WO2018196401A1 - 一种单体法制备的主链降解型聚丙烯酸锌树脂及其方法与应用 - Google Patents

一种单体法制备的主链降解型聚丙烯酸锌树脂及其方法与应用 Download PDF

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WO2018196401A1
WO2018196401A1 PCT/CN2017/116385 CN2017116385W WO2018196401A1 WO 2018196401 A1 WO2018196401 A1 WO 2018196401A1 CN 2017116385 W CN2017116385 W CN 2017116385W WO 2018196401 A1 WO2018196401 A1 WO 2018196401A1
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zinc
acid
acrylate
methacrylate
parts
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French (fr)
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张广照
马春风
潘健森
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South China University of Technology SCUT
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South China University of Technology SCUT
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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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C09D5/165—Macromolecular compounds containing hydrolysable groups

Definitions

  • the invention belongs to the technical field of marine antifouling materials, relates to a polyacrylic acid zinc resin for marine antifouling coatings, in particular to a main chain degradable polyacrylic acid zinc resin prepared by a monomer method, and a method and application thereof; Used in the preparation of marine antifouling coatings.
  • Marine biofouling refers to the biological scale formed by the attachment and growth of sea creatures to the surface immersed in seawater. It poses an immeasurable hazard to marine aquaculture, transportation and marine engineering, and is directly reflected in huge economic losses. For example, marine biofouling can block the cage hole, causing fish to die of oxygen deficiency and reduce production; increasing the ship's own weight and navigational resistance, indirectly leading to a decline in maneuverability and combat capability, increasing fuel consumption and greenhouse gas emissions. Blocking the heat exchange pipeline of nuclear power plants, the efficiency of cold and heat exchange is greatly reduced; and the corrosion of marine equipment steel structures such as oil production platforms is also aggravated. Therefore, solving the problem of marine pollution has important strategic significance for China's economy, energy and military.
  • the existing self-polishing technology is mainly a side chain hydrolysis type, and its performance has certain requirements on the sailing period and the speed.
  • the static antifouling effect is not good.
  • the polymer main chain leaves the surface of the coating and enters the ocean, causing marine micro-plastic pollution, which seriously threatens the marine ecosystem.
  • the introduction of a degradable structure into the main chain of a conventional self-polishing resin is expected to produce a resin which is highly efficient, long-lasting and environmentally friendly for antifouling coatings.
  • the cost is low, the hydrolysis rate is moderate, and the zinc ions generated after the hydrolysis of the zinc ester bond also have certain anti-algae efficiency.
  • the object of the present invention is to provide a main chain degraded polyacrylic acid zinc resin having a polyester structure and a zinc chain ester bond in a side chain, in view of the deficiencies of the self-polishing resin technology for the existing marine antifouling coating.
  • the resin can not only meet the static antifouling demand of the ocean, but also solve the problem of marine microplastic pollution at the same time, and is a main chain degradable polyacrylic acid zinc resin.
  • Another object of the present invention is to provide a process for producing the above-mentioned main chain degradable polyacrylic acid zinc resin.
  • Another object of the present invention is to provide an application of the above-described main chain degradable polyacrylic acid zinc resin.
  • the main chain degraded polyacrylic acid zinc resin is used for preparing a marine antifouling paint.
  • a main chain degradable polyacrylic acid zinc resin is mainly prepared from the following components in parts by weight:
  • the vinyl zinc ester functional monomer is prepared from the following components in parts by weight:
  • the (meth)acrylic acid means acrylic acid or methacrylic acid.
  • the zinc-containing compound is one or more selected from the group consisting of zinc oxide, zinc hydroxide, zinc chloride, zinc acetate, and zinc propionate.
  • zinc oxide zinc oxide
  • deionized water is added to the reaction.
  • the monocarboxylic acid is acrylic acid, methacrylic acid, formic acid, acetic acid, propionic acid, benzoic acid, n-octanoic acid, isooctanoic acid, stearic acid, isostearic acid, naphthenic acid, itaconic acid, maleic acid, oil One or more of acid, palmitic acid, and rosin acid.
  • the solvent is one or more of a hydrocarbon solvent, an alcohol solvent, and deionized water; the hydrocarbon solvent is one or more of toluene and xylene; and the alcohol solvent is isopropanol or n-butanol.
  • a hydrocarbon solvent one or more of toluene and xylene
  • the alcohol solvent is isopropanol or n-butanol.
  • isobutanol and propylene glycol methyl ether One or more of isobutanol and propylene glycol methyl ether.
  • the cyclic monomer is one or more of 1 to 38 compounds: (1) glycolide, (2) lactide, (3) ⁇ -caprolactone, (4) 2-methyl- ⁇ - caprolactone, (5) 2-chloro- ⁇ -caprolactone, (6) ⁇ -butyrolactone, (7) ⁇ -valerolactone, (8) ⁇ -valerolactone, (9) ethylene carbonate Ester, (10) propylene carbonate, (11) trimethylene ring carbonate, (12) 2,2-dimethyltrimethylene carbonate, (13) 2-methyl-2-oxazoline, (14) 2-ethyl-2-oxazoline, (15) ethylene oxide, (16) propylene oxide, (17) epichlorohydrin, (18) ⁇ -glycidyloxypropyl trimethoxy Silane, (19) 2-methylene-1,3-dioxolane, (20) 2-methylene-4-phenyl-1,3-dioxolane, (21)2 -methylene-4-alkyl-1,3
  • the vinyl monomers are acrylates, methacrylates, hydroxy-terminated acrylates, terminal hydroxyl methacrylates, acrylic cyclic hydrocarbon esters, methacrylic cyclic hydrocarbon esters, acrylic acid More than one of polyolefin diol esters and methacrylic acid polyolefin diol esters;
  • the acrylates are methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, octyl acrylate, More than one of isooctyl acrylate, lauryl acrylate, and stearic acid acrylate;
  • the methacrylates are methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, One or more of isobutyl methacrylate, t-butyl methacrylate, octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, and stearyl stearate;
  • the terminal hydroxyl group acrylate is one or more of hydroxyethyl acrylate or hydroxypropyl acrylate;
  • the terminal hydroxyl group methacrylate is one or more of hydroxyethyl methacrylate and hydroxypropyl methacrylate;
  • the cyclic hydrocarbon ester of acrylic acid is one or more of phenyl acrylate, cyclohexyl acrylate, 4-methylcyclohexyl acrylate, and 4-tert-butylcyclohexyl acrylate;
  • the cyclic hydrocarbon ester of methacrylic acid is one or more of phenyl methacrylate, cyclohexyl methacrylate, 4-methylcyclohexyl methacrylate, and 4-tert-butylcyclohexyl methacrylate;
  • the polyacrylic acid diol acrylate is a polyethylene glycol acrylate (preferably having a degree of polymerization of 1 to 10);
  • the polyolefin diol methacrylate is a polyethylene glycol methacrylate (preferably having a degree of polymerization of 1 to 10).
  • the initiator is phosphazene, phosphazene salt, phosphazene oxide, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-tert-butyl peroxide, peroxy-2-ethyl peroxide More than one of t-butyl hexanoate;
  • the component includes a low molecular alcohol or a low molecular amine and/or a telogen, a low molecular alcohol or a low molecular amine is compounded with an initiator, and the telogen and the initiator are initiated.
  • Agent for compounding a low molecular alcohol or a low molecular amine and/or a telogen, a low molecular alcohol or a low molecular amine is compounded with an initiator, and the telogen and the initiator are initiated.
  • the low molecular weight alcohol is one or more of aliphatic or aromatic alcohols having 1 to 12 carbon atoms.
  • the low molecular amine is one or more of aliphatic or aromatic amines having 1 to 12 carbon atoms.
  • the total weight fraction of the initiator and the low molecular alcohol or the low molecular amine is 0.01-10 parts, and the compound initiator and the low molecular alcohol or low molecular compound are compounded.
  • the mass ratio of the amine is preferably 1: (0.1 to 4).
  • the telogen is n-dodecyl mercaptan, tert-dodecyl mercaptan, isooctyl 3-mercaptopropionate, ethylhexyl propionate 3-mercaptopropionate, tetrakis(3-mercaptopropionic acid)
  • quaternary tetraol ester and ⁇ -methylstyrene dimer preferably one or more of ⁇ -methylstyrene dimer and n-dodecyl mercaptan.
  • the telomer When the telogen is compounded with the initiator, the telomer is 0.5 to 5 parts by weight, and the ratio of the telogen to the initiator is (0.5 to 5): (0.01 to 10) .
  • the component of the main chain degradable polyacrylic acid zinc resin contains an initiator which is an initiator, a combination of an initiator and a low molecular alcohol or a low molecular amine, a compounding agent and an initiator. More than one.
  • the initiator is present in the initiator in an amount of from 0.01 to 10 parts by weight.
  • the organic solvent is one or more of a hydrocarbon solvent, an alcohol solvent, a ketone solvent, and an ester solvent;
  • the hydrocarbon solvent is one or more of toluene and xylene;
  • the alcohol solvent is one or more of isopropanol, n-butanol, isobutanol, and propylene glycol methyl ether;
  • the ketone solvent is A One or more of ethyl ethyl ketone, methyl isobutyl ketone, acetone, methyl ethyl ketone, and cyclohexanone;
  • the ester solvent is one or more of ethyl acetate and butyl acetate.
  • the weight fraction of the vinyl zinc ester functional monomer may be based on the total weight of the reaction liquid after preparation of the vinyl zinc ester functional monomer, or may be a vinyl zinc ester functional single The total weight of the reactants in the body (containing zinc compound, (meth)acrylic acid and monocarboxylic acid).
  • the method for preparing the main chain degradable polyacrylic acid zinc resin comprises the following steps:
  • reaction medium 50 to 100 parts by weight of an organic solvent is used as a reaction medium, and 5 to 95 parts by weight of a cyclic monomer, 0 to 95 parts by weight of a vinyl monomer, and 0.01 to 10 parts by weight of an initiator. 5 to 80 parts by weight of a vinyl zinc ester functional monomer is reacted, and the reaction conditions are carried out at 70 to 120 ° C for 8 to 18 hours to obtain a polyacrylic acid zinc polymer.
  • the main chain-degradable polyacrylic acid zinc resin has a zinc element content of 0.5 to 20%, preferably 3 to 10%.
  • the number average molecular weight Mn (measured by GPC using polystyrene as a standard) of the main chain degradable polyacrylic acid zinc resin is from 1,000 to 80,000, preferably from 1,000 to 50,000.
  • the main chain degradable polyacrylic acid zinc resin has an acid value of 30 to 300 mgKOH/g, preferably 50 to 230 mgKOH/g.
  • the main chain degraded polyacrylic acid zinc resin is used for preparing a marine antifouling paint.
  • the invention provides a main chain degradable polyacrylic acid zinc resin whose structure is a random copolymer composed of a polyester segment, a vinyl monomer and a vinyl zinc ester unit, which is prepared by a monomer method.
  • the invention introduces a degradable polyester segment into the main chain of the polyacrylic acid zinc resin, so that the material involved can be degraded in addition to the side chain zinc ester bond under the attack of seawater, and the main chain polyester structure can also be degraded.
  • the zinc content and the content of the cyclic monomer By adjusting the zinc content and the content of the cyclic monomer, the purpose of synergistic hydrolysis and degradation rate is achieved, and the application requirements of static antifouling are met.
  • the material can eventually degrade into small molecules, solving the problem of marine microplastic contamination.
  • a copolymerization of a cyclic monomer and a vinyl zinc ester functional monomer is introduced into a polyacrylic acid zinc resin, and a main chain degraded self-polishing is prepared in which a main chain contains a polyester segment and a side chain contains a zinc ester bond.
  • Antifouling resin The obtained resin can be degraded in addition to the side chain zinc ester bond under the attack of seawater, and the main chain polyester segment can also be degraded, thereby solving the dependence of the conventional self-polishing material on the speed, and also hydrolyzing in static seawater.
  • Degradation makes the surface of the coating self-renewing, which effectively regulates the release of the antifouling agent at a constant rate, ensuring the retention of the active material on the surface of the ship or marine equipment coating, and is well suited to ships with low speeds and offshore oil platforms. Anti-fouling requirements;
  • the material provided by the invention can be uniformly and thoroughly polished because the main side chain can be broken under the attack of seawater, so that the surface of the coating maintains low roughness during the sailing, and the sailing resistance is reduced, and the material is excellent. Drag reduction performance;
  • the present invention can also add different kinds and different contents of vinyl monomers in the copolymerization to regulate the glass transition temperature and mechanical properties of the materials, and at the same time improve the solubility of the materials in the common solvent of marine coatings;
  • the preparation method provided by the invention is simple and feasible, has low cost, and is suitable for industrial production, and the prepared polyacrylic acid zinc resin has a good development prospect in the field of marine antifouling coating.
  • a preparation method of a main chain degraded polyacrylic acid zinc resin which comprises the following steps:
  • the number average molecular weight M n of the resin was 2.5 ⁇ 10 4 g/mol
  • the zinc content was 7.2%
  • the acid value was 124 mgKOH/g
  • the shallow sea hanging plate experiment was carried out, and no sea creature growth was observed for 14 months.
  • a preparation method of a main chain degraded polyacrylic acid zinc resin which comprises the following steps:
  • a number average molecular weight M n of resin is 3.0 ⁇ 10 4 g / mol, the zinc content of 6.7%, an acid value 115mgKOH / g, for shallow plate hanging experiment, 12 months, no biological growth sea.
  • a preparation method of a main chain degraded polyacrylic acid zinc resin which comprises the following steps:
  • n-hexane mixture (1) functional vinyl monomer solution of zinc acetate, 0.15 g of diethylene glycol, and of 1mL of t-BuP 4 (0.5g of t-BuP 4) consisting of addition was complete The mixture was kept for 2 hours, and 8 g of benzoyl peroxide and 100 g of xylene were added dropwise at a constant rate for 30 minutes, and further stirred for 4 hours to obtain a main chain-degradable polyacrylic acid zinc resin (yellow transparent resin solution).
  • the number average molecular weight M n of the resin was 1.2 ⁇ 10 4 g / mol
  • the zinc content was 4.5%
  • the acid value was 77 mg KOH / g
  • the shallow sea hanging plate experiment was carried out, and no sea creature growth was observed for 8 months.
  • a preparation method of a main chain degraded polyacrylic acid zinc resin which comprises the following steps:
  • the number average molecular weight M n of the resin was 2.6 ⁇ 10 4 g / mol
  • the zinc content was 2.3%
  • the acid value was 38 mg KOH / g
  • the shallow sea hanging plate experiment was carried out, and no sea creature growth was observed for 6 months.

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Abstract

本发明属于海洋防污材料的技术领域，公开了一种单体法制备的主链降解型聚丙烯酸锌树脂及其方法与应用。所述主链降解型聚丙烯酸锌树脂主要由以下按重量份数计的组分制备而成：乙烯基锌酯功能单体5～80份、环状单体5～95份、乙烯基单体0～95份、引发剂0.01～10份、有机溶剂50～100份。本发明的树脂侧链锌酯键和主链聚酯链段能在海水的进攻下水解，解决了传统自抛光材料对航速的依赖性，在静态海水中能通过水解降解作用使涂层表面自更新，有效调控防污剂以恒定的速率释放，满足低航速的船舶以及海上采油平台等设施的防污要求；具有优良的减阻性能。所述树脂用于海洋防污涂料。

Description

一种单体法制备的主链降解型聚丙烯酸锌树脂及其方法与应用 技术领域
本发明属于海洋防污材料技术领域，涉及一种海洋防污涂料用聚丙烯酸锌树脂，特别是涉及一种单体法制备的主链降解型聚丙烯酸锌树脂及其方法与应用；所述树脂用于制备海洋防污涂料。
背景技术
海洋生物污损是指海生物对浸泡在海水中的表面进行附着、生长所形成的生物垢。它对海洋养殖业、运输业和海洋工程造成不可估量的危害，直接体现为巨大的经济损失。例如：海洋生物污损会堵塞养殖箱网孔，使鱼类缺氧死亡而减产；增加舰船自重和航行阻力，间接导致机动能力和战斗能力的下降，增加了燃油的消耗和温室气体的排放；堵塞核电站热交换管道，使冷热交换效率大大降低；还加剧了采油平台等海洋装备钢结构的腐蚀。因此解决海洋污损问题对我国经济、能源、军事都有重要的战略意义。
涂装海洋防污涂料是目前解决海洋生物污损问题最经济、最方便和最常用的方法，其中又以自抛光防污涂料应用最广。在涂料的众多组份当中，树脂起着决定性的作用。树脂的结构、分子量、酸值等参数决定着涂料的性能及使用寿命。自从2003年国际海事组织(IMO)决定全面禁止生产含有机锡的防污涂料之后，自抛光技术便进行了更新换代，现在主流自抛光技术包括聚丙烯酸硅烷酯树脂、聚丙烯酸锌树脂和聚丙烯酸铜树脂三类。然而现有自抛光技术主要是侧链水解型的，其性能的发挥对航期和航速都有一定的要求。在静止阶段，仅靠海水的冲刷很难达到理想的自抛光效果，因此静态防污效果不佳。不仅如此，侧链水解后，高分子主链脱离涂层表面进入海洋中，造成海洋微塑料污染，严重威胁着海洋生态系统。
在传统自抛光树脂的主链中引入可降解的结构，有望制备出一种高效、使用寿命长且环境友好的防污涂料用树脂。尤其对于聚丙烯酸锌树脂，其成本较低，水解速度适中，锌酯键水解后生成的锌离子还具有一定的抗藻效能。
发明内容
本发明的目的是针对现有海洋防污涂料用自抛光树脂技术的不足，提供了一种主链含有聚酯结构，侧链含锌酯键的主链降解型聚丙烯酸锌树脂。所述的树脂不仅可以满足海洋静态防污需求，而且同时解决海洋微塑料污染问题，是主链降解型聚丙烯酸锌树脂。
本发明另一目的在于提供由上述主链降解型聚丙烯酸锌树脂的制备方法。
本发明的另一目的在于提供上述主链降解型聚丙烯酸锌树脂的应用。所述主链降解型聚丙烯酸锌树脂用于制备海洋防污涂料。
本发明的目的通过下述技术方案实现：
一种主链降解型聚丙烯酸锌树脂，主要由以下按重量份数计的组分制备而成：
Figure PCTCN2017116385-appb-000001
所述乙烯基锌酯功能单体，由以下按重量份数计的组分制备而成：
Figure PCTCN2017116385-appb-000002
所述(甲基)丙烯酸是指丙烯酸或甲基丙烯酸。
所述含锌化合物为氧化锌、氢氧化锌、氯化锌、乙酸锌、丙酸锌中的一种以上。当含锌化合物为氧化锌时，反应中需加入去离子水。
所述一元羧酸为丙烯酸、甲基丙烯酸、甲酸、乙酸、丙酸、苯甲酸、正辛酸、异辛酸、硬脂酸、异硬脂酸、环烷酸、衣康酸、马来酸、油酸、棕榈酸、松香酸中的一种以上。
所述溶剂为烃类溶剂、醇类溶剂和去离子水中的一种以上；所述烃类溶剂为甲苯、二甲苯中的一种或以上；所述醇类溶剂为异丙醇、正丁醇、异丁醇、 丙二醇甲醚中的一种以上。
所述环状单体为1～38化合物中一种或多种：(1)乙交酯、(2)丙交酯、(3)ε-己内酯、(4)2–甲基–ε-己内酯、(5)2–氯–ε–己内酯、(6)γ-丁内酯、(7)δ-戊内酯、(8)γ-戊内酯、(9)碳酸乙烯酯、(10)碳酸丙烯酯、(11)三亚甲基环碳酸酯、(12)2,2-二甲基三亚甲基环碳酸酯、(13)2-甲基-2-噁唑啉、(14)2-乙基-2-噁唑啉、(15)环氧乙烷、(16)环氧丙烷、(17)环氧氯丙烷、(18)γ-缩水甘油醚氧丙基三甲氧基硅烷、(19)2-亚甲基-1,3-二氧环戊烷、(20)2-亚甲基-4-苯基-1,3-二氧环戊烷、(21)2-亚甲基-4-烷基-1,3-二氧环戊烷、(22)2,4-二亚甲基-1,3-二氧环戊烷、(23)2-亚甲基-1,3-二氧-4,5-苯并环戊烷、(24)2-亚甲基-1,3-二氧环己烷、(25)2,5-二亚甲基-1,3-二氧环己烷、(26)2-亚甲基-5-苯基-1,3-二氧环己烷、(27)2-亚甲基-4-烷基-1,3-二氧环己烷、(28)2-亚甲基-1,3-二氧环庚烷、(29)2-亚甲基-5-烷基-1,3-二氧环庚烷、(30)2-亚甲基-4,7-二甲基-1,3-二氧环庚烷、(31)2-亚甲基-1,3-二氧-5,6-苯并环庚烷、(32)2-亚甲基-5-苯基-1,3-二氧环庚烷、(33)2-乙叉-1,3-二氧环庚烷、(34)2-亚甲基-1,3-二氧-5-环庚烯、(35)2-乙叉-4-烷基-1,3-二氧环戊烷、(36)2-乙叉-1,3-二氧环己烷、(37)2-烯丙叉-4-苯基-1,3-二氧环戊烷、(38)2-乙叉-1,3-二氧-5,6-苯并环庚烷中的一种或多种；
1～38化合物的环状单体结构式如下：
Figure PCTCN2017116385-appb-000003
Figure PCTCN2017116385-appb-000004
其中m＝1-12表示m为1-12的整数。
所述乙烯基单体为丙烯酸酯类，甲基丙烯酸酯类，端羟基的丙烯酸酯类，端羟基的甲基丙烯酸酯类，丙烯酸环状烃酯类，甲基丙烯酸环状烃酯类，丙烯酸聚烯烃二醇酯类，甲基丙烯酸聚烯烃二醇酯类中一种以上；
丙烯酸酯类为丙烯酸甲酯、丙烯酸乙酯、丙烯酸-2-甲氧基乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸辛酯、丙烯酸异辛酯、丙烯酸月桂酯、丙烯酸硬脂酸酯中一种以上；
甲基丙烯酸酯类为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸-2-甲氧基乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸辛酯、甲基丙烯酸异辛酯、甲基丙 烯酸月桂酯、甲基丙烯酸硬脂酸酯中一种以上；
端羟基的丙烯酸酯类为丙烯酸羟乙酯或丙烯酸羟丙酯中一种以上；
端羟基的甲基丙烯酸酯类为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯中一种以上；
丙烯酸环状烃酯类为丙烯酸苯酯、丙烯酸环己基酯、丙烯酸-4-甲基环己基酯、丙烯酸-4-叔丁基环己基酯中一种以上；
甲基丙烯酸环状烃酯类为甲基丙烯酸苯酯、甲基丙烯酸环己基酯、甲基丙烯酸-4-甲基环己基酯、甲基丙烯酸-4-叔丁基环己基酯中一种以上；
丙烯酸聚烯烃二醇酯类为丙烯酸聚乙二醇(聚合度优选为1～10)酯；
甲基丙烯酸聚烯烃二醇酯类为甲基丙烯酸聚乙二醇(聚合度优选为1～10)酯。
所述引发剂为磷腈、磷腈盐、氧化磷腈、偶氮二异丁腈、偶氮二异戊腈、过氧化苯甲酰、过氧化二叔丁基、过氧化-2-乙基己酸叔丁酯中的一种以上；
所述主链降解型聚丙烯酸锌树脂中，所述组分包括低分子醇或低分子胺和/或调聚剂，低分子醇或低分子胺与引发剂进行复配，调聚剂与引发剂进行复配；
所述低分子醇为含碳原子1～12的脂肪族或芳香族醇中的一种或以上。
所述低分子胺为含碳原子1～12的脂肪族或芳香族胺中的一种或以上。
所述低分子醇或低分子胺与引发剂进行复配时，引发剂与低分子醇或低分子胺的总重量份数为0.01～10份，复配的引发剂与低分子醇或低分子胺的质量比优选为1：(0.1～4)。
所述调聚剂为正十二烷基硫醇、叔十二烷基硫醇、3-巯基丙酸异辛酯、3-巯基丙酸乙基己醇酯、四(3-巯基丙酸)季茂四醇酯、α-甲基苯乙烯二聚体的一种或以上；优选α-甲基苯乙烯二聚体、正十二烷基硫醇中一种以上。
所述调聚剂与引发剂进行复配时，所述调聚剂的重量份为0.5～5份，调聚剂与引发剂的重量份数比为(0.5～5)：(0.01～10)。
所述主链降解型聚丙烯酸锌树脂的组分中包含引发物，所述引发物为引发剂、引发剂与低分子醇或低分子胺的复配物、调聚剂与引发剂的复配物中一种以上。所述引发物中引发剂的重量份数0.01～10份。
所述有机溶剂为烃类溶剂、醇类溶剂、酮类溶剂、酯类溶剂中的一种以上；
所述烃类溶剂为甲苯、二甲苯中的一种以上；所述醇类溶剂为异丙醇、正丁醇、异丁醇、丙二醇甲醚中的一种以上；所述酮类溶剂为甲基乙基酮、甲基异丁基甲酮、丙酮、丁酮、环己酮中的一种以上；所述酯类溶剂为乙酸乙酯、乙酸丁酯的一种以上。
所述主链降解型聚丙烯酸锌树脂中，乙烯基锌酯功能单体的重量份数可以以乙烯基锌酯功能单体制备后的反应液总重量计，也可以以乙烯基锌酯功能单体中反应物(含锌化合物、(甲基)丙烯酸和一元羧酸)的总重量计。
所述主链降解型聚丙烯酸锌树脂的制备方法，具体包括以下步骤：
(1)乙烯基锌酯功能单体的合成：
以50～105重量份溶剂为反应介质，将10～40重量份含锌化合物、15～30重量份(甲基)丙烯酸和20～75重量份一元羧酸于50～140℃反应3～8小时，得到乙烯基锌酯功能单体；
(2)聚丙烯酸锌树脂的合成：
在惰性氛围中，以50～100重量份有机溶剂为反应介质，在0.01～10重量份引发剂的作用下，将5～95重量份环状单体、0～95重量份乙烯基单体和5～80重量份乙烯基锌酯功能单体进行反应，反应的条件为于70～120℃反应8～18小时，得到聚丙烯酸锌聚合物。
所述主链降解型聚丙烯酸锌树脂的锌元素含量为0.5～20％，优选3～10％。
所述主链降解型聚丙烯酸锌树脂数均分子量Mn(以聚苯乙烯为标样，通过GPC测定)为1000～80000，优选1000～50000。
所述主链降解型聚丙烯酸锌树脂酸值为30～300mgKOH/g，优选50～230mgKOH/g。
所述主链降解型聚丙烯酸锌树脂用于制备海洋防污涂料。
本发明提供的一种主链可降解的聚丙烯酸锌树脂，其结构是由聚酯链段、乙烯基单体和乙烯基锌酯单元组成的无规共聚物，通过单体法制备得到。本发明在聚丙烯酸锌树脂主链中引入可降解的聚酯链段，使所涉及的材料除了侧链锌酯键在海水的进攻下能水解之外，主链聚酯结构也能发生降解，通过调节锌含量和环状单体的含量，达到协同水解和降解速度的目的，满足静态防污的应用需要。同时，随着水解和降解的不断进行，材料最终能降解成小分子，解决 海洋微塑料污染的问题。
本发明相比于现有技术，具有以下优点和突出效果：
(1)本发明在聚丙烯酸锌树脂中引入环状单体和乙烯基锌酯功能单体的共聚，制备了主链含有聚酯链段，侧链含有锌酯键的主链降解型自抛光防污树脂。所得到的树脂除了侧链锌酯键能在海水的进攻下水解外，主链聚酯链段也能发生降解，从而解决传统自抛光材料对航速的依赖性，在静态海水中也能通过水解降解作用使涂层表面自更新，从而有效调控防污剂以恒定的速率释放，保证了活性物质在船舶或海洋设备涂层表面的保持，很好地满足低航速的船舶以及海上采油平台等设施的防污要求；
(2)本发明提供的材料由于主侧链均可在海水进攻下断裂，因此能均匀并彻底抛光，使得船舶在航行期间涂层表面保持较低的粗糙度，减少航行阻力，赋予材料优良的减阻性能；
(3)本发明还可以在共聚合中加入不同种类和不同含量的乙烯基单体以调控材料的玻璃化转变温度和力学性能，同时改善材料在船舶涂料常用溶剂中的溶解性；
(4)本发明提供的制备方法，简单可行，成本较低，适合工业化生产，制备的聚丙烯酸锌树脂在海洋防污涂层领域具有很好的发展前景。
具体实施方式
下面结合具体实施例对本发明作进一步详细描述，但本发明的实施方式不限于此。
实施例1
一种主链降解型聚丙烯酸锌树脂的制备方法，具体包括以下步骤：
(1)乙烯基锌酯功能单体的合成：
向反应容器中加入81.4g氧化锌、200g丙二醇甲醚和40g二甲苯，加热至65℃，3小时滴加72.1g丙烯酸、86.1g甲基丙烯酸和10g去离子水的混合物，滴加完毕后，保温反应2小时，得到无色透明的乙烯基锌酯功能单体溶液；
(2)聚丙烯酸锌树脂的合成：
在搅拌的条件下，向反应容器中加入500g二甲苯、100g丙二醇甲醚和24g丙烯酸乙酯，氮气氛围下升温至90℃，6小时滴加由44g 2-亚甲基-1,3-二氧环 庚烷、44g甲基丙烯酸-2-甲氧基乙酯、176g甲基丙烯酸甲酯、396g丙烯酸乙酯、449.6g步骤(1)乙烯基锌酯功能单体溶液，22g偶氮二异丁腈和8gα-甲基苯乙烯二聚体组成的混合物，滴加完毕后，30分钟继续滴加8g过氧化二叔丁基和90g二甲苯的混合物，再搅拌1.5小时，得到主链降解型聚丙烯酸锌树脂(无色或微黄色的透明树脂溶液)。
本实施例中树脂数均分子量M n为2.5×10 4g/mol，锌含量为7.2％，酸值为124mgKOH/g，进行浅海挂板实验，14个月无海生物生长。
实施例2
一种主链降解型聚丙烯酸锌树脂的制备方法，具体包括以下步骤：
(1)乙烯基锌酯功能单体的合成：
向反应容器中加入81.4g氧化锌、400g二甲苯和100g异丙醇，加热至80℃，以恒定的速率滴加72.1g丙烯酸、340g环烷酸(酸值165)的混合物，3小时滴完，滴加完毕后，保温反应2小时，得到棕色透明的乙烯基锌酯功能单体溶液；
(2)聚丙烯酸锌树脂的合成：
在搅拌的条件下，向反应容器中加入350g二甲苯、100g甲基异丁基甲酮，氮气氛围下升温至95℃，4小时匀速滴加由100g己内酯、100g丙烯酸甲酯、100g丙烯酸丁酯、200g甲基丙烯酸环己酯、893.5g步骤(1)乙烯基锌酯功能单体溶液、1g甲醇和1mL磷腈(t-BuP 4)的正己烷溶液(0.5g的t-BuP 4)组成的混合物，滴加完毕后，保温2小时，30分钟匀速滴加5g偶氮二异丁腈和50g二甲苯，再搅拌4小时，得到主链降解型聚丙烯酸锌树脂(棕色的透明树脂溶液)。
本实施例中树脂数均分子量M n为3.0×10 4g/mol，锌含量为6.7％，酸值为115mgKOH/g，进行浅海挂板实验，12个月无海生物生长。
实施例3
一种主链降解型聚丙烯酸锌树脂的制备方法，具体包括以下步骤：
(1)乙烯基锌酯功能单体的合成：
向反应容器中加入99.4g氢氧化锌、400g甲苯和74g异丁醇，并加热至75℃，3小时匀速滴加72.1g丙烯酸、302.5g松香酸的混合物，滴加完毕后，保 温反应2小时，得到黄色透明的乙烯基锌酯功能单体溶液；
(2)聚丙烯酸锌树脂的合成：
在搅拌的条件下，向反应容器中加入500g二甲苯、400g乙酸丁酯，氮气氛围下升温至100℃，4小时匀速滴加由150g丙交酯、584g丙烯酸异辛酯、292g甲基丙烯酸乙酯、948g步骤(1)中乙烯基锌酯功能单体溶液，0.15g二乙二醇和1mL的t-BuP 4的正己烷溶液(0.5g的t-BuP 4)组成的混合物，滴加完毕后，保温2小时，30分钟匀速滴加8g过氧化苯甲酰和100g二甲苯，再搅拌4小时，得到主链降解型聚丙烯酸锌树脂(黄色的透明树脂溶液)。
本实施例中树脂数均分子量M n为1.2×10 4g/mol，锌含量为4.5％，酸值为77mgKOH/g，进行浅海挂板实验，8个月无海生物生长。
实施例4
一种主链降解型聚丙烯酸锌树脂的制备方法，具体包括以下步骤：
(1)乙烯基锌酯功能单体的合成：
向反应容器中加入183.5g乙酸锌、114g甲苯和300g正丁醇，并加热至130℃，3小时匀速滴加86.1g甲基丙烯酸和144.2g异辛酸的混合物，滴加完毕后，保温反应2小时，得到无色透明的乙烯基锌酯功能单体溶液；
(2)聚丙烯酸锌树脂的合成：
在搅拌的条件下，向反应容器中加入1800g丙二醇甲醚、400g乙酸乙酯，氮气氛围下升温至100℃，4小时匀速滴加由1172g 2-亚甲基-1,3-二氧环戊烷、293g甲基丙烯酸羟乙酯、586g丙烯酸苯酯、586g甲基丙烯酸叔丁酯、827.8g步骤(1)乙烯基锌酯功能单体溶液、88g过氧化-2-乙基己酸叔丁酯和29gα-甲基苯乙烯二聚体组成的混合物，滴加完毕后，保温2小时，30分钟匀速滴加15g过氧化-2-乙基己酸叔丁酯和300g二甲苯，再搅拌4小时，得到主链降解型聚丙烯酸锌树脂(无色的透明树脂溶液)。
本实施例中树脂数均分子量M n为2.6×10 4g/mol，锌含量为2.3％，酸值为38mgKOH/g，进行浅海挂板实验，6个月无海生物生长。

Claims (10)

  1. 一种主链降解型聚丙烯酸锌树脂，其特征在于：主要由以下按重量份数计的组分制备而成：
    Figure PCTCN2017116385-appb-100001
    所述乙烯基锌酯功能单体，由以下按重量份数计的组分制备而成：
    Figure PCTCN2017116385-appb-100002
    所述(甲基)丙烯酸是指丙烯酸或甲基丙烯酸。
  2. 根据权利要求1所述主链降解型聚丙烯酸锌树脂，其特征在于：
    所述环状单体为以下1～38结构中一种或多种：
    Figure PCTCN2017116385-appb-100003
    Figure PCTCN2017116385-appb-100004
    其中m＝1-12表示m为1-12的整数；
    所述乙烯基单体为丙烯酸酯类，甲基丙烯酸酯类，端羟基的丙烯酸酯类，端羟基的甲基丙烯酸酯类，丙烯酸环状烃酯类，甲基丙烯酸环状烃酯类，丙烯酸聚烯烃二醇酯类，甲基丙烯酸聚烯烃二醇酯类中一种以上。
  3. 根据权利要求2所述主链降解型聚丙烯酸锌树脂，其特征在于：丙烯酸酯类为丙烯酸甲酯、丙烯酸乙酯、丙烯酸-2-甲氧基乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸辛酯、丙烯酸异辛酯、丙烯酸月桂酯、丙烯酸硬脂酸酯中一种以上；
    甲基丙烯酸酯类为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸-2-甲氧基乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯 酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸辛酯、甲基丙烯酸异辛酯、甲基丙烯酸月桂酯、甲基丙烯酸硬脂酸酯中一种以上；
    端羟基的丙烯酸酯类为丙烯酸羟乙酯或丙烯酸羟丙酯中一种以上；
    端羟基的甲基丙烯酸酯类为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯中一种以上；
    丙烯酸环状烃酯类为丙烯酸苯酯、丙烯酸环己基酯、丙烯酸-4-甲基环己基酯、丙烯酸-4-叔丁基环己基酯中一种以上；
    甲基丙烯酸环状烃酯类为甲基丙烯酸苯酯、甲基丙烯酸环己基酯、甲基丙烯酸-4-甲基环己基酯、甲基丙烯酸-4-叔丁基环己基酯中一种以上；
    丙烯酸聚烯烃二醇酯类为丙烯酸聚乙二醇酯；
    甲基丙烯酸聚烯烃二醇酯类为甲基丙烯酸聚乙二醇酯。
  4. 根据权利要求1所述主链降解型聚丙烯酸锌树脂，其特征在于：所述含锌化合物为氧化锌、氢氧化锌、氯化锌、乙酸锌、丙酸锌中的一种以上；
    所述一元羧酸为丙烯酸、甲基丙烯酸、甲酸、乙酸、丙酸、苯甲酸、正辛酸、异辛酸、硬脂酸、异硬脂酸、环烷酸、衣康酸、马来酸、油酸、棕榈酸、松香酸中的一种以上。
  5. 根据权利要求1所述主链降解型聚丙烯酸锌树脂，其特征在于：所述溶剂为烃类溶剂、醇类溶剂和去离子水中的一种以上。
  6. 根据权利要求1所述主链降解型聚丙烯酸锌树脂，其特征在于：所述有机溶剂为烃类溶剂、醇类溶剂、酮类溶剂、酯类溶剂中的一种以上；所述引发剂为磷腈、磷腈盐、氧化磷腈、偶氮二异丁腈、偶氮二异戊腈、过氧化苯甲酰、过氧化二叔丁基、过氧化-2-乙基己酸叔丁酯中的一种以上。
  7. 根据权利要求6所述主链降解型聚丙烯酸锌树脂，其特征在于：所述烃类溶剂为甲苯、二甲苯中的一种以上；所述醇类溶剂为异丙醇、正丁醇、异丁醇、丙二醇甲醚中的一种以上；所述酮类溶剂为甲基乙基酮、甲基异丁基甲酮、丙酮、丁酮、环己酮中的一种以上；所述酯类溶剂为乙酸乙酯、乙酸丁酯的一种以上。
  8. 根据权利要求1所述主链降解型聚丙烯酸锌树脂，其特征在于：所述主链降解型聚丙烯酸锌树脂中，所述组分还包括低分子醇或低分子胺和/或调聚剂， 低分子醇或低分子胺与引发剂进行复配，调聚剂与引发剂进行复配；
    所述低分子醇为含碳原子1～12的脂肪族或芳香族醇中的一种或以上；
    所述低分子胺为含碳原子1～12的脂肪族或芳香族胺中的一种或以上；
    所述调聚剂为正十二烷基硫醇、叔十二烷基硫醇、3-巯基丙酸异辛酯、3-巯基丙酸乙基己醇酯、四(3-巯基丙酸)季茂四醇酯、α-甲基苯乙烯二聚体的一种或以上。
  9. 根据权利要求1～8任一项所述主链降解型聚丙烯酸锌树脂的制备方法，其特征在于：具体包括以下步骤：
    (1)乙烯基锌酯功能单体的合成：
    以50～105重量份溶剂为反应介质，将10～40重量份含锌化合物、15～30重量份(甲基)丙烯酸和20～75重量份一元羧酸于50～140℃反应3～8小时，得到乙烯基锌酯功能单体；
    (2)丙烯酸锌树脂的合成：
    在惰性氛围中，以50～100重量份有机溶剂为反应介质，在0.01～10重量份引发剂的作用下，将5～95重量份环状单体、0～95重量份乙烯基单体和5～80重量份乙烯基锌酯功能单体进行反应，反应的条件为于70～120℃反应8～18小时，得到丙烯酸锌聚合物。
  10. 根据权利要求1～8任一项所述主链降解型聚丙烯酸锌树脂的应用，其特征在于：所述主链降解型聚丙烯酸锌树脂用于制备海洋防污涂料。
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