CN108070054A - Good antiscale property composition - Google Patents

Good antiscale property composition Download PDF

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Publication number
CN108070054A
CN108070054A CN201711083218.8A CN201711083218A CN108070054A CN 108070054 A CN108070054 A CN 108070054A CN 201711083218 A CN201711083218 A CN 201711083218A CN 108070054 A CN108070054 A CN 108070054A
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monosilane
ester copolymer
monosilane ester
ester
methyl
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CN201711083218.8A
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CN108070054B (en
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M·布伦德旺
K·T·博曼
M·达林
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Jotun AS
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Jotun AS
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
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    • C08K5/16—Nitrogen-containing compounds
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    • C08K5/3432—Six-membered rings
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    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
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    • 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
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
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    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • 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
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract

Acrylic acid ethyl diethylene glycol (DEG) ester and the ocean good antiscale property coating composition of methacrylic acid triisopropyl monosilane ester or acrylic acid triisopropyl monosilane ester are included the present invention relates to a kind of.The good antiscale property coating composition is preferably suitable for having than existing coating lower cost in polishing speed of the object long-time with preventing fouling in the case of seawater stationary contact.

Description

Good antiscale property composition
Technical field
The present invention relates to ocean good antiscale property coating compositions, relate more specifically to comprising acrylic acid ethyl diethylene glycol (DEG) ester (EDEGA) and the sea of methacrylic acid triisopropyl monosilane ester (TISMA) or acrylic acid triisopropyl monosilane ester (TISA) Foreign good antiscale property coating composition.Object is protected from the method for fouling and coated with the present invention's the invention further relates to a kind of The object of good antiscale property composition.
Background technology
Flood surface in the seawater can due to marine organisms such as green and brown algae, barnacle, mussel, pipe worm and meet with By fouling.For marine structures such as ship, oil platform, buoys, this fouling is undesirable and with economy Consequence.Fouling may cause the biodegradation on surface, load increases and accelerated corrosion.On ship, fouling will increase friction resistance Power, this will cause, and speed reduces and/or fuel consumption increases.This may also cause maneuvering performance reduces.
When the surface with contact with sea water is static for a long time, the risk higher of fouling.For example, during equipment, ship is not busy The several months is put, causes high fouling risk.It leaves unused for a long time during transaction or the ship of low speed also has very high fouling risk.At this In the case of a little, it is necessary to have the good antiscale property coatings of high polishing speed for fouling in order to prevent.
The sedimentation and growth of marine organisms in order to prevent, is painted using good antiscale property.These paint generally comprise film-forming binder Agent and different components, such as pigment, filler, solvent and bioactive substance.
The most successful good antiscale property system of polishing certainly is common based on monosilane ester function (methyl) acrylic acid currently on the market Polymers.These coating compositions, for example, EP0646630, EP0802243, EP1342756, EP1479737, EP1641862, It is described in WO00/77102, WO03/070832 and WO03/080747.
(methyl) acrylic copolymer of monosilane ester function usually with other adhesives (such as acrylate and rosin or pine Fragrant derivative) be used together, with adjust good antiscale property film layer from polishing performance and mechanical performance.It can also include biocide (such as copper oxide) or organic biocide (the bromo- 2- of such as 4- (4- chlorphenyls) -5- (trifluoromethyl) -1H- pyrroles -3- nitrile [Qu Luo ratios Profit]).
The monosilane ester copolymer including hydrophilic acrylate's comonomer has been described before.EP0646630 is retouched Having stated wherein hydrophilic acrylate's comonomer includes the good antiscale property coating of 1-25 ethylene glycol repeat units.In an implementation In example, acrylic acid ethyl diethylene glycol (DEG) ester (EDEGA) and another hydrophilic acrylic ester copolymer with 9 repetition diol units Monomer, methyl methacrylate and n-butyl acrylate are applied in combination.In this embodiment, monosilane ester comonomer is methyl Acrylic acid three (normal-butyl) monosilane ester.
WO2014/096102 describes the monosilane ester copolymer with hydrophilic co-monomer, and wherein monosilane ester is total to Polycondensation monomer includes two non-branched C1/C2 groups being connected on silicon and the 3rd at least two branches being connected on silicon Group.It lists as the tertiary hexyl dimethyl silane ester of the methacrylic acid of monosilane ester comonomer and the tertiary hexyl of acrylic acid Dimethyl silane ester.The monomer for being currently based on tertiary hexyl dimethyl silane is not available commercial so that they are for oil Caused attention is weaker on paint binder.In addition, with (methyl) acrylic acid triisopropyl monosilane ester and acrylic acid ethyl two The combination of glycol ester (EDEGA) is compared, the tertiary hexyl dimethyl silane ester of (methyl) acrylic acid and acrylic acid ethyl diethylene glycol (DEG) ester (EDEGA) combination causes good antiscale property coating to have relatively low resistance to rupture.
EP1016681 is described to be copolymerized with the monosilane ester of hydrophilic acrylate or methacrylate co-monomers Object.The many polymer enumerated are acrylic acid triisopropyl monosilane ester, the copolymer of methyl methacrylate, with low Horizontal hydrophilic acrylate or the methacrylate that there is hydroxyl at 2,4 or 6.Acrylic acid triisopropyl is also enumerated Monosilane ester, methyl methacrylate and the methacrylic acid macrogol ester with 5,12 or 15 repetition polyethylene glycol units Copolymer.
The present inventor determines in surprise, in combination with the methacrylic acid triisopropyl first silicon as comonomer Alkyl ester (TISMA) or the monosilane of acrylic acid triisopropyl monosilane ester (TISA) and acrylic acid ethyl diethylene glycol (DEG) ester (EDEGA) Ester copolymer provides the polishing good antiscale property system certainly with suitable polishing speed.In addition, in preferred embodiments, this It is to be realized by using the relatively expensive hydrophilic co-monomer EDEGA of reduced levels.With non-hydrophilic (methyl) propylene Acid esters (such as MMA and n-BA) is compared, and EDEGA and other hydrophilic co-monomers (such as MEMA and MEA) are relatively expensive.In the present invention The use of EDEGA is economically may be used in monosilane ester copolymer compared with other hydrophilic co-monomers in the scale that people imagines Capable.
It is therefore an object of the present invention to provide a kind of good antiscale property coating composition, have and be suitable in object long-time (example Such as, ship once static several weeks or several months) with preventing the polishing speed of fouling in the case of seawater stationary contact, preferably with than existing Coating lower cost.
These purposes realize that the monosilane ester copolymer includes methacrylic acid three by using monosilane ester copolymer Isopropyl monosilane ester (TISMA) or acrylic acid triisopropyl monosilane ester (TISA) and acrylic acid ethyl diethylene glycol (DEG) ester (EDEGA) comonomer.
The content of the invention
In a first aspect, the present invention provides a kind of monosilane ester copolymers, it includes following comonomers：
(i) acrylic acid ethyl diethylene glycol (DEG) ester (EDEGA)；With
(ii) (methyl) acrylic acid triisopropyl monosilane ester；Preferably,
In the copolymer, (i):(ii) ratio is 5:95 (mol/mol) to 60:In the range of 40 (mol/mol).
At preferred aspect, the present invention provides a kind of monosilane ester copolymers, and it includes following comonomers：
(i) acrylic acid ethyl diethylene glycol (DEG) ester (EDEGA)；With
(ii) methacrylic acid triisopropyl monosilane ester (TISMA)；Preferably,
In the copolymer, (i):(ii) ratio is 5:95 (mol/mol) to 60:In the range of 40 (mol/mol).
The amount of (i) in monosilane ester copolymer is preferably in the range of 2mol% to 40mol%.Monosilane ester copolymer In (ii) amount preferably in the range of 5mol% to 60mol%.
In one embodiment, monosilane ester copolymer also includes the hydrophilic co-monomer of one or more formulas (I)：
Wherein R1It is H or CH3, R2It is C3-C18 substituent groups, the R2With at least one oxygen atom or nitrogen-atoms, preferably With at least one oxygen atom, condition is that the hydrophilic co-monomer of formula (I) is not EDEGA.
In one embodiment, the also non-hydrophilic copolymerization comprising one or more formulas (II) of monosilane ester copolymer is single Body：
Wherein R1' it is H or CH3, R2' it is C1-C8 hydrocarbyl substituents, preferred C1-C8 alkyl substituents, most preferable, second Base, n-propyl, 2- ethylhexyls or normal-butyl.
In preferred embodiments, the methyl methacrylate as comonomer that monosilane ester copolymer includes (MMA) amount is 10mol% to 70mol%.
The present invention also provides a kind of good antiscale property coating groups comprising scattered copolymer as described herein in a solvent Close object.Good antiscale property coating can also include good antiscale property agent, preferably cuprous oxide and/or copper pyrithione.
The present invention also provides a kind of for protecting object from the method for fouling, the described method includes with defined herein At least a portion of object (it is by fouling) described in good antiscale property coating composition.
The invention further relates to the objects with good antiscale property coating composition defined herein.
Specific embodiment
Definition
Term " ocean good antiscale property coating composition ", " good antiscale property coating composition " or referred to as " coating composition " refers to fit For the composition of marine environment.Good antiscale property coating composition needs good antiscale property agent, such as biocide.
Term alkyl refers to any group only containing C atoms and H atom, therefore including alkyl, alkenyl, aryl, cycloalkanes Base, aryl alkyl etc..
Term " (methyl) acrylate " is methacrylate or acrylate.
The term " rosin " hereinafter used is used to cover " rosin or derivatives thereof ".
Term " adhesive " defines a part for composition, and including monosilane ester copolymer and imparting group is collectively formed Close any other component of the matrix of object entity and intensity.In general, the term as used herein " adhesive " refers to that monosilane ester is total to Polymers and any rosin that can include.
The good antiscale property coating composition of the present invention includes monosilane ester copolymer, including comonomer acrylic acid ethyl two Glycol ester (EDEGA) and (methyl) acrylic acid triisopropyl monosilane ester (i.e. TISMA or TISA, preferably TISMA).In addition (methyl) acrylic acid monosilane ester comonomer, hydrophily (methyl) acrylate co-monomers and/or non-hydrophilic (methyl) Acrylate co-monomers can be additionally present of, these terms are defined herein.
Monosilane ester copolymer
Monosilane ester copolymer includes at least comonomer (methyl) acrylic acid triisopropyl monosilane ester, such as TISMA, With the sweet diol ester of acrylic acid ethyl (EDEGA), but it can also contain other (methyl) acrylic acid monosilane esters copolymerization as described herein Monomer, hydrophily (methyl) acrylate co-monomers and/or non-hydrophilic (methyl) acrylate co-monomers.
When providing the mol% that comonomer is given in monosilane ester copolymer, mol% is compared with being present in copolymer Each comonomer summation (mol).Therefore, if TISMA and EDEGA are that only copolymerization is single in monosilane ester copolymer Body, then the mol% of TISMA be calculated as (TISMA (mol)/(TISMA (mol)+EDEGA (mol))) × 100%.If it only exists TISMA, EDEGA and methyl methacrylate (MMA), then the mol% of TISMA be calculated as (TISMA (mol)/(TISMA (mol)+ EDEGA (mol)+MMA (mol))) × 100%.The weight percent of copolymer similarly calculates.Preferred copolymer is>90wt% , preferably>95wt%'s, particularly>(methyl) acrylic acid monosilane ester of 98wt%, hydrophily (methyl) acrylate and non- Hydrophily (methyl) acrylate co-monomers.
Component (i) is the sweet diol ester of acrylic acid ethyl (EDEGA), and structure is as follows：
Component (i) is preferably formed as the 2mol% to 40mol% of copolymer, the 2mol% to 30mol% of preferred copolymer, special It is not the 5mol% to 30mol% of copolymer, more particularly 5mol% to 25mol%.
The EDEGA of monosilane ester copolymer is used to prepare preferably with >=90%, preferably >=95% or particularly >=97% Purity uses.It is believed that some advantages are provided in terms of the final performance of dry composition using the EDEGA of higher purity.
Component (ii) is (methyl) acrylic acid triisopropyl monosilane ester, is preferably copolymer preferably (TISMA) 5mol% to 60mol% is preferably 15mol% to 50mol%, particularly 20mol% to 45mol%.
Ratio (i):(ii) (mol/mol) is preferably 5:95 to 60:In the range of 40, preferably 10:90 to 50:50 model In enclosing, particularly 20:80 to 50:In the range of 50, most preferably 30:70 to 50:In the range of 50.In an embodiment In, the mole of (ii) is preferably identical with the mole of (i) in copolymer in copolymer or mole bigger than (i).
The amount preferably at most 85wt% of (i)+(ii) in copolymer, such as at most 80wt%, in particular up to 78wt%. The amount of (i)+(ii) can be in the range of 30-85wt% or 40-80wt% in copolymer.
The amount of (i)+(ii) is preferably below 75mol% in copolymer, is, for example, below 70mol%, particularly preferably Below 65mol%.In copolymer the amount of (i)+(ii) can in the range of 30-75mol%, such as 35-70mol% or especially It is 35-65mol%.
Another or a variety of hydrophily (methyl) acrylate co-monomers
In certain embodiments, copolymer can include the comonomer of one or more other formulas (I)：
Wherein R1It is H or CH3, and R2It is containing at least one oxygen atom or nitrogen-atoms (a preferably at least oxygen atom) C3-C18 substituent groups, condition is that the comonomer of formula (I) is not EDEGA (this as component (i) individually count).Such as this paper institutes With the structure defines " hydrophily " (methyl) acrylate co-monomers.
As shown in above formula, term " hydrophily (methyl) acrylate " requires the R in formula (I)2Group includes at least one Oxygen atom or nitrogen-atoms, preferably at least an oxygen atom.As detailed below, there may also be other non-hydrophilics (methyl) acrylate co-monomers, wherein R2' unit is only made of C and H atom.
In one embodiment, monosilane ester copolymer contains the comonomer of at least one above-mentioned formula (I), wherein R2 Group is formula (CH2CH2O)n-R3, wherein R3It is the substitution of C1-C10 hydrocarbyl substituents, preferably C1-C10 alkyl or C6-C10 aryl Base, n is the integer in the range of 1 to 6, the integer preferably in the range of 1 to 3.It is preferred that R2For formula (CH2CH2O)n-R3, wherein R3It is preferably CH for C1-C10 alkyl substituents3Or CH2CH3, n is integer in the range of 1 to 3, preferably 1 or 2.
In one embodiment, monosilane ester copolymer includes methoxyethyl methacrylate (MEMA), acrylic acid One or more in methoxy acrylate (MEA) and ethoxyethyl methacrylates (EEMA).
In one embodiment, monosilane ester copolymer contains the comonomer of at least one above-mentioned formula (I), wherein R2 Group is containing at least one oxygen atom or nitrogen-atoms, the saturated cyclic group of preferably at least one oxygen atom.It is highly preferred that R2 It is group W-R10, wherein R10It is cyclic ethers (as optionally by alkyl-substituted tetrahydrofuran, oxane, dioxolanes, dioxanes), W It is C1-C4 alkylidenes, the tetrahydrofurfuryl acrylate most preferably having following structure (THFA)：
When it is present, the particularly preferred amount of hydrophily (methyl) acrylate of formula (I) is 2mol% to 25mol%, excellent Select 2mol% to 20mol%, such as 5mol% to 15mol%.When there are during the mixture of the comonomer of formula (I), this tittle It is related to the combination molar fraction of the comonomer of formula (I) in copolymer.
When there are during the comonomer of formula (I), particularly preferred comonomer includes methoxyethyl methacrylate (MEMA), methoxyethyl acrylate (MEA), ethoxyethyl methacrylates (EEMA), tetrahydrofurfuryl acrylate (THFA), Tetrahydrofurfuryl methacrylate (THFMA) and methacrylic acid ethyl diethylene glycol (DEG) ester (EDEGMA).
In preferred embodiments, copolymer does not contain the comonomer of the formula (I) of any significant quantity, i.e. copolymer contains There is this comonomer of this hydrophilic co-monomer less than 10mol%, especially less than 5mol%, especially less than Comonomer as 2mol%.
Another or a variety of non-hydrophilic (methyl) acrylate co-monomers
Monosilane ester copolymer can include other non-hydrophilic (methyl) acrylate of one or more formulas (II) Comonomer
Wherein R1' it is H or CH3, R2' it is C1-C8 hydrocarbyl substituents, preferred C1-8 alkyl substituents, most preferable, second Base, n-propyl, normal-butyl or 2- ethylhexyls.It is single that " non-hydrophilic " copolymerization is referred to herein as according to the comonomer of formula (II) Body.
In all embodiments of the present invention, monosilane ester copolymer preferably includes at least one other non-hydrophilic Methacrylic acid and/or non-hydrophilic acrylic comonomers.When in the presence of one or more non-hydrophilic (methyl) acrylic acid copolymers During monomer, the summation of these in monosilane ester copolymer (methyl) acrylic comonomers is preferably below 80mol%, is preferably Below 70mol%, such as in the range of 20mol% to 70mol%, such as in the range of 30mol% to 60mol%, it is special In the range of not being 35mol% to 60mol%.
In a preferred embodiment, comonomer TISMA, EDEGA and any one kind or more according to formula (II) Kind non-hydrophilic (methyl) acrylate co-monomers are collectively formed in monosilane ester copolymer>80mol%, preferably> 85mol%, particularly>The comonomer of 90mol%.
In preferred embodiments, monosilane ester copolymer includes non-hydrophilic comonomer methacrylic acid methyl esters (MMA) and/or the one or more in n-butyl acrylate (n-BA).
In all embodiments of the present invention, in addition to TISMA and EDEGA, methyl methacrylate is preferably included (MMA).When it is present, the content of MMA is preferably the 10mol% to 70mol% of copolymer, is preferably the 30mol% of copolymer To 60mol%.In preferred embodiments, TISMA, EDEGA and MMA are collectively formed in monosilane ester copolymer>80mol%, It is preferred that>85mol%, particularly>The comonomer of 90mol%.
In an especially preferred embodiment, copolymer includes the TISMA of 20mol% to 60mol%, and 2mol% is extremely The MMA of the EDEGA and 10mol% to 70mol% of 40mol%；The TISMA of particularly 20mol% to 50mol%, 5mol% are extremely The MMA of the EDEGA of 30mol%, 30mol% to 60mol%.In these embodiments, other (methyl) third can be included Olefin(e) acid monosilane ester, hydrophily (methyl) acrylate and/or non-hydrophilic (methyl) acrylate co-monomers.
When it is present, n-BA preferably exists with 2mol% to 20mol%, the particularly amount of 2mol% to 15mol%.
In one embodiment, monosilane ester copolymer includes comonomer TISMA, EDEGA, MMA and at least one Hydrophily or non-hydrophilic (methyl) acrylic comonomers.In one embodiment, monosilane ester copolymer includes following Monomer, by following monomer composition or substantially by following monomer composition：TISMA、EDEGA、MMA；TISMA, EDEGA, MMA and n-BA；Or TISMA, EDEGA, MMA, n-BA and THFA.
In addition (methyl) acrylic acid monosilane ester comonomer
Monosilane ester copolymer can include other (methyl) acrylic acid monosilane ester comonomer.When it is present, remove Any other (methyl) acrylic acid monosilane ester comonomer beyond (methyl) acrylic acid triisopropyl monosilane ester is preferred Form the 5mol% no more than 10mol%, preferably no greater than copolymer of copolymer.When it is present, suitable (methyl) propylene Sour monosilane ester comonomer is preferably formula (III)
Wherein
R4And R5It is each independently selected from linear chain or branch chain C1-4Alkyl group；
R6、R7And R8It is each independently selected from by linear chain or branch chain C1-C20 alkyl groups, C3-C12 groups of naphthene base, appoints The substitution C6-C20 aryl group of choosing and-OSi (R9)3The group of group composition；
Each R9It is independently the C1-C4 alkyl groups of linear chain or branch chain,
N is 0 to 5 integer；
X is ethylenically unsaturated groups, such as acryloxy group, methacryloyloxy group, (methacryloxypropyl Base) alkylenecarbonyl oxygroup group and (acryloxy) alkylenecarbonyl oxygroup group.It should be appreciated that (methyl) acrylic acid three Isopropyl monosilane ester should be considered as excluding outside formula (III), because it is inherently present in copolymer.
Term " alkyl " is intended to include straight or branched alkyl group, such as methyl, ethyl, isopropyl, propyl and butyl.It is special Not preferred group of naphthene base includes cyclohexyl and the cyclohexyl of substitution.
The example of substituted aryl group is included by least one alkyl base selected from halogen, with 1 to about 8 carbon atom The aryl group of the substituent group substitution of group, carboxyl groups or nitryl group.Particularly preferred aryl group includes substitution and does not take Phenyl, benzyl, phenylalkyl or the naphthalene in generation.
It is desirable that preferred monosilane ester monomer is based on formula (III) compound that wherein n is 0, i.e., those Formula X- SiR6R7R8Compound.
The example of monomer containing monosilane ester functional group is well-known.The monomer defined by leading to formula (III) includes：
The monosilane ester monomer of acrylic acid and methacrylic acid, such as：(methyl) acrylic acid silicohetane alkyl ester, (first Base) three n-propyl monosilane ester of acrylic acid, three normal-butyl monosilane ester of (methyl) acrylic acid, (methyl) acrylic acid triisobutyl first Silicon ester, (methyl) acrylic acid tri-tert monosilane ester, three sec-butyl monosilane ester of (methyl) acrylic acid, (methyl) acrylic acid Three n-pentyl monosilane esters, (methyl) acrylic acid triisopentyl monosilane ester, three n-hexyl monosilane ester of (methyl) acrylic acid, Three n-octyl monosilane ester of (methyl) acrylic acid, three dodecyl monosilane ester of (methyl) acrylic acid, (methyl) acrylic acid three Benzene monosilane ester, three (p-methylphenyl) monosilane ester of (methyl) acrylic acid, (methyl) acrylic acid tribenzyl monosilane ester, (first Base) acrylic acid ethyl dimethyl silane ester, (methyl) acrylic acid n-propyl dimethyl silane ester, (methyl) acrylic acid isopropyl Base dimethyl silane ester, (methyl) acrylic acid normal-butyl dimethyl silane ester, (methyl) i-butyl base dimethyl methyl Silicon ester, (methyl) acrylic acid t-butyl-dimethylsilyl ester, (methyl) acrylic acid n-pentyl dimethyl silane ester, (first Base) acrylic acid n-hexyl dimethyl silane ester, (methyl) acrylic acid new hexyl (neohexyl) dimethyl silane ester, (first Base) the tertiary hexyl dimethyl silane ester of acrylic acid, (methyl) acrylic acid n-octyl dimethyl silane ester, (methyl) acrylic acid just Decyl dimethyl monosilane ester, (methyl) lauryl base dimethyl silane ester, (methyl) octadecyl base two Methyl silicane ester, (methyl) acrylate base dimethyl silane ester, (methyl) phenylethyl dimethyl silane ester, (methyl) acrylic acid benzyl dimethyl monosilane ester, (methyl) acrylic acid phenyl ethyl dimethyl monosilane ester, (methyl) acrylic acid (3- phenylpropyls) dimethyl silane ester, (methyl) acrylic acid p-methylphenyl dimethyl silane ester, (methyl) acrylic acid isopropyl Base diethylsilane ester, (methyl) acrylic acid normal-butyl diisopropyl monosilane ester, (methyl) acrylic acid n-octyl diisopropyl Base monosilane ester, (methyl) propylene acid methyl di-n-butyl monosilane ester, (methyl) acrylic acid methyldicyclohexyl monosilane ester, (methyl) acrylic acid methyldiphenyl base monosilane ester, (methyl) acrylic acid t-butyidiphenylsilyl ester, (methyl) acrylic acid Double (trimethylsiloxy) methyl of nonyl four monosilane oxygen (nonamethyltetrasiloxy) ester, (methyl) acrylic acid Monosilane ester, (methyl) acrylic acid three (trimethylsiloxy) monosilane ester etc., such as WO2014/064048 and WO03/ Described in 080747.
When monosilane ester copolymer includes acrylic acid tripropylsilyl ester, in addition it can contain methacrylic acid three Isopropyl monosilane ester, vice versa.Above-mentioned formula (III) is intended to cover acrylic acid triisopropyl monosilane ester and methacrylic acid The presence of monosilane ester comonomer beyond triisopropyl monosilane ester.
The property of monosilane ester copolymer
In the presence of polymerization initiator, the polymer containing organic monosilane ester group can pass through polymerisation in solution, sheet Any one of various methods such as body polymerization, emulsion polymerization and suspension polymerisation in a usual manner or by controlled polymerization technique into Row monomer mixture polymerize and obtains.When using the polymer prepares coating composition for containing organic monosilane ester group, It is preferred that with organic solvent diluting polymer, the polymer solution with proper viscosity is obtained.From this viewpoint, it is preferable to use Polymerisation in solution.
The example of polymerization initiator includes：Azo-compound, such as 2,2'- azos double (2 Methylpropionic acid) dimethyl ester, 2,2'- Azo double (2- methylbutyronitriles), 2,2'- azos double (isobutyronitriles) and 1,1'- azos are double (cyano cyclohexane)；And peroxide, Such as tert-Butyl peroxypivalate, peroxide -2-ethyl hexanoic acid tert-butyl, diethyl dioxide tert-butyl acetate, peroxide isobutyl Tert-butyl acrylate, di-tert-butyl peroxide, peroxidized t-butyl perbenzoate and the tertiary fourth fat of isopropyl peroxide carbonic acid, peroxidating are new Valeric acid tert-pentyl ester, peroxidating -2 ethyl hexanoic acid tert-pentyl ester, (t-amyl peroxy) hexamethylenes of 1,1- bis- and dibenzoyl peroxidating Object.These compounds can be used alone, can also two or more be used in mixed way.
The example of organic solvent includes：Aromatic hydrocarbon, such as dimethylbenzene, toluene, mesitylene；Ketone, such as methyl ethyl ketone, first Base isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone；Esters, as butyl acetate, tert-butyl acetate, Pentyl acetate, ethylene glycol monomethyl ether acetate；Ethers, such as glycol dimethyl ether, diethylene glycol dimethyl ether, butyl oxide, dioxanes, tetrahydrochysene Furans；Alcohols, such as n-butanol, isobutanol, benzylalcohol；Ether alcohol class, such as butyl cellosolve, 1- methoxy-2-propanols；Aliphatic hydrocarbon, such as White essential oil；With the mixture of two or more optional solvents.These compounds can be used alone or with two in them Kind or a variety of mixtures use.Copolymer is preferably random copolymer.
The weight average molecular weight of the thus obtained polymer containing organic monosilane ester group is preferably 5,000 to 70,000, Preferably 10,000 to 60,000.The measurement of Mw is carried out as described in embodiment part.
Monosilane ester copolymer can be used as polymer solution to provide.It is appropriate to adjust polymer solution, so that its solid content For 30wt% by weight to 90wt%, preferably by weight 40wt% to 85wt%, by weight more preferably 47wt% To 75wt%.
Based on total coating composition, final good antiscale property coating composition of the invention preferably comprises 0.5wt% to 45wt% The monosilane ester copolymer of (drying solid), such as 1.0wt% to 30wt%, particularly 5wt% to 25wt%.
The glass transition temperature (Tg) of copolymer is preferably at least 15 DEG C, preferably at least 20 DEG C, for example, at least 22 DEG C, institute There is value to be measured all in accordance with the Tg experiments described in embodiment part.Preferably smaller than 80 DEG C of value is, for example, less than 75 DEG C, such as low In 50 DEG C.
Monosilane ester copolymer and other first silicon of the good antiscale property coating composition of the present invention optionally including the present invention The mixture of alkyl ester copolymer, such as US4,593,055, described in EP0646630, WO2009/007276 and EP2781567.
Rosin components
Rosin can be used for adjusting good antiscale property film from polishing performance and mechanical performance.The good antiscale property coatings combine of the present invention Object preferably comprises at least 0.5wt% (drying solid) rosin, for example, at least 1wt%.The upper limit of rosin components can be 25wt%, Such as 15wt%.
The rosin used in the present invention can be rosin or derivatives thereof, such as its salt, such as described below.Rosin material Example include：Wood rosin, toll oil rosin and gum rosin；Rosin derivative, such as hydrogenation and partially hydrogenated rosin, disproportionation pine Perfume, dimerization colophonium, newtrex, maleate, fumarate, glyceride, methyl ester, pentaerythritol ester and rosin and hydrogenation Other esters, copper abietinate, zinc abietate, rosin acid calcium, rosin acid magnesium and the rosin of rosin and other metals of newtrex Rosinate, as described in WO 97/44401.The preferably derivative of gum rosin and gum rosin.
In the present invention, good antiscale property composition as a whole preferably comprises 0.5wt% to 25wt%, preferably 1wt% extremely The rosin material of 15wt% (drying solid) is preferably 2wt% to 7wt% (drying solid).
The performance of good antiscale property coating can be adjusted by changing the relative quantity of monosilane ester copolymer and rosin components.
Therefore, in preferred embodiments, the present invention provides include monosilane ester copolymer as defined above With the adhesive of rosin or derivatives thereof.
Other adhesive components
In addition to monosilane ester copolymer and optional rosin, other adhesive is can also use to adjust good antiscale property The performance of film.The example for the adhesive that can be used in addition to the monosilane ester copolymer and rosin of the present invention includes：
Acid functional polymers, the divalent metal that acidic group is bonded in monovalence organic residue are closed, such as Described in EP0204456 and EP0342276；Or the divalent metal being bonded on OH residues is closed, such as such as Described in GB2311070 and EP0982324；Or closed by amine, such as described in EP0529693；
In hydrophilic copolymers, such as (methyl) acrylate copolymer and EP0526441 described in GB2152947 Poly- (n-vinyl pyrrolidone) copolymer and other copolymers；
(methyl) acrylate copolymer and copolymer, particularly acrylic ester adhesive, such as poly- (n-butyl acrylate) gather (n-butyl acrylate -co- isobutyl vinyl ether), as described in WO03/070832 and EP2128208；
Vinylic-ether polymer and copolymer, such as poly- (methyl vinyl ether), poly- (ethyl vinyl ether), poly- (isobutyl Base vinyl ethers), poly- (vinyl chloride -co- isobutyl vinyl ether)；
Aliphatic polyester, such as poly- (lactic acid), poly- (glycolic), poly- (2- hydroxybutyric acids), poly- (3-hydroxybutyrate), poly- (4- hydroxypentanoic acids), polycaprolactone and the aliphatic polyester copolymer containing two or more units selected from said units Object；
Polyester containing metal, for example, as described in EP0133392 and EP1072625, condition is that the metal is not copper；
Alkyd resin and modified alkyd resin；
Hydrocarbon resins, for example, as described in WO2011/092143, such as only by being selected from C5 aliphatic monomers, C9 aromatic series The hydrocarbon resins that the monomer polymerization of at least one of monomer, indenes coumarone monomer or terpenes or its mixture is formed；
Poly- oxalate as described in WO2009/100908 and other condensation polymers as described in WO96/14362.
If also there are other adhesive, one or more silicyls in addition to rosin and monosilane ester copolymer Copolymer：The weight ratio of adhesive can be 30:70 to 95:5, it is preferably 40:60 to 80:20, particularly 50:50 to 70:30. These preferred ratios only relate to the amount of one or more silicyl copolymers and other adhesive, i.e., do not include rosin.
Specially suitable other adhesive is (methyl) acrylate copolymer and copolymer.
Biocide
Good antiscale property coating further includes a kind of compound, can prevent the ocean fouling on surface or sea is removed from surface Foreign fouling.Traditionally, good antiscale property coating composition contains copper biocide such as metallic copper, cuprous oxide, cupric thiocyanate etc..
The typical particle diameter of cuprous oxide material is distributed as 0.1-70 μm, and average grain diameter (d50) is 1-25 μm.Oxidation is sub- Copper product may contain stabilizer (preventing surface oxidation).The example of commercially available cuprous oxide includes：Labor Haddock Adamss are public Take charge of Nordox Cuprous Oxide Red Paint Grade, the Nordox XLT of (Nordox AS)；The limited public affairs of Furukawa chemistry Take charge of the cuprous oxide of (Furukawa Chemicals Co., Ltd)；Red Copp 97N, the Purple of Chemet companies of the U.S. Copp、Lolo Tint 97N、Chemet CDC、Chemet LD；The Cuprous Oxide Red of Spiess-Urania；Taixing Smelt Cuprous oxide Roast, the Cuprous oxide Electrolytic of Co., Ltd., Factory.
A series of organic biocides can be used to replace copper biocide, such as 4- [1- (2,3- 3,5-dimethylphenyl) second Base] -1H- imidazoles [Medetomidine] and the bromo- 2- of 4- (4- chlorphenyls) -5- (trifluoromethyl) -1H- pyrroles -3- nitriles [bent Lip river Billy]. Any of biocide can be used in the present invention.In the industry using the agent of term good antiscale property, anti-fouling agent, biocide, poison Object describes to prevent the known compound of the ocean fouling on surface.The good antiscale property agent of the present invention is ocean good antiscale property agent.
Coating composition can include copper biocide, preferably cuprous oxide (Cu2) and/or copper pyrithione O.The present invention Coating composition can contain other biocides, as described in WO2014/064048.Preferred biocide is that oxidation is sub- Copper, cupric thiocyanate, zinc pyrithione, copper pyrithione, ethylenebis (dithiocarbamate) zinc [zineb], 2- (uncles Butylamino) -4- (cyclopropylamino) -6- (methyl mercapto) -1,3,5- triazines [cybutryne], bis- chloro- 2- n-octyls of 4,5- - 4- isothiazoline -3- ketone [DCOIT], N- dichloro fluorine methyl mercapto-N', N'- dimethyl-N-phenyl sulfonamide [Euparen], N- bis- Chlorine fluorine methyl mercapto-N', N'- dimethyl-N-para toluene sulfonamide [tolyfluanid], 4- [1- (2,3- 3,5-dimethylphenyls) second Base] -1H- imidazoles [Medetomidine], triphenylborane pyridine [TPBP] and the bromo- 2- of 4- (4- chlorphenyls) -5- (trifluoromethyl) - 1H- pyrroles -3- nitriles [bent Lip river Billy].
As it is known in the art, using the mixture of biocide, because different biocide confrontation is not Same ocean fouling organism.
In an alternate embodiment, good antiscale property coating is no copper.In this embodiment it is preferred to biocide combinations It is related to bent Lip river Billy and one or more in zinc pyrithione, bis- chloro- 2- octyl groups -4- isothiazoline -3- ketone of 4,5- Combination.
If it does, the total amount of biocide can form the at most 70wt% of coating composition, such as 4wt% is extremely 60wt%, such as 5wt% to 60wt%.It is depositing in a case of copper, in coating composition, proper amount of biocide can be with For 20wt% to 60wt%.When relatively low amount, such as 0.1wt% there is no during copper, can be used to 20wt%, such as 0.2wt% to 15wt%.It is appreciated that the amount of biocide will change according to final use and biocide used.
Some biocides can be sealed or adsorbed on a inert carrier or be attached in other materials and be released for controlling It puts.These percentages refer to the amount of existing killing activity agent, therefore do not refer to the amount of any carrier used.
Other components
In addition to above-mentioned monosilane ester copolymer and any optional component, good antiscale property coatings combine according to the present invention Object can also optionally further include one or more components, the one or more component be selected from other adhesives, it is inorganic or Organic pigment, incremental agent and filler, additive, solvent and diluent.
The example of pigment is：Inorganic pigment, such as titanium dioxide, iron oxide, zinc oxide and trbasic zinc phosphate；Organic pigment, example Such as phthalocyanine compound, azo pigments and carbon black.
The example of incremental agent and filler is：Mineral, such as dolomite, plasticity silicate (plastorite), calcite, stone English, barite, magnesite, aragonite, silica, wollastonite, talcum, chlorite, mica, kaolin and feldspar；Synthesize nothing Machine compound, such as calcium carbonate, magnesium carbonate, barium sulfate, calcium silicates and silica；Polymer inorganic microballoon, such as uncoated or painting The hollow glass bead covered and solid glass pearl, uncoated or coating hollow ceramic pearl and solid ceramic pearl and polymeric material Porous bead and fine and close pearl, polymeric material for example poly- (methyl methacrylate), poly- (methyl methacrylate -co- dimethyl allene Sour glycol ester), poly- (styrene-co-ethylene glycol dimethacrylate), poly- (styrene-co-divinyl base benzene), polyphenyl Ethylene, poly- (vinyl chloride).
The example for the additive that can be added in good antiscale property coating composition is reinforcing agent, thixotropic agent, thickener, anti-settling Depressant prescription, wetting dispersing agent, plasticizer and solvent.
The example of reinforcing agent is thin slice and fiber.Fiber includes：Natural inorganic fiber and synthetic inorganic fiber, such as siliceous fibre Dimension, carbon fiber, oxide fibre, carbide fibre, nitride fiber, sulphide fibres, phosphate fiber, mineral fibres；Gold Belong to fiber；Natural organic fiber and synthetic organic fibre, as cellulose fibre, IR fiber, acrylic fiber, polyamide are fine Dimension, polyimide fiber, polyester fiber, polyhydrazide fiber, polyvinyl chloride fibre, polyethylene fibre and other such as WO00/ Described in 77102.Preferably, the average length of fiber is 25 μm to 2000 μm, and average thickness is 1 μm to 50 μm, average long The ratio between degree and average thickness are at least 5.
The example of thixotropic agent, thickener and antisettling agent is：It is silica (such as fumed silica), organically-modified viscous Soil, amide waxe, polyamide wax, amide derivatives, polyethylene wax, oxidized polyethylene wax, rilanit special wax, ethyl cellulose, Aluminum stearate and their mixture.
The example of plasticizer is：Chlorinated paraffin, phthalic acid ester, phosphate, sulfamido, adipate ester and epoxidation are planted Object oil.
The example of dehydrating agent and drier includes：Dead plaster, calcium sulfate hemihydrate, anhydrous magnesium sulfate, anhydrous slufuric acid Sodium, anhydrous zinc sulfate, molecular sieve and zeolite；Ortho esters, such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, original Three isopropyl ester of formic acid, tributyl orthoformate, trimethyl orthoacetate and triethly orthoacetate；Ketal；Acetal；Enol ether；Ortho-boric acid Ester, such as trimethylborate, triethyl borate, triproylborate, three tert-butyl ester of triisopropyl borate ester, butyl borate and boric acid； Silicate, such as trimethoxymethylsila,e, tetraethyl orthosilicate and ethyl polysilicate；And isocyanates, as p-toluenesulfonyl is different Cyanate.
Preferred dehydrating agent and drier are silicate and inorganic compound.
The example for contributing to the stabilizer of the storage stability of good antiscale property coating composition is carbodiimide compound, such as Double (2,6- diisopropyl phenyl) carbodiimides and poly- (1,3,5- triisopropyl phenylene -2,4- carbodiimide) etc., Yi Jiqi It is as described in patent EP 2725073.
In general, any one of these optional components can be led to the 0.1wt% of good antiscale property composition to 20wt% Often it is 0.5wt% to 20wt%, the amount of preferably 0.75wt% to 15wt% exists.It should be appreciated that the amount of these optional components will Changed according to final use.
It is highly preferred if good antiscale property composition contains solvent.The solvent is preferably volatile, preferably has Machine.The example of organic solvent and diluent is：Aromatic hydrocarbon, such as dimethylbenzene, toluene, mesitylene；Ketone, such as Methylethyl Ketone, methyl iso-butyl ketone (MIBK), methyl isoamyl ketone, methyl amyl ketone, diisobutyl ketone, methyl propyl ketone, cyclopentanone, cyclohexanone； Esters, such as butyl acetate, tert-butyl acetate, pentyl acetate, isoamyl acetate, ethylene glycol monomethyl ether acetate, propyl propionate, propionic acid Butyl ester；Ethers, such as glycol dimethyl ether, diethylene glycol dimethyl ether, butyl oxide, dioxanes, tetrahydrofuran；Alcohols, such as n-butanol, different Butanol, benzylalcohol；Ether alcohol, such as butyl cellosolve, 1- methoxy-2-propanols；Aliphatic hydrocarbon, such as white essential oil；And optional two kinds or The mixture of more kinds of solvents and diluent.
Preferred solvent is aromatic solvent, particularly the mixture of dimethylbenzene and aromatic hydrocarbon.
The amount of solvent is preferably as low as possible.Solvent content at most can be the 50wt% of composition, be preferably up to combination The 45wt% of object, such as up to 40wt%, but can be down to 15wt% or less, such as down to 10wt% or following.Equally, It will be understood by those skilled in the art that solvent content becomes the final use according to existing other components and coating composition Change.
Alternatively, coating can be dispersed in the organic non-solvents for film-forming components in coating composition or be dispersed in water In dispersion.
The good antiscale property coating composition of the present invention should preferably have the solid content for being higher than 40vol% by volume, such as Higher than 45vol%, such as higher than 50vol%, preferably above 55vol%.
It is highly preferred that the content for the volatile organic compounds (VOC) that good antiscale property coating composition has should be less than 500g/ L, preferably shorter than 400g/L, such as.Less than 390g/L.VOC content can calculate (ASTMD5201-01) or measure, and preferably survey Amount.
The good antiscale property coating composition of the present invention can be applied to any object all surfaces for being subject to fouling or part table Face.The surface can be for good and all or intermittently under water (such as loaded by tidal motion, different cargos or swelling).Object Body surface face is typically the surface of hull or fixed ocean object (such as oil platform or buoy).The application of coating composition can be with It is realized by any convenient method, for example, by painting (such as with brush or roller) or will be on coating spraying to object. In general, surface needs to separate to allow to carry out coating with seawater.The application of coating can be realized as known in the art.
When good antiscale property coating is applied on object (such as hull), the surface of object is not usually uniquely by single anti- Fouling coating is protected.According to the property on surface, good antiscale property coating can be applied directly on existing coating system.This painting Coating systems can include different universal classes several layers of paint (such as epoxy resin, polyester, vinyl or acrylic resin or Their mixture).If surface is from the clean and complete good antiscale property coating applied in the past, new good antiscale property paint It can directly apply, be under normal conditions one or two layers, in special circumstances more layers.
Alternatively, technical staff can be from uncoated surface (such as steel, aluminium, plastics, composite material, glass fibre or carbon Fiber) start.In order to protect this surface, full coat layer system is typically included one or two layers corrosion-inhibiting coating, one layer of adhesive layer With one or two layers good antiscale property coating.Those skilled in the art will be familiar with these coatings.
Under special circumstances, additional good antiscale property skin of paint can be applied.
Therefore, in another embodiment, the present invention provide it is a kind of thereon coated with corrosion-inhibiting coating such as epoxy primer, The base material of adhesive layer and good antiscale property coating composition defined herein.
The present invention is defined referring now to following non-limiting example.
Material and method
Abbreviation Title Purity (%)
EDEGA Acrylic acid ethyl diethylene glycol (DEG) ester ≥95
EDEGA Acrylic acid ethyl diethylene glycol (DEG) ester >99
EDEGMA Methacrylic acid ethyl diethylene glycol (DEG) ester ≥95
EEMA Methacrylic acid 2- ethoxy ethyl esters 99
MEMA Methacrylic acid 2- methoxy acrylates ≥99
MMA Methyl methacrylate ≥99.5
n-BA N-butyl acrylate ≥99.5
THFA Tetrahydrofurfuryl acrylate ≥97
TISMA Methacrylic acid triisopropyl monosilane ester ≥98
AMBN 2,2 '-azo is double (2- methylbutyronitriles) ≥98
It is used to prepare the conventional method of copolymer solution
It is added in into the temperature control reaction vessel equipped with blender, condenser, nitrogen inlet and feed entrance a certain amount of Solvent.Reaction vessel is heated and maintained under the reaction temperature provided in table 1.Prepare the pre- of monomer, initiator and solvent Mixed object.In a nitrogen atmosphere, premix is added to so that constant rate of speed is interior when 2 is small in reaction vessel.After when 1 is small, The pressor response temperature that reaction vessel is maintained at or be heated to provide in table 1.Then added after being added in into reaction mixture It is pressurized initiator (boost initiator) solution.Reactant is kept again at a given temperature 2 it is small when, be subsequently cooled to room Temperature.
The measure of polymer solution viscosity
The viscosity of polymer is used according to ASTM D2196-15 test methods A with LV-2 or LV-4 rotors Brookfield DV-1 viscosimeters measure under 12rpm.Before measuring, polymer is heat-treated to 23.0 DEG C ± 0.5 DEG C.
The measure of Non-volatile content in polymer solution
Non-volatile content in polymer solution is measured according to ISO 3251.Take out the test specimens of 0.5g ± 0.1g Product, and it is 30 minutes dry at 150 DEG C in ventilated drying oven.The weight of surplus material is considered as nonvolatile matter (NVM). Non-volatile content is in terms of weight percentage.The value provided is the average value of three and train value.
The measure of Polymer average molecular weights distribution
Polymer is characterized with gel permeation chromatography (GPC) measurement.Use polymer laboratory (Polymer Laboratories PL-GPC50 Instrument measurings molecular weight distribution (MWD)), there are two the next of series connection for PL-GPC50 instruments tool From 5 μm of mixing-D chromatographic columns of PL gel of polymer laboratory (Polymer Laboratories), at room temperature and Using tetrahydrofuran (THF) as eluent under the constant flow rate of 1mL/min, and with refractive index (RI) detector.Use height The polystyrene standards EasiVialsPS-H of Molecular Laboratory (Polymer Laboratories) carries out school to chromatographic column It is accurate.Use the Cirrus software data processings of polymer laboratory (Polymer Labs).It is poly- by will be equivalent to 25mg dryings The polymer solution for closing the amount of object is dissolved in 5mL THF to prepare sample.Sample preserve at room temperature at least 3 it is small when, then Carry out gpc measurement.Before analysis, sample is filtered by 0.45 μm of nylon filter.Weight average molecular weight (Mw), number-average molecular weight (Mn) it is listed in polydispersity index (PDI) (being provided with Mw/Mn) in table.
The measure of glass transition temperature
It is measured by differential scanning calorimetry (DSC) and obtains glass transition temperature (Tg).Dsc measurement is in TA It is carried out on Instruments DSC Q200.By the way that a small amount of polymer solution is transferred in aluminum pot and does sample at 50 DEG C It is dry at least 10 it is small when then at 150 DEG C it is dry 3 it is small when prepare sample.About 10mg drying polymerizations are measured in open aluminum pot The sample of object material, and swept with the rate of heat addition of 10 DEG C/min and the cooldown rate of 10 DEG C/min using empty pot as with reference to record Retouch value.The processing of data is carried out using the Universal Analysis softwares of TA Instruments.Second of heating of record Glass transition ranges Tg of the inflection point (as defined in ASTM E1356-08) as polymer.
For the conventional method of the preparation of good antiscale property coating composition
Each component is mixed with the ratio provided in table 2.Using vibration and oscillation device by mixture in the canister of 250ml Disperse 15 minutes in the presence of bead (diameter about 2mm).Filter glass pearl before test.
Paint viscosity is measured using cone and plate viscometer
Using digital cone and plate viscometer according to ISO 2884-1:1999 measure the viscosity of good antiscale property coating composition, temperature Degree is arranged to 23 DEG C, with 10000s-1Shear rate work and provide viscosity measurement scope as 0-10P.As a result to measure three times Average value provide.
The calculating of volatile organic compounds (VOC) content of good antiscale property coating composition
Volatile organic compounds (VOC) content of good antiscale property coating composition is calculated according to ASTM D5201.
Determine the polishing speed of the good antiscale property film in rotating disk in the seawater
Polishing speed is determined by measuring the reduction of the film thickness of film at any time.For the test, PVC disks are used.Make Coating composition is applied to radial streak on disk with film applicator.The thickness of dry coating film is measured by surface profiler.PVC disks It is rotated in the container for being mounted on an axle and being flowed through in seawater.The speed of rotation axis assigns the averaging analog of 16 nautical miles/hour on disk Speed.It is adjusted using filtered and temperature to 25 DEG C ± 2 DEG C of natural sea-water.PVC disks are periodically taken out to measure film thickness.By disk It rinses and is dried at room temperature for overnight, then measuring film thickness.
Table 2：The general ingredient of coating composition, is provided with parts by weight.
(1) Disparlon A603-20X, amide waxe, 20% in dimethylbenzene；It can be from Kumamoto Chemical Co., Ltd. (Kusumoto Chemicals, Ltd.) is obtained
(2) Disparlon 4401-25X, oxidized polyethylene wax, 25% are in dimethylbenzene；It can be from the limited public affairs of Kumamoto chemical industry (Kusumoto Chemicals, Ltd.) is taken charge of to obtain
Table 3：All paint details of example and test result (n.d.=is not determined)

Claims (20)

1. a kind of monosilane ester copolymer, it includes following comonomers：
(i) acrylic acid ethyl diethylene glycol (DEG) ester (EDEGA)；With
(ii) (methyl) acrylic acid triisopropyl monosilane ester；
Preferably, in the copolymer, (i):(ii) ratio is 5:95 (mol/mol) to 60:In the range of 40 (mol/mol).
2. monosilane ester copolymer according to claim 1, wherein component (ii) are methacrylic acid triisopropyl first silicon Alkyl ester (TISMA).
3. monosilane ester copolymer according to any one of claim 1 to 2, wherein, in the monosilane ester copolymer (i) amount is in the range of 2mol% to 40mol%, preferably in the range of 2mol% to 30mol%, more preferably in 5mol% To 25mol%.
4. monosilane ester copolymer according to any one of claim 1 to 3, wherein, in the monosilane ester copolymer (ii) amount is in the range of the 5mol% to 60mol% of the copolymer, preferably in the range of 15mol% to 50mol%, Particularly in the range of 20mol% to 45mol%.
5. monosilane ester copolymer according to any one of claim 1 to 4, wherein, the monosilane ester copolymer is also Include the hydrophilic co-monomer of one or more formulas (I)：
Wherein R1It is H or CH3, R2It is C3-C18 substituent groups, the R2With at least one oxygen atom or nitrogen-atoms, preferably have to A few oxygen atom, condition is that the hydrophilic co-monomer of formula (I) is not EDEGA.
6. monosilane ester copolymer according to claim 5, wherein, one or more hydrophilic co-monomers include Formula (CH2CH2O)n-R3R2Group, wherein R3It is C1-C10 alkyl or C6-C10 aryl substituents, and n is 1 to 6, preferably Integer in the range of 1 to 3, condition are that the comonomer is not EDEGA.
7. monosilane ester copolymer according to claim 5 or 6, wherein, there are one or more hydrophilic co-monomers, And with formula (CH2CH2O)n-R3R2Group, wherein R3It is alkyl substituent, preferably CH3Or CH2CH3, and n is 1 to 3 In the range of integer, preferably 1 or 2, condition is that the comonomer is not EDEGA.
8. monosilane ester copolymer according to any one of the preceding claims, also comprising methoxyethyl methacrylate (MEMA), methoxyethyl acrylate (MEA), ethoxyethyl methacrylates (EEMA) and tetrahydrofurfuryl acrylate (THFA) In one or more.
9. monosilane ester copolymer according to any one of the preceding claims, also comprising one or more formulas (II) Non-hydrophilic comonomer：
Wherein R1'It is H or CH3, R2'It is C1-C8 hydrocarbyl substituents, preferred C1-C8 alkyl substituents, most preferable, ethyl, just Propyl, 2- ethylhexyls or normal-butyl.
10. monosilane ester copolymer according to claim 9, it includes methyl methacrylate (MMA) and acrylic acid just One or more in butyl ester (n-BA).
11. monosilane ester copolymer according to any one of claim 1 to 10, it includes the MMA as comonomer Amount be 10mol% to 70mol%, preferably 30mol% to 60mol%.
12. monosilane ester copolymer according to any one of claim 1 to 11, it includes the propylene as comonomer The amount of sour N-butyl (n-BA) is 2mol% to 20mol%, preferably 2mol% to 15mol%.
13. monosilane ester copolymer according to any one of claim 1 to 12, wherein, the monosilane ester copolymer Comprising following, formed or be made of following by following substantially：
Comonomer TISMA, EDEGA and：
a、MMA；
B, MMA and n-BA；Or
C, MMA, n-BA and THFA.
14. a kind of adhesive for good antiscale property coating composition, it includes the first silicon any one of claim 1 to 13 Alkyl ester copolymer and rosin or rosin derivative.
15. a kind of good antiscale property coating composition, it includes copolymer according to any one of claim 1 to 13 and at least A kind of good antiscale property agent.
16. good antiscale property coating composition according to claim 15, wherein, the good antiscale property agent includes cuprous oxide and/or pyrrole Pyridine thioketones copper.
17. a kind of for protecting object from the method for fouling, the described method includes with any one of claim 15 to 16 institute The good antiscale property coating composition stated is by least a portion of the object of fouling.
18. coat the object just like the good antiscale property coating composition any one of claim 15 to 16.
19. object according to claim 18, wherein, the object is coated with corrosion-inhibiting coating, adhesive layer and as right will Seek the good antiscale property coating composition described in 15 to 16.
20. object according to claim 18, wherein, the object coating is just like the anti-caking described in claim 15 or 16 Dirty coating composition, the object cover pre-existing good antiscale property coating composition on base material.
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