CN100497413C - Process of preparing solvent type fluoric acrylate copolymer - Google Patents
Process of preparing solvent type fluoric acrylate copolymer Download PDFInfo
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- CN100497413C CN100497413C CNB2007100205675A CN200710020567A CN100497413C CN 100497413 C CN100497413 C CN 100497413C CN B2007100205675 A CNB2007100205675 A CN B2007100205675A CN 200710020567 A CN200710020567 A CN 200710020567A CN 100497413 C CN100497413 C CN 100497413C
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Abstract
The present invention is process of preparing solvent type fluoric acrylate copolymer, and features that hydroxyl radical containing acrylate monomer and at least one kind of acrylate monomer are solution polymerized to prepare acrylate copolymer with hydroxyl radical in the side chain, that equal-molar fluoric RfOH and diisocyanate OCN-Z-NCO are reacted in the presence of catalyst to prepare RfO2CNH-Z-NCO with one unreacted -NCO radical, and that the acrylate copolymer with hydroxyl radical in the side chain and RfO2CNH-Z-NCO with one unreacted -NCO radical in certain ratio are further reacted to prepare the solvent type fluoric acrylate copolymer. The solvent type fluoric acrylate copolymer may be used as waterproof and oil-proof agent for fabric, leather, etc.
Description
Technical field
The present invention relates to the preparation method of solvent type fluoric acrylate copolymer, this polymkeric substance can be used for fabric, leather etc. as water and oil repellent agent.
Background technology
As everyone knows, the acrylate copolymer that contains the perfluor side chain has excellent waterproof, oil preventing performance and extremely low surface tension, mainly be since above-mentioned fluorinated copolymer after the solid surface film forming, the outside proper alignment and the stretching, extension of fluorine-containing side chain rule, thus given play to good waterproof oil-proof result.Therefore obtain to use in a plurality of fields such as fabric, leather.
This base polymer generally all is at first to prepare the acrylate monomer that contains perfluoroalkyl side chain, and following several structure is generally arranged:
(1) acrylate of perfluoroalkyl ethanol, structure are R
f-CH
2CH
2O
2CCH=CH
2, R
fThe perfluoroalkyl of 6～8 carbon atoms, i.e. R
f=G
nF
2n+1, n=6～8.
(2) perfluoro-heptanoic acid or Perfluorocaprylic Acid form N-hydroxyethyl perfluor heptan (suffering) acid amides with the thanomin reaction earlier, form acrylate with the acrylate chloride reaction again, and structure is R
fCONHCH
2CH
2O
2CCH=CH
2, R
fBe perfluoro hexyl or perfluor heptyl, i.e. R
f=C
nF
2n+1, n=6,7.
(3) acrylate of N-alkyl-N-hydroxyethyl perfluorinated octyl sulfuryl amine, structure is R
rSO
2N (R) CH
2CH
2O
2CCH=CH
2, R
fBe perfluoro capryl, i.e. R
f=C
8F
17R is the alkyl of 1～3 carbon atom, i.e. R=C
nH
2n+1, n=1～3.
(4) N-alkyl-N-hydroxyethyl perfluorinated octyl sulfuryl amine is earlier with equimolar 2,4-TDI (or IPDI) reaction, and then with wait sour hydroxyl ethyl ester of mol propylene or hydroxypropyl acrylate condensation, structure is::
Or
R
1Be the alkyl of 1～3 carbon, R
2Be H, CH
3
(5) N-hydroxyethyl perfluor heptan (suffering) acid amides is earlier with equimolar 2, the 4-TDI reaction, and then with etc. mol propylene acid-beta-hydroxy ethyl ester or hydroxypropyl acrylate condensation, structure is:
R
fFor-C
7F
15,-C
6F
13R
2Be H, CH
3R
3Be H, CH
3
Because it is relatively poor that above-mentioned monomer forms the physicals of polymkeric substance separately, need form multipolymer to improve use properties with one or more non-fluorine monomers usually.
The polymkeric substance that contains perfluoroalkyl side chain has certain waterproof, grease proofness must make the perfluoroalkyl side chain sufficiently long, usually perfluoroalkyl should be no less than 6 carbon atoms, but long side chain perfluoroalkyl polymkeric substance solvability in common solvent is bad, it is fluorine-containing or contain in the solvent of other halogen that class monomer formed multipolymer in particularly above-mentioned (1)～(3) can only be dissolved in minority usually, consideration for environmental protection, fluoro-acrylate copolymer with these a few class monomer preparations all is to adopt the emulsion polymerisation process preparation basically at present, letex polymerization needs to add tensio-active agent in preparation process, solubility promoter etc., demixing phenomenon takes place if control condition is improper, this is especially obvious for the emulsion copolymerization of fluorinated acrylate monomer, also exists the product package stability poor, problems such as the film forming physicals is relatively poor.Allowing most the people feel helpless is that the product applicable surface is narrow, and versatility is bad, need do customized product at certain concrete application.
Class monomer formed performance of copolymer in above-mentioned (1)～(3) descends very fast, promptly has endurance issues, it is believed that it is owing to due to water and oil repellent agent comes off, understood it is because due to this base polymer perfluoroalkyl side chain orientation confusion now at first.When this base polymer has only fluorine-containing side chain rule outwards proper alignment and stretching, extension after the solid surface film forming, competence exertion goes out good waterproof oil-proof result.
Compare (1)～(3) class monomer, (4), (5) two class monomers and the multipolymer solubility property that is formed by them should make moderate progress, and promptly they can only not be dissolved in a few fluorine-containing solvent.Above-mentioned (4), (5) two class monomers are owing to can form than the more hydrogen bond of (1)～(3) class monomer in the monomer molecule, can alleviate the chaotic situation of perfluoroalkyl side chain orientation, make aligning that perfluoroalkyl side chain is maintained fixed, can also increase the fastness that combines of multipolymer and substrate.But compare (1)～(3) class monomer, other monomers of (4), the monomeric reactivity ratio of (5) two classes and copolymerization differ bigger, if continue to adopt letex polymerization certainly not as adopting solution polymerization effective.After all, the employing solution polymerization can be by regulating the concentration of certain monomer in reactor to reach its intended purposes in the method that the present invention proposes.
Except price factor, the problem of above-mentioned existence has hindered the widespread use of this base polymer.
Summary of the invention
Because the deficiency that above-mentioned this area exists, the present invention provides the preparation method of solvent type fluoric acrylate polymkeric substance from the consideration of aspect of performance and in conjunction with preparation method's characteristics of the present invention, and concrete steps are as follows:
1, adopt the solution polymerization side chain to contain the acrylate copolymer A of hydroxyl with the acrylate that contains hydroxyl or acrylamide monomer M and more than one acrylate monomer, structural representation is:
And
R＝H，CH
3
R
1＝CH
3，C
2H
5，C
4H
9，CH
2CH(C
2H
5)C
4H
9，C
12H
25
R
2＝CH
3，C
2H
5，C
4H
9，CH
2CH(C
2H
5)C
4H
9，C
12H
25，R
1
2, in the presence of catalyzer, by equimolar fluorine-containing alcohol R
fOH and vulcabond OCN-Z-NCO reaction are prepared into reactant B, and structural representation is: R
fO
2CNH-Z-NCO, reactant B keeps a unreacted-NCO base, and reaction is illustrated as:
, fluorine-containing alcohol R
fThe mole number of OH and vulcabond OCN-Z-NCO is the acrylate that contains hydroxyl or 0.8～1.2 times of acrylamide monomer M mole number.
3, the side chain that aforementioned preparation is obtained acrylate copolymer A and reactant B two portions of containing hydroxyl react, and make solvent type fluoric acrylate copolymer; Structural representation is:
And
R＝H，CH
3
R
1＝CH
3，C
2H
5，C
4H
9，CH
2CH(C
2H
5)C
4H
9，C
12H
25
R
2＝CH
3，C
2H
5，C
4H
9，CH
2CH(C
2H
5)C
4H
9，C
12H
25，R
1。
Below be the more detailed description that the present invention is done:
One, prepared side chain contains the acrylate copolymer A of hydroxyl among the present invention:
Side chain contains the acrylate copolymer A of hydroxyl, be in the presence of the radical initiator dibenzoyl peroxide, to carry out solution polymerization with acrylate (or acrylamide) monomer M and more than one the acrylate monomer that contains hydroxyl, 70～100 ℃ of polymerization temperatures, 4～8 hours time.
Initiator dibenzoyl peroxide consumption is 0.03～1.0% of a whole polymerization reaction system total amount, rate of polymerization is directly proportional with the initiator concentration square root, the square root of molecular weight and initiator amount is inversely proportional to, initiator amount is crossed conference and molecular weight of copolymer is reduced greatly influence product performance, but too small then polymerization velocity is slow excessively.
Temperature is bigger to polyreaction influence, and temperature rising polymerization velocity is accelerated, molecular weight and molecular weight, and the half life temperature of determining also will consider initiator of temperature of reaction, the initiator dibenzoyl peroxide that makes adding is continuous and effective within a certain period of time.
Acrylate (or acrylamide) monomer M that contains hydroxyl used in the present invention comprises: senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, N hydroxymethyl acrylamide, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid-β-hydroxypropyl acrylate.In the acrylate monomer of preparation copolymer A, account for 1～25%.
Other unsaturated monomer used in the present invention comprises: methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, lauryl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, lauryl methacrylate(LMA) etc.; In the acrylate monomer of preparation copolymer A, account for 75～99%.
Solvent is selected from: toluene, dimethylbenzene, butanone, hexone, vinyl acetic monomer, N-BUTYL ACETATE etc.In the copolymerization system total amount, account for 33～85%.
Whether it mainly is to consider dissolving power that solvent is selected, have or not influence higher as chain transfer constant to polyreaction.Solvent load is mainly considered the influence to monomer concentration, and the latter is influential to molecular weight of copolymer.Two, prepared reactant B among the present invention contains a unreacted-NCO base, by equimolar vulcabond OCN-z-NCO and fluorine-containing alcohol R
fThe OH reaction forms, and structural representation is: R
fO
2CNH-z-NCO.
Preparing above-mentioned reactant B is in the presence of catalyzer, vulcabond OCN-z-NCO and equimolar fluorine-containing alcohol R
fOH reacts, 50～100 ℃ of temperature of reaction, 2～6 hours time.A vulcabond and a reacted products therefrom R such as mole fluorine-containing alcohol such as grade
fO
2CNH-Z-NCO, promptly reactant B keeps a unreacted-NCO base.Fluorine-containing alcohol R
fOH equates with the mole number of vulcabond OCN-Z-NCO, and is the acrylate that contains hydroxyl or 0.8～1.2 times of acrylamide monomer M mole number.
Vulcabond OCN-Z-NCO comprises:
2,4 toluene diisocyanate (2,4-TDI),
Isophorone diisocyanate (IPDI),
Tolylene diisocyanate (2,4-TDI content is about 80%, 2,6-TDI content about 80%),
Content 80%,
Content 20%
PPDI (PPDI),
Ditan-4,4 '-vulcabond (MDI),
Hexamethylene diisocyanate (HDI), OCN-(CH
2)
6-NCO
Naphthalene-1,5-vulcabond (NDI),
Dicyclohexyl methyl hydride-4,4 '-vulcabond (HMDI),
Deng.
Select vulcabond to consider mainly whether the reactive behavior of two-NCO differs bigger, activity differs the big more vulcabond that helps more and keeps a unreacted-NCO base with waiting mole fluorine-containing alcohol reaction back.Just there is more by product to form if two-NCO base is equally active, two-the NCO of vulcabond that promptly has is reacted away, form a vulcabond and connect two fluorine alcohol, like this just can not contain the acrylate copolymer A reaction of hydroxyl with side chain.2,4 toluene diisocyanate (2,4-TDI) in 2-NCO radical reaction activity differ bigger, 4-NCO specific activity 2-NCO high 6.7 times (50 ℃) and 4.7 times (72～74 ℃), (2,4-TDI) coating has the tendency of flavescence but use 2,4 toluene diisocyanate.For isophorone diisocyanate (IPDI) and describing love affairs condition more complicated, under the catalyst-free situation, the second month in a season-fast 5.5 times (20 ℃ in NCO base than the basic activity of primary-NCO, propyl carbinol), as use dibutyl tin laurate catalysis, the second month in a season-the NCO base is than fast 11.5 times of the basic activity of primary-NCO (20 ℃, propyl carbinol), but as use triethylenediamine catalysis, then primary-NCO base than the second month in a season-the NCO base is active big.PPDI (PPDI) is although two-NCO base non-activity difference, but behind the one-NCO radical reaction owing to form carbamate, descend with respect to original-NCO base sucting electronic effect, make another unreacted-NCO base passivation, use PPDI (PPDI) coating that the tendency of flavescence is also arranged.
The active difference of two-NCO radical reaction is big more in the diisocyanate molecules, and reaction preference is good more, and is favourable more for the solvent type fluoric acrylate copolymer of the present invention's preparation.Therefore use 2 for the present invention, the 4-tolylene diisocyanate (2,4-TDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (2,4-TDI content about 80%), PPDI (PPDI) geometric ratio is used ditan-4,4 '-vulcabond (MDI), 1, hexamethylene-diisocyanate (HDI), naphthalene-1,5-vulcabond (NDI), dicyclohexyl methyl hydride-4,4 '-vulcabond (HMDI) etc. are effective.
Fluorine-containing alcohol R
fOH comprises:
Perfluoro hexyl ethanol C
6F
13CH
2CH
2OH
Perfluoro octyl ethanol C
8F
17CH
2CH
2OH
N-hydroxyethyl perfluor decoylamide C
7F
15CONHCH
2CH
2OH
N-hydroxyethyl perfluor heptamide C
6F
13CONHCH
2CH
2OH
N-methyl-N-hydroxyethyl perfluorinated octyl sulfuryl amine
N-ethyl-N hydroxyethyl perfluorinated octyl sulfuryl amine
N-propyl group-N-hydroxyethyl perfluorinated octyl sulfuryl amine
Deng.
Catalyzer is selected from: dibutyl tin laurate, dibutyltin diacetate, stannous octoate, triethylenediamine, N-Ethylmorphine quinoline, N, N '-dimethylcyclohexylamine, diethylenetriamine.
Organo-tin compounds such as dibutyl tin laurate, dibutyltin diacetate, stannous octoate all have stronger katalysis to aromatic series or aliphatic isocyanates and primary alconol reaction, catalysis-NCO base is more much better than than tertiary amine with the response capacity of primary alconol, organo-tin compound is as catalyzer and stay in the product, might in the product application process, promote that under rayed polymer degradation is aging.Use amine then not have this worry, tertiary amine has stronger katalysis to aromatic diisocyanate TDI, but to a little less than aliphatic diisocyanate such as the HDI katalysis extremely.Triethylenediamine is sterically hindered because of its N atom does not have, and to influence catalytic capability stronger.
Solvent comprises: acetone, butanone, pimelinketone, hexone, trifluoromethylbenzene, Freon 113, trieline, zellon etc.
It mainly is to consider dissolving power that solvent is selected, and the reactivity of right-NCO base has or not influence
Three, the preparation of solvent type fluoric acrylate polymkeric substance:
Acrylate copolymer A and reactant B two portions that the side chain that aforementioned preparation is obtained contains hydroxyl react 50～100 ℃ of temperature of reaction, 2～6 hours time.Make solvent type fluoric acrylate copolymer.
As can be seen from the above description, the preparation method of solvent type fluoric acrylate copolymer proposed by the invention is simple.The formed multipolymer of mentioning with respect to background technology of (1)～(3) class monomer, can form more hydrogen bond in the fluoro-acrylate copolymer molecule of the present invention, can alleviate the chaotic situation of perfluoroalkyl side chain orientation, make aligning that perfluoroalkyl side chain is maintained fixed, thereby delay the decline of waterproof and oilproof performance, increase the fastness that combines of multipolymer and substrate simultaneously, it is narrow to improve (1)～(3) the formed copolymer product applicable surface of class monomer that background technology mentions, the situation that versatility is bad.The monomeric reactivity ratio of (4)～(5) class mentioned of background technology and other monomers of copolymerization differ bigger in addition, the copolymer structure chain link that adopts method of emulsion polymerization to obtain can be very not desirable than homogeneity, might influence the performance of multipolymer, and adopt preparation method of the present invention to adopt different monomers addressing this problem recently during copolymer A in preparation.If control condition is improper then demixing phenomenon takes place in the emulsion polymerization process, this is especially obvious for the emulsion copolymerization of fluorinated acrylate monomer, and also there are problems such as package stability is poor, the film forming physicals is relatively poor in product.
Embodiment
More specifically the present invention is further described below by embodiment, but is not in order to limit the present invention.
Embodiment 1
The preparation of copolymer A:
In four-hole bottle, add toluene 140g, after feeding the nitrogen replacement inner air, be warming up to 85 ℃, stir and drip the mixed solution of forming by methyl acrylate 100.0g, butyl acrylate 28.4g, senecioate-hydroxyl ethyl ester 11.6g (0.1mol) and dissolving dibenzoyl peroxide 0.3g wherein down, keep 83～87 ℃ of temperature of reaction, dripped off in about 2 hours.Drip off the back and continue reaction 2 hours, add 10 milliliters of toluene solutions that are dissolved with the 0.1g dibenzoyl peroxide, continue to keep reaction 2 hours, toluene thing gross weight 700g to the bottle is mended in cooling in four-hole bottle, stop stirring.The copolymer A concentration of preparation is 20%.
The preparation of reactant B:
Add pimelinketone 90g in another four-hole bottle, 2,4 toluene diisocyanate 17.4g (0.1mol), dibutyl tin laurate 0.1g are warming up to 75 ℃.Stir the mixed solution that drips perfluoro hexyl ethanol 36.4g (0.1mol) and pimelinketone 125g down, continue at 75 ℃ of stirring reactions 3 hours after dripping off.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is 20%.
The preparation of solvent type fluoric acrylate copolymer:
Have in above-mentioned reactant B added in the four-hole bottle of copolymer A of aforementioned preparation, be warming up to 75～80 ℃ of stirring reactions 5 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 2
The preparation of copolymer A:
Identical with embodiment 1.
The preparation of reactant B:
Add hexone 90g in another four-hole bottle, tolylene diisocyanate (2,4-TDI content about 80%) 17.4g (0.1mol), dibutyltin diacetate 0.1g are warming up to 75 ℃.Stir the mixed solution that drips perfluoro octyl ethanol 46.4g (0.1mol) and hexone 165g down, drip off the back and continued stirring reaction 3 hours.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is 20%.
The preparation of solvent type fluoric acrylate copolymer:
Have in above-mentioned reactant B added in the four-hole bottle of copolymer A of aforementioned preparation, be warming up to 75～80 ℃ of stirring reactions 4 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 3
The preparation of copolymer A:
Identical with embodiment 1.
The preparation of reactant B:
Add acetone 100g in another four-hole bottle, isophorone diisocyanate 17.8g (0.08mol), stannous octoate 0.035g are warming up to 50 ℃.Stir the mixed solution that drips perfluoro octyl ethanol 37.1g (0.08mol) and acetone 120g down, drip off the back and continued stirring reaction 6 hours.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is 20%.
The preparation of solvent type fluoric acrylate copolymer:
Have in above-mentioned reactant B added in the four-hole bottle of copolymer A of aforementioned preparation, kept 50 ℃ of stirring reactions 6 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 4
The preparation of copolymer A:
Identical with embodiment 1.
The preparation of reactant B:
Add phenylfluoroform 12.8g in another four-hole bottle, PPDI 12.8g (0.08mol), triethylenediamine 1.2g are warming up to 70 ℃.Stir the mixed solution that drips N-hydroxyethyl perfluor decoylamide 36.6g (0.08mol) and phenylfluoroform 36.6g down, drip off the back and continue reaction 4 hours.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is 50%.
The preparation of solvent type fluoric acrylate copolymer:
Above-mentioned reactant B is added phenylfluoroform 153g earlier be diluted to non-volatile part of concentration and be about 20%, have in adding then in the four-hole bottle of copolymer A of aforementioned preparation, keep 75 ℃ and continued stirring reactions 4 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 5
The preparation of copolymer A:
Identical with embodiment 1.
The preparation of reactant B:
In another four-hole bottle, add Freon 113 10.2g, ditan-4,4 '-vulcabond 30.0g (0.12mol), N-Ethylmorphine quinoline 2.0g are warming up to 70 ℃.Stir the mixed solution that drips N-hydroxyethyl perfluor heptamide 48.9g (0.12mol) and Freon 113 10g down, keep 75 ℃ after dripping off and continue reaction 4 hours.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is 80%.
The preparation of solvent type fluoric acrylate copolymer:
Above-mentioned reactant B is added Freon 113 297g earlier be diluted to non-volatile part of concentration and be about 20%, have in adding then in the four-hole bottle of copolymer A of aforementioned preparation, kept 75 ℃ of stirring reactions 4 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 6
The preparation of copolymer A:
Identical with embodiment 1.
The preparation of reactant B:
Add trieline 63g in another four-hole bottle, hexamethylene diisocyanate 20.2g (0.12mol), diethylenetriamine 1.0g are warming up to 60 ℃.Stir the mixed solution that drips N-methyl-N-hydroxyethyl perfluorinated octyl sulfuryl amine 66.9g (0.12mol) and trieline 67g down, keep 60 ℃ after dripping off and continue reaction 5 hours.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is 40%.
The preparation of solvent type fluoric acrylate copolymer:
Above-mentioned reactant B is added trieline 218g earlier be diluted to non-volatile part of concentration and be about 20%, have in adding then in the four-hole bottle of copolymer A of aforementioned preparation, kept 60 ℃ of stirring reactions 5 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 7
The preparation of copolymer A:
Identical with embodiment 1.
The preparation of reactant B:
Add zellon 45g in another four-hole bottle, 2,4 toluene diisocyanate 20.9g (0.12mol), diethylenetriamine 0.5g are warming up to 60 ℃.Stir the mixed solution that drips N-ethyl-N hydroxyethyl perfluorinated octyl sulfuryl amine 68.6g (0.12mol) and zellon 164g down, keep 60 ℃ after dripping off and continue reaction 5 hours.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is 30%.
The preparation of solvent type fluoric acrylate copolymer:
Above-mentioned reactant B is added zellon 151g earlier be diluted to non-volatile part of concentration and be about 20%, have in adding then in the four-hole bottle of copolymer A of aforementioned preparation, kept 60 ℃ of stirring reactions 5 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 8
The preparation of copolymer A:
Identical with embodiment 1.
The preparation of reactant B:
In another four-hole bottle, add butanone 100g, naphthalene-1,5-vulcabond 25.2g (0.12mol), N, N '-dimethylcyclohexylamine 0.5g is warming up to 65 ℃.Stir the mixed solution that drips N-propyl group-N-hydroxyethyl perfluorinated octyl sulfuryl amine 70.2g (0.12mol) and butanone 282g down, keep 65 ℃ after dripping off and continued stirring reactions 5 hours.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is about 20%.
The preparation of solvent type fluoric acrylate copolymer:
Have in above-mentioned reactant B added in the four-hole bottle of copolymer A of aforementioned preparation, kept 65 ℃ of stirring reactions 5 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 9
The preparation of copolymer A:
Identical with embodiment 1.
The preparation of reactant B:
In another four-hole bottle, add hexone 100g, dicyclohexyl methyl hydride-4,4 '-vulcabond 31.5g (0.12mol), triethylenediamine 0.3g are warming up to 70 ℃.Stir the mixed solution that drips N-ethyl-N hydroxyethyl perfluorinated octyl sulfuryl amine 68.6g (0.12mol) and hexone 298g down, keep 100 ℃ after dripping off and continued stirring reactions 2 hours.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is 20%.
The preparation of solvent type fluoric acrylate:
Have in above-mentioned reactant B added in the four-hole bottle of copolymer A of aforementioned preparation, keep 100 ℃ and continued stirring reactions 2 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 10
The preparation of copolymer A:
Identical with embodiment 1.
The preparation of reactant B:
Add pimelinketone 100g in another four-hole bottle, isophorone diisocyanate 22.2g (0.1mol), stannous octoate 0.07g are warming up to 70 ℃.Stir the mixed solution that drips N-methyl-N-hydroxyethyl perfluorinated octyl sulfuryl amine 55.7g (0.1mol) and pimelinketone 212g down, drip off the back and continued stirring reaction 6 hours.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is 20%.
The preparation of solvent type fluoric acrylate copolymer:
Have in above-mentioned reactant B added in the four-hole bottle of copolymer A of aforementioned preparation, kept 75 ℃ of stirring reactions 5 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 1～10 fluoro-acrylate copolymer structural representation is as follows:
In the said structure synoptic diagram ,-Z-and-Rf sees the following form:
Embodiment 11
The preparation of copolymer A:
In four-hole bottle, add N-BUTYL ACETATE 140g and lauryl acrylate 6.0g, after feeding the nitrogen replacement inner air, be warming up to 85 ℃, stir and drip the mixed solution of forming by methyl acrylate 115.0g, lauryl acrylate 6.0g, senecioate-hydroxypropyl acrylate 13.0g (0.1mol) and dissolving dibenzoyl peroxide 0.4g wherein down, keep 83～87 ℃ of temperature of reaction, dripped off in about 2 hours.Drip off the back and continued stirring reaction 2 hours, add 10 milliliters of toluene solutions that are dissolved with the 0.2g dibenzoyl peroxide, continue to keep reaction 2 hours.Stop to stir and mend N-BUTYL ACETATE thing gross weight 700g to the bottle in four-hole bottle, the copolymer A concentration that makes preparation is 20%.
The preparation of reactant B:
Add butanone 100g in another four-hole bottle, 2,4 toluene diisocyanate 17.4g (0.1mol), dibutyl tin laurate 0.1g are warming up to 70 ℃.Stir the mixed solution that drips N-ethyl-N hydroxyethyl perfluorinated octyl sulfuryl amine 57.1g (0.1mol) and butanone 198g down, drip off the back and continued stirring reaction 5 hours.Cooling stops to stir.Get the solution of reactant B, wherein non-volatile part of concentration is 20%.
The preparation of solvent type fluoric acrylate copolymer:
Have in above-mentioned reactant B added in the four-hole bottle of copolymer A of aforementioned preparation, the stirring reaction 5 hours of refluxing down, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.Structural representation is as follows:
Embodiment 12
The preparation of copolymer A:
In four-hole bottle, add vinyl acetic monomer 70g and ethyl acrylate 10.0g, after feeding the nitrogen replacement inner air, be warming up to 75 ℃, stir and drip the mixed solution of forming by ethyl propenoate 120.0g, ethyl acrylate 8.6g, N hydroxymethyl acrylamide 1.4g (13.85mmol) and dissolving dibenzoyl peroxide 1.4g wherein down, keep 75～77 ℃ of temperature of reaction, dripped off in about 2 hours.Drip off the back and continue reaction 2 hours, add 10 milliliters of toluene solutions that are dissolved with the 0.7g dibenzoyl peroxide, continue to be maintained at 75 ℃ of reactions 2 hours again.Stop to stir and mend vinyl acetic monomer thing gross weight 700g to the bottle in four-hole bottle, the copolymer A concentration that makes preparation is 20%.
The preparation of reactant B:
In another four-hole bottle, add acetone 8.8g, PPDI 2.2g (13.85mmol), triethylenediamine 1.0g, be warming up to 56 ℃, reflux, stir the mixed solution that drips N-propyl group-N-hydroxyethyl perfluorinated octyl sulfuryl amine 8.1g (13.85mmol) and acetone 30g down, drip off the back and continued the backflow stirring reaction 6 hours.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is about 20%.
The preparation of solvent type fluoric acrylate copolymer:
Have in above-mentioned reactant B added in the four-hole bottle of copolymer A of aforementioned preparation, be warming up to the back stirring reaction 6 hours of refluxing, solvent type fluoric acrylate copolymer of the present invention.Structural representation is as follows:
Embodiment 13
The preparation of copolymer A:
In four-hole bottle, add dimethylbenzene 500g and lauryl methacrylate(LMA) 14.0g, after feeding the nitrogen replacement inner air, be warming up to 95～100 ℃, stir and drip the mixed solution of forming by dimethylbenzene 293g, methyl methacrylate 100.0g, lauryl methacrylate(LMA) 13.0g, methacrylic acid-beta-hydroxy ethyl ester 13.0g (0.1mo l) and dissolving dibenzoyl peroxide 0.2g wherein down, keep 95～100 ℃ of temperature of reaction, dripped off in about 2 hours.Drip off the back and continue reaction 2 hours, add 10 milliliters of toluene solutions that are dissolved with the 0.08g dibenzoyl peroxide, continue to keep reaction 1 hour.Stop to stir, changing reaction unit is water distilling apparatus, steams solvent 242g, makes a bottle interior thing gross weight 700g, and the copolymer A concentration of preparation is 20%.
The preparation of reactant B:
Identical with embodiment 10.
The preparation of solvent type fluoric acrylate copolymer:
Have in above-mentioned reactant B added in the four-hole bottle of copolymer A of aforementioned preparation, kept 75 ℃ of stirring reactions 5 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 14
The preparation of copolymer A:
In four-hole bottle, add butanone 140g, after feeding the nitrogen replacement inner air, be warming up to 70 ℃, stir and drip the mixed solution of forming by Jia Jibingxisuanyizhi 100.0g, butyl methacrylate 25.6g, methacrylic acid-β-hydroxypropyl acrylate 14.4g (0.1mol) and dissolving dibenzoyl peroxide 0.4g wherein down, keep 70 ℃ of temperature of reaction, dripped off in about 2 hours.Drip off the back and continue reaction 4 hours, add 10 milliliters of toluene solutions that are dissolved with the 0.1g dibenzoyl peroxide, continue to keep reaction 2 hours.Stop to stir in four-hole bottle patch ketone thing gross weight 700g to the bottle, the copolymer A concentration that makes preparation is 20%.
The preparation of reactant B:
Identical with embodiment 10.
The preparation of solvent type fluoric acrylate copolymer:
Have in above-mentioned reactant B added in the four-hole bottle of copolymer A of aforementioned preparation, kept 70 ℃ of stirring reactions 5 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.
Embodiment 13～14 fluoro-acrylate copolymer structural representations are as follows:
In the said structure signal,
Embodiment 13:R
1=CH
3R
2=n-C
12H
25R=H
Embodiment 14:R
1=C
2H
5R
2=n-C
4H
9R=CH
3
Embodiment 15
The preparation of copolymer A:
In four-hole bottle, add hexone 140g, after feeding the nitrogen replacement inner air, be warming up to 87 ℃, stir and drip the mixed solution of forming by Jia Jibingxisuanyizhi 70.0g, ethyl propenoate 35.0g, methacrylic acid-β-hydroxypropyl acrylate 35.0g (0.243mol) and dissolving dibenzoyl peroxide 0.3g wherein down, keep 85～90 ℃ of temperature of reaction, dripped off in about 2 hours.Drip off the back and continue reaction 2 hours, add 10 milliliters of toluene solutions that are dissolved with the 0.1g dibenzoyl peroxide, continue to keep reaction 2 hours again.Stop to stir and mend hexone thing gross weight 700g to the bottle in four-hole bottle, the copolymer A concentration that makes preparation is 20%.
The preparation of reactant B:
Add hexone 125g in another four-hole bottle, 2,4 toluene diisocyanate 42.3g (0.243mol), dibutyl tin laurate 0.09g are warming up to 70 ℃.Stir the mixed solution that drips N-ethyl-N hydroxyethyl perfluorinated octyl sulfuryl amine 138.8g (0.243mol) and hexone 600g down, drip off the back and continue reaction 5 hours.Lower the temperature, get the solution of reactant B, wherein non-volatile part of concentration is 20%.
The preparation of solvent type fluoric acrylate:
Have in above-mentioned reactant B added in the four-hole bottle of copolymer A of aforementioned preparation, kept 70 ℃ of stirring reactions 5 hours, cooling stops to stir.Get solvent type fluoric acrylate copolymer of the present invention.Structural representation is as follows:
Claims (2)
1, the preparation method of solvent type fluoric acrylate copolymer is characterized in that:
(1) adopt the solution polymerization side chain to contain the acrylate copolymer A of hydroxyl with the acrylate that contains hydroxyl or acrylamide monomer M and more than one acrylate monomer, structural representation is:
And
R＝H，CH
3
R
1＝CH
3，C
2H
5，C
4H
9，CH
2CH(C
2H
5)C
4H
9，C
12H
25
R
2＝CH
3，C
2H
5，C
4H
9，CH
2CH(C
2H
5)C
4H
9，C
12H
25，
(2) in the presence of catalyzer, by equimolar fluorine-containing alcohol R
fOH and vulcabond OCN-Z-NCO reaction are prepared into reactant B, and structural representation is: R
fO
2CNH-Z-NCO, reactant B keeps a unreacted-NCO base, and reaction is illustrated as:
, the mole number of fluorine-containing alcohol RfOH and vulcabond OCN-Z-NCO is the acrylate that contains hydroxyl or 0.8～1.2 times of acrylamide monomer M mole number;
(3) side chain that aforementioned preparation is obtained acrylate copolymer A and reactant B two portions of containing hydroxyl react, and make solvent type fluoric acrylate copolymer; Structural representation is:
And
R＝H，CH
3
R
1＝CH
3，C
2H
5，C
4H
9，CH
2CH(C
2H
5)C
4H
9，C
12H
25
R
2＝CH
3，C
2H
5，C
4H
9，CH
2CH(C
2H
5)C
4H
9，C
12H
25，
2, the preparation method of solvent type fluoric acrylate copolymer according to claim 1 is characterized in that:
(1) described side chain contains the acrylate copolymer A of hydroxyl, employing contains the acrylate of hydroxyl or acrylamide monomer M and more than one acrylate monomers and carry out solution polymerization in the presence of the radical initiator dibenzoyl peroxide, dibenzoyl peroxide accounts for 0.03～1.0% of whole polymerization system total amount, 70～100 ℃ of polymerization temperatures, 4～8 hours time;
The polyreaction solvent for use is a toluene or for dimethylbenzene or for butanone or for hexone or for vinyl acetic monomer or for N-BUTYL ACETATE, solvent load accounts for 33～85% in whole polymerization reaction system total amount;
Contain the acrylate of hydroxyl or acrylamide monomer M and be senecioate-hydroxyl ethyl ester or for senecioate-hydroxypropyl acrylate or for N hydroxymethyl acrylamide or for methacrylic acid-beta-hydroxy ethyl ester or be methacrylic acid-β-hydroxypropyl acrylate; In the used comonomer of preparation copolymer A, account for 1～25%;
Described more than one acrylate monomers are methyl acrylate or for ethyl propenoate or for butyl acrylate or for ethyl acrylate or for lauryl acrylate or for methyl methacrylate or for Jia Jibingxisuanyizhi or for butyl methacrylate or for lauryl methacrylate(LMA), account for 75～99% in the used comonomer of preparation copolymer A;
(2) reactant B, the promptly described compound R that contains a unreacted-NCO base
fO
2CNH-Z-NCO is by equimolar vulcabond OCN-Z-NCO and fluorine-containing alcohol R
fThe OH reaction forms, and reaction is in solvent, and catalyzer exists down, 50～100 ℃ of temperature of reaction, 2～6 hours time; The mole number of fluorine-containing alcohol and vulcabond is the acrylate that contains hydroxyl or 0.8～1.2 times of acrylamide monomer M mole number;
Solvent for use is an acetone or for butanone or for pimelinketone or for hexone or for trifluoromethylbenzene or for Freon 113 or for trieline or for zellon, solvent load accounts for 20～80% of whole reaction system total amount;
Described vulcabond OCN-Z-NCO is 2, the 4-tolylene diisocyanate, or be isophorone diisocyanate, or be PPDI, or be ditan-4,4 '-vulcabond, 1, hexamethylene-diisocyanate or be naphthalene-1,5-vulcabond or be dicyclohexyl methyl hydride-4,4 '-vulcabond;
Described fluorine-containing alcohol R
fOH is perfluoro hexyl ethanol or is perfluoro octyl ethanol; Or be N-hydroxyethyl perfluor decoylamide or for N-hydroxyethyl perfluor heptamide; Or be N-methyl-N-hydroxyethyl perfluorinated octyl sulfuryl amine or for N-ethyl-N hydroxyethyl perfluorinated octyl sulfuryl amine or for N-propyl group-N-hydroxyethyl perfluorinated octyl sulfuryl amine;
Described catalyzer is a dibutyl tin laurate or for dibutyltin diacetate or for stannous octoate or for triethylenediamine or for N-Ethylmorphine quinoline or for N, N '-dimethylcyclohexylamine or for diethylenetriamine; Catalyst levels is 0.01%～2% of a whole reaction system total amount;
(3) acrylate copolymer A and the reactant B two portions that the above-mentioned side chain of preparing contained hydroxyl react, and prepare solvent type fluoric acrylate copolymer; 50～100 ℃ of condensation temps, 2～6 hours time.
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| CN101274974B (en) * | 2008-04-29 | 2010-06-30 | 成都理工大学 | Temperature-resistant water-soluble copolymer, preparation and use thereof |
| CN101851462B (en) * | 2010-07-06 | 2012-04-18 | 长沙湘江生力重防腐涂料有限公司 | High-solid-content wear-resistant paint for wind power generators, and preparation method and application thereof |
| CN102070767B (en) * | 2010-12-19 | 2013-04-17 | 南昌航空大学 | Preparation method of anti-aging ultraviolet cured acrylic-polyurethane resin containing fluorine |
| CN102784586A (en) * | 2012-08-22 | 2012-11-21 | 东华大学 | Fluorine-containing surfactant and preparation method thereof |
| EP2904026B1 (en) | 2012-10-04 | 2018-08-15 | BASF Coatings GmbH | Nonaqueous coating composition containing fluorine, coating process and use of said coating composition |
| CN103012663A (en) * | 2012-12-05 | 2013-04-03 | 陕西科技大学 | Preparation method for anionic acrylate polymer surfactant |
| CN103666231B (en) * | 2013-12-11 | 2016-03-23 | 甘肃大禹节水集团股份有限公司 | The anti-sun in a kind of drip irrigation zone is burnt coated material and using method thereof |
| CN103740220B (en) * | 2013-12-11 | 2015-11-18 | 甘肃大禹节水集团股份有限公司 | A kind of high temperature resistant, anti-calcination under-film drip irrigation band coating and preparation method thereof |
| CN104927024A (en) * | 2014-03-20 | 2015-09-23 | 江南大学 | Preparation method of fluorine modified light-cured polyurethane acrylate resin and application thereof as light-cured coating hydrophobic filling material |
| CN110746565A (en) * | 2019-10-14 | 2020-02-04 | 苏州联胜化学有限公司 | Washable fluorine-based waterproof agent and preparation method thereof |
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