CN110483679A - A kind of acrylic acid zinc-type is from polishing resin and polypeptide self polishing copolymer antifouling paint - Google Patents
A kind of acrylic acid zinc-type is from polishing resin and polypeptide self polishing copolymer antifouling paint Download PDFInfo
- Publication number
- CN110483679A CN110483679A CN201910604409.7A CN201910604409A CN110483679A CN 110483679 A CN110483679 A CN 110483679A CN 201910604409 A CN201910604409 A CN 201910604409A CN 110483679 A CN110483679 A CN 110483679A
- Authority
- CN
- China
- Prior art keywords
- parts
- polypeptide
- polishing
- acrylic acid
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- 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
- C09D133/00—Coating 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- 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
Abstract
The invention discloses a kind of acrylic acid zinc-type from polishing resin and polypeptide self polishing copolymer antifouling paint, and the acrylic acid zinc-type is high from polishing resin molecular weight, and hydrolysis rate is very fast, and stability is good.The polypeptide self polishing copolymer antifouling paint is by the acrylic acid zinc-type containing hydroxyl from 60~80 parts of resin of polishing, and 30~40 parts of polypeptide anti-fouling agent, 20~30 parts of filler, 1~3 part of auxiliary agent, 10~15 parts of mixings of organic solvent are prepared.The coating is free of poisonous anti-fouling agent, environmentally friendly, and has good anti-pollution.
Description
Technical field
The invention belongs to technical field of coatings.Resin and polypeptide are polished certainly certainly more particularly, to a kind of acrylic acid zinc-type
Polishing anti-fouling coating.
Background technique
Marine biofouling refers to the various microorganisms for submerging equipment surface in the seawater and being lived in ocean, plant
Object, animal etc. adhere to, constantly growth and breeding, thus the biofouling formed.Marine biofouling in marine environment nowhere
Do not exist, is the main problem that the industries such as shipping business, the exploration for being marine resources, exploitation face.It was found that common ocean is dirty
Up to 2000 kinds of damage biology, most commonly algae, hydra, barnacle, oyster etc., marine organisms attachment will lead to hull mass and
The increase of frictional force, the increase of electric power and fuel consumption are navigated by water, according to statistics, the fuel consumption as caused by marime fouling increases reachable
40%, and flight number totle drilling cost increases up to 77%；Marine biofouling can also block the mesh of fish culture apparatus, so that fishes and shrimps
Death rate aggravation；Marine biofouling can change the surface state of other marine facilities, eventually lead to corrosion rate quickening etc..
Most efficient method is using antifouling paint at present.Start organotin (TBT) the 1970s to have obtained extensively
Using, but it is subsequent research shows that organotin can upset molluscan endocrine, sex distortion is induced, population deterioration, number are caused
Amount falls sharply, and causes huge disaster to the marine eco-environment, and possibly into food chain, cause to endanger to the life security of the mankind
Evil.International Maritime the convention (IMO) provides complete prohibition organo-tin antifouling paint in 2008.Instead mainly it is rich in copper
The anti-fouling paint of substance, however copper-containing substance is constantly accumulated in the seawater, however it remains marine pollution and food chain are enriched with problem,
Also it is gradually used by limitation.Therefore the heat that nontoxic, efficient, wide spectrum antifouling paint has become novel antifouling developing material is developed
Point.
It rises from polishing technology in mid-term the 1970s, has been increasingly becoming the antifouling paint market mainstream at present.The painting
Under the action of alkaline seawater, polymer constantly hydrolyzes material, slowly releases anti-fouling agent and plays the role of antifouling.Wherein propylene
Acid, zinc acrylate resin becomes one of research hotspot, but the acrylic resin stability that traditional preparation process obtains is poor, antifouling
Effect poor repeatability, molecular weight is not high for obtained zinc acrylate resin, and hydrolysis rate is slower, and anti-fouling effect is undesirable.Cause
This, efficient, less toxic, the low VOC of exploitation, long-acting antifouling paint have important application value.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defect of the prior art and deficiencies, provide a kind of zinc acrylate resin first
Type is from the preparation method for polishing resin, and the acrylic acid zinc-type being prepared is high from polishing resin molecular weight, and hydrolysis rate is very fast, surely
It is qualitative good.
Two purposes of the invention are to provide a kind of polypeptide self polishing copolymer antifouling paint.
Above-mentioned purpose of the invention is to give realization by the following technical programs:
A kind of acrylic acid zinc-type polishes the preparation method of resin certainly, includes the following steps:
S1. under stirring, 70~90 parts of dimethylbenzene and 5~15 parts of ethyl acrylates are added in reaction vessel, heating
To 90~110 DEG C；
S2. it is added dropwise into the reaction solution of step S1 by 25~35 parts of methyl methacrylates, 20~35 parts of hydroxy acrylic acids
Ethyl ester, 25~35 parts of zinc acrylate resin small molecule monomers, 2~4 hours of mixing liquid of 2~4 parts of azodiisobutyronitriles composition；
S3. after being added dropwise, 2~4 hours are kept the temperature, then add 0.5~1 part of azodiisobutyronitrile and 8~12 parts of diformazans
Benzene, then 2~3 hours are kept the temperature, it is cooled to room temperature, is obtained with the acrylic acid zinc-type tree containing hydroxyl from polishing performance
Rouge.
As a kind of preferably scheme, the acrylic acid zinc-type includes the following steps: from the preparation method for polishing resin
S1. under stirring, 80 parts of dimethylbenzene and 10 parts of ethyl acrylates is added in reaction vessel, are heated to 100 DEG C；
S2. it is added dropwise into the reaction solution of step S1 by 25 parts of methyl methacrylates, 20 parts of hydroxyl ethyl acrylates, 30 parts
Zinc acrylate resin small molecule monomer, 2 hours of mixing liquid of 4 parts of azodiisobutyronitriles composition；
S3. after being added dropwise, 2 hours are kept the temperature, then add 1 part of azodiisobutyronitrile and 10 parts of dimethylbenzene, then keep the temperature 2
Hour, it is cooled to room temperature, is obtained with the acrylic acid zinc-type resin containing hydroxyl from polishing performance.
The present invention is also claimed the acrylic acid zinc-type that the above method is prepared and polishes resin certainly.
The acrylic acid zinc-type that the present invention is prepared is high from polishing resin molecular weight, and hydrolysis rate is very fast, and stability is good, hand
Photosensitive cunning, the anti-fouling effect with efficient long-acting, can be used as coating matrix, further prepares self polishing copolymer antifouling paint.
Therefore the present invention is also claimed the acrylic acid zinc-type and polishes resin certainly in preparing self polishing copolymer antifouling paint
Using.
A kind of polypeptide self polishing copolymer antifouling paint, is prepared by each raw material component of following parts by weight: any of the above-described institute
State the acrylic acid zinc-type containing hydroxyl from polishing 60~80 parts of resin, 30~40 parts of polypeptide anti-fouling agent, 20~30 parts of filler, auxiliary agent
1~3 part, 10~15 parts of organic solvent.
Present invention number described above is mass fraction.
Preferably, the polypeptide anti-fouling agent is the condensation polymer polypeptide lotion of glutamic acid, alanine and glycine.Use polypeptide
Toxic organotin and cupric anti-fouling agent are replaced as anti-fouling agent, it is environmentally friendly, and cost is relatively low.
Preferably, the filler is titanium dioxide, silica flour and talcum powder 1:1~2:1 in mass ratio~2 composition.
Preferably, the auxiliary agent is made of dispersing agent, levelling agent and defoaming agent by weight 1:1~2:1~2
Specifically, the dispersing agent is PE100, levelling agent 2820, defoaming agent BYK-028.
It is that glutamic acid, alanine and glycine are as one kind preferably scheme, preparation method of the polypeptide anti-fouling agent
Raw material in 180~220 DEG C of progress high temperature polycondensations, reacts 3~4 hours in the presence of catalyst phosphoric acid, generates polypeptide
Then polypeptide emulsion is hydrolyzed to obtain in amide in 60~100 DEG C.
The preparation method of the polypeptide self polishing copolymer antifouling paint is also claimed in the present invention, in the reaction vessel, according to the ratio
The acrylic acid zinc-type containing hydroxyl is added and polishes resin, polypeptide anti-fouling agent, filler, auxiliary agent, organic solvent, filler, auxiliary agent, control certainly
Speed of agitator processed be 1500~2000rpm, mixing time be 1~2h to get.
Compared with prior art, the invention has the following advantages:
(1) the acrylic acid zinc-type that preparation method of the present invention obtains is high from polishing resin molecular weight, and polishing rate is stablized, and has height
Imitate long-acting anti-fouling effect.
(2) for polypeptide of the invention from polishing antifouling coating adhesion up to 8MPa, hardness reaches 4H, flexibility 1mm, prevents
Good in the dirty 36 months time, surface is smooth, without sea organism attachment, and preparation process energy conservation and environmental protection, antifouling paint are easily constructed.
Specific embodiment
Further illustrate the present invention below in conjunction with specification specific embodiment, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method
And equipment.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
Embodiment 1
(1) preparation of the hydroxy acryl acid zinc-type from polishing resin
By mass fraction, four-hole boiling flask is added in 80 parts of dimethylbenzene and 10 parts of ethyl acrylates under stiring, is heated to 100
℃.It is added dropwise from dropping funel by 25 parts of methyl methacrylate, 20 parts of hydroxyl ethyl acrylate, zinc acrylate resin small molecule monomer
30 parts, 2 hours of mixing liquid of 4 parts of azodiisobutyronitrile compositions.After being added dropwise, 2 hours are kept the temperature, then add 1 part
Azodiisobutyronitrile and 10 parts of dimethylbenzene, then after keeping the temperature 2 hours, it is cooled to room temperature, being made has containing from polishing performance
There is the acrylic acid zinc-type resin of hydroxyl.Measuring resin solid content is 56.2%, and molecular weight Mn is 39420, and hydrolysis rate is fast, polishing
Rate is stablized.
(2) preparation of polypeptide
By mass fraction, by 30 part 90% of H3PO4It is added in flask, heating makes solution temperature rise to 95 DEG C, under stiring
Gradually plus 15 parts of glutamic acid of people, 15 parts of alanine and 15 parts of glycine, 195 DEG C are warming up to, polycondensation reaction 3h.Polycondensation reaction terminates
Afterwards, products therefrom is polypeptide amide, and reaction product is allowed to naturally cool to 60 DEG C, water is added, and its temperature is risen to 80 DEG C of progress
2h is hydrolyzed, products therefrom is polypeptide lotion, after filtering is drained, is put into 60 DEG C of drying in baking oven, it is more to obtain antifouling paint anti-fouling agent
Peptide.
(3) preparation of self polishing copolymer antifouling paint
Polypeptide 40g, the titanium that the acrylic acid zinc-type containing hydroxyl is prepared from polishing resin 80g, step 2 are added in a kettle
White powder 10g, silica flour 10g, talcum powder 10g, dispersing agent PE100 1g, 2820 1g of levelling agent, defoaming agent BYK028 1g, In
2h is stirred under 2000rpm obtains antifouling paint.
For the antifouling paint adhesive force that the present embodiment obtains up to 8MPa, hardness reaches 4H, flexibility 1mm, antifouling time
Good in 36 months, surface is smooth, without sea organism attachment.
Embodiment 2
(1) preparation of the hydroxy acryl acid zinc-type from polishing resin
By mass fraction, four-hole boiling flask is added in 80 parts of dimethylbenzene and 10 parts of ethyl acrylates under stiring, is heated to 100
℃.It is added dropwise from dropping funel by 35 parts of methyl methacrylate, 25 parts of hydroxyl ethyl acrylate, zinc acrylate resin small molecule monomer
30 parts, 3 hours of mixing liquid of 2 parts of azodiisobutyronitrile compositions.After being added dropwise, 2 hours are kept the temperature, then add 0.5 part
Azodiisobutyronitrile and 10 parts of dimethylbenzene, then after keeping the temperature 2 hours, be cooled to room temperature, being made has from polishing performance
Acrylic acid zinc-type resin containing hydroxyl.Measuring resin solid content is 51.5%, and molecular weight Mn is 37650, and hydrolysis rate is fast, is thrown
Light rate is stablized.
(2) preparation of polypeptide
By mass fraction, by 20 part 90% of H3PO4It is added in flask, heating makes solution temperature rise to 95 DEG C, under stiring
Gradually plus 10 parts of glutamic acid of people, 10 parts of alanine and 10 parts of glycine, 195 DEG C are warming up to, polycondensation reaction 3h.Polycondensation reaction terminates
Afterwards, products therefrom is polypeptide amide, and reaction product is allowed to naturally cool to 60 DEG C, water is added, and its temperature is risen to 80 DEG C of progress
2h is hydrolyzed, products therefrom is polypeptide lotion, after filtering is drained, is put into 60 DEG C of drying in baking oven, it is more to obtain antifouling paint anti-fouling agent
Peptide.
(3) preparation of self polishing copolymer antifouling paint
Polypeptide 30g, the titanium that the acrylic acid zinc-type containing hydroxyl is prepared from polishing resin 60g, step 2 are added in a kettle
White powder 5g, silica flour 5g, talcum powder 10g, dispersing agent PE100 0.5g, 2820 0.5g of levelling agent, defoaming agent BYK028 0.5g,
Stirring 1h obtains antifouling paint at 1500 rpm.
For the antifouling paint adhesive force that the present embodiment obtains up to 8MPa, hardness reaches 3H, flexibility 1mm, antifouling time
Good in 24 months, surface is smooth, without sea organism attachment.
Embodiment 3
(1) preparation of the hydroxy acryl acid zinc-type from polishing resin
By mass fraction, four-hole boiling flask is added in 80 parts of dimethylbenzene and 10 parts of ethyl acrylates under stiring, is heated to 100
℃.It is added dropwise from dropping funel by 25 parts of methyl methacrylate, 35 parts of hydroxyl ethyl acrylate, zinc acrylate resin small molecule monomer
30 parts, 4 hours of mixing liquid of 3 parts of azodiisobutyronitrile compositions.After being added dropwise, 2 hours are kept the temperature, then add 1 part
Azodiisobutyronitrile and 10 parts of dimethylbenzene, then after keeping the temperature 2 hours, it is cooled to room temperature, being made has containing from polishing performance
There is the acrylic acid zinc-type resin of hydroxyl.Measuring resin solid content is 54.1%, and molecular weight Mn is 38420, and hydrolysis rate is fast, polishing
Rate is stablized.
(2) preparation of polypeptide
By mass fraction, by 30 part 90% of H3PO4It is added in flask, heating makes solution temperature rise to 95 DEG C, under stiring
Gradually plus 15 parts of glutamic acid of people, 15 parts of alanine and 10 parts of glycine, 195 DEG C are warming up to, polycondensation reaction 3h.Polycondensation reaction terminates
Afterwards, products therefrom is polypeptide amide, and reaction product is allowed to naturally cool to 60 DEG C, water is added, and its temperature is risen to 80 DEG C of progress
2h is hydrolyzed, products therefrom is polypeptide lotion, after filtering is drained, is put into 60 DEG C of drying in baking oven, it is more to obtain antifouling paint anti-fouling agent
Peptide.
(3) preparation of self polishing copolymer antifouling paint
Polypeptide 30g, the titanium that the acrylic acid zinc-type containing hydroxyl is prepared from polishing resin 70g, step 2 are added in a kettle
White powder 5g, silica flour 10g, talcum powder 10g, dispersing agent PE100 0.5g, 2820 1g of levelling agent, defoaming agent BYK028 1g, In
1h is stirred under 2000rpm obtains antifouling paint.
For the antifouling paint adhesive force that the present embodiment obtains up to 8MPa, hardness reaches 3H, flexibility 1mm, antifouling time
Good in 30 months, surface is smooth, without sea organism attachment.
Embodiment 4
(1) preparation of the hydroxy acryl acid zinc-type from polishing resin
Four-hole boiling flask is added in 70 parts of dimethylbenzene and 5 parts of ethyl acrylates under stiring, is heated to 90 DEG C.From dropping funel
By 20 parts of methyl methacrylate, 25 parts of hydroxyl ethyl acrylate, 25 parts of zinc acrylate resin small molecule monomer, azo two is different for middle dropwise addition
2 hours of mixing liquid of 2 parts of butyronitrile compositions.After being added dropwise, 3 hours are kept the temperature, then add 0.5 part of azodiisobutyronitrile
With 8 parts of dimethylbenzene, then after keeping the temperature 2 hours, it is cooled to room temperature, is made with the acrylic acid containing hydroxyl from polishing performance
Zinc-type resin.Measuring resin solid content is 53.6%, and molecular weight Mn is 37220, and hydrolysis rate is fast, and polishing rate is stablized.
(2) preparation of polypeptide
By 30 part 90% of H3PO4It is added in flask, heating makes solution temperature rise to 95 DEG C, gradually adds people 15 under stiring
Part glutamic acid, 15 parts of alanine and 10 parts of glycine, are warming up to 195 DEG C, polycondensation reaction 3h.After polycondensation reaction, gained is produced
Object is polypeptide amide, and reaction product is allowed to naturally cool to 60 DEG C, water is added, and its temperature is risen to 80 DEG C, 2h is hydrolyzed, institute
Obtaining product is polypeptide lotion, after filtering is drained, is put into 60 DEG C of drying in baking oven, obtains antifouling paint anti-fouling agent polypeptide.
(3) preparation of self polishing copolymer antifouling paint
Polypeptide 30g, the titanium that the acrylic acid zinc-type containing hydroxyl is prepared from polishing resin 70g, step 2 are added in a kettle
White powder 5g, silica flour 10g, talcum powder 10g, dispersing agent PE100 0.5g, 2820 1g of levelling agent, defoaming agent BYK028 1g, In
1h is stirred under 2000rpm obtains antifouling paint.
For the antifouling paint adhesive force that the present embodiment obtains up to 8MPa, hardness reaches 3H, flexibility 1mm, antifouling time
Good in 30 months, surface is smooth, without sea organism attachment.
Embodiment 5
(1) preparation of the hydroxy acryl acid zinc-type from polishing resin
Four-hole boiling flask is added in 90 parts of dimethylbenzene and 15 parts of ethyl acrylates under stiring, is heated to 110 DEG C.It is leaked from dropping liquid
It is added dropwise in bucket by 25 parts of methyl methacrylate, 35 parts of hydroxyl ethyl acrylate, 35 parts of zinc acrylate resin small molecule monomer, azo two
3 hours of mixing liquid of 4 parts of isobutyronitrile compositions.After being added dropwise, 4 hours are kept the temperature, then add 1 part of azodiisobutyronitrile
With 12 parts of dimethylbenzene, then after keeping the temperature 3 hours, it is cooled to room temperature, is made with the propylene containing hydroxyl from polishing performance
Sour zinc-type resin.Measuring resin solid content is 52.6%, and molecular weight Mn is 36920, and hydrolysis rate is fast, and polishing rate is stablized.
(2) preparation of polypeptide
By 30 part 90% of H3PO4It is added in flask, heating makes solution temperature rise to 95 DEG C, gradually adds people 15 under stiring
Part glutamic acid, 15 parts of alanine and 10 parts of glycine, are warming up to 195 DEG C, polycondensation reaction 3h.After polycondensation reaction, gained is produced
Object is polypeptide amide, and reaction product is allowed to naturally cool to 60 DEG C, water is added, and its temperature is risen to 80 DEG C, 2h is hydrolyzed, institute
Obtaining product is polypeptide lotion, after filtering is drained, is put into 60 DEG C of drying in baking oven, obtains antifouling paint anti-fouling agent polypeptide.
(3) preparation of self polishing copolymer antifouling paint
Polypeptide 30g, the titanium that the acrylic acid zinc-type containing hydroxyl is prepared from polishing resin 70g, step 2 are added in a kettle
White powder 5g, silica flour 10g, talcum powder 10g, dispersing agent PE100 0.5g, 2820 1g of levelling agent, defoaming agent BYK028 1g.In
1h is stirred under 2000rpm obtains antifouling paint.
For the antifouling paint adhesive force that the present embodiment obtains up to 8MPa, hardness reaches 3H, flexibility 1mm, antifouling time
Good in 28 months, surface is smooth, without sea organism attachment.
Claims (10)
1. the preparation method that a kind of acrylic acid zinc-type polishes resin certainly, which comprises the steps of:
S1. under stirring, 70~90 parts of dimethylbenzene and 5~15 parts of ethyl acrylates is added in reaction vessel, are heated to 90
~110 DEG C；
S2. into the reaction solution of step S1 be added dropwise by 25~35 parts of methyl methacrylates, 20~35 parts of hydroxyl ethyl acrylates,
25~35 parts of zinc acrylate resin small molecule monomers, 2~4 hours of mixing liquid of 2~4 parts of azodiisobutyronitriles composition；
S3. after being added dropwise, 2~4 hours are kept the temperature, then add 0.5~1 part of azodiisobutyronitrile and 8~12 parts of dimethylbenzene, then
2~3 hours are kept the temperature, room temperature is cooled to, are obtained with the acrylic acid zinc-type resin containing hydroxyl from polishing performance.
2. the preparation method that acrylic acid zinc-type according to claim 1 polishes resin certainly, which is characterized in that including walking as follows
It is rapid:
S1. under stirring, 80 parts of dimethylbenzene and 10 parts of ethyl acrylates is added in reaction vessel, are heated to 100 DEG C；
S2. it is added dropwise into the reaction solution of step S1 by 25 parts of methyl methacrylates, 20 parts of hydroxyl ethyl acrylates, 30 parts of propylene
Sour zinc small molecule monomer, 2 hours of mixing liquid of 4 parts of azodiisobutyronitriles composition；
S3. after being added dropwise, 2 hours are kept the temperature, then add 1 part of azodiisobutyronitrile and 10 parts of dimethylbenzene, then are kept the temperature 2 small
When, it is cooled to room temperature, is obtained with the acrylic acid zinc-type resin containing hydroxyl from polishing performance.
3. the acrylic acid zinc-type being prepared by preparation method as claimed in claim 1 or 2 polishes resin certainly.
4. acrylic acid zinc-type described in claim 3 is preparing the application in self polishing copolymer antifouling paint from polishing resin.
5. a kind of polypeptide self polishing copolymer antifouling paint, which is characterized in that be prepared by each raw material component of following parts by weight: power
Benefit requires the 3 acrylic acid zinc-type containing hydroxyl from 60~80 parts of resin of polishing, and 30~40 parts of polypeptide anti-fouling agent, filler 20~
30 parts, 1~3 part of auxiliary agent, 10~15 parts of organic solvent.
6. polypeptide self polishing copolymer antifouling paint according to claim 5, which is characterized in that the polypeptide anti-fouling agent is paddy ammonia
The condensation polymer polypeptide lotion of acid, alanine and glycine.
7. polypeptide self polishing copolymer antifouling paint according to claim 5, which is characterized in that the filler is titanium dioxide, quartz
Powder and talcum powder 1:1~2:1 in mass ratio~2 composition.
8. polypeptide self polishing copolymer antifouling paint according to claim 5, which is characterized in that the auxiliary agent is by dispersing agent, levelling
Agent and defoaming agent are formed by weight 1:1~2:1~2.
9. polypeptide self polishing copolymer antifouling paint according to claim 6, which is characterized in that the preparation side of the polypeptide anti-fouling agent
Method is that glutamic acid, alanine and glycine are raw material, in the presence of catalyst phosphoric acid, in 180~220 DEG C of progress high-temperature polycondensations
Reaction is reacted 3~4 hours, generates polypeptide amide, polypeptide emulsion is then hydrolyzed to obtain in 60~100 DEG C.
10. the preparation method of any one of the claim 5~9 polypeptide self polishing copolymer antifouling paint, which is characterized in that hold in reaction
In device, the acrylic acid zinc-type containing hydroxyl is added according to the ratio from polishing resin, polypeptide anti-fouling agent, filler, auxiliary agent, organic solvent,
Filler, auxiliary agent, control speed of agitator be 1500~2000rpm, mixing time be 1~2h to get.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910604409.7A CN110483679A (en) | 2019-07-05 | 2019-07-05 | A kind of acrylic acid zinc-type is from polishing resin and polypeptide self polishing copolymer antifouling paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910604409.7A CN110483679A (en) | 2019-07-05 | 2019-07-05 | A kind of acrylic acid zinc-type is from polishing resin and polypeptide self polishing copolymer antifouling paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110483679A true CN110483679A (en) | 2019-11-22 |
Family
ID=68546813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910604409.7A Pending CN110483679A (en) | 2019-07-05 | 2019-07-05 | A kind of acrylic acid zinc-type is from polishing resin and polypeptide self polishing copolymer antifouling paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110483679A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113122100A (en) * | 2021-05-24 | 2021-07-16 | 上海涂固安高科技有限公司 | Self-polishing anti-pollution rattan-prevention coating and manufacturing method thereof |
| CN115160896A (en) * | 2022-08-11 | 2022-10-11 | 浙江万丰摩轮有限公司 | Preparation method of motorcycle wheel hub with three-dimensional phantom coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182761A (en) * | 1997-10-05 | 1998-05-27 | 中国科学院海洋研究所 | Polypeptide paint for preventing pollution by sea living things and preparing method and usage thereof |
| CN103897092A (en) * | 2014-03-24 | 2014-07-02 | 海洋化工研究院有限公司 | Preparation and application of zinc acrylate-type self-polishing matrix resin for antifouling coating |
-
2019
- 2019-07-05 CN CN201910604409.7A patent/CN110483679A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182761A (en) * | 1997-10-05 | 1998-05-27 | 中国科学院海洋研究所 | Polypeptide paint for preventing pollution by sea living things and preparing method and usage thereof |
| CN103897092A (en) * | 2014-03-24 | 2014-07-02 | 海洋化工研究院有限公司 | Preparation and application of zinc acrylate-type self-polishing matrix resin for antifouling coating |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113122100A (en) * | 2021-05-24 | 2021-07-16 | 上海涂固安高科技有限公司 | Self-polishing anti-pollution rattan-prevention coating and manufacturing method thereof |
| CN115160896A (en) * | 2022-08-11 | 2022-10-11 | 浙江万丰摩轮有限公司 | Preparation method of motorcycle wheel hub with three-dimensional phantom coating |
| CN115160896B (en) * | 2022-08-11 | 2023-09-08 | 浙江万丰摩轮有限公司 | Preparation method of motorcycle hub with three-dimensional phantom coating |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103080249B (en) | Antifouling paint compositions, antifouling paint compositions multipolymer, surface have the coated article of the antifouling coat using said composition to be formed | |
| JP5661766B2 (en) | Antifouling paint composition, antifouling coating film and method for antifouling substrate | |
| CN1709925B (en) | Resin of zinc acrylate or copper acrylate containing capsaicin function group, its preparation and use | |
| CN101166801A (en) | Stain-proof coating composition, stain-proof coating film, substrate having coating film, stain-proof substrate, method for formation of coating film on surface of substrate, and method for stain-proo | |
| CN105199577B (en) | Antibacterial low-surface-energy marine antifouling paint composition | |
| TW200406473A (en) | Antifouling coating composition, antifouling coating film, ship, underwater construction, fishing gear and fishnet coated with the antifouling coating film | |
| JP6360909B2 (en) | Two-pack type antifouling paint composition, antifouling coating film, antifouling substrate and method for producing antifouling substrate | |
| CN102702880A (en) | Anti-fouling paint composition | |
| CN110483679A (en) | A kind of acrylic acid zinc-type is from polishing resin and polypeptide self polishing copolymer antifouling paint | |
| CN104761991A (en) | Environmental-protection type multi-element collaborative marine anti-fouling coating | |
| CN102732122A (en) | Long-acting self-polishing antifouling paint and preparation method thereof | |
| CN109906254A (en) | Antifouling paint compositions, antifouling coat, the substrate with antifouling coat and its manufacturing method and anti-fouling method | |
| CN105837733B (en) | [(12 acryloyl-oxy) dehydroabietic acid capsiate] acrylic copolymer and its preparation and application | |
| CN1709921B (en) | Resin of zinc acrylate or copper acrylate containing indole function group, its preparation and use | |
| CN102369250B (en) | Antifouling coating composition, antifouling coating film formed from the composition, coated object having the coating film on surface, and method of antifouling treatment by forming the coating film | |
| CN109251621A (en) | A kind of antifouling paint and preparation method thereof | |
| JP3396349B2 (en) | Biofouling prevention coating composition | |
| CN110204993A (en) | A kind of preparation method and applications of carbon nanotube assembling capsaicine driving agent bioantifouling ocean paint | |
| CN1234736C (en) | Method for preparation of zinc or copper containing acrylic acid resin | |
| CN111635693B (en) | Intrinsic antifouling resin and preparation method and application thereof | |
| CN104449172A (en) | Antifouling paint containing biological antifouling agent and preparation method thereof | |
| JP2006232808A (en) | Pyrithione metal salt having specific particle size distribution, and, coating composition | |
| JP4846093B2 (en) | Method for producing metal-containing copolymer | |
| CN1772828A (en) | Antifouling Coating for marine nesh cage cover | |
| CN102372817A (en) | Preparation method of amide derivative copolymer and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191122 |
|
| RJ01 | Rejection of invention patent application after publication |