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WO2017049694A1 - Acrylic ester copolymer emulsion for high-water-resistance heavy-duty anticorrosion coating, and preparation method therefor - Google Patents

Acrylic ester copolymer emulsion for high-water-resistance heavy-duty anticorrosion coating, and preparation method therefor Download PDF

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Publication number
WO2017049694A1
WO2017049694A1 PCT/CN2015/092619 CN2015092619W WO2017049694A1 WO 2017049694 A1 WO2017049694 A1 WO 2017049694A1 CN 2015092619 W CN2015092619 W CN 2015092619W WO 2017049694 A1 WO2017049694 A1 WO 2017049694A1
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parts
emulsion
water
copolymer emulsion
acrylate copolymer
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PCT/CN2015/092619
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French (fr)
Chinese (zh)
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葛亮
朱鹏
戴骏骏
刘磊
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南通瑞普埃尔生物工程有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26Emulsion polymerisation with the aid of emulsifying agents anionic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers 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 an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06Hydrocarbons
    • C08F212/08Styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D125/00Coating compositions 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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02Homopolymers or copolymers of hydrocarbons
    • C09D125/04Homopolymers or copolymers of styrene
    • C09D125/08Copolymers of styrene
    • C09D125/14Copolymers of styrene with unsaturated esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate

Definitions

  • the invention relates to an acrylate copolymer emulsion and a preparation method thereof, in particular to an acrylate copolymer emulsion for a high water resistance heavy anti-corrosion coating and a preparation method thereof.
  • Metal corrosion refers to a phenomenon in which a chemical or electrochemical heterogeneous reaction occurs at the interface between a metal and another medium to transfer the metal into an oxidized (ion) state. Effectively isolating oxygen and water vapor to avoid oxidation and electron migration is one of the main means to prevent metal corrosion.
  • the most effective method for metal corrosion protection is to coat a dense polymer film on the surface to prevent oxygen and water vapor from being corroded.
  • the general mechanical strength of the product on the market and the adhesion to the metal surface are not high, causing the metal film to be damaged and detached when the metal is subjected to external force or immersed in water for a long time, and the metal is re-corroded.
  • the present invention is directed to the deficiencies in the prior art, and proposes a method for preparing an acrylate copolymer emulsion by a semi-continuous dropwise addition method, and the obtained acrylate copolymer emulsion has good water resistance, and the coating film is not whitened in water.
  • the acrylate copolymer emulsion with high water resistance and anti-corrosion coating with good salt water resistance and salt spray resistance and preparation method is directed to the deficiencies in the prior art, and proposes a method for preparing an acrylate copolymer emulsion by a semi-continuous dropwise addition method, and the obtained acrylate copolymer emulsion has good water resistance, and the coating film is not whitened in water.
  • the acrylate copolymer emulsion with high water resistance and anti-corrosion coating with good salt water resistance and salt spray resistance and preparation method are examples of the acrylate copolymer emulsion with high water resistance and anti-corrosion coating with good salt water
  • the acrylate copolymer emulsion for high water-resistance heavy-duty anticorrosive coating according to the present invention is composed of the following raw materials by weight ratio: 50-60 parts of styrene, 25-35 parts of butyl acrylate, and methyl group. 10-15 parts of methyl acrylate, 5-10 parts of methyl acrylate, 1-2 parts of acrylic acid, 2-3 parts of glycidyl methacrylate, 0.5-1 part of initiator, 2-4 parts of anionic emulsifier, reactive type 1-2 parts of emulsifier, 100-120 parts of deionized water, 0.0001-0.0002 parts of pH adjuster, and 3-5 parts of film-forming auxiliary.
  • anionic emulsifier is any one of sodium lauryl sulfate or sodium dodecylbenzenesulfonate.
  • the reactive emulsifier is any one of sodium styrene sulfonate or sodium allyl sulfonate.
  • the initiator is any one of ammonium persulfate or sodium persulfate.
  • the pH adjusting agent is any one of ammonia water or sodium hydroxide.
  • the film forming aid is ethylene glycol monobutyl ether.
  • the invention also discloses a preparation method of the above acrylate copolymer emulsion for high water resistance heavy anti-corrosion coating, comprising the following steps:
  • the partial pre-emulsion and the initiator solution described in the step (5) are 20% of the pre-emulsion and 30% of the initiator solution, respectively.
  • the present invention prepares an acrylate copolymer emulsion by using a semi-continuous dropwise addition method, and the obtained acrylate copolymer emulsion has good water resistance, the coating film is not whitened in water, and has good salt water resistance and salt spray resistance. Performance, can be applied to the field of heavy corrosion protection of metal materials.
  • the invention relates to an acrylate copolymer emulsion for high water-resistance heavy-duty anticorrosive coating, which is composed of the following proportion by weight of raw materials:
  • the specific preparation process 4 kg of sodium styrene sulfonate is dissolved in 160 kg of deionized water, put into a pre-emulsion tank, all monomers are added, and the pre-emulsification is continued for at least 30 minutes to obtain a pre-emulsion.
  • 1.5kg of sodium persulfate was dissolved in 20kg of deionized water and put into the initiator tank to obtain the initiator solution; 8kg of sodium lauryl sulfate was dissolved in 180kg of deionized water, put into the reaction kettle, the stirring was started, and the reaction was fully replaced with nitrogen. The air in the kettle was replaced at least twice.
  • the obtained emulsion performance indicators are as follows:
  • Viscosity (mPa ⁇ s): 56.7;
  • the invention relates to an acrylate copolymer emulsion for high water-resistance heavy-duty anticorrosive coating, which is composed of the following proportion by weight of raw materials:
  • the obtained emulsion performance indicators are as follows:
  • Viscosity (mPa ⁇ s): 58.2;
  • the invention relates to an acrylate copolymer emulsion for high water-resistance heavy-duty anticorrosive coating, which is composed of the following proportion by weight of raw materials:
  • the obtained emulsion performance indicators are as follows:
  • Viscosity (mPa ⁇ s): 54.3;
  • the invention prepares the acrylate copolymer emulsion by adopting a semi-continuous dropping method, and the obtained acrylate copolymer emulsion has good water resistance, the coating film is not whitened in water, and has good salt water resistance and salt spray resistance, and can Used in the field of heavy corrosion protection of metal materials.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

An acrylic ester copolymer emulsion for a high-water-resistance heavy-duty anticorrosion coating is prepared from the following raw materials in parts by weight: 50 to 60 parts of styrene, 25 to 35 parts of butyl acrylate, 10 to 15 parts of methyl methacrylate, 5 to 10 parts of methyl acrylate, 1 to 2 parts of acrylic acid, 2 to 3 parts of glycidyl methacrylate, 0.5 to 1 part of initiator, 2 to 4 parts of anionic emulsifier, 1 to 2 parts of reactive emulsifier, 100 to 120 parts of deionized water, 0.0001 to 0.0002 part of pH regulator, and 3 to 5 parts of film coalescing aid. The emulsion is prepared by means of a semi-continuously dropwise adding mode, the emulsion has good water resistance, the formed coating is not whitened when placed into water, and the coating has good saline water resistance and salt spray resistance and can be used in the field of heavy-duty anticorrosion of metal materials.

Description

高耐水性重防腐涂料用丙烯酸酯共聚乳液及制备方法Acrylate copolymer emulsion for high water resistance heavy anti-corrosion coating and preparation method thereof 技术领域Technical field
本发明涉及一种丙烯酸酯共聚乳液及其制备方法,具体涉及一种高耐水性重防腐涂料用丙烯酸酯共聚乳液及制备方法。The invention relates to an acrylate copolymer emulsion and a preparation method thereof, in particular to an acrylate copolymer emulsion for a high water resistance heavy anti-corrosion coating and a preparation method thereof.
背景技术Background technique
每年因金属腐蚀而造成的经济损失是国内生产总值的4%,如何避免此类经济损失是国民领域研究的重要课题之一。金属腐蚀是指在金属与其他介质的界面上发生了化学或电化学的多相反应,使金属转入氧化(离子)状态的一种现象。有效的隔绝氧气和水汽,达到避免氧化和电子迁移的目的,是阻止金属腐蚀的主要手段之一。The annual economic loss caused by metal corrosion is 4% of GDP. How to avoid such economic losses is one of the important topics in national research. Metal corrosion refers to a phenomenon in which a chemical or electrochemical heterogeneous reaction occurs at the interface between a metal and another medium to transfer the metal into an oxidized (ion) state. Effectively isolating oxygen and water vapor to avoid oxidation and electron migration is one of the main means to prevent metal corrosion.
金属防腐目前最有效的方法是在表面涂覆一层致密的高分子膜,从而达到阻隔氧气和水汽,避免金属被腐蚀的效果。但是市面上一般的产品机械强度和与金属表面的附着力均不高,造成金属一旦受到外力或者长时间被水冲洗浸泡则高分子膜损坏脱落,金属重新被腐蚀的情况。针对上述的问题,我们设计了一种具有良好的附着力与耐水性的重防腐涂料用丙烯酸酯共聚乳液,可以很好的防止金属的腐败生锈。The most effective method for metal corrosion protection is to coat a dense polymer film on the surface to prevent oxygen and water vapor from being corroded. However, the general mechanical strength of the product on the market and the adhesion to the metal surface are not high, causing the metal film to be damaged and detached when the metal is subjected to external force or immersed in water for a long time, and the metal is re-corroded. In response to the above problems, we have designed an acrylate copolymer emulsion for heavy anti-corrosion coatings with good adhesion and water resistance, which can prevent the corrosion and rust of metals.
发明内容Summary of the invention
发明目的:本发明针对现有技术中的不足,提出一种采用半连续滴加方式制备丙烯酸酯共聚乳液,得到的丙烯酸酯共聚乳液具有良好的耐水性,涂膜放入水中不会泛白,同时具有良好的耐盐水和耐盐雾性能的高耐水性重防腐涂料用丙烯酸酯共聚乳液及制备方法。OBJECT OF THE INVENTION: The present invention is directed to the deficiencies in the prior art, and proposes a method for preparing an acrylate copolymer emulsion by a semi-continuous dropwise addition method, and the obtained acrylate copolymer emulsion has good water resistance, and the coating film is not whitened in water. At the same time, the acrylate copolymer emulsion with high water resistance and anti-corrosion coating with good salt water resistance and salt spray resistance and preparation method.
技术方案:本发明所述的一种高耐水性重防腐涂料用丙烯酸酯共聚乳液,由如下重量份数的原料配比组成:苯乙烯50-60份、丙烯酸丁酯25-35份、甲基丙烯酸甲酯10-15份、丙烯酸甲酯5-10份、丙烯酸1-2份、甲基丙烯酸缩水甘油酯2-3份、引发剂0.5-1份、阴离子乳化剂2-4份、反应型乳化剂1-2份、去离子水100-120份、PH调节剂0.0001-0.0002份、成膜助剂3-5份。Technical Solution: The acrylate copolymer emulsion for high water-resistance heavy-duty anticorrosive coating according to the present invention is composed of the following raw materials by weight ratio: 50-60 parts of styrene, 25-35 parts of butyl acrylate, and methyl group. 10-15 parts of methyl acrylate, 5-10 parts of methyl acrylate, 1-2 parts of acrylic acid, 2-3 parts of glycidyl methacrylate, 0.5-1 part of initiator, 2-4 parts of anionic emulsifier, reactive type 1-2 parts of emulsifier, 100-120 parts of deionized water, 0.0001-0.0002 parts of pH adjuster, and 3-5 parts of film-forming auxiliary.
进一步的,所述阴离子乳化剂为十二烷基硫酸钠或十二烷基苯磺酸钠中的任意一种。Further, the anionic emulsifier is any one of sodium lauryl sulfate or sodium dodecylbenzenesulfonate.
进一步的,所述反应型乳化剂为苯乙烯磺酸钠或烯丙基磺酸钠中的任意一种。Further, the reactive emulsifier is any one of sodium styrene sulfonate or sodium allyl sulfonate.
进一步的,所述引发剂为过硫酸铵或者过硫酸钠中的任意一种。Further, the initiator is any one of ammonium persulfate or sodium persulfate.
进一步的,所述PH调节剂为氨水或者氢氧化钠中的任意一种。Further, the pH adjusting agent is any one of ammonia water or sodium hydroxide.
进一步的,所述成膜助剂为乙二醇单丁醚。Further, the film forming aid is ethylene glycol monobutyl ether.
本发明还公开了上述一种高耐水性重防腐涂料用丙烯酸酯共聚乳液的制备方法,包括如下步骤:The invention also discloses a preparation method of the above acrylate copolymer emulsion for high water resistance heavy anti-corrosion coating, comprising the following steps:
(1)反应釜中投入45-55份去离子水和全部反应型乳化剂,搅拌至溶解; (1) Injecting 45-55 parts of deionized water and all reactive emulsifiers into the reactor, stirring until dissolved;
(2)在引发剂滴加罐中投入全部引发剂和5-10份去离子水,搅拌至溶解,得引发剂溶液;(2) adding all the initiator and 5-10 parts of deionized water in the initiator dropping tank, stirring until dissolved, to obtain an initiator solution;
(3)在预乳化滴加罐中投入全部阴离子乳化剂和剩余去离子水,搅拌至溶解;并将全部单体投入预乳化滴加罐,持续开启搅拌预乳化至少30min,得预乳化液;(3) adding all the anionic emulsifier and residual deionized water in the pre-emulsified dropping tank, stirring until dissolved; and putting all the monomers into the pre-emulsified dropping tank, and continuously opening and stirring pre-emulsification for at least 30 minutes to obtain a pre-emulsion;
(4)用氮气充分置换反应釜中的空气,至少置换2次;(4) sufficiently replacing the air in the reaction vessel with nitrogen, at least 2 times;
(5)反应釜搅拌开启,保持常压,升温至80-85℃,加入部分预乳化液和部分引发剂溶液,反应时间1h;(5) stirring the reactor, maintaining normal pressure, heating to 80-85 ° C, adding part of the pre-emulsion and part of the initiator solution, reaction time 1h;
(4)保持温度不变,滴加剩余预乳化液和引发剂溶液,滴加时间为3h;(4) keep the temperature unchanged, add the remaining pre-emulsion and initiator solution, the dropping time is 3h;
(5)保持温度不变,保温反应1h;(5) keep the temperature unchanged, the heat preservation reaction for 1h;
(6)降温至常温,用PH调节剂调节PH至7-8,加入成膜助剂,用100目过滤网过滤即得高附着力重防腐涂料用丙烯酸酯共聚乳液。(6) Cooling to normal temperature, adjusting the pH to 7-8 with a pH adjuster, adding a film-forming auxiliary agent, and filtering with a 100-mesh filter to obtain an acrylate copolymer emulsion for a high adhesion heavy-duty anti-corrosion coating.
进一步的,步骤(5)所述的部分预乳化液和引发剂溶液的分别为20%的预乳化液和30%的引发剂溶液。Further, the partial pre-emulsion and the initiator solution described in the step (5) are 20% of the pre-emulsion and 30% of the initiator solution, respectively.
有益效果:本发明通过采用半连续滴加方式制备丙烯酸酯共聚乳液,得到的丙烯酸酯共聚乳液具有良好的耐水性,涂膜放入水中不会泛白,同时具有良好的耐盐水和耐盐雾性能,能够应用于金属材料的重防腐领域。Advantageous Effects: The present invention prepares an acrylate copolymer emulsion by using a semi-continuous dropwise addition method, and the obtained acrylate copolymer emulsion has good water resistance, the coating film is not whitened in water, and has good salt water resistance and salt spray resistance. Performance, can be applied to the field of heavy corrosion protection of metal materials.
具体实施方式detailed description
下面结合具体实施例对本发明作进一步说明:The present invention will be further described below in conjunction with specific embodiments:
实施例1Example 1
一种高耐水性重防腐涂料用丙烯酸酯共聚乳液,由如下重量份数的原料配比组成:The invention relates to an acrylate copolymer emulsion for high water-resistance heavy-duty anticorrosive coating, which is composed of the following proportion by weight of raw materials:
Figure PCTCN2015092619-appb-000001
Figure PCTCN2015092619-appb-000001
Figure PCTCN2015092619-appb-000002
Figure PCTCN2015092619-appb-000002
具体制备过程:将4kg苯乙烯磺酸钠溶于160kg去离子水,投入预乳化罐,加入全部单体,持续开启搅拌预乳化至少30min,得预乳化液。将1.5kg过硫酸钠溶于20kg去离子水中,投入引发剂罐,得引发剂溶液;将8kg十二烷基硫酸钠溶于180kg去离子水中,投入反应釜,开启搅拌,用氮气充分置换反应釜中的空气,至少置换2次。保持常压,升温至80-85℃,加入20%的预乳化液和30%的引发剂溶液,反应时间1h。保持温度不变,滴加预乳化液和引发剂,滴加时间为3h。保持温度不变,保温反应1h。降温至常温,用PH调节剂调节PH至7-8,加入15kg乙二醇丁醚,用100目过滤网过滤即得高附着力重防腐涂料用丙烯酸酯共聚乳液。The specific preparation process: 4 kg of sodium styrene sulfonate is dissolved in 160 kg of deionized water, put into a pre-emulsion tank, all monomers are added, and the pre-emulsification is continued for at least 30 minutes to obtain a pre-emulsion. 1.5kg of sodium persulfate was dissolved in 20kg of deionized water and put into the initiator tank to obtain the initiator solution; 8kg of sodium lauryl sulfate was dissolved in 180kg of deionized water, put into the reaction kettle, the stirring was started, and the reaction was fully replaced with nitrogen. The air in the kettle was replaced at least twice. Maintain normal pressure, heat to 80-85 ° C, add 20% pre-emulsion and 30% initiator solution, reaction time 1h. Keep the temperature constant, add the pre-emulsion and the initiator dropwise, and the dropping time is 3h. Keep the temperature constant and keep the reaction for 1 h. The temperature was lowered to normal temperature, the pH was adjusted to 7-8 with a pH adjuster, 15 kg of ethylene glycol butyl ether was added, and the filter was filtered through a 100 mesh filter to obtain an acrylate copolymer emulsion for a high adhesion heavy-duty anticorrosive coating.
所得乳液性能指标如下:The obtained emulsion performance indicators are as follows:
固含量(%):48.6%;Solid content (%): 48.6%;
粘度(mPa·s):56.7;Viscosity (mPa·s): 56.7;
表面张力(mN/m):43.7;Surface tension (mN/m): 43.7;
稀释稳定性:通过Dilution stability: through
存储稳定性:1年Storage stability: 1 year
附着力:0级Adhesion: 0
耐水性:0级Water resistance: 0
耐盐水:>800hSalt water resistance: >800h
耐盐雾:>800hSalt spray resistance: >800h
实施实例2Implementation example 2
一种高耐水性重防腐涂料用丙烯酸酯共聚乳液,由如下重量份数的原料配比组成:The invention relates to an acrylate copolymer emulsion for high water-resistance heavy-duty anticorrosive coating, which is composed of the following proportion by weight of raw materials:
Figure PCTCN2015092619-appb-000003
Figure PCTCN2015092619-appb-000003
Figure PCTCN2015092619-appb-000004
Figure PCTCN2015092619-appb-000004
具体操作过程:将5kg烯丙基磺酸钠溶于160kg去离子水,投入预乳化罐,加入全部单体,持续开启搅拌预乳化至少30min。将1.5kg过硫酸钠溶于20kg去离子水中,投入引发剂罐,将10kg十二烷基硫酸钠溶于180kg去离子水中,投入反应釜,开启搅拌,用氮气充分置换反应釜中的空气,至少置换2次。保持常压,升温至80-85℃,加入20%的预乳化液和30%的引发剂溶液,反应时间1h。保持温度不变,滴加预乳化液和引发剂,滴加时间为3h。保持温度不变,保温反应1h。降温至常温,用PH调节剂调节PH至7-8,加入15kg乙二醇丁醚,用100目过滤网过滤即得高附着力重防腐涂料用丙烯酸酯共聚乳液。Specific operation process: 5 kg of sodium allyl sulfonate was dissolved in 160 kg of deionized water, put into a pre-emulsion tank, all monomers were added, and the pre-emulsification was continued for at least 30 min. Dissolve 1.5 kg of sodium persulfate in 20 kg of deionized water, put into an initiator tank, dissolve 10 kg of sodium lauryl sulfate in 180 kg of deionized water, put into the reaction kettle, turn on the stirring, and fully replace the air in the reaction vessel with nitrogen. Replace at least 2 times. Maintain normal pressure, heat to 80-85 ° C, add 20% pre-emulsion and 30% initiator solution, reaction time 1h. Keep the temperature constant, add the pre-emulsion and the initiator dropwise, and the dropping time is 3h. Keep the temperature constant and keep the reaction for 1 h. The temperature was lowered to normal temperature, the pH was adjusted to 7-8 with a pH adjuster, 15 kg of ethylene glycol butyl ether was added, and the filter was filtered through a 100 mesh filter to obtain an acrylate copolymer emulsion for a high adhesion heavy-duty anticorrosive coating.
所得乳液性能指标如下:The obtained emulsion performance indicators are as follows:
固含量(%):48.1%;Solid content (%): 48.1%;
粘度(mPa·s):58.2;Viscosity (mPa·s): 58.2;
表面张力(mN/m):44.4;Surface tension (mN/m): 44.4;
稀释稳定性:通过Dilution stability: through
存储稳定性:1年Storage stability: 1 year
附着力:0级Adhesion: 0
耐水性:0级Water resistance: 0
耐盐水:>800hSalt water resistance: >800h
耐盐雾:>800hSalt spray resistance: >800h
实施实例3 Implementation example 3
一种高耐水性重防腐涂料用丙烯酸酯共聚乳液,由如下重量份数的原料配比组成:The invention relates to an acrylate copolymer emulsion for high water-resistance heavy-duty anticorrosive coating, which is composed of the following proportion by weight of raw materials:
Figure PCTCN2015092619-appb-000005
Figure PCTCN2015092619-appb-000005
具体操作过程:将4kg苯乙烯磺酸钠溶于160kg去离子水,投入预乳化罐,加入全部单体,持续开启搅拌预乳化至少30min。将1.5kg过硫酸铵溶于20kg去离子水中,投入引发剂罐,将10kg十二烷基苯磺酸钠溶于180kg去离子水中,投入反应釜,开启搅拌,用氮气充分置换反应釜中的空气,至少置换2次。保持常压,升温至80-85℃,加入20%的预乳化液和30%的引发剂溶液,反应时间1h。保持温度不变,滴加预乳化液和引发剂,滴加时间为3h。保持温度不变,保温反应1h。降温至常温,用PH调节剂调节PH至7-8,加入15kg乙二醇丁醚,用100目过滤网过滤即得高附着力重防腐涂料用丙烯酸酯共聚乳液。Specific operation process: 4 kg of sodium styrene sulfonate was dissolved in 160 kg of deionized water, put into a pre-emulsion tank, all monomers were added, and the pre-emulsification was continued for at least 30 min. Dissolve 1.5kg of ammonium persulfate in 20kg of deionized water, put it into the initiator tank, dissolve 10kg of sodium dodecylbenzene sulfonate in 180kg of deionized water, put it into the reaction kettle, turn on the stirring, and fully replace the reaction kettle with nitrogen. Air, at least 2 times. Maintain normal pressure, heat to 80-85 ° C, add 20% pre-emulsion and 30% initiator solution, reaction time 1h. Keep the temperature constant, add the pre-emulsion and the initiator dropwise, and the dropping time is 3h. Keep the temperature constant and keep the reaction for 1 h. The temperature was lowered to normal temperature, the pH was adjusted to 7-8 with a pH adjuster, 15 kg of ethylene glycol butyl ether was added, and the filter was filtered through a 100 mesh filter to obtain an acrylate copolymer emulsion for a high adhesion heavy-duty anticorrosive coating.
所得乳液性能指标如下:The obtained emulsion performance indicators are as follows:
固含量(%):47.9%;Solid content (%): 47.9%;
粘度(mPa·s):54.3;Viscosity (mPa·s): 54.3;
表面张力(mN/m):45.2; Surface tension (mN/m): 45.2;
稀释稳定性:通过Dilution stability: through
存储稳定性:1年Storage stability: 1 year
耐水性:0级Water resistance: 0
附着力:0级Adhesion: 0
耐盐水:>800hSalt water resistance: >800h
耐盐雾:>800hSalt spray resistance: >800h
本发明通过采用半连续滴加方式制备丙烯酸酯共聚乳液,得到的丙烯酸酯共聚乳液具有良好的耐水性,涂膜放入水中不会泛白,同时具有良好的耐盐水和耐盐雾性能,能够应用于金属材料的重防腐领域。The invention prepares the acrylate copolymer emulsion by adopting a semi-continuous dropping method, and the obtained acrylate copolymer emulsion has good water resistance, the coating film is not whitened in water, and has good salt water resistance and salt spray resistance, and can Used in the field of heavy corrosion protection of metal materials.
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。 The above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the present invention. The skilled person can make some modifications or modifications to the equivalent embodiments by using the above-disclosed technical contents without departing from the technical scope of the present invention, but the present invention does not deviate from the technical solution of the present invention. Technical Substantials Any simple modifications, equivalent changes and modifications made to the above embodiments are still within the scope of the technical solutions of the present invention.

Claims (8)

  1. 一种高耐水性重防腐涂料用丙烯酸酯共聚乳液,其特征在于:由如下重量份数的原料配比组成:苯乙烯50-60份、丙烯酸丁酯25-35份、甲基丙烯酸甲酯10-15份、丙烯酸甲酯5-10份、丙烯酸1-2份、甲基丙烯酸缩水甘油酯2-3份、引发剂0.5-1份、阴离子乳化剂2-4份、反应型乳化剂1-2份、去离子水100-120份、PH调节剂0.0001-0.0002份、成膜助剂3-5份。The invention relates to an acrylate copolymer emulsion for high water-resistance heavy-duty anti-corrosion coating, which is characterized in that the composition is composed of the following parts by weight: 50-60 parts of styrene, 25-35 parts of butyl acrylate, and methyl methacrylate 10 -15 parts, 5-10 parts of methyl acrylate, 1-2 parts of acrylic acid, 2-3 parts of glycidyl methacrylate, 0.5-1 part of initiator, 2-4 parts of anionic emulsifier, reactive emulsifier 1- 2 parts, 100-120 parts of deionized water, 0.0001-0.0002 parts of pH regulator, and 3-5 parts of film-forming auxiliary.
  2. 根据权利要求1所述的一种高耐水性重防腐涂料用丙烯酸酯共聚乳液,其特征在于:所述阴离子乳化剂为十二烷基硫酸钠或十二烷基苯磺酸钠中的任意一种。The acrylate copolymer emulsion for a highly water-resistant heavy-duty anticorrosive coating according to claim 1, wherein the anionic emulsifier is any one of sodium lauryl sulfate or sodium dodecylbenzenesulfonate. Kind.
  3. 根据权利要求1所述的一种高耐水性重防腐涂料用丙烯酸酯共聚乳液,其特征在于:所述反应型乳化剂为苯乙烯磺酸钠或烯丙基磺酸钠中的任意一种。The acrylate copolymer emulsion for a highly water-resistant heavy-duty anticorrosive coating according to claim 1, wherein the reactive emulsifier is any one of sodium styrene sulfonate or sodium allyl sulfonate.
  4. 根据权利要求1所述的一种高耐水性重防腐涂料用丙烯酸酯共聚乳液,其特征在于:所述引发剂为过硫酸铵或者过硫酸钠中的任意一种。The acrylate copolymer emulsion for a highly water-resistant heavy-duty anticorrosive coating according to claim 1, wherein the initiator is any one of ammonium persulfate or sodium persulfate.
  5. 根据权利要求1所述的一种高耐水性重防腐涂料用丙烯酸酯共聚乳液,其特征在于:所述PH调节剂为氨水或者氢氧化钠中的任意一种。The acrylate copolymer emulsion for a highly water-resistant heavy-duty anticorrosive coating according to claim 1, wherein the pH adjuster is any one of ammonia water or sodium hydroxide.
  6. 根据权利要求1所述的一种高耐水性重防腐涂料用丙烯酸酯共聚乳液,其特征在于:所述成膜助剂为乙二醇单丁醚。The acrylate copolymer emulsion for a highly water-resistant heavy-duty anticorrosive coating according to claim 1, wherein the film-forming auxiliary agent is ethylene glycol monobutyl ether.
  7. 根据权利要求1-6任意一项所述的一种高耐水性重防腐涂料用丙烯酸酯共聚乳液的制备方法,其特征在于:包括如下步骤:The method for preparing an acrylate copolymer emulsion for a high water-resistance heavy-duty anticorrosive coating according to any one of claims 1 to 6, which comprises the following steps:
    (1)反应釜中投入45-55份去离子水和全部反应型乳化剂,搅拌至溶解;(1) Injecting 45-55 parts of deionized water and all reactive emulsifiers into the reactor, stirring until dissolved;
    (2)在引发剂滴加罐中投入全部引发剂和5-10份去离子水,搅拌至溶解,得引发剂溶液;(2) adding all the initiator and 5-10 parts of deionized water in the initiator dropping tank, stirring until dissolved, to obtain an initiator solution;
    (3)在预乳化滴加罐中投入全部阴离子乳化剂和剩余去离子水,搅拌至溶解;并将全部单体投入预乳化滴加罐,持续开启搅拌预乳化至少30min,得预乳化液;(3) adding all the anionic emulsifier and residual deionized water in the pre-emulsified dropping tank, stirring until dissolved; and putting all the monomers into the pre-emulsified dropping tank, and continuously opening and stirring pre-emulsification for at least 30 minutes to obtain a pre-emulsion;
    (4)用氮气充分置换反应釜中的空气,至少置换2次;(4) sufficiently replacing the air in the reaction vessel with nitrogen, at least 2 times;
    (5)反应釜搅拌开启,保持常压,升温至80-85℃,加入部分预乳化液和部分引发剂溶液,反应时间1h;(5) stirring the reactor, maintaining normal pressure, heating to 80-85 ° C, adding part of the pre-emulsion and part of the initiator solution, reaction time 1h;
    (4)保持温度不变,滴加剩余预乳化液和引发剂溶液,滴加时间为3h;(4) keep the temperature unchanged, add the remaining pre-emulsion and initiator solution, the dropping time is 3h;
    (5)保持温度不变,保温反应1h;(5) keep the temperature unchanged, the heat preservation reaction for 1h;
    (6)降温至常温,用PH调节剂调节PH至7-8,加入成膜助剂,用100目过滤网过滤即得高附着力重防腐涂料用丙烯酸酯共聚乳液。(6) Cooling to normal temperature, adjusting the pH to 7-8 with a pH adjuster, adding a film-forming auxiliary agent, and filtering with a 100-mesh filter to obtain an acrylate copolymer emulsion for a high adhesion heavy-duty anti-corrosion coating.
  8. 根据权利要求7所述的一种高耐水性重防腐涂料用丙烯酸酯共聚乳液的制备方法,其特征在于:步骤(5)所述的部分预乳化液和引发剂溶液的分别为20%的预乳化液和30%的引发剂溶液。 The method for preparing an acrylate copolymer emulsion for a high water-resistance heavy-duty anticorrosive coating according to claim 7, wherein the partial pre-emulsion and the initiator solution according to the step (5) are respectively 20% pre-prepared. Emulsion and 30% initiator solution.
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