CN102391520A - P(MAh-AA)-PEG4000 cross-linked polymer and preparation method thereof - Google Patents

P(MAh-AA)-PEG4000 cross-linked polymer and preparation method thereof Download PDF

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Publication number
CN102391520A
CN102391520A CN2011102788985A CN201110278898A CN102391520A CN 102391520 A CN102391520 A CN 102391520A CN 2011102788985 A CN2011102788985 A CN 2011102788985A CN 201110278898 A CN201110278898 A CN 201110278898A CN 102391520 A CN102391520 A CN 102391520A
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polyacrylate
cross
mah
peg4000
linked polymer
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CN102391520B (en
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黄韵
王煦
刘丽
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Southwest Petroleum University
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Southwest Petroleum University
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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 (5)

1. polyacrylate(s) cross-linked polymer, it is characterized in that: the synthetic composition of raw materials is that multipolymer gathers (maleic acid anhydride-propenoic 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.
2. the 3 D cross-linked polymkeric substance of a kind of polyacrylate(s) according to claim 1; It is characterized in that: synthesis step has comprised two step esterifications; The first step is that P (MAh-AA) with PEG4000 esterification takes place, and 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.
3. a kind of polyacrylate(s) cross-linked polymer according to claim 1 is characterized in that: the temperature of two step esterifications is 60 ℃; The solvent of two step esterifications is respectively butanone and methyl alcohol; The initiator of two step esterifications is methyl-sulfate (DMS); The time of two step esterifications is respectively 15 ~ 20 h and 10 ~ 13h.
4. a kind of polyacrylate(s) cross-linked polymer according to claim 1 is characterized in that: be solvent with the butanone, pure water is a precipitation agent, dissolves repeatedly, precipitates 4 times.
5. method for preparing the polyacrylate(s) cross-linked polymer of claim 1～4, 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.
CN201110278898A 2011-09-20 2011-09-20 P(MAh-AA)-PEG4000 cross-linked polymer and preparation method thereof Expired - Fee Related CN102391520B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016110271A1 (en) * 2015-01-09 2016-07-14 Nano And Advanced Materials Institute Limited Built-in antimicrobial plastic resins and methods for making the same
CN110564469A (en) * 2019-10-08 2019-12-13 万华化学（宁波）有限公司 polar high-molecular additive for coal water slurry, and preparation method and application thereof

Citations (2)

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US20090238854A1 (en) * 2004-08-05 2009-09-24 Advanced Cardiovascular Systems, Inc. Plasticizers for coating compositions
CN102093568A (en) * 2010-11-09 2011-06-15 西南石油大学 Polyacrylate spatially-crosslinked polymer and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090238854A1 (en) * 2004-08-05 2009-09-24 Advanced Cardiovascular Systems, Inc. Plasticizers for coating compositions
CN102093568A (en) * 2010-11-09 2011-06-15 西南石油大学 Polyacrylate spatially-crosslinked polymer and preparation method thereof

Non-Patent Citations (1)

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Title
胡伟兆等: "大分子分散改性剂PEG400-PMAH-PAA的合成及应用", 《合成化学》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016110271A1 (en) * 2015-01-09 2016-07-14 Nano And Advanced Materials Institute Limited Built-in antimicrobial plastic resins and methods for making the same
CN106715568A (en) * 2015-01-09 2017-05-24 纳米及先进材料研发院有限公司 Built-in antimicrobial plastic resins and methods for making the same
US10525614B2 (en) 2015-01-09 2020-01-07 Nano And Advanced Materials Institute Limited Built-in antimicrobial plastic resins and methods for making the same
CN110564469A (en) * 2019-10-08 2019-12-13 万华化学（宁波）有限公司 polar high-molecular additive for coal water slurry, and preparation method and application thereof

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