CN103755902A - Bottle brush-shaped PDMS-b-P(mPEGA ) copolymers and preparation thereof - Google Patents

Abstract

The invention discloses a bottle brush-shaped polydimethylsiloxane-b poly(polyethylene glycol methyl ether acrylate) copolymer and a preparation method thereof. The block copolymer consists of two blocks of polydimethylsiloxane and poly(polyethylene glycol methyl ether acrylate). Its preparation process: prepare polydimethylsiloxane reversible addition-fragmentation chain transfer agent B with trithiocarbonate and polydimethylsiloxane, and then use B to adjust polyethylene glycol methyl ether acrylate unit Reversible addition-fragmentation chain-transfer radical solution polymerization of a body to prepare a bottle-brush polydimethylsiloxane-b-poly(polyethylene glycol methyl ether acrylate) copolymer. The present invention has the advantages of mild reaction conditions and easy operation during the preparation of the copolymer, and can prepare bottle-brush-shaped block copolymers with different molecular weights required and a molecular weight distribution of 1.0 to 1.2. The copolymer has good protein adsorption resistance Performance and fouling release properties, can be used as additives to prepare coatings against marine biofouling.

Description

Bottlebrush-like PDMS-b-P(mPEGA) Copolymer and Its Preparation

technical field

The invention relates to a bottle brush-like polydimethylsiloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymer and a preparation method thereof. The invention belongs to the technical field of elemental organic polymers-carbon chain polymer block copolymers resistant to protein adsorption.

Background technique

Silicone resin has low surface energy and is widely used in marine antifouling coatings; polyethylene glycol (PEG) has excellent anti-protein adsorption properties and is also an ideal material for preparing marine antifouling coatings. Combining the excellent fouling release properties of silicone resins with the excellent anti-protein adsorption properties of PEG to achieve anti-biofouling is our purpose of synthesizing this amphiphilic block polymer. the

A variety of methods can be used to prepare amphiphilic block polymers. Wu Limin et al. proposed a simple and feasible method for synthesizing polydimethylsiloxane macromolecular azo initiators: through hydroxyl-terminated polydimethylsiloxane (HO-PDMS-OH) and 4 ,4' -Azo-bis(4-cyanovaleric acid) synthesis of macromolecular azo initiators containing PDMS segments. Using this macroinitiator to initiate free radical solution polymerization of poly(ethylene glycol) monomethyl ether methacrylate macromer (mPEGMA), a series of amphiphilic comb-like block copolymers were obtained (Feng Libang , Fang Hongxia, Zhou Shuxue, Gu Guangxin, Wu Limin. Acta Polymerica Sinica, 2007, (5), 472-477). the

As a living controllable polymerization reaction, reversible addition-fragmentation chain transfer (RAFT) polymerization can realize the controllability of free radical polymerization, which lays a good foundation for the preparation of block polymers with specific structure and narrow molecular weight distribution. Kennedy et al. synthesized PDMAAm-b - PDMS - b-PDMAAm triblock polymers by regulating the polymerization of N , N -dimethylacrylamide (DMAAm) through the prepared polydimethylsiloxane chain transfer agent (PDMS-CTA) , with narrow molecular weight distribution and regular structure (Karunakaran R, Kennedy JP. J. Polym. Sci. Part A: Polym. Chem. 2007 , 45 , 4284–4290).

Bottlebrush polymers are a class of copolymers with a linear polymer backbone and dense side chains, and their synthesis methods include "Grafting to", "Grafting through" and "Grafting from". In particular, the "Grafting through" method makes it possible to prepare bottlebrush polymers with a graft density of 100% by living polymerization. Tang et al. directly synthesized bottlebrush polymers through ring-opening polymerization of macromonomers (Yao KJ, Chen Y, Zhang C, Tang CB. Macromol. Rapid Commun. 2013 , 34 , 645-651). Atom transfer radical polymerization was also reported (Thong-on B, Rutnakornpituk B, Wichai U, Rutnakornpituk M. J. Nanopart. Res. 2012 , 14 , 953-964). Wooley et al. used the RAFT method to first synthesize macromonomers with norbornene end groups, and then synthesized bottlebrush polymers by ring-opening polymerization (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).

In summary, there are few methods for preparing bottlebrush-like amphiphilic block polymers by using polydimethylsiloxane as a macromolecular RAFT reagent to directly regulate the polymerization of polyethylene glycol methyl ether acrylate macromonomers. reports. the

Contents of the invention

The object of the present invention is to provide a bottle brush polydimethylsiloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymer and a preparation method. The copolymer has excellent fouling removal performance and protein adsorption resistance, and the preparation method has mild reaction conditions and simple operation, and the copolymer is mainly used in marine antifouling coatings.

The present invention is achieved through the following technical solutions, a bottle brush-like polydimethylsiloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymer, characterized in that the structure of the copolymer is as follows As shown in formula 1 or formula 2, its number average molecular weight is 2 000~200 000 g/mol; the nuclear magnetic spectrum of the copolymer, wherein the characteristic peaks are: 0.1ppm peak a corresponds to polysiloxane and Si linked methyl Proton peak, peak b at 0.5ppm corresponds to the proton peak of the methylene group connected to polysiloxane and Si, the peak at 3.4ppm corresponds to the peak of the methyl group on the side chain of PEG, and the peak at 3.5-3.8ppm corresponds to the peak of the methylene group on the side chain of PEG Peak, the peak i of 4.2ppm corresponds to the methylene peak directly connected with the ester group on the PEG side chain,

In the formula: m is an integer from 1 to 100; n is an integer from 5 to 400; p is an integer from 1 to 200;

R is -H or -CH ₃ ; R' is -C(CH ₃ ) ₂ -, or -C(CN)(CH ₃ )-CH ₂ -CH ₂ -;

Z is -SC ₁₂ H ₂₅ , or -SC ₄ H ₉ , or -O-CH ₂ -CH ₃ , or -C ₆ H ₅ .

The bottle brush shape polydimethylsiloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymer preparation method of above-mentioned structure is characterized in that comprising following process:

1) Preparation of polysiloxane reversible addition-fragmentation chain transfer agent B with number average molecular weight of 500~30000 g/mol

Add carboxyl-containing trithiocarbonate and oxalyl chloride ((COCl) ₂ ) in a molar ratio of 1:(1~2) to anhydrous dichloromethane to prepare a trithiocarbonate containing concentration of 0.1~0.5 mol/L solution, stirred at room temperature for 2-8 hours, and the solvent and unreacted (COCl) ₂ were distilled off under reduced pressure to obtain acid-chlorinated trithiocarbonate A; Polysiloxane containing hydroxyl groups at one or both ends and acyl chloride trithiocarbonate A are added to anhydrous dichloromethane according to the molar ratio of hydroxyl and acid chloride groups of 1: (1~3) to prepare polysiloxane containing polysiloxane The alkane concentration is 0.1~0.5mol/L solution, stirred at room temperature for 24~72 hours, distilled under reduced pressure, then washed with methanol to remove unreacted acyl chlorinated trithiocarbonate A, and vacuum dried at room temperature for 12~48 hours to obtain A polysiloxane reversible addition-fragmentation chain transfer agent B with a number-average molecular weight of 500-30,000 g/mol trithiocarbonate A containing acid chloride at one or both ends;

2) Reversible addition-fragmentation chain transfer of bottlebrush-like polydimethylsiloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymers

preparation

According to the carbon-carbon double bond of polyethylene glycol methyl ether (meth)acrylate and the trithioester group of the reversible addition-fragmentation chain transfer agent B prepared in step 1), and with the initiator azobisisobutyl The molar ratio of the azo group of nitrile is (1 ~ 100): 1: (0.1 ~ 0.3), and the three are added to dissolve in toluene, and it is formulated to contain polyethylene glycol methyl ether (meth) acrylate with a mass concentration of 10~80% reaction solution, react in water bath or oil bath at 50~80°C for 4~24 hours, the reaction product is distilled under reduced pressure or precipitated with ether, and the solvent and a small amount of unreacted monomer are removed to obtain bottle brush polydimethylformaldehyde siloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymer.

The bottle brush polydimethylsiloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymer prepared by the above method is used in marine antifouling coatings.

The advantage of the present invention is that the preparation conditions of the copolymer are mild and easy to operate, and bottle-brush-like block copolymers with different molecular weights required and a molecular weight distribution of 1.0 to 1.2 can be prepared by controlling the polymerization time; The length of the bulk segment controls the length of the side chains of the bottlebrush block copolymers. At the same time, due to the low surface energy of the PDMS block of the copolymer, the stains on it are easy to desorb, and the P(mPEGA) block of the copolymer has anti-protein adsorption properties, so the prepared bottlebrush polydimethylene Siloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymer has anti-fouling properties; it can be used as an additive to epoxy resins, (fluorinated) acrylate resins or silicone resins to prepare anti-marine biofouling coating.

Description of drawings

Fig. 1 is the NMR spectrum of the bottlebrush-shaped PDMS- b -P(mPEGA) copolymer C prepared in Example 1 of the present invention.

Detailed ways

The technical solution of the present invention will be further described through examples below. The following examples are further illustrations of the present invention, but do not limit the application scope of the present invention. the

Example 1

(1) Preparation of PDMS reversible addition-fragmentation chain transfer agent B

Dissolve 1.82 g of S -1-dodecyl- S (α,α'-dimethyl-α''-acetic acid) trithiocarbonate (DDMAT), 0.76 g of oxalyl chloride in 15 mL of anhydrous dichloro In methane, magnetically stirred at room temperature for 4 h, and distilled under reduced pressure to obtain acid chloride DDMAT (A). Dissolve A in 10 mL of anhydrous dichloromethane, add it to a mixture of 9 g of single-ended hydroxyl polydimethylsiloxane (PDMS, 2000 g/mol) and 10 mL of anhydrous dichloromethane, and stir magnetically at room temperature for 24 h, the volatile components were distilled off under reduced pressure, then washed three times with 50 mL of methanol to remove unreacted DDMAT, and dried in vacuum at 40°C for 24 h to obtain a PDMS reversible addition-fragmentation chain transfer agent B containing DDMAT at one end.

(2) Reversible addition-fragmentation chain transfer preparation of bottlebrush-like PDMS- b -P(mPEGA) copolymer C

Weigh 0.4 g of PDMS reversible addition-fragmentation chain transfer agent B prepared in step (1), 4.8 g of polyethylene glycol methyl ether acrylate (mPEGA, 480 g/mol) and 4.3 mg of azobisisobutyronitrile, Dissolve in 5 g of toluene, bubble nitrogen for 30 min, heat up to 65 °C, and react for 4 h under water bath conditions. After the reaction is completed, the reaction product is distilled under reduced pressure to remove the solvent and a small amount of unreacted monomer. Vacuum-dried overnight at 25°C to obtain a bottle-like brush-like PDMS- b -P(mPEGA) copolymer C as a yellow product.

Example 2

(1) Preparation of PDMS reversible addition-fragmentation chain transfer agent B

Dissolve 1.82 g of S -1-dodecyl- S (α,α'-dimethyl-α''-acetic acid) trithiocarbonate (DDMAT), 0.76 g of oxalyl chloride in 15 mL of anhydrous dichloro In methane, magnetically stirred at room temperature for 4 h, and distilled under reduced pressure to obtain acid chloride DDMAT (A). Dissolve A in 10 mL of anhydrous dichloromethane, add it to a mixture of 4.5 g of double-terminated hydroxyl polydimethylsiloxane (PDMS, 2000 g/mol) and 5 mL of anhydrous dichloromethane, and stir magnetically at room temperature After 24 h, the volatile components were distilled off under reduced pressure, then washed three times with 50 mL of methanol to remove unreacted DDMAT, and dried in vacuum at 40 °C for 24 h to obtain a PDMS reversible addition-fragmentation chain transfer agent B containing DDMAT at both ends.

(2) Reversible addition-fragmentation chain transfer preparation of bottlebrush-like P(mPEGA) -b -PDMS- b -P(mPEGA) copolymer C

Weigh 0.2 g of PDMS reversible addition-fragmentation chain transfer agent B prepared in step (1), 4.8 g of polyethylene glycol methyl ether acrylate (mPEGA, 480 g/mol) and 4.3 mg of azobisisobutyronitrile, Dissolve in 5 g of toluene, bubble nitrogen for 30 min, heat up to 65 °C, and react for 4 h under water bath conditions. After the reaction is completed, the reaction product is distilled under reduced pressure to remove the solvent and a small amount of unreacted monomer. Vacuum-dried overnight at 25°C to obtain a bottle-like P(mPEGA) -b -PDMS- b -P(mPEGA) copolymer C as a yellow product.

Example 3

(1) Preparation of PDMS reversible addition-fragmentation chain transfer agent B

Dissolve 1.82 g of S -1-dodecyl- S (α,α'-dimethyl-α''-acetic acid) trithiocarbonate (DDMAT), 0.76 g of oxalyl chloride in 15 mL of anhydrous dichloro In methane, magnetically stirred at room temperature for 4 h, and distilled under reduced pressure to obtain acid chloride DDMAT (A). Dissolve A in 10 mL of anhydrous dichloromethane, add it to a mixture of 11.25 g of double-terminated hydroxyl polydimethylsiloxane (PDMS, 5000 g/mol) and 10 mL of anhydrous dichloromethane, and stir magnetically at room temperature After 24 h, the volatile components were distilled off under reduced pressure, then washed three times with 50 mL of methanol to remove unreacted DDMAT, and dried in vacuum at 40 °C for 24 h to obtain a PDMS reversible addition-fragmentation chain transfer agent B containing DDMAT at both ends.

(2) Reversible addition-fragmentation chain transfer preparation of bottlebrush-like PDMS- b -P(mPEGA) copolymer C

Weigh 1.0 g of PDMS reversible addition-fragmentation chain transfer agent B prepared in step (1), 4.8 g of polyethylene glycol methyl ether acrylate (mPEGA, 480 g/mol) and 4.3 mg of azobisisobutyronitrile, Dissolve in 5 g of toluene, bubble nitrogen for 30 min, heat up to 65 °C, and react for 4 h under water bath conditions. After the reaction is completed, the reaction product is distilled under reduced pressure to remove the solvent and a small amount of unreacted monomer. Vacuum-dried overnight at 25°C to obtain a bottle-like brush-like PDMS- b -P(mPEGA) copolymer C as a yellow product.

Example 4

(1) Preparation of PDMS reversible addition-fragmentation chain transfer agent B

Dissolve 1.82 g of S -1-dodecyl- S (α,α'-dimethyl-α''-acetic acid) trithiocarbonate (DDMAT), 0.76 g of oxalyl chloride in 15 mL of anhydrous dichloro In methane, magnetically stirred at room temperature for 4 h, and distilled under reduced pressure to obtain acid chloride DDMAT (A). Dissolve A in 10 mL of anhydrous dichloromethane, add it to a mixture of 9 g of single-ended hydroxyl polydimethylsiloxane (PDMS, 2000 g/mol) and 10 mL of anhydrous dichloromethane, and stir magnetically at room temperature for 24 h, the volatile components were distilled off under reduced pressure, then washed three times with 50 mL of methanol to remove unreacted DDMAT, and vacuum-dried at 40°C for 24 h to obtain a single-ended PDMS reversible addition-fragmentation chain transfer agent B.

(2) Reversible addition-fragmentation chain transfer preparation of bottlebrush-like PDMS- b -P(mPEGA) copolymer C

Weigh 0.04 g of PDMS reversible addition-fragmentation chain transfer agent B prepared in step (1), 1.0 g of polyethylene glycol methyl ether acrylate (mPEGA, 1000 g/mol) and 0.43 mg of azobisisobutyronitrile, Dissolve in 1 g of toluene, bubble nitrogen for 30 min, raise the temperature to 65 ° C, and react for 4 h in a water bath. After the reaction is completed, the reaction product is precipitated and washed with ether three times. Vacuum-dried overnight at 25°C to obtain a bottle-like brush-like PDMS- b -P(mPEGA) copolymer C as a yellow product.

The present invention has been described as an example above, and it should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacements that can be made by those skilled in the art without creative labor all fall within the scope of this invention. protection scope of the invention. the

Claims (3)

1. a bottle brush shape polydimethylsiloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymer, it is characterized in that, the structure of this copolymer is as shown in formula 1 or formula 2, number The average molecular weight is 2 000~200 000 g/mol; the NMR spectrum of the copolymer, in which the characteristic peaks are: 0.1ppm peak a corresponds to the methyl proton peak linked to polysiloxane and Si, and 0.5ppm peak b corresponds to polysiloxane Siloxane and Si are connected to the methylene proton peak, the 3.4ppm peak corresponds to the terminal methyl peak on the polyethylene glycol side chain, and the 3.5-3.8ppm peak corresponds to the methylene peak on the polyethylene glycol side chain. The peak i of 4.2ppm corresponds to the methylene peak directly connected to the ester group on the polyethylene glycol side chain,

In the formula: m is an integer from 1 to 100; n is an integer from 5 to 400; p is an integer from 1 to 200; R is -H or -CH ₃ ; R' is -C(CH ₃ ) ₂ -, or -C(CN)(CH ₃ )-CH ₂ -CH ₂ -; Z is -SC ₁₂ H ₂₅ , or -SC ₄ H ₉ , or -O-CH ₂ -CH ₃ , or -C ₆ H ₅ . 2. a bottle brush shape polydimethylsiloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymer preparation method according to claim 1, is characterized in that comprising the following process: Preparation of polysiloxane reversible addition-fragmentation chain transfer agent B with number average molecular weight of 500~30000 g/mol: Add carboxyl-containing trithiocarbonate and (COCl) ₂ in a molar ratio of 1:(1~2) into anhydrous dichloromethane to prepare a solution containing trithiocarbonate with a concentration of 0.1~0.5mol/L , stirred at room temperature for 2-8 hours, and distilled off the solvent and unreacted (COCl) ₂ under reduced pressure to obtain acyl-chlorinated trithiocarbonate A; Hydroxyl-containing polysiloxane and acyl chloride trithiocarbonate A are added into anhydrous dichloromethane according to the molar ratio of hydroxyl and acid chloride groups at 1:(1~3) to form a polysiloxane-containing concentration of 0.1 ~0.5mol/L solution, stirred at room temperature for 24~72 hours, distilled under reduced pressure, then washed with methanol to remove unreacted acyl chloride trithiocarbonate A, and vacuum dried at room temperature for 12~48 hours to obtain single-ended or double-ended The number average molecular weight of trithiocarbonate A containing acid chloride at the end is 500~30000 g/mol polysiloxane reversible addition-fragmentation chain transfer agent B; Reversible addition-fragmentation chain transfer preparation of bottlebrush polydimethylsiloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymers: According to the carbon-carbon double bond of polyethylene glycol methyl ether (meth)acrylate and the trithioester group of the reversible addition-fragmentation chain transfer agent B prepared in step 1), and with the initiator azobisisobutyl The molar ratio of the azo group of nitrile is (1 ~ 100): 1: (0.1 ~ 0.3), and the three are added to dissolve in toluene, and it is formulated to contain polyethylene glycol methyl ether (meth) acrylate with a mass concentration of 10~80% reaction solution, react in water bath or oil bath at 50~80°C for 4~24 hours, the reaction product is distilled under reduced pressure or precipitated with ether, and the solvent and a small amount of unreacted monomer are removed to obtain bottle brush polydimethylformaldehyde siloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymer. 3. a bottle brush shape polydimethylsiloxane- b -poly(polyethylene glycol methyl ether acrylate) copolymer application obtained by the method claimed in claim 2 is used for marine antifouling coatings middle.

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