CN101875707B - Fluorin-containing POSS acrylate polymer, preparation method thereof and paint - Google Patents
Fluorin-containing POSS acrylate polymer, preparation method thereof and paint Download PDFInfo
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- CN101875707B CN101875707B CN200910107167A CN200910107167A CN101875707B CN 101875707 B CN101875707 B CN 101875707B CN 200910107167 A CN200910107167 A CN 200910107167A CN 200910107167 A CN200910107167 A CN 200910107167A CN 101875707 B CN101875707 B CN 101875707B
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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 compound 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 propenoate is one type of silicoorganic compound with the special molecular structure shown in the formula 7,
Formula 7 formulas 9
POSS group wherein has the structure shown in the formula 9; Wherein inorganic silica scaffold core is that material provides good inorganic nature; 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, R
4Be H, C
1-C
5The straight or branched alkyl.
Disclose the hydrophobic automatic cleaning coating material of a kind of Using P OSS in the prior art, introduced the nanostructure of fluorine-containing POSS through 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 compound method thereof are also disclosed in the prior art; This method adopts the end capped TEB 3K 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 processed 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, cost is high, and 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 Yodo Sol GH 28 is provided; Wherein,---M---structure shown in the M ' that said 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 said 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 Yodo Sol GH 28 also be provided, comprise following steps:
(a) polymerisable monomer is contacted with initiator, carry out polyreaction under the nitrogen protection, contain the compound of formula 6 and structure shown in the formula 7 in the said polymerization single polymerization monomer, obtain product after polyreaction is accomplished and be designated as A;
(b) in A, add mixture B, contain the fluorinated acrylate of structure shown in the formula 5 among the said mixture B and contain fluorous solvent, obtain fluorine-containing POSS Yodo Sol GH 28 through 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 Yodo Sol GH 28, solidifying agent and thinner in the said coating, it is characterized in that, said fluorine-containing POSS Yodo Sol GH 28 is a fluorine-containing POSS Yodo Sol GH 28 provided by the invention.
According to fluorine-containing POSS Yodo Sol GH 28 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, can obtain the fluorine-containing POSS Yodo Sol GH 28 that fluorinated acrylate structural unit provided by the invention is distributed in the multipolymer two ends through controlling the addition sequence of fluorinated acrylate monomer; Technology is simple, and is with low cost.
[embodiment]
The invention provides a kind of fluorine-containing POSS Yodo Sol GH 28, wherein,---M---structure shown in the M ' that said 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 said 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 said fluorine-containing POSS Yodo Sol GH 28.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 Yodo Sol GH 28 provided by the invention; Said 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 reactive group Y and POSS group in the M structural unit, its backbone structure is the two key copolymerization structures of propenoate C=C.Suc as formula 2 with formula 3 shown in, said reactive 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 said M structural unit through the mode of random copolymerization, thereby makes reactive 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 said M structural unit can be-M1M2M2M1 ... M2M1M2M2M1-.
Wherein, Y for reactive group Y be COOH ,-OH or
j are the integer of 0-8, k is the integer of 0-6.
In the fluorine-containing POSS Yodo Sol GH 28 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, said 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, therefore, the molecular weight of resin be synthesize, needs are considered in processing and the application process important indicator.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 Yodo Sol GH 28 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 said fluorine-containing POSS Yodo Sol GH 28 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 said fluorine-containing POSS Yodo Sol GH 28 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 Yodo Sol GH 28 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 Yodo Sol GH 28 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 Yodo Sol GH 28, may further comprise the steps:
(a) polymerisable monomer is contacted with initiator, carry out polyreaction under the nitrogen protection, contain the monomer of formula 6 and structure shown in the formula 7 in the said polymerization single polymerization monomer, obtain product after polyreaction is accomplished and be designated as A;
(b) in A, add mixture B, contain the fluorinated acrylate monomer shown in the formula 5 among the said mixture B and contain fluorous solvent, obtain fluorine-containing POSS Yodo Sol GH 28 through 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 reactive group carboxyl, hydroxyl or epoxy ethyl in the monomer of structure shown in the said polymerisable monomer Chinese style 6, contain the POSS group shown in the formula 7 in the monomer of structure, initiator exists down; Through the olefinic polyreaction of acrylate structural, can be contained reactive group acrylate structural unit and the unitary random copolymers of POSS acrylate structural simultaneously.The purpose of introducing reactive group in the random copolymers is to make reactive 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 reactive group Y, and said reactive group Y is carboxyl, hydroxyl or epoxy ethyl.Said reactive group Y through methylene radical or directly with propenoate on ester group link to each other.Wherein the number of methylene radical is designated as j, and j is the integer of 0-8.The said acrylate monomer that contains reactive group can be in hydroxy ethyl methacrylate, hydroxymethyl acrylate, the ethyloic propenoate 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), BPO, di-t-butyl peroxide or peroxo-two tert-pentyls are preferably Diisopropyl azodicarboxylate.More preferably under the situation, the mass ratio of said polymerisable monomer and initiator is 1: 0.001-0.05.
The condition of said 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 reactive group is 0.1-50%, and the content of POSS acrylate monomer is 0.1-50%.
Designer of the present invention finds through a large amount of experiments: adopt preparation method provided by the invention; Addition sequence through the control fluorinated acrylate monomer; Promptly after containing reactive group acrylate monomer and POSS acrylate monomer polymerization reaction take place; Add fluorinated acrylate monomer again, can obtain the end capped fluorine-containing POSS Yodo Sol GH 28 of fluorinated acrylate structural unit, be i.e. the 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 reactive group propenoate and POSS propenoate.
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 Yodo Sol GH 28 provided by the invention through Raolical polymerizable.Said 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, said fluorinated acrylate is a perfluoro-methyl ethyl propylene acid esters; M=0, n=7, R
2For-CH
3The time, said fluorinated acrylate is a perfluoro capryl ethyl-methyl propenoate.Among the present invention, said fluorinated acrylate is preferably at least a in perfluoro capryl ethyl propylene acid esters, the perfluoro capryl ethyl-methyl propenoate.
According to preparation method provided by the invention, also contain fluorous solvent among the mixture B.Saidly 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, like 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 kinds of fluorine-containing solvent are used.
In the step (b), the reaction conditions of said Raolical polymerizable is: temperature of reaction is 70-90 ℃, and the reaction times is 0.5-10h.Said 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 said mixture B.The initiator that the said 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), BPO, di-t-butyl peroxide or peroxo-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 method of the present invention can adopt this area polymerization method 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 method 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, YLENE, THF, butylacetate, isobutyl acetate, ethanol, pimelinketone,, hexone, acetone, methylethylketone, butyl glycol ether, Ucar 35 butyl ether, 1-Methoxy-2-propyl acetate (PMA).Above-mentioned solvent both can use separately, also can be the mixture of several kinds of 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 said 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 said 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 said 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 propenoate commonly used in the polymerisable monomer.According to preparation method provided by the invention, add propenoate 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 Yodo Sol GH 28, solidifying agent and thinner in the said coating, it is characterized in that, said fluorine-containing POSS Yodo Sol GH 28 is a fluorine-containing POSS Yodo Sol GH 28 provided by the invention.
Inorganic silica scaffold core structure among the POSS in the fluorine-containing POSS Yodo Sol GH 28 of the present invention makes coating of the present invention have good hardness and intensity; And said POSS links to each other through covalence key with propenoate, 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 Yodo Sol GH 28 of the present invention extremely is suitable as antifouling paint.Adopt that the antifouling paint of fluorine-containing POSS Yodo Sol GH 28 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 comes the excellent antifouling paint of obtained performance through the method for the chemical structure that changes resin, so the present invention do not have special restriction for the preparation method of coating, adopts this area method commonly used to get final product.Contain fluorine-containing POSS Yodo Sol GH 28 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 according to the invention can be variously can make fluorine-containing POSS Yodo Sol GH 28 of the present invention form the organic solvent of uniform and stable system; For example; Can be for the fluorine-containing POSS Yodo Sol GH 28 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.
Said solidifying agent can take place crosslinked with the reactive group Y in the fluorine-containing POSS Yodo Sol GH 28, after paint solidification obtains coating, can effectively improve the hardness of coating.Among the present invention, said solidifying agent can adopt various solidifying agent of the prior art, for example can directly adopt CYMEL-303, the CYMEL-370 of the special company of Ciba-EFKA-3886, Ciba-EFKA-3886 or cyanogen of vapour Bagong department.
In order further to practice thrift cost and further to reduce the pollution that environment is produced, be benchmark with the total mass of said coating, the content of said thinner is 10-99 weight %, the content of said 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 skimmer, flow agent.Said skimmer 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 among the AFCONA-3033, AFCONA-3034, AFCONA-3750 of company one or more.Under the preferable case, be benchmark with the total mass of said coating, the content of said skimmer is 0.1-10wt%; The content of said 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 under 90-180 ℃ temperature, solidify 1-20 hour, can obtain the coating that is formed by antifouling paint of the present invention.The present invention does not have special restriction 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.
Through embodiment the present invention is further described below, the raw material that is adopted all is available commercially.
Embodiment 1
Present embodiment is used to explain fluorine-containing POSS Yodo Sol GH 28 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 TEB 3K, 2g NSC 20949,1g hydroxy ethyl methacrylate, 3g POSS propenoate (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 continued reaction 3h; After reaction finished, 60 ℃ of following vacuum distillings added xylene solvent then, prepared solid content and be 30% fluorine-containing POSS Yodo Sol GH 28, were designated as A1.
Embodiment 2
Present embodiment is used to explain fluorine-containing POSS Yodo Sol GH 28 provided by the invention and preparation method thereof.
Adopt to prepare fluorine-containing POSS Yodo Sol GH 28 with embodiment 1 identical method, difference is: in the step (1), only contain 2g hydroxy ethyl methacrylate, 4g POSS propenoate (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 Yodo Sol GH 28 that obtains at last is designated as A2.
Embodiment 3
Embodiment is used to explain fluorine-containing POSS Yodo Sol GH 28 provided by the invention and preparation method thereof.
Adopt to prepare fluorine-containing POSS Yodo Sol GH 28 with embodiment 1 identical method, difference is: in the step (1), polymerisable monomer comprises 2g hydroxymethyl acrylate, 4g POSS propenoate (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 BPO and 5g solvent toluene, and 15g contains fluorous solvent FHT-6500; The fluorine-containing POSS Yodo Sol GH 28 that obtains at last is designated as A3.
Embodiment 4
Embodiment is used to explain fluorine-containing POSS Yodo Sol GH 28 provided by the invention and preparation method thereof.
Adopt to prepare fluorine-containing POSS Yodo Sol GH 28 with embodiment 1 identical method, difference is: in the step (2), fluorinated acrylate is 23.25g fluorinated acrylate (60 a quality % perfluoro capryl ethyl-methyl propenoate); The fluorine-containing POSS Yodo Sol GH 28 that obtains at last is designated as A4.
Embodiment 5
Embodiment is used to explain fluorine-containing POSS Yodo Sol GH 28 provided by the invention and preparation method thereof.
Adopt to prepare fluorine-containing POSS Yodo Sol GH 28 with embodiment 1 identical method, difference is: in the step (1), polymerisable monomer is 4g hydroxy ethyl methacrylate, 2g POSS propenoate (k=5, R in the formula 7
4=-CH
3, R=-C in the formula 9
4H
9); The fluorine-containing POSS Yodo Sol GH 28 that obtains at last is designated as A5.
Comparative Examples 1
This Comparative Examples is used for explaining embodiment 2 disclosed fluorine-containing POSS acrylate block copolymer resin and the compound methods thereof of CN101029137A: two mouthfuls of flasks add 10g THF, CuBr0.006g, PMDETA0.012g, TEB 3K 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 through 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 TEB 3K successively, 2g NSC 20949,1g hydroxy ethyl methacrylate, 3gPOSS propenoate (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 Yodo Sol GH 28, were designated as D2.
Embodiment 6
Present embodiment is used to explain coating provided by the invention.
The solid content that takes by weighing 10g embodiment 1 preparation is 30% fluorine-containing POSS Yodo Sol GH 28 A1,2.5g solidifying agent CYMEL-303,20g thinner (wherein 8g YLENE, 12g butylacetate, 2g contain fluorous solvent FHT-6500); 0.3g the flow agent BYK-333 of skimmer 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 explain coating provided by the invention.
Adopt the method identical with embodiment 6; Respectively the fluorine-containing POSS Yodo Sol GH 28 A2-A5 (being designated as F-POSS) that embodiment 2-5 makes is mixed with thinner, solidifying agent, skimmer, flow agent by component in the table 1 and content; Make coating of the present invention, be designated as A7-A10 successively.Concrete each component and content are seen table 1.
Comparative Examples 3-4
Comparative Examples 3-4 is used to explain the coating of prior art.
Adopt the method identical with embodiment 6; Respectively the fluorine-containing POSS Yodo Sol GH 28 D1-D2 (being designated as F-POSS) that Comparative Examples 1-2 makes is mixed with thinner, solidifying agent, skimmer, flow agent by component in the table 1 and content; Make coating of the present invention, be designated as D3-D4 successively.Concrete each component and content are seen table 1.
Table 1
| F-POSS | Thinner | Solidifying agent | Skimmer | Flow agent | |
| ?A6 | ?10g | YLENE 8g butylacetate 12g FHT-6500 2g | CYMEL-303 2.5g | AFCONA-2045 0.3g | BYK-333 0.12g |
| ?A7 | ?10g | YLENE 6g butylacetate 9g FHT-4500 4g | CYMEL-303 2.5g | AFCONA-2045 0.3g | BYK-333 0.12g |
| ?A8 | ?10g | YLENE 8g butylacetate 12g FHT-6500 2g | CYMEL-303 4g | AFCONA-2045 0.3g | BYK-333 0.12g |
| ?A9 | ?10g | YLENE 8g butylacetate 12g FHT-254 2g | CYMEL-303 2.5g | AFCONA-2045 3g | BYK-333 3.4g |
| ?A10 | ?10g | YLENE 8g butylacetate 12g FHT-6500 2g | CYMEL-303 2.5g | ?-- | ?-- |
| ?D3 | ?10g | Butylacetate 9g pimelinketone 1g | ?- | AFCONA-2045 ?0.3g | BYK-333 ?0.12g |
| ?D4 | ?10g | YLENE 8g butylacetate 12g FHT-6500 2g | CYMEL-303 2.5g | AFCONA-2045 0.3g | BYK-333 0.12g |
Performance test
(1) copolymer resin molecular weight test: the PL-GPC50 type gel permeation chromatograph (moving phase: THF that adopts Polymer Laboratories company to produce; Temperature: 30 ℃) measure fluorine-containing POSS Yodo Sol GH 28 A1-A5 that embodiment 1-5 and Comparative Examples 1-2 make and number-average molecular weight Mn and the MWD 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 using Minnesota Mining and Manufacturing Company to produce 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 to have no depainting be 5B, and 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 |
| MWD | 1.15 | 1.2 | 1.3 | 1.2 | 1.3 | 1.4 | 1.35 |
Table 3
| Specimen | Hardness | Glossiness (60 °) | Sticking power | Scratch resistance | Surface energy | Surface energy after the scrubbing resistance |
| A6 | 6H | 95.8 | 4B | 3.5N | 11.6 | 13.1 |
| A7 | 6H | 92.9 | 3B | 4N | 12.1 | 14.5 |
| A8 | 6H | 96.7 | 4B | 3.5N | 11.8 | 13.6 |
| A9 | 4H | 92.5 | 3B | 2.5N | 10.5 | 14.8 |
| A10 | 4H | 92.3 | 4B | 3N | 11.4 | 13.4 |
| D3 | 2H | 92.5 | 4B | 2N | 11.5 | 15.0 |
| D4 | 4H | 91.4 | 4B | 2.5N | 13.5 | 17.2 |
Test result by last table 2 can find out that the number-average molecular weight of the fluorine-containing POSS Yodo Sol GH 28 that the present invention makes is 3000-20000, MWD between 1.1-1.4, narrow distribution;
Test result by last table 3 can find out that the present invention adopts the coating that makes keeping having stronger scratch resistance ability and low surface energy under hardness, glossiness and the unabated prerequisite of sticking power, and promptly the antifouling property of coating is high; 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, preparing method's technology of fluorine-containing POSS Yodo Sol GH 28 provided by the invention is simple, with low cost.
Claims (15)
1. fluorine-containing POSS Yodo Sol GH 28, wherein,---M---structure shown in the M ' that said 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 said POSS is a polyhedral oligomeric silsesquioxane, and the number-average molecular weight of said fluorine-containing POSS acrylate block copolymer resin is 3000-20000;
Formula 1 formula 2 formulas 3
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
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 Yodo Sol GH 28 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.
3. fluorine-containing POSS Yodo Sol GH 28 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
4. fluorine-containing POSS Yodo Sol GH 28 according to claim 3 is characterized in that: formula 1 is 1 with the weight ratio of the structural unit shown in the formula 4: 1-20.
5. the preparation method of a fluorine-containing POSS Yodo Sol GH 28 may further comprise the steps:
(a) polymerisable monomer is contacted with initiator, carry out polyreaction under the nitrogen protection, contain the compound of formula 6 and structure shown in the formula 7 in the said polymerisable monomer, obtain product after polyreaction is accomplished and be designated as A, said POSS is a polyhedral oligomeric silsesquioxane;
(b) in A, add mixture B; Contain the fluorinated acrylate of structure shown in the formula 5 among the said mixture B and contain fluorous solvent; Obtain fluorine-containing POSS Yodo Sol GH 28 through Raolical polymerizable, the number-average molecular weight of said fluorine-containing POSS acrylate block copolymer resin is 3000-20000;
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.
6. preparation method according to claim 5 is characterized in that, initiator described in the step (a) is at least a in Diisopropyl azodicarboxylate, Di Cumyl Peroxide 99, BPO, di-t-butyl peroxide or peroxo-two tert-pentyls.
7. preparation method according to claim 5 is characterized in that, fluorinated acrylate described in the step (b) is a perfluoro capryl ethyl propylene acid esters.
8. preparation method according to claim 5 is characterized in that, the mass ratio of polymerisable monomer and initiator is 1 described in the step (a): 0.001-0.05.
9. preparation method according to claim 5 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%.
10. preparation method according to claim 5 is characterized in that, in the step (b), said A, fluorinated acrylate, the weight ratio that contains fluorous solvent are 1: 0.05-1: 0.1-10.
11. preparation method according to claim 5 is characterized in that, in the step (a), also contains the acrylate monomer shown in the formula 8 in the said 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
12. preparation method according to claim 11 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%.
13. preparation method according to claim 5 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.
14. a coating contains fluorine-containing POSS Yodo Sol GH 28, thinner and solidifying agent in the said coating, it is characterized in that, said fluorine-containing POSS Yodo Sol GH 28 is each described fluorine-containing POSS Yodo Sol GH 28 of claim 1-4.
15. coating according to claim 14 is characterized in that, is benchmark with the total mass of coating, the content of said thinner is 10-99%, and the content of solidifying agent is 0.1-40%.
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| 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 |
Citations (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 |
| CN101029137A (en) * | 2007-03-09 | 2007-09-05 | 厦门大学 | Fluoride POSS acrylic ester block multipolymer resin and its synthesis |
| CN101712840A (en) * | 2008-10-07 | 2010-05-26 | 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
Patent Citations (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 |
| CN101029137A (en) * | 2007-03-09 | 2007-09-05 | 厦门大学 | Fluoride POSS acrylic ester block multipolymer resin and its synthesis |
| CN101712840A (en) * | 2008-10-07 | 2010-05-26 | 北京理工大学 | Ultrathin water-based epoxy resin expandable fireproof paint and preparation method thereof |
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