CN102391520B - P(MAh-AA)-PEG4000 cross-linked polymer and preparation method thereof - Google Patents

Abstract

The invention relates to a polyacrylate cross-linked polymer and a preparation method thereof. The polyacrylate cross-linked polymer P(MAh-AA)-PEG4000 synthesized by two-step esterification reaction is technically characterized in that the formula comprises the following raw materials in mass by weight: 45.0-55.0g of copolymer (P(MAh-AA)), 2.0-4.5g of polyethylene glycol (PEG4000) and 250ml of methyl alcohol (CH3OH) (the methyl alcohol is reactant and a solvent); the process conditions are as follows: the temperature of the two-step esterification reaction is respectively 60 DEG C, the solvents are butanone and methyl alcohol, the initiators are dimethyl sulfate (DMS) respectively, and the reaction time is respectively 15-20 hours and 10-13 hours. The invention has the beneficial effects that a new polyacrylate cross-linked polymer is synthesized, so that not only is the variety of the polyacrylate polymer expanded, but also the foundation is laid for application of the polyacrylate polymer in wider fields. The invention has the advantages of cheap needed materials, more direct and simpler operation and process, wide applicability and certain actual popularization significance.

Description

A kind of P (MAh-AA)-PEG4000 cross-linked polymer and preparation method thereof

Technical field

The present invention relates to 3 D cross-linked polymkeric substance of a kind of polyacrylate(s) and preparation method thereof.

Background technology

Polyacrylate polymers has obtained widespread use as a kind of macromolecular material cheap and easy to get in fields such as the energy, automobile, electrical equipment, machinery, environment, buildings.But the application of different field has proposed different performance requirements to polyacrylate polymers.In order to address this problem, one of method of taking is at present carried out modification to polyacrylate polymers exactly, as adding filler, blend etc.This method really in scope widely all obtained the achievement that attracts people's attention, for very big contribution has been made in the application of polyacrylate polymers, yet this method but exists a very important shortcoming, reunites, is separated like filler etc.Therefore, to polyacrylate polymers form, structure Design, prepare this method of polymkeric substance that satisfies performance requriements from the chemosynthesis angle and just can overcome this shortcoming.At present, based on the thought of molecular designing, to polyacrylate polymers form, structure design, synthetic to obtain new polymkeric substance be the comparatively practicable method of this base polymer of development, also is research focus in recent years.

With maleic anhydride, vinylformic acid is monomer, and a kind of HPMA-PEMULEN TR2 P (MAh-AA) is synthesized in copolymerization, and the synthesis technique of this multipolymer field very ripe, practical application is also very extensive.Clearly; Let vinylformic acid and polyethylene glycol long chain generation esterification in this copolymer chain just can prepare the 3 D cross-linked polymkeric substance of a kind of polyacrylate(s); This 3 D cross-linked structure will inevitably be improved the performance of polyacrylate polymers, like good mechanical performance, thermal property and solvent retentivity etc.At present, do not see any relevant research report as yet.

Summary of the invention

The technical problem that solves

In order to enlarge the Application Areas of polyacrylate polymers, simultaneously also in order to expand this base polymer of polyacrylic ester, the present invention proposes a kind of preparation method of polymkeric substance, the synthetic 3 D cross-linked polymkeric substance of a kind of polyacrylate(s) that obtained.

Technical scheme

The present invention gathers (maleic acid anhydride-propenoic acid) P (MAh-AA) with a kind of multipolymer and with polyoxyethylene glycol (PEG4000), methyl alcohol two step esterifications, synthetic polyacrylate(s) cross-linked polymer P (MAh-AA)-PEG4000 takes place.Its purpose is to obtain the 3 D cross-linked polymer P of a kind of new polyacrylate(s) (MAh-AA)-PEG4000.

A kind of method for preparing polyacrylate(s) cross-linked polymer P (MAh-AA)-PEG4000 of the present invention, its technical characterictic is:

Synthesizing formula

P(MAh-AA) 45.0～55.0?g

PEG4000 (the first step esterification) 2.0～4.5 g

CH ₃OH (the second step esterification) 250 ml

(promptly make reactant and make solvent again)

Processing condition

Initiator DMS (the first step esterification) 2.0 g

DMS (the second step esterification) 0.5 g

Solvent butanone (the first step esterification) 200 ml

CH ₃OH (the second step esterification) 250ml

60 ℃ of temperature (the first step esterification)

60 ℃ (second step esterification)

The environment nitrogen protection

Reaction times 15～20 h (the first step esterification)

10～13 h (the first step esterification)

A kind of method for preparing polyacrylate(s) cross-linked polymer P (MAh-AA)-PEG4000, it is characterized in that: concrete steps are following:

A) take by weighing the P (MMA-MAh) of 45.0 ~ 55.0g and the PEG4000 of 2.0～4.5g, add the butanone dissolving of 200ml, add 2.0g methyl-sulfate (DMS) then, mix being placed in three mouthfuls of reaction flasks;

B) under the nitrogen protection, at 60 ℃ of following constant temperature stirring reaction 15 ~ 20 h;

C) adopt the method for underpressure distillation that the solvent butanone is all distilled, add 250ml methyl alcohol and 0.5g methyl-sulfate (DMS), under the nitrogen protection, 60 ℃ of constant temperature stir 10 ~ 13h;

D) sloughing methyl alcohol and promptly get crude product, is that solvent, pure water are the precipitation agent reprecipitation then with the butanone, dissolves repeatedly, precipitates 4 times, can obtain the white rubber shaped polymer;

E) at last products therefrom is washed 4 times with sherwood oil respectively repeatedly, vacuum-drying 3 days obtains purified polymer.

Beneficial effect

The invention has the beneficial effects as follows; The synthesis technique that a kind of method is feasible, be easy to realize is provided; Synthesize and obtained a kind of new polyacrylate(s) cross-linked polymer P (MAh-AA)-PEG4000; This has not only expanded this base polymer of polyacrylic ester, and lays the first stone in the application in the wide spectrum more for this base polymer.

Description of drawings

Fig. 1 is the synthesis process flow diagram of polymkeric substance.

Embodiment

Obtain polymer P (MAh-AA)-PEG4000 for synthetic, the present invention has taked following embodiment:

Take by weighing 45.0 ~ 55.0g P (MMA-MAh) and 2.0～4.5g PEG4000, add the dissolving of 200ml butanone, add 2.0g methyl-sulfate (DMS) then, mix being placed in three mouthfuls of reaction flasks; Under the nitrogen protection, at 60 ℃ of following constant temperature stirring reaction 15 ~ 20 h; After reaction finishes, adopt the method for underpressure distillation that the solvent butanone is all distilled, add 250ml methyl alcohol and 0.5g methyl-sulfate (DMS), under the nitrogen protection, 60 ℃ of constant temperature stir 10 ~ 13h; Reaction is sloughed methyl alcohol and is promptly got crude product after finishing, and is that solvent, pure water are the precipitation agent reprecipitation then with the butanone, dissolves repeatedly, precipitates 4 times, can obtain the white rubber shaped polymer; At last products therefrom is washed 4 times with sherwood oil respectively repeatedly, vacuum-drying 3 days obtains purified polymer.

Claims (2)

1. a polyacrylate(s) cross-linked polymer is characterized in that: composition of raw materials: multipolymer HPMA-vinylformic acid P (MAh-AA) 45.0～55.0g, polyoxyethylene glycol PEG4000 2.0～4.5g, methyl alcohol CH ₃OH 250ml, wherein, CH ₃OH is not only as reactant but also as solvent; Processing condition: comprised two step esterifications: the first step is P (MAh-AA) and esterification takes place PEG4000, and temperature of reaction is that 60 ℃, solvent are that butanone, initiator are that methyl-sulfate DMS, reaction times are 15～20 h; Second step continued and CH for hydroxy-acid group in the intact vinylformic acid of unreacted in the product of the first step ₃Esterification takes place in OH, and temperature of reaction is that 60 ℃, solvent are that methyl alcohol, initiator are that methyl-sulfate DMS, reaction times are 10～13h.

2. method for preparing the polyacrylate(s) cross-linked polymer of claim 1, it is characterized in that: concrete steps are following:

A) take by weighing the P (MAh-AA) of 45.0～55.0g and the PEG4000 of 2.0～4.5g, add the butanone dissolving of 200ml, add 2.0g methyl-sulfate DMS then, mix being placed in three mouthfuls of reaction flasks;

B) under the nitrogen protection, at 60 ℃ of following constant temperature stirring reaction 15～20 h;

C) adopt the method for underpressure distillation that the solvent butanone is all distilled, add 250ml methyl alcohol and 0.5g methyl-sulfate DMS, under the nitrogen protection, 60 ℃ of constant temperature stir 10～13h;

D) sloughing methyl alcohol and promptly get crude product, is that solvent, pure water are the precipitation agent reprecipitation then with the butanone, dissolves repeatedly, precipitates 4 times, can obtain the white rubber shaped polymer;

E) at last products therefrom is washed 4 times with sherwood oil respectively repeatedly, vacuum-drying 3 days obtains purified polymer.

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