为1.53g/cm3，玻璃化转变温度为84℃。
实施例2
取甲基丙烯酸十三氟辛酯45g、甲基丙烯酸四氟丙酯40g；甲基丙烯酸羟丙酯4.90g。
取引发剂过氧化甲乙酮0.55g、过氧化二苯甲酰0.35g、过氧化月桂酰0.15g，加入乙酸乙酯3g预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸二环己酯2.25g、邻苯二甲酸二异壬酯4.80g，预混在一起，静止20min待用，标为混合液B。
按下列顺序将甲基丙烯酸十三氟辛酯、甲基丙烯酸四氟丙酯加入到耐温玻璃杯中，油浴加热至50℃时开启搅拌，转速100r/min，当杯中温度升至80℃时加入甲基丙烯酸羟丙酯，继续搅拌，转速100r/min，20min后，加入混合液A，继续搅拌5min后，加入混合液B，混合均匀后升温至120℃，反应15min，然后降温至80℃，反应7h，得到包含如下式2-1所示结构的含氟(甲基)丙烯酸酯胶黏剂。
[式2-1]
Figure PCTCN2015092166-appb-000003
其中，a、b、e范围为4-18。
产物的数均据分子量为12000，密度为1.32g/cm3，玻璃化转变温度为77℃。
实施例3
取甲基丙烯酸十氟己酯62g、丙烯酸六氟丁酯22g；甲基丙烯酸羟丙酯4.90g。
取引发剂过氧化甲乙酮0.55g、过氧化二苯甲酰0.35g、过氧化月桂酰0.15g，加入 乙酸乙酯3g预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸丁苄酯2.25g、邻苯二甲酸二环己酯4.80g，预混在一起，静止20min待用，标为混合液B。
按下列顺序将甲基丙烯酸十氟己酯、丙烯酸六氟丁酯加入到耐温玻璃杯中，水浴加热至50℃时开启搅拌，转速100r/min，当杯中温度升至80℃时加入甲基丙烯酸羟丙酯，继续搅拌，转速100r/min，20min后，加入混合液A，继续搅拌5min后，加入混合液B，混合均匀后升温至90℃，反应50min；然后降温至80℃，反应7h，得到包含如下式3-1所示结构的含氟(甲基)丙烯酸酯胶黏剂。
[式3-1]
Figure PCTCN2015092166-appb-000004
其中，a、b、e范围为7-25。
产物的数均分子量为14000，密度为1.48g/cm3，玻璃化转变温度为82℃。
实施例4
取丙烯酸十二氟庚酯64g、甲基丙烯酸六氟丁酯20g；甲基丙烯酸羟乙酯4.90g。
取引发剂过氧化甲乙酮0.55g、过氧化二苯甲酰0.35g、过氧化月桂酰0.15g，加入乙酸乙酯3g预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸二丁酯2.25g、邻苯二甲酸二正辛酯4.80g，预混在一起，静止20min待用，标为混合液B。
按下列顺序将丙烯酸十二氟庚酯、甲基丙烯酸六氟丁酯加入到耐温玻璃杯中，水浴加热至50℃时开启搅拌，转速100r/min，当杯中温度升至80℃时加入甲基丙烯酸羟乙 酯，继续搅拌，转速100r/min，20min后，加入混合液A，继续搅拌5min后，加入混合液B，混合均匀后升温至90℃，反应50min；然后降温至80℃，反应7h，得到包含如下式4-1所示结构的含氟(甲基)丙烯酸酯胶黏剂。
[式4-1]
Figure PCTCN2015092166-appb-000005
其中，a、b、e的范围为8-30。
产物的数均分子量为13000，密度为1.29g/cm3，玻璃化转变温度为79℃。
实施例5
取甲基丙烯酸十三氟辛酯82g；甲基丙烯酸环氧丙酯5.60g。
取引发剂过氧化甲乙酮0.60g、过氧化二苯甲酰0.60g、偶氮二异庚腈0.3g，并加入乙酸乙酯3g预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸二丁酯2.45g、邻苯二甲酸二异壬酯5.45g，预混在一起，静止20min待用，标为混合液B。
将甲基丙烯酸十三氟辛酯加入到耐温玻璃杯中，水浴加热至50℃时开启搅拌，转速100r/min，当杯中温度升至80℃时加入甲基丙烯酸环氧丙酯，继续搅拌，转速100r/min，20min后，加入混合液A，继续搅拌5min后，加入混合液B，混合均匀后升温至90℃，反应50min，然后降温至80℃，反应7h，得到包含如下式5-1所示结构的含氟(甲基)丙烯酸酯胶黏剂。
[式5-1]
Figure PCTCN2015092166-appb-000006
其中，a、e范围为8-35。
产物的数均分子量为13000，密度1.59g/cm3，玻璃化转变温度为80℃。
实施例6
取甲基丙烯酸十氟己酯82g；丙烯酸乙酯5.60g。
取引发剂过氧化二苯甲酰0.60g、过氧化甲乙酮0.60g、偶氮二异庚腈0.3g，加入乙酸乙酯3g预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸二丁酯2.45g、邻苯二甲酸二正辛酯5.45g，预混在一起，静止20min待用，标为混合液B。
将甲基丙烯酸十氟己酯加入到耐温玻璃杯中，水浴加热至50℃时开启搅拌，转速100r/min，当杯中温度升至80℃时加入丙烯酸乙酯，继续搅拌，转速100r/min，20min后，加入混合液A，继续搅拌5min后，加入混合液B，混合均匀后升温至90℃，反应50min，然后降温到80℃，反应7h，得到包含如下式6-1所示结构的含氟(甲基)丙烯酸酯胶黏剂。
[式6-1]
Figure PCTCN2015092166-appb-000007
其中，a、e范围为12-35。
产物的数均分子量为12500，密度为1.53g/cm3，玻璃化转变温度为79℃。
实施例7
取甲基丙烯酸八氟戊酯82g；丙烯酸异冰片酯5.60g。
取引发剂过氧化二苯甲酰0.60g、过氧化甲乙酮0.60g、偶氮二异庚腈0.3g，并加入乙酸乙酯3g预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸二环己酯2.45g、邻苯二甲酸二正辛酯5.45g，预混在一起，静止20min待用，标为混合液B。
将甲基丙烯酸八氟戊酯加入到耐温玻璃杯中，水浴加热至50℃时开启搅拌，转速100r/min，当杯中温度升至80℃时加入丙烯酸异冰片酯，继续搅拌，转速100r/min，20min后，加入混合液A，继续搅拌5min后，加入混合液B，混合均匀后升温至90℃，反应50min；然后降温到80℃，反应7h，得到包含如下式7-1所示结构的含氟(甲基)丙烯酸酯胶黏剂。
[式7-1]
Figure PCTCN2015092166-appb-000008
其中，a、e范围为10-30。
产物的数均分子量为11500，密度1.47g/cm3，玻璃化转变温度为76℃。
实施例8
取甲基丙烯酸六氟丁酯82g；甲基丙烯酸十八烷基酯5.60g。
取引发剂过氧化二苯甲酰0.60g、过氧化甲乙酮0.60g、偶氮二异庚腈0.3g，加入乙酸乙酯3g预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸二丁酯2.45g、邻苯二甲酸二正辛酯5.45g，预混在一起，静止20min待用，标为混合液B。
将甲基丙烯酸六氟丁酯加入到耐温玻璃杯中，水浴加热至50℃时开启搅拌，转速100r/min，当杯中温度升至80℃时加入甲基丙烯酸十八烷基酯，继续搅拌，转速100r/min，20min后，加入混合液A，继续搅拌5min后，加入混合液B，混合均匀后升温至90℃，反应50min；然后降温到80℃，反应7h，得到包含如下式8-1所示结构的含氟(甲基)丙烯酸酯胶黏剂。
[式8-1]
Figure PCTCN2015092166-appb-000009
其中，a、e范围为8-35。
产物的数均分子量为11500，密度1.39g/cm3，玻璃化转变温度为76℃。
实施例9
取甲基丙烯酸十二氟庚酯82g；甲基丙烯酸羟丙酯5.60g。
取引发剂过氧化二苯甲酰0.60g、过氧化甲乙酮0.60g、偶氮二异庚腈0.3g，并加入乙酸乙酯3g预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸二丁酯2.45g、邻苯二甲酸二正辛酯5.45g，预混在一起静止20min待用，标为混合液B。
将甲基丙烯酸十二氟庚酯加入到耐温玻璃杯中，水浴加热至50℃时开启搅拌，转速100r/min，当杯中温度升至80℃时加入甲基丙烯酸羟丙酯，继续搅拌，转速100r/min，20min后，加入混合液A，继续搅拌5min后，加入混合液B，混合均匀后升温至90℃，反应50min；然后降温到80℃，反应7h，得到包含如下式9-1所示结构的含氟(甲基)丙烯酸酯胶黏剂。
[式9-1]
Figure PCTCN2015092166-appb-000010
其中，a、e范围为8-30。
产物的数均分子量为11000，密度1.62g/cm3，玻璃化转变温度为76℃。
实施例10
取甲基丙烯酸十三氟辛酯1.28Kg、甲基丙烯酸八氟戊酯0.4Kg；甲基丙烯酸羟丙酯0.098Kg。
取引发剂过氧化二苯甲酰0.007Kg、过氧化甲乙酮0.011Kg、偶氮二异庚腈0.003Kg，加入乙酸乙酯0.06Kg预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸二丁酯0.045Kg、邻苯二甲酸丁苄酯0.096Kg，预混在一起，静止20min待用，标为混合液B。
按下列顺序将甲基丙烯酸十三氟辛酯、甲基丙烯酸八氟戊酯加入到特制反应容器中，油浴加热至60℃时开启搅拌，转速100r/min，当反应容器内温度升至80℃时加入甲基丙烯酸羟丙酯，继续搅拌，转速100r/min，2min后，加入混合液A，继续搅拌5min后，加入混合液B，混合均匀后升温至120℃，反应15min；然后降温到75-80℃，反应7h后结束，装入软管中，得到包含如下式10-1所示结构的含氟(甲基)丙烯酸酯胶黏剂。
使用时加热至软化后挤出涂覆于两种物体表面，粘合后施加少许压力使胶黏剂与表面充分接触。保持压力待胶黏剂固化3h后达到最佳效果。
[式10-1]
Figure PCTCN2015092166-appb-000011
其中，a、b、e范围为4-25。
产物的数均分子量为14000，密度1.43g/cm3，玻璃化转变温度为82℃。
实施例11
取甲基丙烯酸十三氟辛酯21Kg、甲基丙烯酸八氟戊酯10.5Kg、甲基丙烯酸六氟丁酯10.5Kg；甲基丙烯酸羟乙酯2.45Kg。
取引发剂过氧化二苯甲酰0.175Kg、过氧化甲乙酮0.275Kg、偶氮二异庚腈0.075Kg，并加入乙酸乙酯1.5Kg预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸二丁酯1.125Kg、邻苯二甲酸二正辛酯2.4Kg，预混在一起，静止20min待用，标为混合液B。
按下列顺序将甲基丙烯酸十三氟辛酯、甲基丙烯酸八氟戊酯、甲基丙烯酸六氟丁酯加入到70L的不锈钢桶内，开启搅拌，转速100r/min，升温到一定程度加入甲基丙烯酸羟乙酯，15min后，加入混合液A继续搅拌，2min后加入混合液B，混合均匀后油浴加热至120℃，反应15min，达到临界状态后取出不锈钢桶放入冷水浴降温至80℃后，用远红外加热器保温7h，结束搅拌后装入软管中，冷却得到包含如下式11-1所示结构的含氟(甲基)丙烯酸酯胶黏剂固体。
使用时加热至软化后挤出涂覆于两种物体表面，粘合后施加少许压力使胶黏剂与表面充分接触。保持压力待胶黏剂固化3h后达到最佳效果。
[式11-1]
Figure PCTCN2015092166-appb-000012
其中，a、b、c、e范围为7-14。
产物的数均分子量为15000，密度1.54g/cm3，玻璃化转变温度为85℃。
实施例12
取甲基丙烯酸十三氟辛酯420Kg、甲基丙烯酸八氟戊酯210Kg、甲基丙烯酸六氟丁酯210Kg；甲基丙烯酸羟乙酯49Kg。
取引发剂过氧化二苯甲酰3.5Kg、过氧化甲乙酮5.5Kg、偶氮二异庚腈1.5Kg，并加入乙酸乙酯30Kg预混在一起，静止20min待用，标为混合液A；取增塑剂邻苯二甲酸二丁酯22.5Kg、邻苯二甲酸二正辛酯48Kg，预混在一起，静止20min待用，标为混合液B。
依次将甲基丙烯酸十三氟辛酯，甲基丙烯酸八氟戊酯，甲基丙烯酸六氟丁酯加入到不锈钢特制反应釜中，搅拌，转速100r/min，升温到一定程度后加入甲基丙烯酸羟乙酯，5min后，加入混合液A继续搅拌，1min后加入混合液B，使用循环油浴快速加温至120℃，加压使釜内压力达到1.05Mpa，15-20min，均质，转速200r/min，通过视镜观察，达到临界状态后，泵入冷却油排出热油快速降温至80℃后，保温继续聚合，搅拌，转速100r/min，6h后反应结束，打开反应釜底部阀门，装入软管中，冷却得到包含如下式 12-1所示结构的含氟(甲基)丙烯酸酯胶黏剂固体。
使用时用开水加热至胶黏剂软化后挤出涂覆于两种物体表面，粘合后施加少许压力使胶黏剂与表面充分接触。保持压力待胶黏剂固化3h后达到最佳效果。
[式12-1]
Figure PCTCN2015092166-appb-000013
其中，a、b、c、e范围为7-15。
产物的数均分子量为16000，密度1.56g/cm3，玻璃化转变温度为85℃。
下面对实施例1-12制备的含氟(甲基)丙烯酸酯聚合物的性能进行测试。以下测试所用仪器均为信任达仪器(上海)有限公司所生产的万能材料试验机，型号为XD-121。
剪切强度测试依据为GB/T 7124-2008，载体为不锈钢。
剥离强度测试依据为GB/T 2790-1995，载体为不锈钢-铝合金。
剪切强度和剥离强度的测试结果见表1。
表1
Figure PCTCN2015092166-appb-000014
Figure PCTCN2015092166-appb-000015
经过盐雾试验1000h后的测试结果见表2。
表2
Figure PCTCN2015092166-appb-000016
经过浸泡实验2000h后的测试结果见表3。
表3
Figure PCTCN2015092166-appb-000017
经98％浓硫酸(50％氢氧化钠)处理240h后的测试结果见表4。
表4
Figure PCTCN2015092166-appb-000018
Figure PCTCN2015092166-appb-000019
由上述实施例的结果可以得出，在实施例1-9的9个平行配方中，实施例1的综合性能最优，而从实施例10、11、12放大生产产品的效果来看，产品质量稳定，工艺成熟，便于生产。
由表2、表3数据可知，实施例产品分别经过盐雾试验1000h和浸泡实验2000h后，仍然具有优异的性能。
另外，本发明含氟(甲基)丙烯酸酯聚合物对聚四氟乙烯也具有良好的胶粘作用，测试结果如表5所示。
表5
  剪切强度(Mpa)
聚四氟乙烯--聚四氟乙烯 1.47
聚四氟乙烯--铝合金 1.53
聚四氟乙烯--不锈钢 1.51
聚四氟乙烯--钛合金 1.53

Claims (8)

  1. 一种包含如下式1所示结构的含氟(甲基)丙烯酸酯聚合物，
    [式1]
    Figure PCTCN2015092166-appb-100001
    其中，a、b、c、d、e分别为0-40的整数；
    RF1、RF2、RF3、RF4分别为-(CF2)n-CFH2或-(CF2)m-CF2H，其中，n、m分别为1-15的整数；
    R1、R2、R3、R4、R5分别为H或甲基；
    R选自未取代或由羟基、3-7元杂环基取代的C1-C20烷基；C3-C10环烷基；C5-C10桥环基；3-7元杂环基；
    所述含氟(甲基)丙烯酸酯聚合物的数均分子量为10000-18000。
  2. 一种权利要求1所述的含氟(甲基)丙烯酸酯聚合物的制备方法，以重量份计，包括：
    取引发剂共0.2-2份，加入乙酸乙酯1.5-5份预混在一起，静止20-30min，得到混合液A；
    取增塑剂共5-15份，预混在一起，静止20-30min，得到混合液B；
    将含氟(甲基)丙烯酸酯60-80份加入到反应容器中，加热至45-60℃，开启搅拌，升温至70-85℃时，向其中加入(甲基)丙烯酸酯2-15份，搅拌15-25min后，加入混合液A，继续搅拌4-8min后，加入混合液B，边搅拌边升温至90-125℃，反应15-60min；然后降温到70-85℃，反应5-8h，得到含氟(甲基)丙烯酸酯聚合物。
  3. 根据权利要求2所述的制备方法，其中，
    所述含氟(甲基)丙烯酸酯为选自丙烯酸三氟乙酯、丙烯酸六氟丁酯、丙烯酸十二氟庚酯、甲基丙烯酸三氟乙酯、甲基丙烯酸四氟丙酯、甲基丙烯酸六氟丁酯、甲基丙烯 酸八氟戊酯、甲基丙烯酸十氟己酯、甲基丙烯酸十二氟庚酯、甲基丙烯酸十三氟辛酯中的至少一种。
  4. 根据权利要求2所述的制备方法，其中，
    所述(甲基)丙烯酸酯为选自丙烯酸乙酯、丙烯酸异冰片酯、甲基丙烯酸环氧丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟丁酯、甲基丙烯酸十八烷基酯中的至少一种。
  5. 根据权利要求2所述的制备方法，其中，
    所述引发剂为选自过氧化月桂酰、过氧化甲乙酮、过氧化二苯甲酰、偶氮二异庚腈中的至少一种。
  6. 根据权利要求2所述的制备方法，其中，
    所述增塑剂为选自邻苯二甲酸丁苄酯、邻苯二甲酸二环己酯、邻苯二甲酸二丁酯、邻苯二甲酸二正辛酯、邻苯二甲酸二异壬酯中的至少一种。
  7. 权利要求1所述的含氟(甲基)丙烯酸酯聚合物对玻璃、陶瓷、木材、橡胶、纺织品、皮革、金属、建筑材料的胶黏用途。
  8. 权利要求1所述的含氟(甲基)丙烯酸酯聚合物在聚四氟乙烯与聚四氟乙烯之间以及聚四氟乙烯与金属之间的胶黏用途。
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CN115807287A (zh) * 2022-12-13 2023-03-17 龙帛生物科技有限公司 一种防水抗菌复合纤维制品及其制备工艺

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