CN103289007A - Improved preparation method for zinc/copper acrylate resin - Google Patents

Abstract

The invention belongs to the technical field of marine antifouling coatings, in particular to an improved preparation method of acrylic acid zinc/copper resin. Using the mixed system of water and organic solvent as the dispersion medium, the metal salt solution and the alkali solution are reacted to form zinc hydroxide/copper, which is fully dispersed in the dispersant, filtered and dried after dispersion to obtain highly dispersible zinc hydroxide/copper Copper; at a constant temperature, acrylic acid soft and hard monomers undergo free radical polymerization through an initiator to generate acrylic acid prepolymers containing carboxyl groups; at a constant temperature, the acrylic acid prepolymers in the above steps are dispersed in organic Under the action of acid, react to produce zinc/copper acrylic acid resin with hydrolysis properties; the zinc hydroxide/copper prepared by the present invention has good dispersion, no agglomeration phenomenon, short reaction time and low cost in the reaction with acrylic acid prepolymer , and does not need to improve the original equipment.

Description

A kind of preparation method of improved zinc acrylate/copper resin

technical field

The invention belongs to the technical field of marine antifouling coatings, in particular to an improved preparation method of acrylic acid zinc/copper resin. the

Background technique

Marine fouling organisms mainly refer to the general term of animals, plants and microorganisms attached to the bottom of ships, buoys and all artificial facilities, and are one of the important factors affecting the safety and service life of marine facilities. The hazards of biofouling mainly include the following aspects: increase ship resistance, block pipelines, accelerate metal corrosion, and compete with marine shellfish for attachment base and bait. the

A common solution to biofouling is to apply antifouling paint. Organotin self-polishing antifouling technology emerged in the 1970s. Organotin self-polishing coating is a combination of tributyltin methacrylate and methyl methacrylate copolymer and cuprous oxide. Fouling coatings can effectively prevent the attachment of marine fouling organisms. The mechanism is that the methyl methacrylate copolymer is continuously hydrolyzed with seawater immersion, and tributyltin (TBT) is released to play an antifouling role. It has broad-spectrum, high efficiency, and antifouling properties. The advantages of long pollution period and low cost. After the 1980s, it was found that the TBT released by the paint could be deposited in sea mud for a long time and accumulate in organisms, causing serious harm to the marine ecological environment. In 2003, the International Maritime Organization requested to ban the use of organotin as marine antifouling agent. In 2008, all ships banned the use of organotin antifouling paint. Therefore, the development of tin-free self-polishing antifouling paint is an environmentally friendly, economical, low-toxic, non-polluting antifouling paint that can meet the current environmental requirements. the

In recent years, all countries are starting to study the alternatives of organotin and other toxic antifouling agents, and are striving to develop new tin-free self-polishing antifouling coatings, among which copper/zinc acrylate has become one of the research hotspots. In 1990, U.S. Patent No. 5,080,892 described a method for synthesizing zinc acrylate/copper resin. The method synthesized carboxyl-containing acrylic resin and reacted with zinc hydroxide/copper and organic acid to obtain zinc acrylate/copper resin. In 2004, Chinese patent CN1544488A firstly synthesized basic organic acid zinc/copper salt, and then synthesized acrylic acid polymer with carboxyl groups, and the two reacted to obtain zinc/copper acrylate. In 2011, Chinese patent CN102167775 firstly synthesized zinc acrylate/copper small molecular monomers, and then free-radically polymerized with acrylic soft and hard monomer initiators to form zinc acrylate/copper resins. During the formation of zinc/copper acrylate in the above method, metal bases (basic organic acid salts) tend to agglomerate or settle at the bottom of the equipment, resulting in low stability of the zinc acrylate/copper resin and poor repeatability of the antifouling effect. the

Contents of the invention

The object of the present invention is to provide a kind of improved acrylate zinc/copper resin preparation method. the

To achieve the above object, the technical solution adopted in the present invention is:

An improved preparation method of acrylated zinc/copper resin, using a mixed system of water and organic solvent as a dispersion medium, reacting a metal salt solution with an alkali solution to generate zinc hydroxide/copper, and fully dispersing it in a dispersant, after dispersion Filter and dry to obtain highly dispersible zinc hydroxide/copper;

At a constant temperature, acrylic soft and hard monomers undergo free radical polymerization through an initiator to generate acrylic acid prepolymers containing carboxyl groups;

The acrylic acid prepolymer of the above steps and the dispersed zinc hydroxide/copper are reacted under the action of an organic acid at a constant temperature to make acrylic acid zinc/copper resin with hydrolysis properties;

The specific process is as follows:

Where: R=H or CH ₃ ; R ₁ =CH ₃ , C ₂ H ₅ , C ₄ H ₉ or C ₈ H ₁₇ ;

R ₂ =C ₆ H ₅ or C ₅ H ₉ (CH ₂ ) _n ; M=Cu or Zn.

Using the mixed system of water and organic solvent as the dispersion medium, react the soluble inorganic zinc/copper salt solution with the inorganic alkali solution to form zinc hydroxide/copper, and fully disperse in the dispersant, filter and dry after dispersion to obtain high dispersion The molar ratio of inorganic base to soluble inorganic zinc/copper salt is 1.0-1.2:1; the volume ratio between water and organic solvent in the dispersion medium is 100:0.2-6. the

The organic solvent in the dispersion medium is a mixed solution of alcohol and ketone, wherein alcohol and ketone are mixed in a ratio of 1-5:1 by volume;

The alcohol is methanol, ethanol, propanol or butanol; the ketone is methyl ethyl ketone, acetone or butanone; the volume ratio between the zinc hydroxide/copper and the dispersion medium is 1:2-5. the

The dispersant is borax, sodium silicate, sodium hexametaphosphate, sodium pyrophosphate, sodium citrate, sodium dodecylsulfonate, sodium dodecylsulfate, sodium dodecylbenzenesulfonate, fatty acid poly One of ethylene glycol esters, cetyl phosphate, triethylhexyl phosphate, methylpentanol, cellulose derivatives, polyacrylamide, hexenyl bisstearamide, polyethylene glycol; The mass ratio of dispersant to zinc hydroxide/copper is 0.1%-1%. the

Stir and disperse the generated zinc hydroxide/copper in the dispersion system, the dispersion time is 1-3h, the dispersion temperature is 40-50°C, and the stirring speed is 100-500r/min. the

At a constant temperature, the acrylic soft and hard monomers are subjected to radical polymerization in the presence of an organic solvent through an initiator to generate acrylic acid prepolymers containing carboxyl groups; the polymerization reaction temperature is 70-90°C; the polymerization reaction time is 4- 8h;

Described acrylic soft and hard monomer is acrylate or methacrylate; Wherein, acrylate is acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, octyl acrylate, Isooctyl acrylate or n-octyl acrylate;

Methacrylates are methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, octyl methacrylate, methyl Isooctyl acrylate or n-octyl methacrylate;

Described organic solvent is composed of organic solution and xylene, wherein xylene and organic solution are mixed by volume ratio of 4:1; Organic solution is n-butanol, isobutanol, tert-butanol, toluene, ethyl acetate, cyclohexane alkanes, n-hexane, cyclohexanone, acetone or ethylene glycol methyl ether. the

Described initiator is a kind of in azo initiator, peroxide initiator, and wherein initiator accounts for 0.1-5% of polymerization system quality; Wherein azo initiator can be azobisisobutyronitrile ( AIBN) or azobisisoheptanonitrile (ABVN); peroxide initiators can be benzoyl peroxide, benzoyl tert-butyl peroxide or methyl ethyl ketone peroxide. the

The acrylic acid prepolymer in the above step is reacted with the dispersed zinc hydroxide/copper and organic acid under the action of an organic solvent at a constant temperature at 70-110°C and a stirring speed of 100-500r/min. Acrylic acid zinc/copper resin with hydrolysis properties; wherein the organic acid is benzoic acid or naphthenic acid; the ratio of organic acid to zinc hydroxide/copper is 1.0-1.5:1; the organic solvent is xylene and normal The mixed solvent of butanol, the volume ratio between xylene and n-butanol is 4:1. the

The acrylic acid zinc/copper resin is mixed with plasticizers, pigments, fillers, antifouling agents, auxiliary agents, exudation aids and organic solvents as resins to obtain marine antifouling coatings; by weight percentage, 20-30% Resin, 1-10% plasticizer, 5-10% pigment, 5-10% filler, 5-10% antifouling agent, 0.1-0.5% additive, 4-10% exudation aid, and the balance is organic solvent. the

The organic solvent in the coating is one of n-butanol, isobutanol, tert-butanol, toluene, xylene, ethyl acetate, cyclohexane, n-hexane, cyclohexanone, acetone, and ethylene glycol methyl ether. species, the mass fraction is 40-60%; the antifouling agent is capsaicin, 1,2-benzisothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-iso Thiazolin-3-one, pyridinetriphenylborane, zinc pyrithione or pyrithione ketone; the pigments are ferric oxide, titanium dioxide, zinc oxide, carbon black, iron black, calcium carbonate, silicic acid One of calcium and talcum powder; the filler is polytetrafluoroethylene, paraffin oil or graphite fluoride; the auxiliary agent is a leveling agent, a dispersant, a defoamer, a wetting agent, and an anti-settling agent; The exudation aid is rosin. the

The present invention has the following advantages:

1. Zinc hydroxide/copper uses water and organic solvents as the dispersion medium. After the dispersant is dispersed, its dispersion effect is good and can reach nanoscale;

2. The synthesis method of zinc acrylate or copper acrylate resin is compared with the previous method adopted at home and abroad. This method does not need to increase the equipment cost. Due to the high dispersion of zinc hydroxide/copper, the reaction time is shortened, thereby reducing the production cost and optimizing the synthesis process;

3. The antifouling coating made of zinc acrylate or copper acrylate resin as the base material has good adhesion to the substrate, high antifouling performance, and can effectively inhibit the adhesion and growth of marine fouling organisms, and has no pollution to the marine ecological environment . the

Detailed ways

The following examples are further illustrations of the present invention, but the present invention is not limited thereto. the

Improved preparation method of zinc acrylate/copper resin:

The first step is to react the metal salt solution with the alkali solution to form zinc/copper hydroxide, in which the mixed system of water and organic solvent is used as the dispersion medium. After the dispersant is dispersed, filter and dry to obtain highly dispersible zinc/copper hydroxide; 

In the second step, at a constant temperature, acrylic acid soft and hard monomers undergo free radical polymerization of an initiator to generate acrylic acid prepolymers containing carboxyl groups;

In the third step, the acrylic acid prepolymer reacts with the dispersed zinc hydroxide/copper and organic acid at a constant temperature to produce a hydrolytic zinc/copper resin. the

As follows. the

Where: R=H,CH ₃ ; R ₁ =CH ₃ ,C ₂ H ₅ ,C ₄ H ₉ ,C ₈ H ₁₇ ;

R ₂ =C ₆ H ₅ ,C ₅ H ₉ (CH ₂ ) _n ; M=Cu,Zn;

The reaction temperature of the second step and the third step is 70-110° C.; the stirring speed is 100-500 r/min. The above resin is used as a film-forming material to prepare a self-polishing antifouling coating. the

Example 1

1) Preparation of zinc hydroxide

Add 32.2g of sodium hydroxide to a solution containing 2.5ml of ethanol, 0.5ml of acetone, and 97ml of water, stir continuously until the sodium hydroxide is completely dissolved, use 0.2g of sodium hexametaphosphate as a dispersant, and fully Stir for 0.5 hour, slowly add 100ml of 4.0mol/L zinc nitrate dropwise until the pH of the solution becomes neutral. Insulate and disperse for 1 hour, vacuum filter, wash with 100ml of distilled water for 3 times, drain, and dry at 80°C for 12 hours. the

2) Preparation of Acrylic Prepolymer

In a 500ml three-necked round-bottomed flask equipped with stirring, condenser, and constant pressure dropping funnel, add 100g of mixed solvent (the mass ratio of xylene to n-butanol is 4:1), 80°C, 400r/min, dropwise within 3h Complete 100 g of acrylic acid monomer mixture (23 g of acrylic acid, 31 g of methyl methacrylate, 41 g of butyl acrylate) containing 4 g of azobisisobutyronitrile (AIBN) and 1 g of n-dodecyl mercaptan, and keep the reflux state during the dropping process. Keep warm for 1 hour, add 25 g of mixed solvent containing 4% AIBN within half an hour, keep warm for 2 hours, and the reaction ends, and a light yellow, clear and transparent acrylic acid prepolymer is obtained. the

3) Synthesis of zinc acrylate resin

In a 250ml three-necked round bottom flask equipped with stirring, condenser, and oil-water separator, add 100g of acrylic acid prepolymer, 9.7g of zinc hydroxide, 12.2g of benzoic acid, and 30g of xylene and n-butanol at a mass ratio of 4:1 , 80°C, 400r/min, react for 6 hours, wait for the reaction mixture to become transparent, heat up to 105°C to remove water until no water distills off, and obtain yellow transparent zinc acrylate resin. the

4) Preparation of zinc acrylate antifouling paint (antifouling paint prepared in a conventional manner),

Weigh in turn 120g zinc acrylate resin, 20g chlorinated paraffin, 15g rosin, 60g xylene, 1.75g additives (dispersant, defoamer, leveling agent, defoamer, anti-settling agent, thickener), 400r /min high-speed dispersion for 1 hour, add talc powder 15g, BIT25g, iron oxide red 25g, xylene 30g, 2000r/min, high-speed dispersion for 0.5 hours, grinder until the fineness reaches below 25μm. the

In order to test the performance of marine antifouling coatings, the adhesion was measured with reference to the national standard GB/T1720 "Determination of Paint Film Adhesion". In this experiment, the tinplate coated with a primer, intermediate paint and antifouling paint was soaked in artificial seawater for 48 hours, taken out and dried, and the adhesion of the paint film was measured by the circle method. The adhesion of the paint film is divided into seven grades from 1 to 7, with grade 1 having the best adhesion and grade 7 being the worst. the

In order to test the antifouling performance of the obtained antifouling paint, with reference to the national standard GB-5370-2007, spray the antifouling paint on a low carbon steel with a length of 250mm, a width of 150mm, and a thickness of 2mm, and apply epoxy primer 2- 4 times, after drying at room temperature for 24 hours, apply antifouling paint 3 times. The test sample is fixed with bolts at both ends of a rectangular wooden bar with grooves, and the shallow sea immersion test is carried out. This experiment was carried out in the breeding season of fouling organisms—May. Yantai offshore mariculture area was selected for hanging boards at sea. The boarding time was 3 months. The samples were inspected regularly, and the fouling of the samples was recorded by means of text and photos. During observation, use seawater to gently remove the sea mud on the sample plate, and at the same time remove the area of 20mm from the edge of the sample plate to eliminate the edge effect. At the same time, shorten the sample removal and observation time as soon as possible, and immediately immerse the sample in seawater after observation to avoid the impact of the death of attached organisms on the results. Calculate the area occupied by fouling organisms in the sample according to the photographed results. The experimental results are shown in Table 1

Example 2

Unlike Example 1, the preparation of copper hydroxide:

Add 32.2g of sodium hydroxide to a solution containing 2.5ml of ethanol, 0.5ml of acetone, and 97ml of water, and stir continuously until the sodium hydroxide is completely dissolved. Use 0.2g of sodium hexametaphosphate as a dispersant, and fully stir at 500r/min at 40C After 0.5 hour, slowly add 100 ml of 4.0 mol/L copper hydroxide dropwise until the pH of the solution becomes neutral. Insulate and disperse for 1 hour, vacuum filter, wash with 100ml of distilled water for 3 times, drain, and dry at 80°C for 12 hours. the

The operation example of other steps is the same as Example 1, promptly obtains acrylic acid copper antifouling paint, and the results are shown in Table 1. the

Example 3

Unlike Example 1, the preparation of copper hydroxide:

Add 32.0g of sodium hydroxide to a solution containing 2.0ml of ethanol, 1.0ml of methyl ethyl ketone, and 97ml of water, stir continuously until the sodium hydroxide is completely dissolved, use 0.2g of polyacrylamide as a dispersant, and stir fully at 40°C at 500r/min After 0.5 hour, 100ml of 4.0mol/L zinc chloride was slowly added dropwise until the pH of the solution became neutral. Insulate and disperse for 1 hour, vacuum filter, wash with distilled water until no chloride ions can be detected, drain, and dry at 80°C for 12 hours. the

The operation example of other steps is the same as Example 1, promptly obtains zinc acrylic acid antifouling paint, and the result of hanging board is shown in Table 1. the

Table 1 Performance comparison of improved zinc acrylate/copper resin antifouling coatings

Note: 1. The blank sample is not coated with marine antifouling paint except epoxy primer

2. Self-made zinc acrylate resin without antifouling agent

3. Chlorinated rubber resin refers to an antifouling coating prepared by adding BIT to chlorinated rubber resin as a film-forming substance. the

Claims (10)

1. improved zinc acrylate resin/resin of copper preparation method, it is characterized in that: with the mixed system of water, organic solvent as dispersion medium, metal salt solution and alkaline solution reaction are generated zinc hydroxide/copper, and in dispersion agent, fully disperse, disperse the after-filtration drying, the zinc hydroxide/copper of the diffusing property that secures satisfactory grades;

Under steady temperature, vinylformic acid soft or hard monomer is generated the acrylic polymer that contains carboxyl by initiator generation Raolical polymerizable;

Steady temperature with the acrylic polymer of above-mentioned steps with disperse after zinc hydroxide/copper under the organic acid effect, react and make the zinc acrylate resin/resin of copper with hydrolysis properties;

Detailed process is as follows:

Wherein: R=H or CH ₃R ₁=CH ₃, C ₂H ₅, C ₄H ₉Or C ₈H ₁₇

R ₂=C ₆H ₅Or C ₅H ₉(CH ₂) _nM=Cu or Zn.

2. improved zinc acrylate resin according to claim 1/resin of copper preparation method, it is characterized in that: with the mixed system of water, organic solvent as dispersion medium, inorganic zinc/copper salt solution and the inorganic alkali solution reaction of solubility are generated zinc hydroxide/copper, and in dispersion agent, fully disperse, disperse the after-filtration drying, the zinc hydroxide/copper of the diffusing property that secures satisfactory grades; Wherein the mol ratio of the inorganic zinc/mantoquita of mineral alkali and solubility is 1.0-1.2:1; In the described dispersion medium between water and the organic solvent volume ratio be 100:0.2-6.

3. by claim 1 or 2 described improved zinc acrylate resin/resin of copper preparation methods, it is characterized in that: the organic solvent in the described dispersion medium is the mixed solution of alcohol with ketone, and wherein alcohol is the mixed of 1-5:1 with ketone by volume; Described alcohol is methyl alcohol, ethanol, propyl alcohol or butanols; Ketone is methylethylketone, acetone or butanone; Volume ratio between described zinc hydroxide/copper and dispersion medium is 1:2-5.

4. by claim 1 or 2 described improved zinc acrylate resin/resin of copper preparation methods, it is characterized in that: described dispersion agent is a kind of in borax, water glass, Sodium hexametaphosphate 99, trisodium phosphate, Trisodium Citrate, sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, fatty acid polyglycol ester, hexadecyl phosphoric acid fat, triethyl hexyl phosphoric acid, methyl amyl alcohol, derivatived cellulose, polyacrylamide, hexenyl bis-stearamides, the polyoxyethylene glycol; Wherein the mass ratio of dispersion agent and zinc hydroxide/copper is 0.1%-1%.

5. by the described improved zinc acrylate resin of claim 2/resin of copper preparation method, it is characterized in that: the zinc hydroxide/copper that generates is carried out dispersed with stirring in dispersion system, jitter time is 1-3h, and dispersion temperature is 40-50 ℃, and stirring velocity is 100-500r/min.

6. by the described improved zinc acrylate resin of claim 1/resin of copper preparation method, it is characterized in that: under steady temperature, vinylformic acid soft or hard monomer is issued the acrylic polymer that living Raolical polymerizable generation contains carboxyl by initiator in the existence of organic solvent; Described polymeric reaction temperature is 70-90 ℃; Polymerization reaction time is 4-8h;

Described vinylformic acid soft or hard monomer is acrylate or methacrylic ester; Wherein, acrylate is vinylformic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Octyl acrylate, Isooctyl acrylate monomer or vinylformic acid n-octyl;

Methacrylic ester is methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, Octyl methacrylate, Isooctyl methacrylate or n octyl methacrylate;

Described organic solvent is that organic solution and dimethylbenzene are formed, and wherein dimethylbenzene mixes by the volume ratio of 4:1 with organic solution; Organic solution is propyl carbinol, isopropylcarbinol, the trimethyl carbinol, toluene, ethyl acetate, hexanaphthene, normal hexane, pimelinketone, acetone or ethylene glycol monomethyl ether.

7. by the described improved zinc acrylate resin of claim 6/resin of copper preparation method, it is characterized in that: described initiator is a kind of in azo-initiator, the peroxide initiator, and wherein initiator accounts for the 0.1-5% of polymerization system quality; Wherein azo-initiator can be Diisopropyl azodicarboxylate (AIBN) or 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN); The peroxide initiator can be benzoyl peroxide, the benzoyl peroxide tert-butyl ester or methylethyl ketone peroxide.

8. by the described improved zinc acrylate resin of claim 1/resin of copper preparation method, it is characterized in that: described under steady temperature with the acrylic polymer of above-mentioned steps with disperse after zinc hydroxide/copper and organic acid under the effect of organic solvent at 70-110 ℃, the zinc acrylate resin/resin of copper with hydrolysis properties is made in reaction under the stirring velocity of 100-500r/min; Wherein, organic acid is phenylformic acid or naphthenic acid; Organic acid is 1.0-1.5:1 with the amount of substance ratio of zinc hydroxide/copper; Described organic solvent is the mixed solvent of dimethylbenzene and propyl carbinol, and volume ratio is 4:1 between dimethylbenzene and the propyl carbinol.

9. by the described improved zinc acrylate resin of claim 1/resin of copper preparation method, it is characterized in that: described zinc acrylate resin/resin of copper as resin with softening agent, pigment, filler, stain control agent, auxiliary agent, help and ooze out agent and organic solvent mixes, namely obtain marine antifouling coating; By weight percentage, 20-30% resin, 1-10% softening agent, 5-10% pigment, 5-10% filler, 5-10% stain control agent, 0.1-0.5% auxiliary agent, 4-10% help ooze out agent, surplus is organic solvent.

10. by the described improved zinc acrylate resin of claim 9/resin of copper preparation method, it is characterized in that: organic solvent is a kind of in propyl carbinol, isopropylcarbinol, the trimethyl carbinol, toluene, dimethylbenzene, ethyl acetate, hexanaphthene, normal hexane, pimelinketone, acetone, the ethylene glycol monomethyl ether in the described coating, and massfraction is 40-60%; Described stain control agent is capsicine, 1,2-benzisothiazole-3-ketone, 4,5-dichloro--2-n-octyl-4-isothiazoline-3-ketone, pyridine triphenylborane, Zinc Pyrithione or pyrithione ketone; Described pigment is a kind of in ferric oxide, titanium dioxide, zinc oxide, carbon black, iron oxide black, calcium carbonate, Calucium Silicate powder, the talcum powder; Described filler is tetrafluoroethylene, paraffin oil or fluorographite.