WO2021237405A1 - 一种无溶剂海洋防污涂料及其制备方法 - Google Patents

一种无溶剂海洋防污涂料及其制备方法 Download PDF

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Publication number
WO2021237405A1
WO2021237405A1 PCT/CN2020/092084 CN2020092084W WO2021237405A1 WO 2021237405 A1 WO2021237405 A1 WO 2021237405A1 CN 2020092084 W CN2020092084 W CN 2020092084W WO 2021237405 A1 WO2021237405 A1 WO 2021237405A1
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Prior art keywords
solvent
agent
antifouling paint
marine antifouling
paint according
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PCT/CN2020/092084
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English (en)
French (fr)
Inventor
陈珊珊
叶章基
李春光
刘轶龙
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厦门双瑞船舶涂料有限公司
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Priority to CN202080005835.XA priority Critical patent/CN112955513A/zh
Priority to PCT/CN2020/092084 priority patent/WO2021237405A1/zh
Publication of WO2021237405A1 publication Critical patent/WO2021237405A1/zh

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    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • 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
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • 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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2248—Oxides; Hydroxides of metals of copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

Definitions

  • the invention relates to the technical field of coatings, in particular to a solvent-free marine antifouling coating and a preparation method thereof.
  • degradable polyurethane has been used as a new type of antifouling coating resin in the field of marine antifouling, and its antifouling effect is remarkable.
  • the polyester segment of the degradable polyurethane molecular chain is degraded under the action of seawater to form small molecules, which continuously renew the surface of the coating and release the fouling organisms on the surface, thereby achieving the purpose of antifouling.
  • the publication number is CN102964557A
  • the publication date is March 13, 2013,
  • the patent document titled "A hydrolytically degradable resin for antifouling and its preparation method and application” discloses a hydrolyzed degradable resin for antifouling, which is Degradable polyol, diisocyanate and hydrolyzable chain extender alternately copolymerized multi-block polymer, which has a certain antifouling effect.
  • the publication number is CN107163224A
  • the publication date is September 15, 2017,
  • the patent document titled "A biodegradable polymer marine antifouling material and its preparation and application” discloses a biodegradable polymer marine antifouling Material, the polymer is obtained by the reaction of degradable polyol, diisocyanate and chain extender, and then the hydrolyzable functional unit is introduced into the side chain of the polymer through acid-base reaction or transesterification reaction, and the degradable anti-fouling material has anti-fouling effect Up to 12 months.
  • the publication number is CN110835495A
  • the publication date is February 25, 2020
  • the patent document titled "A moisture-curing polyurethane antifouling coating for fishing nets and its preparation method” discloses a moisture-curing polyurethane antifouling coating for fishing nets , After the solvent in the coating volatilizes, the isocyanate-terminated polyester resin is cured into a film by absorbing the moisture in the humid air, the paint film can be slowly hydrolyzed, and the antifouling agent in the coating is released at the same time, which has a good antifouling effect.
  • the above-mentioned degradable polyurethane antifouling coatings are solvent-based antifouling coatings, and organic solvents need to be added to the coatings. Because solvent-based coatings will release volatile organic compounds (VOC), they will pollute the environment and affect the health of construction workers.
  • VOC volatile organic compounds
  • my country issued GB/T 38597-2020 "Technical Requirements for Low Volatile Organic Compound Content Coating Products" which formulated the VOC content limit in coatings from the source, prompting the coating industry to raise awareness of environmental protection and further promote low VOC content coatings Promotion and application of products. It can be seen that low-pollution and environmentally friendly coatings are the development trend of future coating products. Solvent-free coatings are safe and environmentally friendly, with the lowest VOC content, which is one of the future development directions of antifouling coatings.
  • the present invention provides a solvent-free marine antifouling coating, which includes component A and component B;
  • the component A includes degradable polyester polyol, castor oil derivatives, Composite antifouling agent, dewatering agent, defoaming agent, dispersant and pigment and filler;
  • the B component is a curing agent polyisocyanate.
  • the component A includes the following raw materials by weight: 30-40 parts by weight of degradable polyester polyol, 10-20 parts by castor oil derivatives, 40-50 parts by composite antifouling agent, and 0.5-3.5 parts by water scavenger , 0.1-0.5 parts of defoamer, 0.1-0.9 parts of dispersant and 1-10 parts of pigments and fillers;
  • the B component includes the following parts by weight of raw materials: curing agent polyisocyanate 10-50 parts.
  • the degradable polyester polyol is polylactide, polycaprolactone, polyethylene adipate, polyethylene adipate, poly(caprolactone- One or more combinations of lactide), poly(caprolactone-ethylene glycol), and poly(lactide-ethylene glycol), with a molecular weight of 100-2000.
  • the castor oil derivative is prepared by a transesterification method, and the method is:
  • the small molecular polyol is one or more combinations of ethylene glycol, pentaerythritol, glycerin, sorbitol, trimethylolpropane, diethylene glycol, and butylene glycol;
  • the catalyst is one of calcium oxide, magnesium oxide, calcium hydroxide, lead oxide, sodium methoxide, a mixture of sodium methoxide and triethanolamine, lithium hydroxide, and tetrabutyl titanate, and the protective gas It is a kind of nitrogen, argon.
  • the curing agent polyisocyanate is hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI), polymethylene One or more combinations of polyphenyl isocyanate (PAPI).
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TDI toluene diisocyanate
  • HMDI dicyclohexylmethane diisocyanate
  • PAPI polymethylene One or more combinations of polyphenyl isocyanate
  • the composite antifouling agent is composed of a main antifouling agent and an auxiliary antifouling agent;
  • the main antifouling agent is cuprous oxide, cuprous thiocyanate, copper pyrithione, zinc pyrithione, and Zinc, medetomidine, 4-bromo-2-(4-chlorophenyl)-5-trifluoromethyl-1H-pyrrole-3-carbonitrile, 4,5-dichloro-2-n-octyl- One or more combinations of 3-isothiazolinone;
  • the auxiliary antifouling agent is zinc oxide with a particle size of 5-30 microns.
  • the cuprous oxide is electrolytic cuprous oxide or smelted cuprous oxide.
  • the pigment and filler are one or more combinations of titanium dioxide, barium sulfate, talc, quartz sand, carbon black, iron red, iron black, and iron yellow, and the particle size of the pigment and filler is less than or equal to 30 microns .
  • the dewatering agent is one or a mixture of molecular sieve activation powder and oxazolidine type latent curing agent, for example, molecular sieve activation powder is commercially available molecular sieve activation powder 4A, and oxazolidine type latent curing agent is commercially available.
  • ALT-201 molecular sieve activation powder has a uniform microporous structure, which can remove the free water of the system;
  • the oxazolidine type latent curing agent is a monooxazolidine containing terminal hydroxyl groups, which can react preferentially with water to form ⁇ -alcoholamine , ⁇ -alcoholamine preferentially reacts with isocyanate to cure into a film, no gas is generated during the reaction, and there are no bubbles and pinholes on the surface of the coating film.
  • the defoaming agent is a silicone defoaming agent, such as commercially available Tego Airex962, Airex947, etc.
  • the silicone defoaming agent has low surface tension, rapid defoaming, and long foam suppression time.
  • the dispersant is a wetting and dispersing agent, such as the commercially available Tego wet280.
  • the present invention also provides a method for preparing a solvent-free marine antifouling paint as described above, which includes the following preparation steps:
  • Step 1 The pigments and fillers are heated at 105-180°C to remove water for more than 8 hours;
  • Step 2 Mix the degradable polyester polyol, castor oil derivative, water remover, defoamer, and dispersant according to the mass ratio and disperse uniformly at a high speed;
  • Step 3 Add the composite antifouling agent and the pigments and fillers in step one at a rotation speed of 2000-2500 revolutions/min, and then use sand milling or ball milling to process to a fineness of less than 50 microns to obtain component A.
  • Step 4 Mix components A and B uniformly to obtain the solvent-free marine antifouling paint, wherein the ratio of n(-NCO)/n(-OH) is 1.5-1:1.
  • the solvent-free marine antifouling paint provided by the present invention has the following technical principles and effects:
  • the antifouling principle is that the degradable polyester polyurethane resin will break the ester bond of the main chain under the action of seawater or biological enzymes, breaking the network structure of the surface coating , It is beneficial to the release of antifouling agent; at the same time, as the surface network structure is broken, the resin is degraded into small molecular fragments and dispersed in the seawater, the surface of the coating is constantly updated, and marine organisms are not easy to adhere, so as to achieve the purpose of antifouling; in addition, isocyanate The introduction of and the formation of a network structure make the coating film have excellent mechanical properties and adhesion properties;
  • castor oil derivatives the use of castor oil derivatives and polyester polyols has good solubility, its own viscosity is low, and it can be used as a viscosity regulator. If castor oil derivatives are not added, the system viscosity is too large, add antifouling agent Paint with pigments and fillers cannot be applied; castor oil derivatives contain primary hydroxyl groups, which participate in the curing reaction. By changing the type and content of castor oil derivatives, the cross-linking density and cross-linking speed of the coating can be adjusted to optimize the coating’s performance. Mechanical properties and a reasonable pot life for a two-component coating system; the aliphatic hydrophobic segment in the castor oil derivative molecule can adjust the hydrophilic and hydrophobic type of the coating, thereby regulating the degradation rate of the polyester;
  • the degradable polyester polyol and castor oil derivatives are compounded as the hydroxyl component to give full play to the coordination effect of the two, so that the coating has excellent mechanical properties and antifouling properties while achieving convenient construction. Strong environmental applicability, safety and environmental protection effect;
  • the solvent-free marine antifouling paint of the present invention uses dewatering agents and defoamers, and heats and removes water from pigments and fillers, and uses a combination of physical and chemical methods to eliminate bubbles and pinholes on the surface of the coating film. Ensure the excellent appearance of the coating film, improve the physical and chemical properties of the coating film, and avoid the phenomenon that the NCO contained in the curing agent reacts with moisture to form urea and carbon dioxide, which causes the film to foam;
  • the solvent-free marine antifouling paint of the present invention has excellent mechanical properties, good antifouling performance, no organic solvents, low VOC content, and meets environmental protection requirements.
  • the present invention also provides the formulas of the examples shown in the following table: (unit: parts by weight)
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Degradable polyester polyol 35 30 40 35 35 Castor oil derivatives 15 20 10 15 15
  • Composite antifouling agent 45 45
  • 45 45
  • the dewatering agent in Examples 1-5 is composed of molecular sieve activation powder 4A and ALT-201 in a mass ratio of 3:0.1, the dispersant is a commercially available Tego wet 280, and the defoaming agent is a commercially available Tego Airex 962;
  • the degradable polyester polyol in Example 1 is polylactide containing terminal hydroxyl groups, the number average molecular weight is 1000, the pigment and filler are carbon black, and the composite antifouling agent is composed of electrolytic cuprous oxide, copper pyrithione and zinc oxide.
  • the mass ratio is 35:5:5, and the curing agent polyisocyanate is hexamethylene diisocyanate (HDI);
  • Example 1 The preparation method of Example 1 is:
  • Step 1 Put castor oil and ethylene glycol in a reaction vessel at a ratio of 1:1.2, fill with nitrogen, and after heating to 120°C, add 0.1% tetrabutyl titanate; heating to 210°C , After 2h of heat preservation, stop the nitrogen flow, reduce the small molecule products and water by distillation under reduced pressure, and then cool and discharge the castor oil derivative, with a hydroxyl value of 345mgKOHg -1 and a viscosity of 250mPa ⁇ s;
  • Step 2 Heat the pigment filler carbon black at 120°C to remove water for 10 hours;
  • Step 3 Mix the castor oil derivative, degradable polyester polyol, water scavenger, defoamer, and dispersant prepared in step 1 according to the formula ratio and disperse uniformly at high speed; add the compound at 2300 revolutions/min.
  • the antifouling agent and the pigments and fillers of step two are then sanded to a fineness of less than 50 microns to obtain component A.
  • Step 4 Mix the B component hexamethylene diisocyanate (HDI) and the above A combination uniformly to obtain the solvent-free marine antifouling paint provided by the present invention.
  • HDI hexamethylene diisocyanate
  • the degradable polyester polyol in Example 2 is a polycaprolactone containing terminal hydroxyl groups, the number average molecular weight is 800, the pigment and filler are iron red, and the composite antifouling agent is composed of zinc pyrithione and 4-bromo-2-( 4-chlorophenyl)-5-trifluoromethyl-1H-pyrrole-3-carbonitrile and zinc oxide are composed of a mass ratio of 5:15:25.
  • the curing agent polyisocyanate is polymethylene polyphenyl isocyanate (PAPI );
  • Example 2 The preparation method of Example 2 is:
  • Step 1 Put castor oil and ethylene glycol in a reaction vessel at a ratio of 1:1.2, fill with nitrogen, and after heating to 120°C, add 0.5% of a mixture of sodium methoxide and triethanolamine (sodium methoxide and triethanolamine) The mass ratio of triethanolamine is 0.1:20), the temperature is increased to 220°C, after 2 hours, the nitrogen is stopped, the small molecule products and water are removed by vacuum distillation, and the material is cooled and discharged to obtain the castor oil derivative, the hydroxyl value of which is 332mgKOHg -1 , The viscosity is 260mPa ⁇ s.
  • Step 2 Heat the pigments and fillers at 150°C to remove water for 8 hours;
  • Step 3 Mix the castor oil derivative, degradable polyester polyol, water scavenger, defoamer, and dispersant prepared in step 1 according to the formula ratio and disperse uniformly at high speed; add the compound at 2300 revolutions/min.
  • the antifouling agent and the pigments and fillers of step two are then ball milled to a fineness of less than 50 microns to obtain component A.
  • Step 4 Mix the B-component polymethylene polyphenyl isocyanate (PAPI) and the above A combination uniformly to obtain the solvent-free marine antifouling paint provided by the present invention.
  • PAPI polymethylene polyphenyl isocyanate
  • the degradable polyester polyol in Example 3 is polyethylene adipate containing terminal hydroxyl groups, with a number average molecular weight of 800, and the pigment and filler are composed of barium sulfate and carbon black in a mass ratio of 5:1.
  • the composite antifouling The agent is composed of 4,5-dichloro-2-n-octyl-3-isothiazolinone, medetomidine and zinc oxide in a mass ratio of 10:10:25.
  • the curing agent polyisocyanate is toluene diisocyanate (TDI) ;
  • Example 3 The preparation method of Example 3 is:
  • Step 1 Put castor oil and ethylene glycol in a reaction vessel with a substance ratio of 1:1.2, fill it with nitrogen, add 0.04% calcium oxide after heating to 120°C; heating to 210°C, hold for 2h , Stop the introduction of nitrogen, remove the small molecule products and water by vacuum distillation, cool and discharge the castor oil derivative, the hydroxyl value of which is 345mgKOHg -1 and the viscosity is 240mPa ⁇ s;
  • Step 2 Heat the pigments and fillers at 110°C to remove water for 12 hours;
  • Step 3 Mix the castor oil derivative, degradable polyester polyol, water scavenger, defoamer, and dispersant prepared in step 1 according to the formula ratio and disperse uniformly at high speed; add the compound at 2300 revolutions/min.
  • the antifouling agent and the pigments and fillers of step two are then sanded to a fineness of less than 50 microns to obtain component A;
  • Step 4 Mix the B component toluene diisocyanate (TDI) with the above A combination uniformly to obtain the solvent-free marine antifouling paint provided by the present invention.
  • TDI toluene diisocyanate
  • the degradable polyester polyol in Example 4 is a polylactide containing terminal hydroxyl groups, with a number average molecular weight of 1000, pigment filler carbon black, and a composite antifouling agent consisting of electrolytic cuprous oxide, copper pyrithione, and zinc oxide.
  • the ratio is 35:5:5, and the curing agent polyisocyanate is dicyclohexylmethane diisocyanate (HMDI);
  • Example 4 The preparation method of Example 4 is:
  • Step 1 Put the ratio of castor oil to glycerin 1:1.3 in a reaction vessel, fill it with nitrogen, add 0.1% tetrabutyl titanate after heating up to 120°C; heating up to 230°C, hold for 2h , Stop the introduction of nitrogen, remove the small molecule products and water by distillation under reduced pressure, then cool and discharge the castor oil derivative, with a hydroxyl value of 405mgKOHg -1 and a viscosity of 300mPa ⁇ s;
  • Step 2 Heat the pigments and fillers at 120°C to remove water for 10 hours;
  • Step 3 Mix the castor oil derivative, degradable polyester polyol, water scavenger, defoamer, and dispersant prepared in step 1 according to the formula ratio and disperse uniformly at high speed; add the compound at 2300 revolutions/min.
  • the antifouling agent and the pigments and fillers of step two are then sanded to a fineness of less than 50 microns to obtain component A;
  • Step 4 Mixing the B component dicyclohexylmethane diisocyanate (HMDI) and the above A combination uniformly to obtain the solvent-free marine antifouling paint provided by the present invention.
  • HMDI dicyclohexylmethane diisocyanate
  • the degradable polyester polyol in Example 5 is poly(caprolactone-lactide) containing terminal hydroxyl groups, the molecular weight is 1200, the pigment and filler are carbon black, and the composite antifouling agent is composed of electrolytic cuprous oxide and pyridinethione. Copper and zinc oxide are composed in a mass ratio of 35:5:5, and the curing agent polyisocyanate is hexamethylene diisocyanate (IPDI);
  • Example 5 The preparation method of Example 5 is:
  • Step 1 Put castor oil and pentaerythritol in a reaction vessel at a ratio of 1:1.4. Fill it with nitrogen. After the temperature is raised to 120°C, add 0.1% tetrabutyl titanate; heat to 230°C and keep warm After 2h, stop the introduction of nitrogen, remove small molecule products and water by distillation under reduced pressure, cool and discharge to obtain castor oil derivative, its hydroxyl value is 460mgKOHg -1 , viscosity is 340mPa ⁇ s;
  • Step 2 Heat the pigments and fillers at 120°C to remove water for 10 hours;
  • Step 3 Mix the castor oil derivative, degradable polyester polyol, water scavenger, defoamer, and dispersant prepared in step 1 according to the formula ratio and disperse uniformly at high speed; add the compound at 2300 revolutions/min.
  • the antifouling agent and the pigments and fillers of step two are then ball milled to a fineness of less than 50 microns to obtain component A;
  • Step 4 Mixing the B component hexamethylene diisocyanate (IPDI) and the above A combination uniformly to obtain the solvent-free marine antifouling paint provided by the present invention.
  • IPDI hexamethylene diisocyanate
  • a commercially available degradable polyurethane D220 is used as the main resin, in which the composite antifouling agent, the pigments and fillers are the same as in Example 1, and the solvent is xylene.
  • the solvent-free marine antifouling coating provided by the present invention has excellent adhesion and impact resistance due to the introduction of isocyanate and the formation of a network structure in the degradable polyester polyurethane resin. ; At the same time, due to the rupture of the ester bond, the paint film can be slowly degraded, releasing the antifouling agent in the coating, which has a good antifouling effect.
  • degradable polyester polyol and castor oil derivatives can not only adjust the cross-linking density and cross-linking speed of the coating, thereby optimizing the mechanical properties of the coating and obtaining a reasonable pot life for the two-component coating system, but also can control the coating
  • the viscosity of the system does not require the addition of organic solvents, which is environmentally friendly.

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  • Engineering & Computer Science (AREA)
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Abstract

本发明涉及涂料技术领域，特别涉及一种无溶剂海洋防污涂料及其制备方法。其中，包括A组分和B组分；A组分包括降解型聚酯多元醇、蓖麻油衍生物、复合防污剂、除水剂、消泡剂、分散剂和颜填料；B组分为固化剂多异氰酸酯。本发明所提供的无溶剂海洋防污涂料，降解型聚酯聚氨酯树脂中由于异氰酸酯的引入和网状结构的形成，使涂膜具有优异的附着力和耐冲击性；同时由于酯键的断裂，使得漆膜能够缓慢降解，释放出涂层内的防污剂，具有良好的防污效果。降解型聚酯多元醇与蓖麻油衍生物结合，不仅可调节涂层的交联密度和交联速度，从而优化涂层的力学性能和获得涂料体系合理的适用期，同时可调控涂料体系粘度，无需添加有机溶剂，具有环保的特性。

Description

一种无溶剂海洋防污涂料及其制备方法 技术领域
本发明涉及涂料技术领域，特别涉及一种无溶剂海洋防污涂料及其制备方法。
背景技术
随着海洋业的发展，海洋生物污损问题日益突显。近几年来，降解型聚氨酯作为新型的防污涂料树脂在海洋防污领域应用，防污效果显著。降解型聚氨酯分子链上的聚酯链段在海水的作用下降解，形成小分子，使涂层表面不断更新，表面的污损生物脱离，从而达到防污的目的。
如公开号为CN102964557A，公开日为2013年3月13日，名称为《一种防污用水解降解树脂及其制备方法与应用》的专利文件公开了一种防污用水解降解树脂，其为可降解多元醇，二异氰酸酯和可水解扩链剂交替共聚而成的多嵌段聚合物，具有一定的防污效果。
公开号为CN107163224A，公开日为2017年9月15日，名称为《一种生物降解型高分子海洋防污材料及其制备与应用》的专利文件公开了一种生物降解型高分子海洋防污材料，采用可降解多元醇、二异氰酸酯和扩链剂反应得到聚合物，再通过酸碱反应或酯交换反应在聚合物侧链引入水解性功能单元，得到的降解型防污材料防污期效可达12个月。
又如公开号为CN110835495A，公开日为2020年2月25日，名称为《一种渔网用潮气固化聚氨酯防污涂料及其制备方法》的专利文件公开了一种渔网用潮气固化聚氨酯防污涂料，涂料中的溶剂挥发后，端异氰酸酯基聚酯树脂通过吸收潮湿空气中的水分固化成膜，漆膜可缓慢水解，同时释放出涂层 内防污剂，防污效果良好。
上述的降解型聚氨酯防污涂料均为溶剂型防污涂料，涂料中需要加入有机溶剂，由于溶剂型涂料会释放出挥发性有机化合物(VOC)，污染环境及影响施工人员的身体健康。2020年3月我国发布了GB/T 38597-2020《低挥发性有机化合物含量涂料产品技术要求》，从源头制定了涂料中VOC含量限值，促使涂料行业提高环保意识，进一步促进低VOC含量涂料产品的推广应用。可见，低污染的环境友好型涂料是未来涂料产品的发展趋势，其中无溶剂涂料安全环保，VOC含量最低，是防污涂料未来发展方向之一。
发明内容
为解决上述背景技术中的问题，本发明提供一种无溶剂海洋防污涂料，其中，包括A组分和B组分；所述A组分包括降解型聚酯多元醇、蓖麻油衍生物、复合防污剂、除水剂、消泡剂、分散剂和颜填料；所述B组分为固化剂多异氰酸酯。
进一步地，所述A组分包括以下重量份原料：降解型聚酯多元醇30-40份、蓖麻油衍生物10-20份、复合防污剂40-50份、除水剂0.5-3.5份、消泡剂0.1-0.5份、分散剂0.1-0.9份和颜填料1-10份；所述B组分包括以下重量份原料：固化剂多异氰酸酯10-50份。
进一步地，所述降解型聚酯多元醇为含端羟基的聚丙交酯、聚己内酯、聚己二酸乙二醇酯、聚己二酸二乙二醇酯、聚(己内酯-丙交酯)、聚(己内酯-乙二醇)、聚(丙交酯-乙二醇)中的一种或多种组合，其分子量为100-2000。
进一步地，所述蓖麻油衍生物采用酯交换法制备，其方法为：
将蓖麻油和小分子多元醇按物质的量比1:1-2置于反应容器中，充入保护气体，升温至100-120℃后,加入0.01-1.00％的催化剂；升温至180-250℃， 保温1-4h后，停止通入保护气体，减压蒸馏除去小分子产物和水后，即得到蓖麻油衍生物，其羟值为200-500mgKOHg -1，黏度为100-500mPa·s。
进一步地，所述小分子多元醇为乙二醇，季戊四醇，甘油，山梨醇，三羟甲基丙烷，二乙二醇，丁二醇中的一种或多种组合；
进一步地，所述催化剂为氧化钙、氧化镁、氢氧化钙、氧化铅、甲醇钠、甲醇钠与三乙醇胺的混合物、氢氧化锂、四丁基钛酸酯中的一种，所述保护气体为氮气，氩气的一种。
进一步地，所述固化剂多异氰酸酯为六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、二环己基甲烷二异氰酸酯(HMDI)、多亚甲基多苯基异氰酸酯(PAPI)中的一种或多种组合。
进一步地，所述复合防污剂由主防污剂和辅助防污剂组成；所述主防污剂为氧化亚铜、硫氰酸亚铜、吡啶硫酮铜、吡啶硫酮锌、代森锌、美托咪啶、4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈、4,5-二氯-2-正辛基-3-异噻唑啉酮中的一种或多种组合；所述辅助防污剂为粒径5-30微米的氧化锌。
优选地，氧化亚铜为电解氧化亚铜或冶炼氧化亚铜。
进一步地，所述颜填料为钛白粉、硫酸钡、滑石粉、石英砂、碳黑、铁红、铁黑、铁黄中的一种或多种组合，所述颜填料的粒径≤30微米。
进一步地，所述除水剂为分子筛活化粉和恶唑烷型潜固化剂一种或两种混合，例如分子筛活化粉采用市售的分子筛活化粉4A、恶唑烷型潜固化剂采用市售的ALT-201；分子筛活化粉具有均匀的微孔结构，可以脱除体系的游离水分；恶唑烷型潜固化剂为含端羟基的单恶唑烷可优先与水反应，生成β–醇胺，β–醇胺优先与异氰酸根反应而固化成膜，反应无气体产生，涂膜表面没有气泡和针孔。
进一步地，所述消泡剂为有机硅类消泡剂，例如市售的迪高Airex962，Airex947等，有机硅类消泡剂表面张力低、消泡迅速、抑泡时间长。
进一步地，所述分散剂为润湿分散剂，例如市售的迪高wet280等。
本发明还提供如上任意所述的一种无溶剂海洋防污涂料的制备方法，包括以下制备步骤：
步骤一、颜填料加热105-180℃除水8小时以上；
步骤二、按质量配比将降解型聚酯多元醇、蓖麻油衍生物、除水剂、消泡剂、分散剂混合高速分散均匀；
步骤三、在2000-2500转/分钟转速分散下加入复合防污剂和步骤一中的颜填料，然后采用砂磨或球磨处理至细度小于50微米即可得到A组分。
步骤四、将A和B组分混合均匀得到所述无溶剂海洋防污涂料，其中，n(-NCO)/n(-OH)的比值为1.5-1：1。
本发明提供的无溶剂海洋防污涂料与现有的技术相比，具有以下的技术原理和效果：
1、采用降解型聚酯多元醇和异氰酸酯作为主体成膜树脂，其防污原理为可降解聚酯聚氨酯树脂在海水或生物酶的作用下，主链的酯键断裂，打破表面涂层的网络结构，有利于防污剂的释放；同时，随着表面网络结构的破除，树脂降解成小分子片段分散到海水中，涂层表面不断更新，海生物不易附着，从而达到防污目的；另外，异氰酸酯的引入和网状结构的形成，使涂膜具有优异的力学性能和粘附性能；
2、添加蓖麻油衍生物，利用蓖麻油衍生物与聚酯多元醇溶解性良好，其本身粘度低，可作为粘度调节剂，若不添加蓖麻油衍生物，体系粘度太大，加入防污剂和颜填料后的涂料没法施工；蓖麻油衍生物含有伯羟基，参与固化反应，通过改变蓖麻油衍生物的种类和含量可以调节涂层的交联密度 和交联速度，从而优化涂层的力学性能和获得双组分涂料体系合理的适用期；蓖麻油衍生物分子中的脂肪族疏水链段可调节涂层的亲疏水型，从而调控聚酯的降解速率；
3、本发明将降解型聚酯多元醇和蓖麻油衍生物复配作为羟基组分，充分发挥二者的协调作用，使涂料在具有优异的力学性能和防污性能的同时能够达到施工便利，对环境的适用性强，安全环保的效果；
4、本发明的无溶剂海洋防污涂料中使用了除水剂、消泡剂，并对颜填料加热除水，采用物理与化学方法相结合，消除了涂膜表面产生的气泡和针孔，保证优异的涂膜外观，提高了涂膜的理化性能，避免了因固化剂组分中含有的—NCO与水分反应生成脲并产生二氧化碳导致涂膜起泡的现象；
5、本发明的无溶剂海洋防污涂料，力学性能优异，防污性能良好，不添加有机溶剂，VOC含量低，符合环保要求。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明还提供如下表所示实施例的配方：(单位：重量份)
表1
A组份材料名称 实施例1 实施例2 实施例3 实施例4 实施例5
降解型聚酯多元醇 35 30 40 35 35
蓖麻油衍生物 15 20 10 15 15
复合防污剂 45 45 45 45 45
除水剂 3.1 3.1 3.1 3.1 3.1
消泡剂 0.1 0.1 0.1 0.1 0.1
分散剂 0.5 0.5 0.5 0.5 0.5
颜填料 1 6 6 1 1
B组份材料名称 实施例1 实施例2 实施例3 实施例4 实施例5
固化剂多异氰酸酯 19 12 17 31 28
注：
实施例1-5中的除水剂由分子筛活化粉4A和ALT-201按质量比3:0.1组成，分散剂为市售的迪高wet 280，消泡剂为市售的迪高Airex 962；
实施例1中的降解型聚酯多元醇为含有端羟基的聚丙交酯，数均分子量为1000，颜填料为碳黑，复合防污剂由电解氧化亚铜、吡啶硫酮铜和氧化锌按质量比35:5:5组成，固化剂多异氰酸酯为六亚甲基二异氰酸酯(HDI)；
实施例1的制备方法为：
步骤一、将蓖麻油和乙二醇以1:1.2的物质的量比置于反应容器中，充入氮气，升温至120℃后，加入0.1％的四丁基钛酸酯；升温至210℃，保温2h后，停止通入氮气，减压蒸馏除去小分子产物和水后，降温出料得到蓖麻油衍生物，其羟值为345mgKOHg -1，黏度为250mPa·s；
步骤二、将颜填料碳黑加热120℃除水10小时；
步骤三、将步骤一制得的蓖麻油衍生物、降解型聚酯多元醇、除水剂、消泡剂、分散剂按配方比例混合并高速分散均匀；在2300转/分钟转速分散下加入复合防污剂和步骤二的颜填料，然后采用砂磨处理到细度小于50微米得到A组分。
步骤四、将B组分六亚甲基二异氰酸酯(HDI)与上述A组合混合均匀得到本发明提供的无溶剂海洋防污涂料。
实施例2中的降解型聚酯多元醇为含有端羟基的聚已内酯，数均分子量为800，颜填料为铁红，复合防污剂由吡啶硫酮锌、4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈和氧化锌按质量比5:15:25组成，固化剂多异氰 酸酯为多亚甲基多苯基异氰酸酯(PAPI)；
实施例2的制备方法为：
步骤一、将蓖麻油和乙二醇以1:1.2的物质的量比置于反应容器中，充入氮气，升温至120℃后，加入0.5％的甲醇钠与三乙醇胺的混合物(甲醇钠与三乙醇胺质量比0.1:20),升温至220℃，保温2h后，停止通入氮气，减压蒸馏除去小分子产物和水后，降温出料得到蓖麻油衍生物，其羟值为332mgKOHg -1，黏度为260mPa·s。
步骤二、将颜填料加热150℃除水8小时；
步骤三、将步骤一制得的蓖麻油衍生物、降解型聚酯多元醇、除水剂、消泡剂、分散剂按配方比例混合并高速分散均匀；在2300转/分钟转速分散下加入复合防污剂和步骤二的颜填料，然后采用球磨处理到细度小于50微米得到A组分。
步骤四、将B组分多亚甲基多苯基异氰酸酯(PAPI)与上述A组合混合均匀得到本发明提供的无溶剂海洋防污涂料。
实施例3中的降解型聚酯多元醇为含有端羟基的聚己二酸乙二醇酯，数均分子量为800，颜填料由硫酸钡和碳黑按质量比5：1组成，复合防污剂由4,5-二氯-2-正辛基-3-异噻唑啉酮、美托咪啶和氧化锌按质量比10:10:25组成，固化剂多异氰酸酯为甲苯二异氰酸酯(TDI)；
实施例3的制备方法为：
步骤一、将蓖麻油和乙二醇以1:1.2的物质的量比置于反应容器中，充入氮气，升温至120℃后，加入0.04％的氧化钙；升温至210℃，保温2h后，停止通入氮气，减压蒸馏除去小分子产物和水后，降温出料得到蓖麻油衍生物，其羟值为345mgKOHg -1，黏度为240mPa·s；
步骤二、将颜填料加热110℃除水12小时；
步骤三、将步骤一制得的蓖麻油衍生物、降解型聚酯多元醇、除水剂、消泡剂、分散剂按配方比例混合并高速分散均匀；在2300转/分钟转速分散下加入复合防污剂和步骤二的颜填料，然后采用砂磨处理到细度小于50微米得到A组分；
步骤四、将B组分甲苯二异氰酸酯(TDI)与上述A组合混合均匀得到本发明提供的无溶剂海洋防污涂料。
实施例4中的降解型聚酯多元醇为含有端羟基的聚丙交酯，数均分子量为1000，颜填料碳黑，复合防污剂由电解氧化亚铜、吡啶硫酮铜和氧化锌按质量比35:5:5组成，固化剂多异氰酸酯为二环己基甲烷二异氰酸酯(HMDI)；
实施例4的制备方法为：
步骤一、将蓖麻油和甘油1:1.3物质的量比置于反应容器中，充入氮气，升温至120℃后，加入0.1％的四丁基钛酸酯；升温至230℃，保温2h后，停止通入氮气，减压蒸馏除去小分子产物和水后，降温出料得到蓖麻油衍生物，其羟值为405mgKOHg -1，黏度为300mPa·s；
步骤二、将颜填料加热120℃除水10小时；
步骤三、将步骤一制得的蓖麻油衍生物、降解型聚酯多元醇、除水剂、消泡剂、分散剂按配方比例混合并高速分散均匀；在2300转/分钟转速分散下加入复合防污剂和步骤二的颜填料，然后采用砂磨处理到细度小于50微米得到A组分；
步骤四、将B组分二环己基甲烷二异氰酸酯(HMDI)与上述A组合混合均匀得到本发明提供的无溶剂海洋防污涂料。
实施例5中的降解型聚酯多元醇为含有端羟基的聚(己内酯-丙交酯)，分子量为1200，颜填料为碳黑，复合防污剂由电解氧化亚铜、吡啶硫酮铜 和氧化锌按质量比35:5:5组成，固化剂多异氰酸酯为六亚甲基二异氰酸酯(IPDI)；
实施例5的制备方法为：
步骤一、将蓖麻油和季戊四醇以1：1.4的物质的量比置于反应容器中，充入氮气，升温至120℃后，加入0.1％的四丁基钛酸酯；升温至230℃，保温2h后，停止通入氮气，减压蒸馏除去小分子产物和水后，降温出料得到蓖麻油衍生物，其羟值为460mgKOHg -1，黏度为340mPa·s；
步骤二、将颜填料加热120℃除水10小时；
步骤三、将步骤一制得的蓖麻油衍生物、降解型聚酯多元醇、除水剂、消泡剂、分散剂按配方比例混合并高速分散均匀；在2300转/分钟转速分散下加入复合防污剂和步骤二的颜填料，然后采用球磨处理到细度小于50微米得到A组分；
步骤四、将B组分六亚甲基二异氰酸酯(IPDI)与上述A组合混合均匀得到本发明提供的无溶剂海洋防污涂料。
对比例1：
采用市售的可降解聚氨酯D220作为主体树脂，其中复合防污剂，颜填料与实施例1相同，溶剂为二甲苯。
本发明提供的各实施例、对比例中的组分均采用同一公司，同一系列的产品。
将实施例和对比例制备得到的涂料根据表2中的主要技术指标进行性能测试,测试结果如表3所示。
表2
序号 项目 检测方法
1 粘度(23±2)℃，mPa·s GB/T 2794-2013
2 干燥时间(23±2)℃，h GB/T 1728-1979
3 适用期(23±2)℃，h -
4 VOC，g/L GB/T 23985-2009
5 防污性能,1年，评分 GB/T 5370-2007
6 附着力，MPa GB/T 5210-2006
7 耐冲击性，cm GB/T 1732-1993
表3
Figure PCTCN2020092084-appb-000001
从上述测试结果可以得出：本发明所提供的无溶剂海洋防污涂料，降解型聚酯聚氨酯树脂中由于异氰酸酯的引入和网状结构的形成，使涂膜具有优异的附着力和耐冲击性；同时由于酯键的断裂，使得漆膜能够缓慢降解，释放出涂层内的防污剂，具有良好的防污效果。降解型聚酯多元醇与蓖麻油衍生物结合，不仅可以调节涂层的交联密度和交联速度，从而优化涂层的力学性能和获得双组分涂料体系合理的适用期，同时可以调控涂料体系的粘度，无需添加有机溶剂，具有环保的特性。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (23)

  1. 一种无溶剂海洋防污涂料，其特征在于：包括A组分和B组分；所述A组分包括降解型聚酯多元醇、蓖麻油衍生物、复合防污剂、除水剂、消泡剂、分散剂和颜填料；所述B组分为固化剂多异氰酸酯。
  2. 根据权利要求1所述的无溶剂海洋防污涂料，其特征在于：
    所述A组分包括以下重量份原料：降解型聚酯多元醇30-40份、蓖麻油衍生物10-20份、复合防污剂40-50份、除水剂0.5-3.5份、消泡剂0.1-0.5份、分散剂0.1-0.9份和颜填料1-10份；
    所述B组分包括以下重量份原料：固化剂多异氰酸酯10-50份。
  3. 根据权利要求1所述的无溶剂海洋防污涂料，其特征在于：所述降解型聚酯多元醇为含端羟基的聚丙交酯、聚己内酯、聚己二酸乙二醇酯、聚己二酸二乙二醇酯、聚(己内酯-丙交酯)、聚(己内酯-乙二醇)、聚(丙交酯-乙二醇)中的一种或多种组合，其数均分子量为100-2000。
  4. 根据权利要求1所述的无溶剂海洋防污涂料，其特征在于：所述蓖麻油衍生物采用酯交换法制备，其方法为：
    将蓖麻油和小分子多元醇按物质的量比1:1-2置于反应容器中，充入保护气体,升温至100-120℃后,加入0.01-1.00％的催化剂,升温至180-250℃,保温1-4h后，停止通入保护气体，减压蒸馏除去小分子产物和水后，即得到蓖麻油衍生物，其羟值为200-500mgKOHg -1，黏度为100-500mPa·s。
  5. 根据权利要求4所述的无溶剂海洋防污涂料，其特征在于：所述小分子多元醇为乙二醇，季戊四醇，甘油，山梨醇，三羟甲基丙烷，二乙二醇，丁二醇中的一种或多种组合。
  6. 根据权利要求4所述的无溶剂海洋防污涂料，其特征在于：所述催化剂为氧化钙、氧化镁、氢氧化钙、氧化铅、甲醇钠、甲醇钠与三乙醇胺的混合物、氢氧化锂、四丁基钛酸酯中的一种，所述保护气体为氮气，氩气的一 种。
  7. 根据权利要求1所述的无溶剂海洋防污涂料，其特征在于：所述固化剂多异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、多亚甲基多苯基异氰酸酯中的一种或多种组合。
  8. 根据权利要求1所述的无溶剂海洋防污涂料，其特征在于：所述复合防污剂由主防污剂和辅助防污剂组成；所述主防污剂为氧化亚铜、硫氰酸亚铜、吡啶硫酮铜、吡啶硫酮锌、代森锌、美托咪啶、4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈、4,5-二氯-2-正辛基-3-异噻唑啉酮中的一种或多种组合；所述辅助防污剂为粒径5-30微米的氧化锌。
  9. 根据权利要求1所述的无溶剂海洋防污涂料，其特征在于：所述颜填料为钛白粉、硫酸钡、滑石粉、石英砂、碳黑、铁红、铁黑、铁黄中的一种或多种组合，所述颜填料的粒径≤30微米。
  10. 根据权利要求1所述的无溶剂海洋防污涂料，其特征在于：所述除水剂为分子筛活化粉和恶唑烷型潜固化剂一种或两种混合。
  11. 根据权利要求1所述的无溶剂海洋防污涂料，其特征在于：所述消泡剂为有机硅类消泡剂。
  12. 根据权利要求1所述的无溶剂海洋防污涂料，其特征在于：所述分散剂为润湿分散剂。
  13. 一种无溶剂海洋防污涂料的制备方法，其特征在于：包括以下制备步骤：
    步骤一、颜填料加热105-180℃除水；
    步骤二、按质量配比将降解型聚酯多元醇、蓖麻油衍生物、除水剂、消泡剂、分散剂混合高速分散均匀；
    步骤三、分散后加入复合防污剂和步骤一中的颜填料，然后采用砂磨或球磨处理至细度小于50微米即可得到A组分；
    步骤四、将A和B组分固化剂多异氰酸酯混合均匀得到所述无溶剂海洋防污涂料。
  14. 根据权利要求13所述的无溶剂海洋防污涂料的制备方法，其特征在于：
    所述A组分包括以下重量份原料：降解型聚酯多元醇30-40份、蓖麻油衍生物10-20份、复合防污剂40-50份、除水剂0.5-3.5份、消泡剂0.1-0.5份、分散剂0.1-0.9份和颜填料1-10份；
    所述B组分包括以下重量份原料：固化剂多异氰酸酯10-50份。
  15. 根据权利要求13所述的无溶剂海洋防污涂料的制备方法，其特征在于：所述降解型聚酯多元醇为含端羟基的聚丙交酯、聚己内酯、聚己二酸乙二醇酯、聚己二酸二乙二醇酯、聚(己内酯-丙交酯)、聚(己内酯-乙二醇)、聚(丙交酯-乙二醇)中的一种或多种组合，其数均分子量为100-2000。
  16. 根据权利要求13所述的无溶剂海洋防污涂料的制备方法，其特征在于：所述蓖麻油衍生物采用酯交换法制备，其方法为：
    将蓖麻油和小分子多元醇按物质的量比1:1-2置于反应容器中，充入保护气体，升温至100-120℃后，加入0.01-1.00％的催化剂；升温至180-250℃，保温1-4h后，停止通入保护气体，减压蒸馏除去小分子产物和水后，即得到蓖麻油衍生物，其羟值为200-500mgKOHg -1，黏度为100-500mPa·s。
  17. 根据权利要求16所述的无溶剂海洋防污涂料的制备方法，其特征在于：所述小分子多元醇为乙二醇，季戊四醇，甘油，山梨醇，三羟甲基丙烷，二乙二醇，丁二醇中的一种或多种组合。
  18. 根据权利要求16所述的无溶剂海洋防污涂料的制备方法，其特征在于：所述催化剂为氧化钙、氧化镁、氢氧化钙、氧化铅、甲醇钠、甲醇钠与三乙醇胺的混合物、氢氧化锂、四丁基钛酸酯中的一种，所述保护气体为氮气或氩气的一种。
  19. 根据权利要求13所述的无溶剂海洋防污涂料的制备方法，其特征在于：所述固化剂多异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、多亚甲基多苯基异氰酸酯中的一种或多种组合。
  20. 根据权利要求13所述的无溶剂海洋防污涂料的制备方法，其特征在于：所述复合防污剂由主防污剂和辅助防污剂组成；所述主防污剂为氧化亚铜、硫氰酸亚铜、吡啶硫酮铜、吡啶硫酮锌、代森锌、美托咪啶、4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈、4,5-二氯-2-正辛基-3-异噻唑啉酮中的一种或多种组合；所述辅助防污剂为粒径5-30微米的氧化锌。
  21. 根据权利要求13所述的无溶剂海洋防污涂料的制备方法，其特征在于：所述颜填料为钛白粉、硫酸钡、滑石粉、石英砂、碳黑、铁红、铁黑、铁黄中的一种或多种组合，所述颜填料的粒径≤30微米。
  22. 根据权利要求13所述的无溶剂海洋防污涂料的制备方法，其特征在于：所述除水剂为分子筛活化粉和恶唑烷型潜固化剂一种或两种混合。
  23. 根据权利要求13所述的无溶剂海洋防污涂料的制备方法，其特征在于：所述消泡剂为有机硅类消泡剂。
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