CN103755902A - Bottle brush-shaped PDMS-b-P(mPEGA ) copolymers and preparation thereof - Google Patents
Bottle brush-shaped PDMS-b-P(mPEGA ) copolymers and preparation thereof Download PDFInfo
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Abstract
The invention discloses bottle brush-shaped polydimethylsiloxane-b-poly(polyethylene glycol methyl ether acrylate) copolymers and a preparation method thereof. The block copolymers are composed of two blocks: polydimethylsiloxane and poly(polyethylene glycol methyl ether acrylate). The preparation process comprises the steps: a polydimethylsiloxane reversible addition-fragmentation chain transfer agent B is prepared from trithiocarbonate and polydimethylsiloxane, then the agent B is used for adjusting a reversible addition-fragmentation chain transfer free radical solution polymerization reaction of polyethylene glycol methyl ether acrylate monomers, and thus the bottle brush-shaped polydimethylsiloxane-b-poly(polyethylene glycol methyl ether acrylate) copolymers are prepared. The preparation method has the advantages that the preparation process of the copolymers is mild in reaction conditions and easy to operate, can prepare the required bottle brush-shaped block copolymers having different molecular weights and the molecular weight distribution of 1.0-1.2 and having neat structure; and the copolymers have good protein adsorption resistance performance and fouling desorption performance, and can be used as additives for preparation of marine organism pollution-resisting coating layers.
Description
Technical field
The present invention relates to a kind of bottle brush shape polydimethylsiloxane-
b-poly-(methoxypolyethylene glycol acrylate) multipolymer and preparation method thereof.Elemento-organic polymer-carbon chain polymer segmented copolymer the technical field that belongs to anti-protein adsorption.
Background technology
Silicone resin has low surface energy, is widely used in marine anti-pollution coating; Polyoxyethylene glycol (PEG) has excellent anti-protein adsorption performance, is also the ideal material of preparing marine anti-pollution coating.The stained anti-protein adsorption performance that removes performance and PEG excellence of silicone resin excellence is combined, with reach anti-biological stained be the order ground of our synthetic this Amphipathilic block polymer.
Prepare Amphipathilic block polymer and can adopt several different methods.Military favorable to the people grade has proposed a kind of method of simple synthetic polydimethylsiloxane macromole azo initiator: by hydroxy-end capped polydimethylsiloxane (HO-PDMS-OH) and 4, and the synthetic macromole azo initiator that contains PDMS segment of 4 '-azo-bis-(4-cyanopentanoic acid).With this macromole evocating agent, cause PEG monomethyl ether metacrylic acid ester macromonomer (mPEGMA) and carry out free radical solution polymerization, a series of amphipathic Comb-block copolymer (Feng Libang have been obtained, Fang Hongxia, Zhou Shuxue, Gu Guangxin, military favorable to the people. polymer journal, 2007, (5), 472-477).
Reversible addition-fracture chain shifts (RAFT) polymerization can realize the controllability of radical polymerization as a kind of living control polymerization reaction, for preparing ad hoc structure, the narrower block polymer of molecular weight distribution is had laid a good foundation.Kennedy etc. regulate by the PolydimethylsiloxaneChain Chain transfer agent (PDMS-CTA) of preparation
n,
n-DMAA (DMAAm) polymerization, synthetic PDMAAm-
b-PDMS-
b-PDMAAm triblock polymer, its narrow molecular weight distribution, compound with regular structure (Karunakaran R, Kennedy JP.
j. Polym. Sci. Part A:Polym. Chem. 2007,
45, 4284 – 4290).
Bottle brush shaped polymer is the multipolymer that a class has linear polymer main chain and fine and close side chain, and its synthetic method has " Grafting to ", " Grafting through " and " Grafting from ".Particularly " Grafting through " method, makes the bottle brush shaped polymer of preparing grafting density 100% by the method for living polymerization become possibility.Tang etc., directly to macromonomer ring-opening polymerization, have synthesized bottle brush shaped polymer (Yao KJ, Chen Y, Zhang C, Tang CB.
macromol. Rapid Commun. 2013,
34, 645-651).Also there is report to use method (Thong-on B, Rutnakornpituk B, Wichai U, the Rutnakornpituk M. of atom transfer radical polymerization
j. Nanopart. Res. 2012,
14, 953-964).Wooley etc. utilize RAFT method, first synthesize the macromonomer with norbornylene end group, then use ring-opening polymerization to synthesize bottle brush shaped polymer (Li A, Ma J, Sun G, Li Z, Cho S, Clark C, Wooley KL.
j. Polym. Sci. Part A:Polym. Chem.,
2012, 50,1681 – 1688).
To sum up, about take polydimethylsiloxane as Macro RAFT agent, directly regulate the polymerization of methoxypolyethylene glycol esters of acrylic acid macromonomer, the method for preparing bottle brush shape Amphipathilic block polymer rarely has report.
Summary of the invention
The object of the present invention is to provide a kind of bottle brush shape polydimethylsiloxane-
b-poly-(methoxypolyethylene glycol acrylate) multipolymer and preparation method.This multipolymer has excellent stained performance and the anti-protein adsorption performance of removing, and its preparation method reaction conditions is gentle, and simple to operate, multipolymer is mainly used in marine anti-pollution coating.
The present invention is realized by the following technical programs, a kind of bottle brush shape polydimethylsiloxane-
b-poly-(methoxypolyethylene glycol acrylate) multipolymer, is characterized in that, the structure of this multipolymer suc as formula 1 or formula 2 shown in, its number-average molecular weight is 2 000 ~ 200 000 g/mol; The nuclear magnetic spectrogram of multipolymer, wherein characteristic peak is respectively: the corresponding polysiloxane of the peak a of the 0.1ppm methyl proton peak that is connected with Si, the corresponding polysiloxane of the peak b of the 0.5ppm methene proton peak that is connected with Si, terminal methyl peak on the corresponding PEG side chain in peak of 3.4ppm, the peak of methylene radical on the corresponding PEG side chain in peak of 3.5-3.8ppm, the methylene peak being directly connected with ester group on the corresponding PEG side chain of peak i of 4.2ppm
In formula: the integer that m is 1 ~ 100; N is 5 ~ 400 integer; P is 1 ~ 200 integer;
R is-H or be-CH
3; R' is-C (CH
3)
2-, or be-C (CN) (CH
3)-CH
2-CH
2-;
Z is-S-C
12h
25, or be-S-C
4h
9, or be-O-CH
2-CH
3, or be-C
6h
5.
The bottle brush shape polydimethylsiloxane of said structure-
b-poly-(methoxypolyethylene glycol acrylate) multipolymer preparation method, is characterized in that comprising following process:
1) number-average molecular weight is the preparation of the reversible addition-fracture of 500 ~ 30000 g/mol polysiloxane chain-transfer agent B
By the trithiocarbonate that contains carboxyl and oxalyl chloride ((COCl)
2) 1:(1 ~ 2 in molar ratio) join in anhydrous methylene chloride, be made into that to contain trithiocarbonic acid ester concentration be 0.1 ~ 0.5mol/L solution, stirring at room 2 ~ 8 hours, underpressure distillation is except desolventizing and unreacted (COCl)
2, obtain the trithiocarbonate A of chloride, the polysiloxane that the single-ended or both-end that is 500 ~ 30000 g/mol by number-average molecular weight contains hydroxyl and the trithiocarbonate A of chloride are 1:(1 ~ 3 by hydroxyl and acid chloride group mol ratio) join that in anhydrous methylene chloride, to be made into containing polysiloxane concentration be 0.1 ~ 0.5mol/L solution, stirring at room 24 ~ 72 hours, underpressure distillation, then by methanol wash to remove the trithiocarbonate A of unreacted chloride, room temperature vacuum-drying 12 ~ 48 hours, the number-average molecular weight that obtains single-ended or trithiocarbonate A that both-end contains chloride is the reversible addition-fracture of 500 ~ 30000 g/mol polysiloxane chain-transfer agent B,
2) bottle brush shape polydimethylsiloxane-
breversible addition-fracture chain of-poly-(methoxypolyethylene glycol acrylate) multipolymer shifts
Preparation
Three thioester groups of the reversible addition-fracture chain-transfer agent B making by the carbon-carbon double bond of methoxypolyethylene glycol (methyl) acrylate and step 1), and with the mol ratio of the azo group of initiator Diisopropyl azodicarboxylate be (1 ~ 100): 1:(0.1 ~ 0.3), three is added in toluene and dissolved, be mixed with that to contain methoxypolyethylene glycol (methyl) acrylate mass concentration be 10 ~ 80% reaction solns, in 50 ~ 80 ℃ of water-baths or oil bath, react 4 ~ 24 hours, reaction product is with underpressure distillation or with ether sedimentation, except desolventizing and unreacted a small amount of monomer, obtain bottle brush shape polydimethylsiloxane-
b-poly-(methoxypolyethylene glycol acrylate) multipolymer.
The bottle brush shape polydimethylsiloxane that aforesaid method makes-
b-poly-(methoxypolyethylene glycol acrylate) multipolymer application, for marine anti-pollution coating.
Advantage of the present invention is that the preparation condition of this multipolymer is gentle, and easy handling can be by controlling polymerization time, and preparing required different molecular weight and molecular weight distribution is the bottle brush shape segmented copolymer of 1.0 ~ 1.2 compound with regular structure; The monomer chain length adding by control is controlled the length of bottle brush shape segmented copolymer side chain.Simultaneously the PDMS block due to this multipolymer has low surface energy, and it on, stained thing is easy to desorption, and the P of this multipolymer (mPEGA) block has anti-protein adsorption performance, so prepared bottle brush shape polydimethylsiloxane-
b-poly-(methoxypolyethylene glycol acrylate) multipolymer has antifouling properties; The additive that can be used as epoxy resin, (fluorine-containing) acrylate resin or silicone resin is prepared the coating of resisting contamination from marine organism.
Accompanying drawing explanation
Fig. 1 is the bottle brush shape PDMS-that the embodiment of the present invention 1 makes
bthe nmr spectrum of-P (mPEGA) multipolymer C.
Embodiment
Below by case study on implementation, technical scheme of the present invention is further described, following case study on implementation is to further illustrate of the present invention, but does not limit use range of the present invention.
(1) preparation of the reversible addition-fracture of PDMS chain-transfer agent B
By 1.82g
s-1-dodecyl-
s(α, α '-dimethyl-α ' '-acetic acid) trithiocarbonate (DDMAT), 0.76g oxalyl chloride are dissolved in 15 mL anhydrous methylene chlorides, room temperature magnetic agitation 4 h, and underpressure distillation obtains the DDMAT (A) of chloride.A is dissolved in to 10 mL anhydrous methylene chlorides, joined 9g one-ended hydroxy polydimethylsiloxane (PDMS, 2000g/mol) and in the mixed solution of 10mL anhydrous methylene chloride, room temperature magnetic agitation 24 h, volatiles is removed in underpressure distillation, then with methyl alcohol 50mL washing 3 times to remove unreacted DDMAT, 40 ℃ of vacuum-drying 24h, obtain the reversible addition-fracture of the PDMS chain-transfer agent B of the single-ended DDMAT of containing.
(2) bottle brush shape PDMS-
breversible addition-fracture chain of-P (mPEGA) multipolymer C shifts preparation
Take respectively the reversible addition-fracture of PDMS chain-transfer agent B prepared by 0.4 g step (1), 4.8 g methoxypolyethylene glycol acrylate (mPEGA, 480 g/mol) and 4.3mg Diisopropyl azodicarboxylate, be dissolved in 5 g toluene, nitrogen bubble 30min, is warming up to 65 ℃, reacts 4 h under water bath condition, after having reacted, reaction product is removed desolventizing and unreacted a small amount of monomer by the mode of underpressure distillation.25 ℃ of vacuum-dryings are spent the night, and obtain yellow product bottle brush shape PDMS-
b-P (mPEGA) multipolymer C.
embodiment 2
(1) preparation of the reversible addition-fracture of PDMS chain-transfer agent B
By 1.82g
s-1-dodecyl-
s(α, α '-dimethyl-α ' '-acetic acid) trithiocarbonate (DDMAT), 0.76g oxalyl chloride are dissolved in 15 mL anhydrous methylene chlorides, room temperature magnetic agitation 4 h, and underpressure distillation obtains the DDMAT (A) of chloride.A is dissolved in to 10 mL anhydrous methylene chlorides, joined the two hydroxyl-terminated injecting two methyl siloxane (PDMS of 4.5g, 2000g/mol) and in the mixed solution of 5mL anhydrous methylene chloride, room temperature magnetic agitation 24 h, volatiles is removed in underpressure distillation, then with methyl alcohol 50mL, wash 3 times to remove unreacted DDMAT, 40 ℃ of vacuum-drying 24h, obtain the reversible addition-fracture of the PDMS chain-transfer agent B that both-end contains DDMAT.
(2) bottle brush shape P (mPEGA)-
b-PDMS-
breversible addition-fracture chain of-P (mPEGA) multipolymer C shifts preparation
Take respectively the reversible addition-fracture of PDMS chain-transfer agent B prepared by 0.2 g step (1), 4.8 g methoxypolyethylene glycol acrylate (mPEGA, 480 g/mol) and 4.3mg Diisopropyl azodicarboxylate, be dissolved in 5 g toluene, nitrogen bubble 30min, is warming up to 65 ℃, reacts 4 h under water bath condition, after having reacted, reaction product is removed desolventizing and unreacted a small amount of monomer by the mode of underpressure distillation.25 ℃ of vacuum-dryings are spent the night, obtain yellow product bottle brush shape P (mPEGA)-
b-PDMS-
b-P (mPEGA) multipolymer C.
embodiment 3
(1) preparation of the reversible addition-fracture of PDMS chain-transfer agent B
By 1.82g
s-1-dodecyl-
s(α, α '-dimethyl-α ' '-acetic acid) trithiocarbonate (DDMAT), 0.76g oxalyl chloride are dissolved in 15 mL anhydrous methylene chlorides, room temperature magnetic agitation 4 h, and underpressure distillation obtains the DDMAT (A) of chloride.A is dissolved in to 10 mL anhydrous methylene chlorides, joined the two hydroxyl-terminated injecting two methyl siloxane (PDMS of 11.25g, 5000g/mol) and in the mixed solution of 10mL anhydrous methylene chloride, room temperature magnetic agitation 24 h, volatiles is removed in underpressure distillation, then with methyl alcohol 50mL, wash 3 times to remove unreacted DDMAT, 40 ℃ of vacuum-drying 24h, obtain the reversible addition-fracture of the PDMS chain-transfer agent B that both-end contains DDMAT.
(2) bottle brush shape PDMS-
breversible addition-fracture chain of-P (mPEGA) multipolymer C shifts preparation
Take respectively the reversible addition-fracture of PDMS chain-transfer agent B prepared by 1.0 g steps (1), 4.8 g methoxypolyethylene glycol acrylate (mPEGA, 480 g/mol) and 4.3mg Diisopropyl azodicarboxylate, be dissolved in 5 g toluene, nitrogen bubble 30min, is warming up to 65 ℃, reacts 4 h under water bath condition, after having reacted, reaction product is removed desolventizing and unreacted a small amount of monomer by the mode of underpressure distillation.25 ℃ of vacuum-dryings are spent the night, and obtain yellow product bottle brush shape PDMS-
b-P (mPEGA) multipolymer C.
embodiment 4
(1) preparation of the reversible addition-fracture of PDMS chain-transfer agent B
By 1.82g
s-1-dodecyl-
s(α, α '-dimethyl-α ' '-acetic acid) trithiocarbonate (DDMAT), 0.76g oxalyl chloride are dissolved in 15 mL anhydrous methylene chlorides, room temperature magnetic agitation 4 h, and underpressure distillation obtains the DDMAT (A) of chloride.A is dissolved in to 10 mL anhydrous methylene chlorides, joined 9g one-ended hydroxy polydimethylsiloxane (PDMS, 2000g/mol) and in the mixed solution of 10mL anhydrous methylene chloride, room temperature magnetic agitation 24 h, volatiles is removed in underpressure distillation, then with methyl alcohol 50mL, wash 3 times to remove unreacted DDMAT, 40 ℃ of vacuum-drying 24h, obtain the reversible addition-fracture of single-ended PDMS chain-transfer agent B.
(2) bottle brush shape PDMS-
breversible addition-fracture chain of-P (mPEGA) multipolymer C shifts preparation
Take respectively the reversible addition-fracture of PDMS chain-transfer agent B prepared by 0.04 g step (1), 1.0 g methoxypolyethylene glycol acrylate (mPEGA, 1000 g/mol) and 0.43 mg Diisopropyl azodicarboxylate, be dissolved in 1 g toluene, nitrogen bubble 30min, is warming up to 65 ℃, reacts 4 h under water bath condition, after having reacted, ether sedimentation washing 3 times for reaction product.25 ℃ of vacuum-dryings are spent the night, and obtain yellow product bottle brush shape PDMS-
b-P (mPEGA) multipolymer C.
Above the present invention has been done to exemplary description; should be noted that; in the situation that not departing from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (3)
- A bottle brush shape polydimethylsiloxane- b-poly-(methoxypolyethylene glycol acrylate) multipolymer, is characterized in that, the structure of this multipolymer suc as formula 1 or formula 2 shown in, number-average molecular weight is 2 000 ~ 200 000 g/mol; The nuclear magnetic spectrogram of multipolymer, wherein characteristic peak is respectively: the corresponding polysiloxane of the peak a of the 0.1ppm methyl proton peak that is connected with Si, the corresponding polysiloxane of the peak b of the 0.5ppm methene proton peak that is connected with Si, terminal methyl peak on the corresponding side-chain of polyelycol in peak of 3.4ppm, the peak of methylene radical on the corresponding side-chain of polyelycol in peak of 3.5-3.8ppm, the methylene peak being directly connected with ester group on the corresponding side-chain of polyelycol of peak i of 4.2ppm
In formula: the integer that m is 1 ~ 100; N is 5 ~ 400 integer; P is 1 ~ 200 integer;R is-H or be-CH 3; R' is-C (CH 3) 2-, or be-C (CN) (CH 3)-CH 2-CH 2-;Z is-S-C 12h 25, or be-S-C 4h 9, or be-O-CH 2-CH 3, or be-C 6h 5. - One kind by bottle brush shape polydimethylsiloxane claimed in claim 1- b-poly-(methoxypolyethylene glycol acrylate) multipolymer preparation method, is characterized in that comprising following process:Number-average molecular weight is the preparation of the reversible addition-fracture of 500 ~ 30000 g/mol polysiloxane chain-transfer agent B:By the trithiocarbonate that contains carboxyl with (COCl) 21:(1 ~ 2 in molar ratio) join in anhydrous methylene chloride, be made into that to contain trithiocarbonic acid ester concentration be 0.1 ~ 0.5mol/L solution, stirring at room 2 ~ 8 hours, underpressure distillation is except desolventizing and unreacted (COCl) 2, obtain the trithiocarbonate A of chloride, the polysiloxane that the single-ended or both-end that is 500 ~ 30000 g/mol by number-average molecular weight contains hydroxyl and the trithiocarbonate A of chloride are 1:(1 ~ 3 by hydroxyl and acid chloride group mol ratio) join that in anhydrous methylene chloride, to be made into containing polysiloxane concentration be 0.1 ~ 0.5mol/L solution, stirring at room 24 ~ 72 hours, underpressure distillation, then by methanol wash to remove the trithiocarbonate A of unreacted chloride, room temperature vacuum-drying 12 ~ 48 hours, the number-average molecular weight that obtains single-ended or trithiocarbonate A that both-end contains chloride is the reversible addition-fracture of 500 ~ 30000 g/mol polysiloxane chain-transfer agent B,Bottle brush shape polydimethylsiloxane- breversible addition-fracture chain of-poly-(methoxypolyethylene glycol acrylate) multipolymer shifts preparation:Three thioester groups of the reversible addition-fracture chain-transfer agent B making by the carbon-carbon double bond of methoxypolyethylene glycol (methyl) acrylate and step 1), and with the mol ratio of the azo group of initiator Diisopropyl azodicarboxylate be (1 ~ 100): 1:(0.1 ~ 0.3), three is added in toluene and dissolved, be mixed with that to contain methoxypolyethylene glycol (methyl) acrylate mass concentration be 10 ~ 80% reaction solns, in 50 ~ 80 ℃ of water-baths or oil bath, react 4 ~ 24 hours, reaction product is with underpressure distillation or with ether sedimentation, except desolventizing and unreacted a small amount of monomer, obtain bottle brush shape polydimethylsiloxane- b-poly-(methoxypolyethylene glycol acrylate) multipolymer.
- The bottle brush shape polydimethylsiloxane making by method claimed in claim 2- b-poly-(methoxypolyethylene glycol acrylate) multipolymer application, for marine anti-pollution coating.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892873A (en) * | 2015-05-29 | 2015-09-09 | 浙江大学 | Multi-functional amphiphilic low-surface-energy polymer, and preparation method and application thereof |
| CN105754105B (en) * | 2016-02-29 | 2018-06-22 | 南京林业大学 | One kind is containing amphipathic organic silicon block copolymer of oleic acid derivatives and preparation method thereof |
| CN110183926A (en) * | 2019-05-09 | 2019-08-30 | 华南理工大学 | A kind of anti-pollution organic and inorganic silicon hybridization coating and the preparation method and application thereof |
| EP3496759B1 (en) * | 2016-08-09 | 2022-03-16 | The University of Liverpool | Ophthalmic compositions |
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| CN105754105B (en) * | 2016-02-29 | 2018-06-22 | 南京林业大学 | One kind is containing amphipathic organic silicon block copolymer of oleic acid derivatives and preparation method thereof |
| EP3496759B1 (en) * | 2016-08-09 | 2022-03-16 | The University of Liverpool | Ophthalmic compositions |
| CN110183926A (en) * | 2019-05-09 | 2019-08-30 | 华南理工大学 | A kind of anti-pollution organic and inorganic silicon hybridization coating and the preparation method and application thereof |
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Application publication date: 20140430 |