CN106986969A - A kind of main chain degradation-type polyacrylic acid resin of copper and preparation method and application - Google Patents

A kind of main chain degradation-type polyacrylic acid resin of copper and preparation method and application Download PDF

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CN106986969A
CN106986969A CN201710292938.9A CN201710292938A CN106986969A CN 106986969 A CN106986969 A CN 106986969A CN 201710292938 A CN201710292938 A CN 201710292938A CN 106986969 A CN106986969 A CN 106986969A
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acid
copper
weight
parts
esters
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CN106986969B (en
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张广照
马春风
潘健森
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Guangdong Haiwei New Material Technology Co.,Ltd.
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds

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  • Engineering & Computer Science (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention belongs to the technical field of marine anti-pollution material, a kind of main chain degradation-type polyacrylic acid resin of copper and preparation method and application is disclosed.The main chain degradation-type polyacrylic acid resin of copper is prepared from by the following component counted by weight：100 parts of acrylic ester prepolymer, 5~50 parts of copper-containing compound, 0~75 part of monocarboxylic acid, 5~150 parts of organic solvent；The acrylic ester prepolymer, is mainly prepared from the following components：Solvent, cyclic monomer, vinyl monomer, (methyl) acrylic acid, initiator.The resin side chain copper ester bond and main chain polyester segment of the present invention can capture hydrolysis in entering for seawater, tradition is solved from dependence of the polishing material to the speed of a ship or plane, coating surface self refresh can be made by hydrolytic degradation effect in static seawater, Effective Regulation anti-fouling agent is discharged with constant speed, meets the antifouling requirement of the facilities such as the ship and offshore production platform of the low speed of a ship or plane；With excellent resistance reducing performance.

Description

A kind of main chain degradation-type polyacrylic acid resin of copper and preparation method and application
Technical field
The invention belongs to marine anti-pollution field of material technology, it is related to a kind of marine antifouling coating polyacrylic acid resin of copper, Degradable polyacrylic acid resin of copper of more particularly to a kind of main chain and preparation method and application；The resin is used to prepare sea Foreign antifouling paint.
Background technology
In recent years, limited land resources is by exhaustive exploitation, and sight and footprint are gradually turned to ocean by people, therefore are also lifted One ocean heat is played.But serious sea marine organism pollution problem is lain across in face of people, and countries in the world are annoying always Scientific research personnel.At present, application is that commercial degree highest, technology be most ripe, service life is most long from polishing marine antifouling coating Means.The resin of main flow self polishing copolymer antifouling paint includes polyacrylic acid silicon ester resin, polyacrylic acid zinc resin and polypropylene The sour class of resin of copper three.Wherein, copper ester bond is more unstable compared to estersil key and zinc ester bond, therefore enters to capture hydrolysis in seawater Speed is faster.In addition, the copper ion generated after copper ester linkage hydrolyzing has the efficiency of antifouling sterilization.
But it is existing be mainly side-chain hydrolysis type from polishing technology, the performance of its performance has necessarily to voyage schedule and the speed of a ship or plane Requirement.In quiescent phase, only it is extremely difficult to by washing away for seawater preferably from polishing effect, therefore static anti-fouling effect is not It is good.Moreover, after side-chain hydrolysis, high polymer main chain departs from coating surface and entered in seawater, because it can not be degraded, causes sea The micro- plastic pollution in ocean, if things go on like this can seriously threaten the stability and security of marine ecosystems.In polyacrylic acid resin of copper Degradable polyester construction is introduced in main chain, is expected to prepare a kind of antifouling paint resin of efficient and service life length.
The content of the invention
The purpose of the present invention is to be led for existing marine antifouling coating resin material and the not enough of technology there is provided one kind Chain contains polyester construction, the main chain degradable polyacrylic acid resin of copper of side chain cupric ester bond.Described main chain degradation-type poly- third Olefin(e) acid resin of copper can not only meet the static antifouling demand in ocean, and solve the problems, such as the micro- plastic pollution in ocean simultaneously.
Another object of the present invention is to provide the preparation method by above-mentioned main chain degradation-type polyacrylic acid resin of copper.
Another object of the present invention is to provide the application of above-mentioned main chain degradation-type polyacrylic acid resin of copper.The main chain drop Solution type polyacrylic acid resin of copper is used to prepare marine antifouling coating.
The purpose of the present invention is achieved through the following technical solutions：
A kind of main chain degradation-type polyacrylic acid resin of copper, is prepared from by the following component counted by weight：
100 parts of the acrylic ester prepolymer are monomer (cyclic monomer, the ethene to be reacted in acrylic ester prepolymer Base monomer, (methyl) acrylic acid) total amount meter)
The copper-containing compound is one or more of cupric oxide, Kocide SD, copper chloride, copper acetate, propionic acid copper.
The monocarboxylic acid be acrylic acid, methacrylic acid, formic acid, acetic acid, propionic acid, benzoic acid, caprylic acid, isooctyl acid, One or more of stearic acid, isostearic acid, aphthenic acids, itaconic acid, maleic acid, oleic acid, palmitic acid, rosin acid.
The acrylic ester prepolymer, is mainly prepared from the following components：
50~100 parts by weight solvent, 5~95 parts by weight cyclic monomers, 0~95 weight part ethenyl monomer, 5~30 weight Part (methyl) acrylic acid, 0.01~10 parts by weight initiator；(methyl) acrylic acid represents methacrylic acid or acrylic acid.
The solvent is one or more of varsol, alcohols solvent, ketones solvent, esters solvent；
The varsol is one or more of toluene, dimethylbenzene；The alcohols solvent is isopropanol, n-butanol, different One or more of butanol, propylene glycol monomethyl ether；The ketones solvent is methyl ethyl ketone, hexone, acetone, fourth One or more of ketone, cyclohexanone；The esters solvent be ethyl acetate, butyl acetate more than one；
The cyclic monomer is one or more in following 1~38 compound：(1) glycolide, (2) lactide, (3) ε-oneself Lactone, (4) 2-methyl-6-caprolactone, (5) 2-chloro- ε-caprolactone, (6) gamma-butyrolacton, (7) δ-valerolactone, in (8) γ-penta Ester, (9) ethylene carbonate, (10) propene carbonate, (11) TMC, (12) 2,2- dimethyltrimethylene rings Carbonic ester, (13) 2- methyl -2- oxazolines, (14) 2- ethyl-2-oxazolines, (15) oxirane, (16) expoxy propane, (17) Epoxychloropropane, (18) γ-glycidyl ether oxygen propyl trimethoxy silicane, (19) 2- methylene -1,3- dioxolanes, (20) 2- methylene -4- phenyl -1,3- dioxolanes, (21) 2- methylene -4- alkyl -1,3- dioxolanes, (22) 2, 4- dimethylene -1,3- dioxolanes, (23) 2- methylene -1,3- dioxy -4,5- benzocyclopentanes, (24) 2- methylene - 1,3- dioxacyclohexanes, (25) 2,5- dimethylene -1,3- dioxacyclohexanes, (26) 2- methylene -5- phenyl -1,3- dioxy rings Hexane, (27) 2- methylene -4- alkyl -1,3- dioxacyclohexanes, (28) 2- methylene -1,3- cyclic heptane dioxides, (29) 2- are sub- Methyl -5- alkyl -1,3- cyclic heptane dioxides, (30) 2- methylene -4,7- dimethyl -1,3- cyclic heptane dioxides, (31) 2- methylenes Base -1,3- dioxy -5,6- benzo rings heptane, (32) 2- methylene -5- phenyl -1,3- cyclic heptane dioxides, (33) 2- ethylidenes -1,3- Cyclic heptane dioxide, (34) 2- methylene -1,3- dioxy -5- cycloheptenes, (35) 2- ethylidene -4- alkyl -1,3- dioxolanes, (36) 2- ethylidenes -1,3- dioxacyclohexanes, (37) 2- allylidene -4- phenyl -1,3- dioxolanes, (38) 2- ethylidenes -1,3- One or more in dioxy -5,6- benzo ring heptane；
The cyclic monomer structural formula of 1~38 compound is as follows：
Wherein, m=1-12 represents the integer that m is 1~12.
The vinyl monomer be esters of acrylic acid, methyl acrylic ester, the esters of acrylic acid of terminal hydroxy group, terminal hydroxy group Methyl acrylic ester, acrylic acid cyclic hydrocarbon esters, methacrylic acid cyclic hydrocarbon esters, acrylic acid polyolefin diols esters, first More than one in base acrylic acid polyolefin diols esters；
Esters of acrylic acid is methyl acrylate, ethyl acrylate, acrylic acid -2- methoxy acrylates, propyl acrylate, propylene Isopropyl propionate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethyl hexyl acrylate, Isooctyl acrylate monomer, propylene More than one in sour lauryl, stearyl acrylate acid esters；
Methyl acrylic ester is methyl methacrylate, EMA, methacrylic acid -2- methoxyl group second Ester, propyl methacrylate, isopropyl methacrylate, n-BMA, Isobutyl methacrylate, metering system Tert-butyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, EHMA, lauryl methacrylate, stearyl methacrylate In more than one；
The esters of acrylic acid of terminal hydroxy group is more than one in hydroxy-ethyl acrylate or hydroxypropyl acrylate；
The methyl acrylic ester of terminal hydroxy group is more than one in hydroxyethyl methacrylate, hydroxy propyl methacrylate；
Acrylic acid cyclic hydrocarbon esters are phenyl acrylate, cyclohexyl acrylate, acrylic acid -4- methyl cyclohexanes base ester, third More than one in olefin(e) acid -4- t-butylcyclohexyl base esters；
Methacrylic acid cyclic hydrocarbon esters are phenyl methacrylate, cyclohexyl methacrylate, methacrylic acid -4- More than one in methyl cyclohexane base ester, methacrylic acid -4- t-butylcyclohexyl base esters；
Acrylic acid polyolefin diols esters are polyalkylene glycol acrylate ester；The degree of polymerization of wherein polyethylene glycol is preferably 1~ 10。
Methacrylic acid polyolefin diols esters are methacrylic acid macrogol ester；The degree of polymerization of wherein polyethylene glycol is excellent Elect 1~10 as.
The initiator is phosphonitrile, phosphonitrile salt, phosphine oxide, azodiisobutyronitrile, AMBN, benzoyl peroxide first One or more of acyl, di-t-butyl peroxide, peroxide -2-ethyl hexanoic acid tert-butyl；
In the preparation, the component also includes low mass molecule alcohol or low molecule amine or telogen to the acrylic ester prepolymer, Low mass molecule alcohol or the low molecule amine or telogen are compounded with initiator；
The low mass molecule alcohol is one or more of in the aliphatic or aromatic alcohols of carbon atoms 1~12.
The low molecule amine is one or more of in the aliphatic or aromatic amine of carbon atoms 1~12.
The gross weight number of the initiator and low mass molecule alcohol or low molecule amine is 0.01~10 part.
The telogen is n-dodecyl mercaptan, tert-dodecylmercaotan, 3- isooctyl mercaptopropionates, 3- mercaptopropionic acids Ethyl hexyl alcohol ester, four (3- mercaptopropionic acids) Ji Maosi alcohol esters, α-methylstyrene dimer it is one or more of.It is preferred that Alpha-Methyl More than one in styrene dimer, n-dodecyl mercaptan.
The consumption of the telogen is 0.5~5 parts by weight, and the weight ratio of the telogen and initiator is (0.5~5)： (0.01~10).
The organic solvent is varsol, preferably one or more of toluene, dimethylbenzene；
The preparation method of the main chain degradation-type polyacrylic acid resin of copper, comprises the following steps：
(1) synthesis of acrylic ester prepolymer：
In inert gas, using 50~100 parts by weight solvent as reaction medium, in the work of 0.01~10 parts by weight initiator Under, by 5~95 parts by weight cyclic monomers, 0~95 weight part ethenyl monomer and 5~30 parts by weight (methyl) acrylic acid, in 70~120 DEG C are reacted 5~18 hours, obtain acrylic ester prepolymer；
(2) synthesis of polyacrylic acid resin of copper：
Using 5~150 weight parts organic solvents as reaction medium, by 100 parts by weight propylene acid esters prepolymers, 5~50 weight Part copper-containing compound and 0~75 parts by weight monocarboxylic acid react 4~10 hours in 70~180 DEG C, obtain polyacrylic acid resin of copper.
The copper coin cellulose content of the main chain degradation-type polyacrylic acid resin of copper is 1~20%, preferably 5~10%.
The number-average molecular weight Mn of the main chain degradation-type polyacrylic acid resin of copper (using polystyrene as standard specimen, is surveyed by GPC It is fixed) it is 3000~50000, preferably 3000~30000.
The main chain degradation-type polyacrylic acid resin of copper acid number is 50~350mgKOH/g, preferably 70~250mgKOH/g.
The main chain degradation-type polyacrylic acid resin of copper is used to prepare marine antifouling coating.
A kind of degradable polyacrylic acid resin of copper of main chain that the present invention is provided, its structure is by polyester segment, vinyl The random copolymer of monomer and vinyl copper ester units composition, is prepared by rear grafting method and obtained.The present invention is in polyacrylic acid copper Degradable polyester segment is introduced in resin backbone, make involved material except side chain copper ester bond seawater enter to capture can water Outside solution, main chain polyester construction can also degrade, by adjusting the content of copper content and cyclic monomer, reach synergetic hydrolysis and The purpose of degradation speed, meets static antifouling application needs.Meanwhile, with hydrolysis and the continuous progress of degraded, material is final Small molecule can be degraded into, the problem of solving the micro- plastic pollution in ocean.
The present invention is compared to prior art, with advantages below and prominent effect：
(1) present invention introduces cyclic monomer in polyacrylic acid resin of copper, is prepared for main chain and contains polyester segment, side chain contains The main chain degradation-type for having copper ester bond polishes resin material certainly；Resulting resin can enter capture except side chain copper ester bond in seawater Hydrolysis is outer, and main chain polyester segment can also degrade, so that tradition is solved from dependence of the polishing material to the speed of a ship or plane, in static sea Also coating surface self refresh can be made by hydrolytic degradation effect in water, so that Effective Regulation anti-fouling agent is discharged with constant speed, Holding of the active material in ship or oceanographic equipment coating surface is ensure that, the ship and sea that the low speed of a ship or plane is met well are adopted The antifouling requirement of the facilities such as oily platform；
(2) material that provides of the present invention can enter to capture fracture due to master chain in seawater, therefore can be uniformly and thorough Polishing so that ship coating surface during navigating by water keeps relatively low roughness, reduces ship resistance, assigns that material is excellent to be subtracted Resistive energy；
(3) present invention can also add the vinyl monomer of variety classes and different content with controlled material in combined polymerization Glass transition temperature and mechanical property, while improving dissolubility of the material in marine paint common solvent.
(4) the preparation method simple possible that the present invention is provided, cost is relatively low, is adapted to industrialized production, the polypropylene of preparation Sour resin of copper has good development prospect in marine anti-pollution coatings art.
Embodiment
The present invention is described in further detail with reference to specific embodiment, but embodiments of the present invention are not limited to This.
Embodiment 1
(1) in reaction vessel, add under 64 parts by weight methyl iso-butyl ketone (MIBK)s and 16 part by weight of n-butanol, nitrogen atmosphere and add Heat is added dropwise by 25 parts by weight of acrylic acid stearates, 40 weight parts of methacrylic acid ethyl esters, 15 parts by weight 2- for 3 hours to 90 DEG C Methylene -5- phenyl -1,3- cyclic heptane dioxides, 20 parts by weight of acrylic acid, 4 parts by weight di-t-butyl peroxides and 2 parts by weight four After the mixture of (3- mercaptopropionic acids) Ji Maosi alcohol esters composition, completion of dropping, 4 hours are incubated, acrylic ester prepolymer is obtained；
(2) added into the acrylic ester prepolymer of step (1) 58.2 parts by weight propionic acid copper, 16.7 parts by weight acetic acid and 100 parts by weight of xylene, react 8 hours in 130 DEG C, obtain polyacrylic acid resin of copper (resin solution of green transparent).
Resin number-average molecular weight M in the present embodimentnFor 1.0 × 104G/mol, copper content is 13.2%, and acid number is 233mgKOH/g, carries out shallow sea panel experiment, 12 months without marine growth.
Embodiment 2
(1) in reaction vessel, add under 64 parts by weight of xylene and 16 parts by weight of propylene glycol methyl ethers, nitrogen atmosphere and heat To 95 DEG C, it is added dropwise by 20 weight parts of methacrylic acid cyclohexyls, 40 weight parts of methacrylic acid isooctyls, 10 parts by weight within 3 hours Hydroxy-ethyl acrylate, 20 parts by weight 2- ethyl-2-oxazolines, 10 parts by weight of acrylic acid, 0.02 parts by weight Methanol and t-BuP4's Hexane solution (the t-BuP containing 0.04 parts by weight4) composition mixture, after completion of dropping, be incubated 4 hours, obtain propylene Acid esters prepolymer；
(2) added into the acrylic ester prepolymer of step (1) 11.1 parts by weight cupric oxide, 20.0 parts by weight isooctyl acids and 60 parts by weight of xylene, react 8 hours in 140 DEG C, obtain polyacrylic acid resin of copper (resin solution of green transparent).
Resin number-average molecular weight M in the present embodimentnFor 1.5 × 104G/mol, copper content is 6.8%, and acid number is 121mgKOH/g, carries out shallow sea panel experiment, 10 months without marine growth.
Embodiment 3
(1) in reaction vessel, 80 parts by weight of xylene are added, 100 DEG C are heated under nitrogen atmosphere, be added dropwise within 3 hours by 10 weight parts of methacrylic acid macrogol esters (degree of polymerization is 9), 10 weight parts of methacrylic acid butyl esters, 10 parts by weight propylene Acid -2- methoxy acrylates, 40 parts by weight propylene acid esters, 20 parts by weight gamma-valerolactones, 10 weight parts of methacrylic acid, 0.01 weight Measure part diethylene glycol and t-BuP4N-hexane (contain 0.04 parts by weight t-BuP4) composition mixture, after completion of dropping, insulation 4 Hour, obtain acrylic ester prepolymer；
(2) 11.33 parts by weight Kocide SDs, 35.1 parts by weight rosin are added into the acrylic ester prepolymer of step (1) Acid and 80 parts by weight of xylene, react 8 hours in 140 DEG C, obtain polyacrylic acid resin of copper (resin of green transparent).
Resin number-average molecular weight M in the present embodimentnFor 2.0 × 104G/mol, copper content is 5.2%, and acid number is 91mgKOH/ G, carries out shallow sea panel experiment, 8 months without marine growth.
Embodiment 4
(1) in reaction vessel, add under 64 parts by weight of propylene glycol methyl ethers and 16 parts by weight butyl acetates, nitrogen atmosphere and add Heat is added dropwise by 25 weight parts of methacrylic acid macrogol esters (degree of polymerization is 9), 40 parts by weight of acrylic acid second for 3 hours to 100 DEG C Ester, 30 parts by weight 2- methylene -1,3- dioxy -4,5- benzocyclopentanes, 5 parts by weight of acrylic acid, the isobutyl of 2 parts by weight azo two After the mixture of nitrile, 2 parts by weight AMBNs and 1 parts by weight n-dodecyl mercaptan composition, completion of dropping, insulation 4 is small When, obtain acrylic ester prepolymer；
(2) 11.8 parts by weight copper chlorides, 4.2 parts by weight acetic acid and 20 are added into the acrylic ester prepolymer of step (1) Parts by weight of xylene, reacts 8 hours in 120 DEG C, obtains polyacrylic acid resin of copper (resin solution of green transparent).
Resin number-average molecular weight M in the present embodimentnFor 9.5 × 103G/mol, copper content is 3.9%, and acid number is 70mgKOH/ G, carries out shallow sea panel experiment, 6 months without marine growth.
Embodiment 5
(1) in reaction vessel, add under 64 weight part of ethylacetate and 16 pbw acetones, nitrogen atmosphere and be heated to 90 DEG C, it is added dropwise by 10 parts by weight of acrylic acid macrogol esters (degree of polymerization is 9), 10 parts by weight of acrylic acid cyclohexyls, 30 weight within 3 hours Part lauryl methacrylate, 35 parts by weight 2- methylene -4- butyl -1,3- dioxacyclohexanes, 15 parts by weight of acrylic acid, 4.5 After the mixture of parts by weight benzoyl peroxide and 0.5 parts by weight 3- isooctyl mercaptopropionates composition, completion of dropping, insulation 4 is small When, obtain acrylic ester prepolymer；
(2) 37.7 parts by weight copper acetates, 70.8 parts by weight aphthenic acids are added into the acrylic ester prepolymer of step (1) (acid number 165) and 150 parts by weight of xylene, react 8 hours in 130 DEG C, obtain the polyacrylic acid resin of copper (resin of green transparent Solution).
Resin number-average molecular weight M in the present embodimentnFor 1.7 × 104G/mol, copper content is 7.2%, and acid number is 127mgKOH/g, carries out shallow sea panel experiment, 10 months without marine growth.
Embodiment 6
(1) in reaction vessel, add under 64 parts by weight of xylene and 16 part by weight of n-butanol, nitrogen atmosphere and be heated to 90 DEG C, 3 hours be added dropwise by 40 weight parts of methacrylic acid ethyl esters, 20 parts by weight of methylmethacrylate, 20 parts by weight δ-valerolactones, 20 weight parts of methacrylic acid, 0.1 parts by weight of ethanol and t-BuP4Hexane solution (contain 0.04 parts by weight t-BuP4) composition Mixture, after completion of dropping, be incubated 4 hours, obtain acrylic ester prepolymer；
(2) added into the acrylic ester prepolymer of step (1) 42.2 parts by weight copper acetates, 28.4 parts by weight and 100 parts by weight of xylene, react 8 hours in 130 DEG C, obtain polyacrylic acid resin of copper (resin solution of green transparent).
Resin number-average molecular weight M in the present embodimentnFor 1.0 × 104G/mol, copper content is 10.3%, and acid number is 182mgKOH/g, carries out shallow sea panel experiment, 12 months without marine growth in Sanya marine site.

Claims (10)

1. a kind of main chain degradation-type polyacrylic acid resin of copper, it is characterised in that：Prepared by the following component counted by weight and Into：
100 parts of the acrylic ester prepolymer are in terms of the monomer total amount reacted in acrylic ester prepolymer；
The acrylic ester prepolymer, is mainly prepared from the following components：
50~100 parts by weight solvent, 5~95 parts by weight cyclic monomers, 0~95 weight part ethenyl monomer, 5~30 parts by weight (methyl) acrylic acid, 0.01~10 parts by weight initiator；(methyl) acrylic acid represents methacrylic acid or acrylic acid.
2. main chain degradation-type polyacrylic acid resin of copper according to claim 1, it is characterised in that：The copper-containing compound is oxygen Change one or more of copper, Kocide SD, copper chloride, copper acetate, propionic acid copper；
The monocarboxylic acid is acrylic acid, methacrylic acid, formic acid, acetic acid, propionic acid, benzoic acid, caprylic acid, isooctyl acid, tristearin One or more of acid, isostearic acid, aphthenic acids, itaconic acid, maleic acid, oleic acid, palmitic acid, rosin acid.
3. main chain degradation-type polyacrylic acid resin of copper according to claim 1, it is characterised in that：
The cyclic monomer is more than one in following structural formula 1~38,
Wherein m=1-12 represents the integer that m is 1~12；
The vinyl monomer is esters of acrylic acid, methyl acrylic ester, the esters of acrylic acid of terminal hydroxy group, the methyl of terminal hydroxy group Esters of acrylic acid, acrylic acid cyclic hydrocarbon esters, methacrylic acid cyclic hydrocarbon esters, acrylic acid polyolefin diols esters, methyl-prop More than one in olefin(e) acid polyolefin diols esters.
4. main chain degradation-type polyacrylic acid resin of copper according to claim 3, it is characterised in that：Esters of acrylic acid is acrylic acid Methyl esters, ethyl acrylate, acrylic acid -2- methoxy acrylates, propyl acrylate, isopropyl acrylate, n-butyl acrylate, propylene One in sour isobutyl ester, tert-butyl acrylate, 2-ethyl hexyl acrylate, Isooctyl acrylate monomer, lauryl acrylate, stearyl acrylate acid esters More than kind；
Methyl acrylic ester is methyl methacrylate, EMA, methacrylic acid -2- methoxy acrylates, first Base propyl acrylate, isopropyl methacrylate, n-BMA, Isobutyl methacrylate, methacrylic acid uncle One in butyl ester, 2-Propenoic acid, 2-methyl-, octyl ester, EHMA, lauryl methacrylate, stearyl methacrylate More than kind；
The esters of acrylic acid of terminal hydroxy group is more than one in hydroxy-ethyl acrylate or hydroxypropyl acrylate；
The methyl acrylic ester of terminal hydroxy group is more than one in hydroxyethyl methacrylate, hydroxy propyl methacrylate；
Acrylic acid cyclic hydrocarbon esters be phenyl acrylate, cyclohexyl acrylate, acrylic acid -4- methyl cyclohexanes base ester, acrylic acid - More than one in 4- t-butylcyclohexyl base esters；
Methacrylic acid cyclic hydrocarbon esters are phenyl methacrylate, cyclohexyl methacrylate, methacrylic acid -4- methyl More than one in cyclohexyl ester, methacrylic acid -4- t-butylcyclohexyl base esters；
Acrylic acid polyolefin diols esters are polyalkylene glycol acrylate ester；
Methacrylic acid polyolefin diols esters are methacrylic acid macrogol ester.
5. main chain degradation-type polyacrylic acid resin of copper according to claim 1, it is characterised in that：
The initiator be phosphonitrile, phosphonitrile salt, phosphine oxide, azodiisobutyronitrile, AMBN, benzoyl peroxide, One or more of di-t-butyl peroxide, peroxide -2-ethyl hexanoic acid tert-butyl；
In acrylic ester prepolymer：The solvent is one kind in varsol, alcohols solvent, ketones solvent, esters solvent More than.
6. main chain degradation-type polyacrylic acid resin of copper according to claim 5, it is characterised in that：The varsol is first One or more of benzene, dimethylbenzene；The alcohols solvent be in isopropanol, n-butanol, isobutanol, propylene glycol monomethyl ether it is a kind of with On；The ketones solvent is one or more of methyl ethyl ketone, hexone, acetone, butanone, cyclohexanone；It is described Esters solvent be ethyl acetate, butyl acetate more than one.
7. main chain degradation-type polyacrylic acid resin of copper according to claim 1, it is characterised in that：The acrylic ester prepolymer Component also include low mass molecule alcohol or low molecule amine or telogen, low mass molecule alcohol or the low molecule amine and initiator are compounded；
The low mass molecule alcohol is one or more of in the aliphatic or aromatic alcohols of carbon atoms 1~12；
The low molecule amine is one or more of in the aliphatic or aromatic amine of carbon atoms 1~12；
The telogen is n-dodecyl mercaptan, tert-dodecylmercaotan, 3- isooctyl mercaptopropionates, 3- mercaptopropionic acid ethyls Hexanol ester, four (3- mercaptopropionic acids) Ji Maosi alcohol esters, α-methylstyrene dimer it is one or more of.
8. according to the preparation method of any one of the claim 1~7 main chain degradation-type polyacrylic acid resin of copper, its feature exists In：Comprise the following steps：
(1) synthesis of acrylic ester prepolymer：
In inert gas, with the reaction medium of 50~100 parts by weight solvent, in the effect of 0.01~10 parts by weight initiator Under, by 5~95 parts by weight cyclic monomers, 0~95 weight part ethenyl monomer and 5~30 parts by weight (methyl) acrylic acid, in 70 ~120 DEG C are reacted 5~18 hours, obtain acrylic ester prepolymer；
(2) synthesis of polyacrylic acid resin of copper：
Using 5~150 weight parts organic solvents as reaction medium, 100 parts by weight propylene acid esters prepolymers, 5~50 parts by weight are contained Copper compound and 0~75 parts by weight monocarboxylic acid react 4~10 hours in 70~180 DEG C, obtain polyacrylic acid resin of copper.
9. the preparation method of main chain degradation-type polyacrylic acid resin of copper according to claim 8, it is characterised in that：The main chain The copper coin cellulose content of degradation-type polyacrylic acid resin of copper is 1~20%；
The number-average molecular weight Mn of the main chain degradation-type polyacrylic acid resin of copper is 3000~50000；
The acid number of the main chain degradation-type polyacrylic acid resin of copper is 50~350mgKOH/g.
10. according to the application of any one of the claim 1~7 main chain degradation-type polyacrylic acid resin of copper, it is characterised in that：Institute Stating main chain degradation-type polyacrylic acid resin of copper is used to prepare marine antifouling coating.
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