CN101875707A - Fluorin-containing POSS acrylate polymer, preparation method thereof and paint - Google Patents
Fluorin-containing POSS acrylate polymer, preparation method thereof and paint Download PDFInfo
- Publication number
- CN101875707A CN101875707A CN2009101071677A CN200910107167A CN101875707A CN 101875707 A CN101875707 A CN 101875707A CN 2009101071677 A CN2009101071677 A CN 2009101071677A CN 200910107167 A CN200910107167 A CN 200910107167A CN 101875707 A CN101875707 A CN 101875707A
- Authority
- CN
- China
- Prior art keywords
- formula
- fluorine
- acrylate
- containing poss
- acrylate copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a fluorin-containing POSS acrylate polymer. The fluorin-containing POSS acrylate segmented polymer resin has a structure shown by M'-M-M', wherein the M' is a fluorin-containing acrylate structure unit; and M is an irregular polymerization unit containing active group acrylate and POSS acrylate, and the fluorin-containing POSS is fluorin-containing polyhedral oligomeric silsesquioxane. The invention also provides a method for preparing the fluorin-containg POSS acrylate polymer and a paint containing the fluorin-containing POSS acrylate polymer. The preparation method adopts the POSS acrylate monomer with lower cost and fluorin-containing acrylate monomers to prepare the fluorin-containing POSS acrylate polymer with fluorin-containing acrylate structure units distributed on the two ends of the polymer by controlling the adding sequence of the fluorin-containing acrylate monomers, and has the advantages of simple process and low cost; and the prepared paint has low surface energy and high fouling resistance.
Description
[technical field]
The present invention relates to a kind of acrylate copolymer resin and synthetic method thereof, especially an organic-inorganic hybrid nanometer bunch fluorine-containing cage-type silsesquioxane replaces (methyl) acrylic acid esters co-polymer.
[background technology]
In order to improve hardness, scratch resistance, obtain transparent damage resistant antifouling paint, usually with SiO
2, TiO
2Be incorporated in the acrylate containing fluorine polymkeric substance Deng inorganics, common method has: direct blending, sol-gel method and situ aggregation method.Polyhedral oligomeric silsesquioxane class acrylate is the silicoorganic compound that a class has the special molecular structure shown in the formula 7,
POSS group wherein has the structure shown in the formula 9, wherein inorganic silica scaffold core provides good inorganic nature for material, peripheral organic group R can strengthen and polymeric matrix between consistency, be that presoma can obtain the molecular level organic-inorganic nano hybrid material that the silica skeleton is a core with it; R is-CH
3,-C
6H
5,-n-C
6H
13,-n-C
4H
9Or-C
5H
11K is the integer of 0-6, and R4 is H, C
1-C
5The straight or branched alkyl.
Disclose the hydrophobic automatic cleaning coating material of a kind of POSS of application in the prior art, introduced the nanostructure of fluorine-containing POSS by polymkeric substance, changed the microtexture of coatingsurface effectively, the contact angle of water is reached more than 130 °, transmitance reaches 90%.A kind of fluorine-containing POSS acrylate block copolymer resin and synthetic method thereof are also disclosed in the prior art, this method adopts the end capped methyl methacrylate prepolymer reaction of fluorine-containing polyhedral oligomeric silsesquioxane (F-POSS) and Br, obtained inorganic-organic hybridization nano bunch fluorinated block copolymer resin, the contact angle that this resin is made after the coating with water can reach 100 °.
Directly on POSS, introduce fluorine-containing organic group in the prior art, be applied in the acrylic ester polymer, prepare transparent wear-resisting antifouling paint, but POSS introduces the plain group complex process of fluorine, the cost height, productive rate is low.And in the various antifouling paints of the prior art, the distribution of the plain group of fluorine makes its effective rate of utilization very low in the molecular structure of resin, thereby the antifouling ability of coating is also relatively poor.
[summary of the invention]
The present invention is directed to the complex process that exists in the prior art, the problem that the antifouling ability of cost height and coating is relatively poor, a kind of fluorine-containing POSS acrylate copolymer is provided, wherein,---M---structure shown in the M ' that described fluorine-containing POSS acrylate block copolymer resin has M ', wherein M ' is the structural unit shown in the formula 1; M is the random copolymerized units that contains formula 2 and formula 3, and described fluorine-containing POSS is fluorine-containing polyhedral oligomeric silsesquioxane;
Formula 1 formula 2 formulas 3
Wherein, R
1, R
2, R
3, R
4Be H, C independently of one another
1-C
5The straight or branched alkyl;
X＝-OCH
2(CH
2)
mCH
2(CF
2)
nCF
3；
Y=-COOH ,-OH or
I is the integer of 1-1000, and j, n are the integer of 0-8 independently of one another, and k, m are the integer of 0-6 independently of one another.
The present invention is directed to the problems referred to above, a kind of preparation method of fluorine-containing POSS acrylate copolymer also be provided, comprise following steps:
(a) polymerisable monomer is contacted with initiator, carry out polyreaction under the nitrogen protection, contain the compound of structure shown in formula 6 and the formula 7 in the described polymerization single polymerization monomer, obtain product after polyreaction is finished and be designated as A;
(b) in A, add mixture B, contain the fluorinated acrylate of structure shown in the formula 5 among the described mixture B and contain fluorous solvent, obtain fluorine-containing POSS acrylate copolymer by Raolical polymerizable;
Formula 5 formulas 6 formulas 7
Wherein, R
2, R
3, R
4Be H, C independently of one another
1-C
5The straight or branched alkyl;
X＝-OCH
2(CH
2)
mCH
2(CF
2)
nCF
3；
Y=-COOH ,-OH or
J, n are the integer of 0-8 independently of one another, and k, m are the integer of 0-6 independently of one another.
The present invention is directed to the problems referred to above, a kind of coating also is provided, contain fluorine-containing POSS acrylate copolymer, solidifying agent and thinner in the described coating, it is characterized in that, described fluorine-containing POSS acrylate copolymer is a fluorine-containing POSS acrylate copolymer provided by the invention.
According to fluorine-containing POSS acrylate copolymer provided by the invention, fluorine-containing cell distribution is at the two ends of multipolymer, and promptly fluorine-containing cell distribution has improved the fluorine content of coatingsurface on the surface of nano hybridization coating, make the coating that makes have low surface energy, promptly have high antifouling ability; The utilization ratio of the fluorine in the coating effectively improves simultaneously, can effectively reduce cost.In addition, among the preparation method of fluorine-containing POSS acrylate block copolymer resin provided by the invention, adopt lower-cost POSS Acrylic Acid Monomer and fluorinated acrylate monomer, and addition sequence by the control fluorinated acrylate monomer, can obtain the fluorine-containing POSS acrylate copolymer that fluorinated acrylate structural unit provided by the invention is distributed in the multipolymer two ends, technology is simple, and is with low cost.
[embodiment]
The invention provides a kind of fluorine-containing POSS acrylate copolymer, wherein,---M---structure shown in the M ' that described fluorine-containing POSS acrylate block copolymer has M ', wherein M ' is the structural unit shown in the formula 1; M is the random copolymerized units that contains formula 2 and formula 3, and described fluorine-containing POSS is fluorine-containing polyhedral oligomeric silsesquioxane;
Formula 1 formula 2 formulas 3
Wherein, R
1, R
2, R
3, R
4Be H, C independently of one another
1-C
5The straight or branched alkyl;
X＝-OCH
2(CH
2)
mCH
2(CF
2)
nCF
3
Y=COOH ,-OH or
I is the integer of 1-1000, and j, n are the integer of 0-6 independently of one another, and k, m are the integer of 0-6 independently of one another.
M ' structural unit is for containing the plain substituent structural unit of fluorine, and this cell distribution is at the two ends of described fluorine-containing POSS acrylate copolymer.X in the M ' structural unit is-OCH
2(CH
2)
mCH
2(CF
2)
nCF
3, wherein m is the integer of 0-6, n is the integer of 0-8.According to fluorine-containing POSS acrylate copolymer provided by the invention, described M ' can be in perfluoro-methyl ethylacrylic acid ester units, perfluoro-methyl ethyl-methyl acrylic ester unit, perfluoro capryl ethylacrylic acid ester units, the perfluoro capryl ethyl-methyl acrylic ester unit etc. a kind of, be preferably perfluoro capryl ethylacrylic acid ester units, perfluoro capryl ethyl-methyl acrylic ester unit among the present invention.
Contain active group Y and POSS group in the M structural unit, its backbone structure is the two key copolymerization structures of acrylate C=C.Suc as formula 2 and formula 3 shown in, described active group Y and POSS group all are positioned on the side chain of M structural unit.Structural unit shown in formula 2 and the formula 3 obtains described M structural unit by the mode of random copolymerization, thereby makes active group and POSS group uniform distribution in resin, prevents agglomeration, the favourable transparent coating of height that obtains.For example, the structural unit shown in the formula 2 is designated as M1, and the structural unit shown in the formula 3 is designated as M2, and described M structural unit can be-M1M2M2M1 ... M2M1M2M2M1-.
Wherein, Y for active group Y be COOH ,-OH or
J is the integer of 0-8, and k is the integer of 0-6.
In the fluorine-containing POSS acrylate copolymer provided by the present invention, R
1, R
2, R
3, R
4Be H, C independently of one another
1-C
5The straight or branched alkyl.Among the present invention, described C
1-C
5The straight or branched alkyl can be methyl, ethyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl or n-pentyl.
The molecular weight of resin and the intensity of resin and processing characteristics are closely related, and therefore, the molecular weight of resin is to synthesize, need in processing and the application process important indicator considered.For the further intensity that improves resin further reduces the viscosity of resin, the processibility of raising resin simultaneously, under the preferable case, the number-average molecular weight of fluorine-containing POSS acrylate copolymer provided by the invention is 3000-20000, and number-average molecular weight is 1.0-1.8 with the ratio of weight-average molecular weight.More preferably under the situation, the number-average molecular weight of described fluorine-containing POSS acrylate copolymer is 5000-10000, and number-average molecular weight is 1.1-1.6 with the ratio of weight-average molecular weight.
Among the present invention, the ratio of the structural unit shown in described fluorine-containing POSS acrylate copolymer Chinese style 1, formula 2 and the formula 3 can be selected in a big way, but under the preferable case, the weight ratio of the structural unit shown in formula 1, formula 2, the formula 3 is 1: 0.5-10: 0.5-10.
Under the preferable case, in the fluorine-containing POSS acrylate copolymer provided by the invention, M also contains the structural unit of formula 4,
Formula 4
Wherein, R
5Be H, C
1-C
5The straight or branched alkyl; Z=-OCH
3,-OC (CH
3)
3Or-O (CH
2)
3CH
3, the structural unit shown in the formula 4 is the acrylate monomer copolymerization structure that those skilled in the art use always.In the fluorine-containing POSS acrylate copolymer provided by the present invention, the structural unit shown in the formula 4 can effectively reduce the cost of resin, and resin flexibility and viscosity preferably are provided, and makes the coating that obtains at last have sticking power and film-forming properties preferably.The content of the structural unit shown in the formula 4 can be selected in a big way, but under the preferable case, formula 1 is 1 with the weight ratio of the structural unit shown in the formula 4: 1-20.
The present invention also provides a kind of preparation method of fluorine-containing POSS acrylate copolymer, may further comprise the steps:
(a) polymerisable monomer is contacted with initiator, carry out polyreaction under the nitrogen protection, contain the monomer of structure shown in formula 6 and the formula 7 in the described polymerization single polymerization monomer, obtain product after polyreaction is finished and be designated as A;
(b) in A, add mixture B, contain the fluorinated acrylate monomer shown in the formula 5 among the described mixture B and contain fluorous solvent, obtain fluorine-containing POSS acrylate copolymer by Raolical polymerizable;
Formula 5 formulas 6 formulas 7
Wherein, R
2, R
3, R
4Be H, C independently of one another
1-C
5The straight or branched alkyl;
X＝-OCH
2(CH
2)
mCH
2(CF
2)
nCF
3；
Y=-COOH ,-OH or
J, n are the integer of 0-8 independently of one another, and k, m are the integer of 0-6 independently of one another.
According to preparation method provided by the present invention, in the step (a), contain active group carboxyl, hydroxyl or epoxy ethyl in the monomer of structure shown in the described polymerisable monomer Chinese style 6, contain the POSS group shown in the formula 7 in the monomer of structure, initiator exists down, by the olefinic polyreaction of acrylate structural, can be contained active group acrylate structural unit and the unitary random copolymers of POSS acrylate structural simultaneously.The purpose of introducing active group in the random copolymers is to make active group and POSS group uniform distribution in resin, prevents agglomeration, the favourable transparent coating of height that obtains.
The monomer of structure shown in the formula 6 is the acrylate monomer that contains active group Y, and described active group Y is carboxyl, hydroxyl or epoxy ethyl.Described active group Y links to each other by methylene radical or ester group direct and on the acrylate.Wherein the number of methylene radical is designated as j, and j is the integer of 0-8.The described acrylate monomer that contains active group can be in hydroxy ethyl methacrylate, hydroxymethyl acrylate, the carboxymethyl acrylate a kind of.
Monomer shown in the formula 7 is the POSS acrylate monomer, the various POSS acrylate monomers that this monomer can adopt those skilled in the art to use always, and wherein R is-CH
3,-C
6H
11,-C
4H
9,-C
8H
17Or-C
6H
5, the POSS monomer that for example can directly adopt U.S. Hybridplastics company to produce, wherein R=-C
4H
9, k=5, R
4=-CH
3
The employed initiator of olefinic polyreaction of the present invention can be this area various initiators commonly used, and for example: Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide, di-t-butyl peroxide or peroxidation two tert-pentyls are preferably Diisopropyl azodicarboxylate.More preferably under the situation, the mass ratio of described polymerisable monomer and initiator is 1: 0.001-0.05.
The condition of described polyreaction is: the temperature of reaction is 70-90 ℃, and the reaction times is 0.5-10h.Total mass with polymerisable monomer is a benchmark, and the content that contains the acrylate monomer of active group is 0.1-50%, and the content of POSS acrylate monomer is 0.1-50%.
Designer of the present invention finds by a large amount of experiments: adopt preparation method provided by the invention, addition sequence by the control fluorinated acrylate monomer, promptly after containing active group acrylate monomer and POSS acrylate monomer polymerization reaction take place, add fluorinated acrylate monomer again, can obtain the end capped fluorine-containing POSS acrylate copolymer of fluorinated acrylate structural unit, the i.e. two ends distribution fluorinated acrylate structural unit of this copolymer resin,---M---structure shown in the M ' that has M ', wherein M ' is the fluorinated acrylate structural unit; M is the random copolymerized units that contains active group acrylate and POSS acrylate.
In the step (b), add mixture B among the reaction product A that obtains toward step (a), contain fluorinated acrylate monomer among the mixture B and contain fluorous solvent, can obtain fluorine-containing POSS acrylate copolymer provided by the invention by Raolical polymerizable.Described fluorinated acrylate has as shown in the formula the structure shown in 5,
Formula 5
Wherein, X is the plain substituted radical of fluorine, and structural formula is-OCH
2(CH
2)
mCH
2(CF
2)
nCF
3, m is the integer of 0-6, n is the integer of 0-8.R
2Be H, C
1-C
5The straight or branched alkyl.
For example, m, n are 0, R
2During for H, described fluorinated acrylate is a perfluoro-methyl ethyl propylene acid esters; M=0, n=7, R
2For-CH
3The time, described fluorinated acrylate is a perfluoro capryl ethyl-methyl acrylate.Among the present invention, described fluorinated acrylate is preferably at least a in perfluoro capryl ethyl propylene acid esters, the perfluoro capryl ethyl-methyl acrylate.
According to preparation method provided by the invention, also contain fluorous solvent among the mixture B.Describedly contain the various fluorous solvents that contain that fluorous solvent is used always for those skilled in the art, for example can be the fluorinated ester kind solvent, as contain ethyl fluoroacetate or fluorine-containing butylacetate; Also can be hydrogen fluorine ether solvent, as too general FHT-254, FHT-4500, the FHT-6500 that fluoridizes company.The above-mentioned fluorous solvent that contains can use separately, also can be that several fluorine-containing solvent are used.
In the step (b), the reaction conditions of described Raolical polymerizable is: temperature of reaction is 70-90 ℃, and the reaction times is 0.5-10h.Described A, fluorinated acrylate, the weight ratio that contains fluorous solvent are 1: 0.05-1: 0.1-10 is preferably 1: 0.1-0.5: 0.5-5.
Under the preferable case, the carrying out for the Raolical polymerizable that promotes fluorinated acrylate and reaction product A can also contain initiator among the described mixture B.The initiator that the described initiator that contains among the mixture B and step (a) are adopted can be identical, also can be different, be the various initiators that those skilled in the art use always, for example: Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide, di-t-butyl peroxide or peroxidation two tert-pentyls.More preferably under the situation, be benchmark with the quality of fluorinated acrylate, the content of the initiator among the mixture B is 0.1-5%.
Polymerization process of the present invention can adopt this area polymerization process commonly used, for example: solution polymerization, letex polymerization or suspension polymerization.The good fluidity of the polymkeric substance that the employing solution polymerization makes, and can form uniform coating after the drying, therefore, polymerization process preferred solution of the present invention polymerization, promptly polyreaction is carried out in solvent.Under the preferable case, (a) solvent that is adopted in the step is the various common solvent in present technique field, for example can for as toluene, dimethylbenzene, tetrahydrofuran (THF), butylacetate, isobutyl acetate, ethanol, pimelinketone,, hexone, acetone, methylethylketone, butyl glycol ether, propylene glycol butyl ether, 1-Methoxy-2-propyl acetate (PMA).Above-mentioned solvent both can use separately, also can be the mixture of several solvents.Preparation in accordance with the present invention, (a) consumption of solvent can be 1-3 times of polymerisable monomer total amount in the step.(b) in the step, contain fluorous solvent among the described mixture B, under the preferable case, can also contain the various common solvent in above-mentioned present technique field among the mixture B.More preferably under the situation, the described volume ratio that contains fluorous solvent and usual vehicle is 1: 0.1～10.
According to preparation method provided by the invention, (a) compound of structure shown in all right formula 8 in the described polymerisable monomer of step,
Formula 8
Wherein, R
5Be H, C
1-C
5The straight or branched alkyl; Z=-OCH
3,-OC (CH
3)
3Or-O (CH
2)
3CH
3Be also to contain present technique field acrylate commonly used in the polymerisable monomer.According to preparation method provided by the invention, add acrylate commonly used in the polymerisable monomer, can effectively reduce the cost of resin, and resin flexibility and viscosity preferably are provided, make the coating that obtains at last have sticking power and film-forming properties preferably.Under the preferable case, be benchmark with the total mass of polymerisable monomer, the content of the compound of structure shown in the formula 8 is 50-95%.
The present invention also provides a kind of coating, contains fluorine-containing POSS acrylate copolymer, solidifying agent and thinner in the described coating, it is characterized in that, described fluorine-containing POSS acrylate copolymer is a fluorine-containing POSS acrylate copolymer provided by the invention.
Inorganic silica scaffold core structure among the POSS in the fluorine-containing POSS acrylate copolymer of the present invention makes coating of the present invention have good hardness and intensity; And described POSS links to each other by covalence key with acrylate, and therefore, the two has good consistency; A large amount of fluorine atoms are also contained at the two ends of the molecular structure of fluorine-containing POSS acrylic copolymer resin of the present invention, can reduce the surface energy of resin, and fluorine atom can also give resin other good performance, for example: chemical proofing, oxidative stability and weathering resistance.Therefore, fluorine-containing POSS acrylate copolymer of the present invention extremely is suitable as antifouling paint.Adopt that the antifouling paint of fluorine-containing POSS acrylate copolymer preparation of the present invention has good hardness, low surface energy, to have good tack and weather resistance and humidity resistance good with base material, can life-time service.
Because the present invention is the antifouling paint that comes the obtained performance excellence by the method for the chemical structure that changes resin, so the present invention adopts this area method commonly used to get final product for the preparation method of coating and without particular limitation.Contain fluorine-containing POSS acrylate copolymer of the present invention, thinner and solidifying agent in the coating of the present invention.
The introducing of thinner can reduce the viscosity of coating, improves the processibility of coating, makes coating have the coating performance.Thinner of the present invention can be variously can make fluorine-containing POSS acrylate copolymer of the present invention form the organic solvent of uniform and stable system, for example, can be for the fluorine-containing POSS acrylate copolymer of preparation the time employed identical or organic solvent that mixes, preferred to adopt the volume ratio that contains fluorous solvent and usual vehicle in (b) step be 1: 0.1～10 mixed solvent.The usage quantity of thinner all has relation to the processibility and the cost of coating.
Described solidifying agent can take place crosslinked with the active group Y in the fluorine-containing POSS acrylate copolymer, after paint solidification obtains coating, can effectively improve the hardness of coating.Among the present invention, described solidifying agent can adopt various solidifying agent of the prior art, for example can directly adopt Ciba-EFKA-3886, the Ciba-EFKA-3886 of vapour Bagong department or CYMEL-303, the CYMEL-370 of the special company of cyanogen.
In order further to save cost and further to reduce the pollution that environment is produced, be benchmark with the total mass of described coating, the content of described thinner is 10-99 weight %, the content of described solidifying agent is 0.1-40 weight %.
For improving the various performances of coating, can also in coating, add the various auxiliary agents that those skilled in the art use always, for example defoamer, flow agent.Described defoamer can adopt BYK-071, BYK-072, BYK-1790 or the EFKA of Bi Ke company to receive the AFCONA-2022 of company, among the AFCONA-2045 one or more.Flow agent can adopt BYK-333, BYK-072, BYK-1790 or the EFKA of Bi Ke company to receive AFCONA-3033, the AFCONA-3034 of company, among the AFCONA-3750 one or more.Under the preferable case, be benchmark with the total mass of described coating, the content of described defoamer is 0.1-10wt%; The content of described flow agent is 0.1-10wt%.
Antifouling paint of the present invention is adopted this area method commonly used, and for example spraying, dip-coating or spin coating are applied on the base material, and solidify 1-20 hour under 90-180 ℃ temperature, can obtain the coating that is formed by antifouling paint of the present invention.The present invention is also without particular limitation to the thickness of the coating of formation, adopts thickness well known to those skilled in the art to get final product, and is generally 0.5-50 μ m, and the thickness of embodiments of the invention floating coat is 10 μ m, but is not limited to this.
The present invention is further illustrated below by embodiment, and the raw material that is adopted all is available commercially.Embodiment 1
Present embodiment is used to illustrate fluorine-containing POSS acrylate copolymer provided by the invention and preparation method thereof.
(1) exsiccant 250ml four-hole boiling flask is loaded onto mechanical stirring and reflux condensing tube after, logical nitrogen 10min; In four-hole boiling flask, add 16.5g polymerisable monomer (wherein, 10.5g methyl methacrylate, 2g isobutyl acrylate, 1g hydroxy ethyl methacrylate, 3g POSS acrylate (k=5, R in the formula 7
4=-CH
3, R=-C in the formula 9
4H
9), 0.3g initiator A IBN and 30g. solvent toluene; Vigorous stirring, under the nitrogen protection, 85 ℃ of reaction 3h;
(2) then in the reaction system of step (1), drip 3.875g fluorinated acrylate (20 quality % perfluoro capryl ethyl propylene acid esters), 0.18g initiator A IBN and 5g solvent toluene lentamente, 10g contains fluorous solvent FHT-6500, and the dropping time is 50min, dropwises the back and continues reaction 3h; After reaction finished, 60 ℃ of following vacuum distillings added xylene solvent then, prepared solid content and be 30% fluorine-containing POSS acrylate copolymer, were designated as A1.
Embodiment 2
Present embodiment is used to illustrate fluorine-containing POSS acrylate copolymer provided by the invention and preparation method thereof.
Adopt the method identical with embodiment 1 to prepare fluorine-containing POSS acrylate copolymer, difference is: in the step (1), only contain 2g hydroxy ethyl methacrylate, 4g POSS acrylate (k=5, R in the formula 7 in the polymerisable monomer
4=-CH
3, R=-C in the formula 9
4H
9), i=5, Y=-CH
3), 0.2g initiator A IBN and 15g. solvent toluene; In the step (2), slowly drip 6g fluorinated acrylate (50 quality % perfluoro capryl ethyl propylene acid esters), 0.24g initiator A IBN and 5g solvent toluene, 15g contains fluorous solvent FHT-6500; The fluorine-containing POSS acrylate copolymer that obtains at last is designated as A2.
Embodiment 3
Embodiment is used to illustrate fluorine-containing POSS acrylate copolymer provided by the invention and preparation method thereof.
Adopt the method identical with embodiment 1 to prepare fluorine-containing POSS acrylate copolymer, difference is: in the step (1), polymerisable monomer comprises 2g hydroxymethyl acrylate, 4g POSS acrylate (k=6, R in the formula 7
4=-H, R=-C in the formula 9
5H
6), 0.2g initiator A IBN and 15g. solvent toluene; In the step (2), polymerisable monomer is 3.875g fluorinated acrylate (20 quality % perfluoro capryl ethyl propylene acid esters), 0.2g initiator dibenzoyl peroxide and 5g solvent toluene, and 15g contains fluorous solvent FHT-6500; The fluorine-containing POSS acrylate copolymer that obtains at last is designated as A3.
Embodiment 4
Embodiment is used to illustrate fluorine-containing POSS acrylate copolymer provided by the invention and preparation method thereof.
Adopt the method identical with embodiment 1 to prepare fluorine-containing POSS acrylate copolymer, difference is: in the step (2), fluorinated acrylate is 23.25g fluorinated acrylate (60 a quality % perfluoro capryl ethyl-methyl acrylate); The fluorine-containing POSS acrylate copolymer that obtains at last is designated as A4.
Embodiment 5
Embodiment is used to illustrate fluorine-containing POSS acrylate copolymer provided by the invention and preparation method thereof.
Adopt the method identical with embodiment 1 to prepare fluorine-containing POSS acrylate copolymer, difference is: in the step (1), polymerisable monomer is 4g hydroxy ethyl methacrylate, 2g POSS acrylate (k=5, R in the formula 7
4=-CH
3, R=-C in the formula 9
4H
9); The fluorine-containing POSS acrylate copolymer that obtains at last is designated as A5.
Comparative Examples 1
This Comparative Examples is used for illustrating embodiment 2 disclosed fluorine-containing POSS acrylate block copolymer resin and the synthetic methods thereof of CN101029137A: two mouthfuls of flasks add 10g tetrahydrofuran (THF), CuBr0.006g, PMDETA0.012g, methyl methacrylate performed polymer 10g, 1.5ml F-POSS (R=-CH3, X=-OCH in its structural formula
2CH
2CH
2(CF
2)
5CF
3, q=5, Y=-H.) tetrahydrofuran solution, sealing vacuumizes, logical nitrogen, 80 ℃ of reaction 30h down.Remove catalyzer by alumina adsorption, with methyl alcohol 350ml sedimentation, filter, vacuum-drying is to constant temperature.The fluorine-containing POSS acrylate block copolymer resin that obtains at last is designated as D1.
Comparative Examples 2
After exsiccant 250ml four-hole boiling flask loaded onto mechanical stirring and reflux condensing tube, logical nitrogen 10min; In four-hole boiling flask, add the 10.5g methyl methacrylate successively, 2g isobutyl acrylate, 1g hydroxy ethyl methacrylate, 3gPOSS acrylate (k=5, R in the formula 7
4=-CH
3, R=-C in the formula 9
4H
9), 3.875g fluorinated acrylate (20 quality % perfluoro capryl ethyl propylene acid esters), 0.48g initiator A IBN, 45g. solvent toluene and 15g contain fluorous solvent FHT-6500; Vigorous stirring, under the nitrogen protection, 85 ℃ of reaction 3h; After reaction finished, 60 ℃ of vacuum distillings added xylene solvent then, prepared solid content and be 30% fluorine-containing POSS acrylate copolymer, were designated as D2.
Embodiment 6
Present embodiment is used to illustrate coating provided by the invention.
The solid content that takes by weighing 10g embodiment 1 preparation is 30% fluorine-containing POSS acrylate copolymer A1,2.5g solidifying agent CYMEL-303,20g thinner (wherein 8g dimethylbenzene, 12g butylacetate, 2g contain fluorous solvent FHT-6500), 0.3g the flow agent BYK-333 of defoamer AFCONA-2045 and 0.12g, mixing preparation is even under the normal temperature, promptly obtain coating of the present invention, be designated as A6.
Embodiment 7-10
Embodiment 7-10 is used to illustrate coating provided by the invention.
Adopt the method identical with embodiment 6, the fluorine-containing POSS acrylate copolymer A2-A5 (being designated as F-POSS) that respectively embodiment 2-5 is made by component in the table 1 and content mixes with thinner, solidifying agent, defoamer, flow agent, make coating of the present invention, be designated as A7-A10 successively.Concrete each component and content see Table 1.
Comparative Examples 3-4
Comparative Examples 3-4 is used to illustrate the coating of prior art.
Adopt the method identical with embodiment 6, the fluorine-containing POSS acrylate copolymer D1-D2 (being designated as F-POSS) that respectively Comparative Examples 1-2 is made by component in the table 1 and content mixes with thinner, solidifying agent, defoamer, flow agent, make coating of the present invention, be designated as D3-D4 successively.Concrete each component and content see Table 1.
Table 1
Performance test
(1) copolymer resin molecular weight test: the PL-GPC50 type gel permeation chromatograph (moving phase: tetrahydrofuran (THF) that adopts Polymer Laboratories company to produce; Temperature: 30 ℃) measure fluorine-containing POSS acrylate copolymer A1-A5 that embodiment 1-5 and Comparative Examples 1-2 make and number-average molecular weight Mn and the molecular weight distribution of D1-D2, test result is as shown in table 2.
Method pulling film forming on high polishing stainless steel surface that coating A6-A10 that embodiment 6-10 and Comparative Examples 3-4 are made and D3-D4 adopt dip-coating, solidified 5 hours at 120 ℃ then, can obtain completion of cure, transparent and uniform film as paint coatings, wherein, the thickness of coating is 10 μ m.
(2) hardness test: the hardness of antifouling paint coating is tested according to the described method of GB/6739T.
(3) glossiness test: adopt the glossiness of the miniature vancometer test antifouling paint coating of BYK-Gardner4030 under 60 ℃ of angles.
(4) sticking power test: on the antifouling paint coatingsurface, draw the square lattice of 100 1mm * 1mm with drawing the lattice device.The model of producing with Minnesota Mining and Manufacturing Company is 600 smooth being bonded on the grid of scotch tape, does not stay a space, uncovers with the fastest speed 60 degree angles then, and whether observe cut edge has depainting.As being 5B without any depainting, the depainting amount is 4B between 0-5 weight %, and the depainting amount is 3B between 5-15 weight %, and the depainting amount is 2B between 15-35 weight %, and the depainting amount is 1B between 35-65 weight %, and the depainting amount is 0B more than 65 weight %.
(5) scratch resistance test: use DUR-O-TEST hardness test rod (German BTK-gardner company), range is 0-1000N;
(6) surface energy test: use the Data physics OCA of company series contact angle measurement to measure the contact angle of antifouling paint coating and water and methylene iodide, calculate the surface energy of coating then.
(7) scrubbing resistance test: select for use elcometer 1720 wear-resisting, anti-brushes, scrubbing resistance experiment instrument to come and go according to scrubbing resistance standard A STM D4213-96 and clean test sample plate surface energy behind the model (with the sponge is washing scrubber, load-carrying 250g) 500 times with the speed of 37 times/min.Test result is as shown in table 3.
Table 2
| Specimen | ??A1 | ??A2 | ??A3 | ??A4 | ??A5 | ??D1 | ??D2 |
| ??Mn(/10 3) | ??10 | ??8 | ??12 | ??11 | ??10 | ??14 | ??10 |
| Molecular weight distribution | ??1.15 | ??1.2 | ??1.3 | ??1.2 | ??1.3 | ??1.4 | ??1.35 |
Table 3
By the test result of last table 2 as can be seen, the number-average molecular weight of the fluorine-containing POSS acrylate copolymer that the present invention makes is 3000-20000, molecular weight distribution between 1.1-1.4, narrow distribution;
By the test result of last table 3 as can be seen, the present invention adopts the coating that makes keeping having stronger scratch resistance ability and low surface energy, i.e. the antifouling property height of coating under hardness, glossiness and the unabated prerequisite of sticking power; In addition, after coating of the present invention was tested through scrubbing resistance, surface energy variation was littler than the prior art, and promptly coating has wear resistance preferably.Simultaneously, preparation method's technology of fluorine-containing POSS acrylate copolymer provided by the invention is simple, with low cost.
Claims (16)
1. fluorine-containing POSS acrylate copolymer, wherein,---M---structure shown in the M ' that described fluorine-containing POSS acrylate block copolymer resin has M ', wherein M ' is the structural unit shown in the formula 1; M is the random copolymerized units that contains formula 2 and formula 3, and described fluorine-containing POSS is fluorine-containing polyhedral oligomeric silsesquioxane;
Formula 1 formula 2 formulas 3
Wherein, R
1, R
2, R
3, R
4Be H, C independently of one another
1-C
5The straight or branched alkyl;
X＝-OCH
2(CH
2)
mCH
2(CF
2)
nCF
3；
Y=COOH ,-OH or
I is the integer of 1-1000, and j, n are the integer of 0-8 independently of one another, and k, m are the integer of 0-6 independently of one another.
2. fluorine-containing POSS acrylate copolymer according to claim 1 is characterized in that: the number-average molecular weight of described fluorine-containing POSS acrylate block copolymer resin is 3000-20000, and number-average molecular weight is 1.0-1.8 with the ratio of weight-average molecular weight.
3. fluorine-containing POSS acrylate copolymer according to claim 1 is characterized in that: the weight ratio of the structural unit shown in formula 1, formula 2, the formula 3 is 1: 0.5-10: 0.5-10.
4. fluorine-containing POSS acrylate copolymer according to claim 1, it is characterized in that: M also contains the structural unit of formula 4,
Formula 4
Wherein, R
5Be H, C
1-C
5The straight or branched alkyl; Z=-OCH
3,-OC (CH
3)
3Or-O (CH
2)
3CH
3
5. fluorine-containing POSS acrylate copolymer according to claim 4 is characterized in that: formula 1 is 1 with the weight ratio of the structural unit shown in the formula 4: 1-20.
6. the preparation method of a fluorine-containing POSS acrylate copolymer may further comprise the steps:
(a) polymerisable monomer is contacted with initiator, carry out polyreaction under the nitrogen protection, contain the compound of structure shown in formula 6 and the formula 7 in the described polymerization single polymerization monomer, obtain product after polyreaction is finished and be designated as A;
(b) in A, add mixture B, contain the fluorinated acrylate of structure shown in the formula 5 among the described mixture B and contain fluorous solvent, obtain fluorine-containing POSS acrylate copolymer by Raolical polymerizable;
Formula 5 formulas 6 formulas 7
Wherein, R
2, R
3, R
4Be H, C independently of one another
1-C
5The straight or branched alkyl;
X＝-OCH
2(CH
2)
mCH
2(CF
2)
nCF
3；
Y=-COOH ,-OH or
J, n are independently of one another for to be that the integer of 0-8, k, m are the integer of 0-6 independently of one another.
7. preparation method according to claim 6 is characterized in that, initiator described in the step (a) is at least a in Diisopropyl azodicarboxylate, dicumyl peroxide, dibenzoyl peroxide, di-t-butyl peroxide or peroxidation two tert-pentyls.
8. preparation method according to claim 6 is characterized in that, fluorinated acrylate described in the step (b) is at least a in perfluoro capryl ethyl propylene acid esters, the perfluoro capryl ethyl-methyl acrylate.
9. preparation method according to claim 6 is characterized in that, the mass ratio of polymerisable monomer and initiator is 1 described in the step (a): 0.001-0.05.
10. preparation method according to claim 6 is characterized in that, in the step (a), is benchmark with the total mass of polymerisable monomer, and the content of the compound of structure shown in the formula 6 is 0.1-50%, and the content of the compound of structure shown in the formula 7 is 0.1-80%.
11. preparation method according to claim 6 is characterized in that, in the step (b), described A, fluorinated acrylate, the weight ratio that contains fluorous solvent are 1: 0.05-1: 0.1-10.
12. preparation method according to claim 6 is characterized in that, in the step (a), also contains the acrylate monomer shown in the formula 8 in the described polymerisable monomer,
Formula 8
Wherein, R
5Be H, C
1-C
5The straight or branched alkyl; Z=-OCH
3,-OC (CH
3)
3Or-O (CH
2)
3CH
3
13. preparation method according to claim 12 is characterized in that, is benchmark with the total mass of polymerisable monomer, the content of the compound of structure shown in the formula 8 is 50-95%.
14. preparation method according to claim 6 is characterized in that, the condition of polyreaction is described in the step (a): temperature of reaction is 70-90 ℃, and the reaction times is 0.5-10h.
15. a coating contains fluorine-containing POSS acrylate copolymer, thinner and solidifying agent in the described coating, it is characterized in that, described fluorine-containing POSS acrylate copolymer is each described fluorine-containing POSS acrylate copolymer of claim 1-5.
16. coating according to claim 15 is characterized in that, is benchmark with the total mass of coating, the content of described thinner is 10-99%, and the content of solidifying agent is 0.1-40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910107167A CN101875707B (en) | 2009-04-30 | 2009-04-30 | Fluorin-containing POSS acrylate polymer, preparation method thereof and paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910107167A CN101875707B (en) | 2009-04-30 | 2009-04-30 | Fluorin-containing POSS acrylate polymer, preparation method thereof and paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101875707A true CN101875707A (en) | 2010-11-03 |
| CN101875707B CN101875707B (en) | 2012-09-26 |
Family
ID=43018396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910107167A Expired - Fee Related CN101875707B (en) | 2009-04-30 | 2009-04-30 | Fluorin-containing POSS acrylate polymer, preparation method thereof and paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101875707B (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120914A (en) * | 2011-01-18 | 2011-07-13 | 中科院广州化学有限公司 | Ultraviolet light curing coating modified by fluorine-containing polymer nano particle and preparation method thereof |
| CN102277060A (en) * | 2011-08-10 | 2011-12-14 | 天津大学 | Hydrophobic ice-snow preventing coating material of fluorosilicone acrylate copolymer and preparation method of coating layer thereof |
| CN102443099A (en) * | 2011-09-16 | 2012-05-09 | 陕西科技大学 | Preparation method of (sesqui) siloxane hybrid modified fluorinated polyacrylate emulsion |
| CN103435741A (en) * | 2013-08-27 | 2013-12-11 | 华南理工大学 | POSS (Polyhedral Oligomeric Silsesquioxane) based hybridized fluorinated acrylate resin, and preparation method and application thereof |
| CN103435742A (en) * | 2013-08-27 | 2013-12-11 | 华南理工大学 | Hydrophobic POSS (Polyhedral Oligomeric Silsesquioxane)-based hybridization fluorinated acrylate resin as well as preparation method and application thereof |
| JP2014101435A (en) * | 2012-11-19 | 2014-06-05 | Nippon Steel & Sumikin Chemical Co Ltd | Cage silsesquioxane compound, curable resin composition using the same, and resin cured product |
| CN104583255A (en) * | 2012-06-22 | 2015-04-29 | Ppg涂料欧洲有限责任公司 | Antifouling coating composition |
| CN105017910A (en) * | 2014-04-17 | 2015-11-04 | 浙江省海洋开发研究院 | Modified super-hydrophobic marine antifouling coating and preparation method thereof |
| CN105131835A (en) * | 2015-08-04 | 2015-12-09 | 天津大学 | UV-cured POSS fluorine-containing acrylate segmented copolymer coating, preparation and application thereof |
| WO2016037403A1 (en) * | 2014-09-11 | 2016-03-17 | 天津大学 | Fluorinated poss composite organosilicon coating, preparation method and anti-icing application |
| CN106854436A (en) * | 2016-12-29 | 2017-06-16 | 中科院广州化学有限公司南雄材料生产基地 | A kind of fluorine-containing prepolymer modified acrylate coating material of Amino End Group and preparation method thereof |
| EP3197949A4 (en) * | 2014-09-24 | 2018-04-11 | Nbd Nanotechnologies, Inc. | F-poss coatings and additives and methods of making same |
| EP3204450A4 (en) * | 2014-10-07 | 2018-06-20 | Nbd Nanotechnologies, Inc. | Synthetic blend f-poss compositions formed from multiple feedstock materials |
| CN110130103A (en) * | 2019-06-03 | 2019-08-16 | 华南理工大学 | Modified POSS base super-amphiphobic coating material of fluorochemical monomer and the preparation method and application thereof |
| CN111690103A (en) * | 2019-03-13 | 2020-09-22 | 中国科学院上海有机化学研究所 | Water-and oil-repellent fluorine-containing silicon copolymer and preparation method and application thereof |
| CN114015056A (en) * | 2021-10-13 | 2022-02-08 | 佛山市顺德区永创翔亿电子材料有限公司 | Voltage-resistant electrolyte-resistant copolymer, tab adhesive and tab tape |
| WO2022054851A1 (en) * | 2020-09-09 | 2022-03-17 | 日本ペイント・オートモーティブコーティングス株式会社 | Composition for coating materials |
| CN114369412A (en) * | 2021-12-29 | 2022-04-19 | 惠州瑞德新材料科技股份有限公司 | Photocuring composition containing perfluoropolyether/alkenyl silicone resin and method for constructing waterproof and antifouling coating |
| CN114381172A (en) * | 2021-12-31 | 2022-04-22 | 山东东岳未来氢能材料股份有限公司 | Stripping-resistant ethylene-tetrafluoroethylene copolymer powder coating and preparation method thereof |
| CN115368571A (en) * | 2022-09-01 | 2022-11-22 | 珠海赛纳三维科技有限公司 | Fluorine-containing siloxane acrylate and preparation method and application thereof |
| US11702433B2 (en) | 2014-10-07 | 2023-07-18 | Nbd Nanotechnologies, Inc. | Functionalized F-POSS monomer compositions and uses thereof |
| CN116510419A (en) * | 2022-12-01 | 2023-08-01 | 大连理工大学盘锦产业技术研究院 | V-shaped flow control particle coalescence device with coaxial speed difference jet flow |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040061564A (en) * | 2002-12-31 | 2004-07-07 | 제일모직주식회사 | Acetal Group-Containing Hydroxystyrene/POSS-Methacrylate Copolymer and Positive-Type Photoresist Composition Comprising the Same |
| CN100564427C (en) * | 2007-03-09 | 2009-12-02 | 厦门大学 | A kind of fluorine-containing POSS acrylate block copolymer resin and synthetic method thereof |
| CN101712840B (en) * | 2008-10-07 | 2012-03-21 | 北京理工大学 | Ultrathin water-based epoxy resin expandable fireproof paint and preparation method thereof |
-
2009
- 2009-04-30 CN CN200910107167A patent/CN101875707B/en not_active Expired - Fee Related
Cited By (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120914B (en) * | 2011-01-18 | 2012-10-03 | 中科院广州化学有限公司 | Ultraviolet light curing coating modified by fluorine-containing polymer nano particle and preparation method thereof |
| CN102120914A (en) * | 2011-01-18 | 2011-07-13 | 中科院广州化学有限公司 | Ultraviolet light curing coating modified by fluorine-containing polymer nano particle and preparation method thereof |
| CN102277060A (en) * | 2011-08-10 | 2011-12-14 | 天津大学 | Hydrophobic ice-snow preventing coating material of fluorosilicone acrylate copolymer and preparation method of coating layer thereof |
| CN102443099A (en) * | 2011-09-16 | 2012-05-09 | 陕西科技大学 | Preparation method of (sesqui) siloxane hybrid modified fluorinated polyacrylate emulsion |
| CN104583255A (en) * | 2012-06-22 | 2015-04-29 | Ppg涂料欧洲有限责任公司 | Antifouling coating composition |
| EP2864379A1 (en) * | 2012-06-22 | 2015-04-29 | PPG Coatings Europe B.V. | Antifouling coating composition |
| CN104583255B (en) * | 2012-06-22 | 2017-11-14 | Ppg涂料欧洲有限责任公司 | Antifouling paint compositions |
| JP2014101435A (en) * | 2012-11-19 | 2014-06-05 | Nippon Steel & Sumikin Chemical Co Ltd | Cage silsesquioxane compound, curable resin composition using the same, and resin cured product |
| CN103435741B (en) * | 2013-08-27 | 2016-01-20 | 华南理工大学 | POSS base hydridization fluorinated acrylate resin and preparation method thereof and application |
| CN103435741A (en) * | 2013-08-27 | 2013-12-11 | 华南理工大学 | POSS (Polyhedral Oligomeric Silsesquioxane) based hybridized fluorinated acrylate resin, and preparation method and application thereof |
| CN103435742A (en) * | 2013-08-27 | 2013-12-11 | 华南理工大学 | Hydrophobic POSS (Polyhedral Oligomeric Silsesquioxane)-based hybridization fluorinated acrylate resin as well as preparation method and application thereof |
| CN103435742B (en) * | 2013-08-27 | 2015-12-02 | 华南理工大学 | Hydrophobicity POSS base hydridization fluorinated acrylate resin and preparation method thereof and application |
| CN105017910B (en) * | 2014-04-17 | 2018-04-17 | 浙江省海洋开发研究院 | Modified super-hydrophobic marine antifouling coating of one kind and preparation method thereof |
| CN105017910A (en) * | 2014-04-17 | 2015-11-04 | 浙江省海洋开发研究院 | Modified super-hydrophobic marine antifouling coating and preparation method thereof |
| WO2016037403A1 (en) * | 2014-09-11 | 2016-03-17 | 天津大学 | Fluorinated poss composite organosilicon coating, preparation method and anti-icing application |
| US9840631B2 (en) | 2014-09-11 | 2017-12-12 | Tianjin University | Polysiloxane/fluorinated POSS hybrid coatings, preparation and anti-icing application thereof |
| EP3197949A4 (en) * | 2014-09-24 | 2018-04-11 | Nbd Nanotechnologies, Inc. | F-poss coatings and additives and methods of making same |
| EP3204450A4 (en) * | 2014-10-07 | 2018-06-20 | Nbd Nanotechnologies, Inc. | Synthetic blend f-poss compositions formed from multiple feedstock materials |
| US10208070B2 (en) | 2014-10-07 | 2019-02-19 | Nbd Nanotechnologies, Inc. | Synthetic blend F-POSS compositions formed from multiple feedstock materials |
| US11702433B2 (en) | 2014-10-07 | 2023-07-18 | Nbd Nanotechnologies, Inc. | Functionalized F-POSS monomer compositions and uses thereof |
| US10584137B2 (en) | 2014-10-07 | 2020-03-10 | Nbd Nanotechnologies, Inc. | Synthetic blend F-POSS compositions formed from multiple feedstock materials |
| CN105131835A (en) * | 2015-08-04 | 2015-12-09 | 天津大学 | UV-cured POSS fluorine-containing acrylate segmented copolymer coating, preparation and application thereof |
| CN106854436A (en) * | 2016-12-29 | 2017-06-16 | 中科院广州化学有限公司南雄材料生产基地 | A kind of fluorine-containing prepolymer modified acrylate coating material of Amino End Group and preparation method thereof |
| CN106854436B (en) * | 2016-12-29 | 2019-03-22 | 中科院广州化学有限公司南雄材料生产基地 | A kind of fluorine-containing prepolymer modified acrylate coating material of Amino End Group and preparation method thereof |
| CN111690103B (en) * | 2019-03-13 | 2021-06-08 | 中国科学院上海有机化学研究所 | Water-and oil-repellent fluorine-containing silicon copolymer and preparation method and application thereof |
| CN111690103A (en) * | 2019-03-13 | 2020-09-22 | 中国科学院上海有机化学研究所 | Water-and oil-repellent fluorine-containing silicon copolymer and preparation method and application thereof |
| CN110130103A (en) * | 2019-06-03 | 2019-08-16 | 华南理工大学 | Modified POSS base super-amphiphobic coating material of fluorochemical monomer and the preparation method and application thereof |
| WO2022054851A1 (en) * | 2020-09-09 | 2022-03-17 | 日本ペイント・オートモーティブコーティングス株式会社 | Composition for coating materials |
| JP7061241B1 (en) * | 2020-09-09 | 2022-04-27 | 日本ペイント・オートモーティブコーティングス株式会社 | Composition for paint |
| CN114015056A (en) * | 2021-10-13 | 2022-02-08 | 佛山市顺德区永创翔亿电子材料有限公司 | Voltage-resistant electrolyte-resistant copolymer, tab adhesive and tab tape |
| CN114015056B (en) * | 2021-10-13 | 2023-02-21 | 佛山市顺德区永创翔亿电子材料有限公司 | Voltage-resistant electrolyte-resistant copolymer, tab adhesive and tab tape |
| CN114369412A (en) * | 2021-12-29 | 2022-04-19 | 惠州瑞德新材料科技股份有限公司 | Photocuring composition containing perfluoropolyether/alkenyl silicone resin and method for constructing waterproof and antifouling coating |
| CN114381172A (en) * | 2021-12-31 | 2022-04-22 | 山东东岳未来氢能材料股份有限公司 | Stripping-resistant ethylene-tetrafluoroethylene copolymer powder coating and preparation method thereof |
| CN115368571A (en) * | 2022-09-01 | 2022-11-22 | 珠海赛纳三维科技有限公司 | Fluorine-containing siloxane acrylate and preparation method and application thereof |
| CN115368571B (en) * | 2022-09-01 | 2023-10-31 | 珠海赛纳三维科技有限公司 | Fluorine-containing siloxane acrylate, and preparation method and application thereof |
| CN116510419A (en) * | 2022-12-01 | 2023-08-01 | 大连理工大学盘锦产业技术研究院 | V-shaped flow control particle coalescence device with coaxial speed difference jet flow |
| CN116510419B (en) * | 2022-12-01 | 2023-09-22 | 大连理工大学盘锦产业技术研究院 | V-shaped flow control particle coalescence device with coaxial speed difference jet flow |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101875707B (en) | 2012-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101875707B (en) | Fluorin-containing POSS acrylate polymer, preparation method thereof and paint | |
| US9840631B2 (en) | Polysiloxane/fluorinated POSS hybrid coatings, preparation and anti-icing application thereof | |
| EP2990838B1 (en) | Substrate having antireflective layer | |
| CN101107280B (en) | Compositions containing photosensitive fluorochemical and uses thereof | |
| CN101775144B (en) | Fluorine silicon resin, preparation method thereof and antifouling paint | |
| CN100503757C (en) | Ultraviolet light solidifying paint containing POSS and its preparation method | |
| CN104755514A (en) | Curable composition containing fluorine-containing hyperbranched polymer and siloxane oligomer | |
| CN102351983A (en) | Fluorine silicon acrylate copolymer, preparation process thereof and application thereof | |
| US9708486B2 (en) | Highly branched lipophilic polymer, and photopolymerizable composition containing the same | |
| CN102911582A (en) | Ultraviolet light cured antifogging coating | |
| CN103237848A (en) | Curable composition for coating containing fluorine-containing hyperbranched polymer | |
| CN102712783A (en) | Plastic substrates having a scratch-resistant coating, in particular housings of electronic devices, having high transparency, method for the production thereof, and use thereof | |
| CN106752233B (en) | A kind of UV solidification multifunctional anti-soil agent | |
| CN106939064B (en) | A kind of composition comprising perfluoropolyether active constituent | |
| CN101560278A (en) | Methyl methacrylate-styrene copolymer containing fluoro-acrylate and preparation method thereof | |
| CN109135551A (en) | A kind of high-flexibility waterborne UV coating | |
| CN102225945B (en) | A kind of (methyl) vinylformic acid esterification oxazole heterocyclic boronic acids ester and its preparation method and application | |
| CN104558580A (en) | Fluorine-containing hyperbranched polyester maleic acid ester, preparation and application thereof and coating composition comprising fluorine-containing hyperbranched polyester maleic acid ester | |
| CN101014633A (en) | Fluorochemical having hydrolyzable metal alkoxide moiety, curable fluoropolymer obtained from the compound, and curable fluororesin composition containing the polymer | |
| CN115806760B (en) | Long-acting anti-fouling resin coating and preparation method thereof | |
| CN106675129A (en) | High-hardness antifogging UV (ultraviolet) automobile varnish and preparation method thereof | |
| Zhang et al. | Synthesis, characterization and properties of a novel fluorinated methacrylate polymer | |
| CN103130955B (en) | Photosensitive oligomer for photoresist, preparation method and negative photoresist composition thereof | |
| CN101177485B (en) | Low surface-energy fluorosiloxane containing double parallel main-chain structure and method for synthesizing the same | |
| CN106905842B (en) | Wear-resisting super-hydrophobic self-cleaning coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120926 Termination date: 20190430 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |