CN101456932A - Method for preparing maleic anhydride-alkyl vinyl ether co-polymer - Google Patents
Method for preparing maleic anhydride-alkyl vinyl ether co-polymer Download PDFInfo
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- CN101456932A CN101456932A CNA2008101875202A CN200810187520A CN101456932A CN 101456932 A CN101456932 A CN 101456932A CN A2008101875202 A CNA2008101875202 A CN A2008101875202A CN 200810187520 A CN200810187520 A CN 200810187520A CN 101456932 A CN101456932 A CN 101456932A
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- maleic anhydride
- vinyl ether
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Abstract
The invention relates to a solution copolymerization method for preparing a maleic anhydride-alkyl vinyl ether alternate copolymer. The method is characterized in that the method comprises the following steps: carrying out the solution copolymerization reaction of the maleic anhydride and the alkyl vinyl ether in the mol ratio of 1:1 in the mixed solvent through the initiation of an initiator, setting the polymerization temperature between 81 and 90 DEG C and the reaction time between 5 and 7 hours, obtaining slurry copolymer solution, filtrating and drying the solution in vacuum, and finally obtaining the white polymer powder.
Description
Technical field
The invention belongs to organic chemical industry's production technical field, be specifically related to the solution copolymerization method of maleic anhydride, methylvinylether and IVE terpolymer.
Background technology
Maleic anhydride-alkyl vinyl ether co-polymer is linearity molecular structure, water-soluble electrolytic polymer, because it is nontoxic and have good chemical stability, binding property, cohesiveness, water-retentivity, film-forming properties (institute's film forming is easily peeled off) to human body, has obtained widespread use in many fields such as medicine, chemical industry.It can be used as the washing assistant of additive, tackiness agent, sanitas, hair style aerosol spray fixative, synthetic detergent of stablizer and dentures material etc.In addition, the esterified prod of this multipolymer is used in above-mentioned field equally widely.
The research of maleic anhydride-alkyl vinyl ether co-polymer starts from the fifties in last century, develops into and mainly contains two kinds of operational paths now: solution polymerization and mass polymerization.Solution polymerization is that monomer and initiator are dissolved in the polyreaction of carrying out in the appropriate solvent, owing to used solvent, the viscosity of polymerization system is lower, mixing of materials and conducting heat all than being easier to, and gel effect is not remarkable, and temperature of reaction is controlled easily.Substance law technology is simple, production process cleans, the production efficiency height, but polymerization control difficulty is big, is not used for industrial production at present yet.What initial solution polymerization used is the bigger benzene kind solvent of toxicity, and for the consideration of environmental protection and safety, adopting low poison solvent to replace benzene kind solvent is the direction of Future Development.
By retrieval, use normal hexane and methylethylketone mixed solvent, peroxy dicarbonate two (2-ethyl-hexyl) ester is an initiator, by methylvinylether, IVE and maleic anhydride solution copolymerization, the method of synthetic macromolecule amount, Powdered maleic anhydride-alkyl vinyl ether co-polymer is not appeared in the newspapers up to now.
Summary of the invention
The objective of the invention is to solve the big problem of solvent toxicity in traditional solution polymerization process, in methylvinylether, add a certain amount of IVE simultaneously, polymkeric substance is carried out modification, its processing characteristics is improved.
The solution copolymerization method of a kind of maleic anhydride provided by the invention, methylvinylether and IVE terpolymer; under the nitrogen protection condition; be dissolved in maleic anhydride and the methylvinylether and the IVE mixture reaction that are dissolved with initiator in the solvent; at 81 ℃～90 ℃; reacted 5～7 hours; obtain the pulpous state copolymer solution, filtration, vacuum-drying finally obtain the white polymer powder.
The mol ratio 0.03:1 of IVE and methylvinylether～0.1:1 wherein;
Described initiator is organo-peroxide or azo-compound, is preferably peroxy dicarbonate two (2-ethyl-hexyl) ester, and initiator concentration is 0.04%～0.16% of a reaction monomers in the reaction system;
Described solvent is the mixture of alkane and ketone, wherein, alkane is selected from hexanaphthene, normal hexane, octane, octane-iso, ketone is selected from acetone, methylethylketone, pimelinketone, should satisfy that chain transfer constant is little, toxicity is little or nontoxic, requirement such as boiling point suitable, environmental pollution is little, cost is low according to solvent, be preferably normal hexane and methylethylketone, proportioning is 3:1～5:1 (weight); Massfraction should be to guarantee that conducting heat, avoid taking place caking is advisable in system for described solvent.When the massfraction of solvent in polymerization system was 70% left and right sides, response behaviour was good.Solvent load is less than 55% in polymerization system, and system viscosity is higher, and caking phenomenon easily takes place for the mixing of material and heat-transfer effect variation; Solvent load is higher than at 85% o'clock in the polymerization system, and reaction condition and quality product there is no obvious improvement.On the contrary, because monomer concentration is low excessively, can cause the reduction of speed of reaction, solvent load increases, and running cost also increases, so the present invention is controlled at 60%～80% with solvent load in the polymerization system.
The present invention adopts water-bath or oil bath heating, under described initiator and consumption condition thereof, and preferred 81 ℃～90 ℃ of polymeric reaction temperature, preferred 5～7 hours of reaction times.
Embodiment
Embodiment 1
The 98.0g maleic anhydride is dissolved in the 200g mixed solvent, and (normal hexane and methylethylketone ratio are 4:1; down together); add in the autoclave of 1000mL band stirring rake; under nitrogen protection; start stirring; be warmed up to 81 ℃; in 1 hour with the 34g mixed solvent; 55.1g methylvinylether; 2.85g IVE; 0.04g the mixture that peroxy dicarbonate two (2-ethyl-hexyl) ester is formed is added drop-wise to reactor; kept 81 ℃ of polyreactions 7 hours; obtain the pulpous state copolymer solution; filter; vacuum-drying finally obtains 150.3g white polymer powder, yield 96.4%.Analytical test the results are shown in Table 1.
Embodiment 2
The 98.0g maleic anhydride is dissolved in the 200g mixed solvent, and (normal hexane and methylethylketone ratio are 4:1; down together); add in the autoclave of 1000mL band stirring rake; under nitrogen protection; start stirring; be warmed up to 85 ℃; in 1 hour with the 160g mixed solvent; 55.1g methylvinylether; 5.0g IVE; 0.16g the mixture that peroxy dicarbonate two (2-ethyl-hexyl) ester is formed is added drop-wise to reactor; kept 85 ℃ of polyreactions 6 hours; obtain the pulpous state copolymer solution; filter; vacuum-drying finally obtains 150.3g white polymer powder, yield 95.1%.Analytical test the results are shown in Table 1.
Embodiment 3
The 98.0g maleic anhydride is dissolved in the 200g mixed solvent, and (normal hexane and methylethylketone ratio are 3:1; down together); add in the autoclave of 1000mL band stirring rake; under nitrogen protection; start stirring; be warmed up to 90 ℃; in 1 hour with the 160g mixed solvent; 55.1g methylvinylether; 5.0g IVE; 0.16g the mixture that peroxy dicarbonate two (2-ethyl-hexyl) ester is formed is added drop-wise to reactor; kept 90 ℃ of polyreactions 5 hours; obtain the pulpous state copolymer solution; filter; vacuum-drying finally obtains 148.1g white polymer powder, yield 93.7%.Analytical test the results are shown in Table 1.
Embodiment 4
The 98.0g maleic anhydride is dissolved in the 200g mixed solvent, and (normal hexane and methylethylketone ratio are 5:1; down together); add in the autoclave of 1000mL band stirring rake; under nitrogen protection; start stirring; be warmed up to 85 ℃; in 1 hour with the 160g mixed solvent; 55.1g methylvinylether; 5.0g IVE; 0.16g the mixture that peroxy dicarbonate two (2-ethyl-hexyl) ester is formed is added drop-wise to reactor; kept 85 ℃ of polyreactions 7 hours; obtain the pulpous state copolymer solution; filter; vacuum-drying finally obtains 150.5g white polymer powder, yield 95.2%.Analytical test the results are shown in Table 1.
Embodiment 5
The 98.0g maleic anhydride is dissolved in the 200g mixed solvent, and (normal hexane and methylethylketone ratio are 4:1; down together); add in the autoclave of 1000mL band stirring rake; under nitrogen protection; start stirring; be warmed up to 85 ℃; in 1 hour with the 160g mixed solvent; 55.1g methylvinylether; 5.0g IVE; 0.16g the mixture that peroxy dicarbonate two (2-ethyl-hexyl) ester is formed is added drop-wise to reactor; kept 85 ℃ of polyreactions 7 hours; obtain the pulpous state copolymer solution, filter; vacuum-drying finally obtains 150.4g white polymer powder; yield, yield 95.1%.Analytical test the results are shown in Table 1.
Embodiment 6
The 98.0g maleic anhydride is dissolved in the 200g mixed solvent, and (normal hexane and methylethylketone ratio are 4:1; down together); add in the autoclave of 1000mL band stirring rake; under nitrogen protection; start stirring; be warmed up to 90 ℃; in 1 hour with the 451g mixed solvent; 55.1g methylvinylether; 9.5g IVE; 0.16g the mixture that peroxy dicarbonate two (2-ethyl-hexyl) ester is formed is added drop-wise to reactor; kept 90 ℃ of polyreactions 5 hours; obtain the pulpous state copolymer solution; filter; vacuum-drying finally obtains 150.3g white polymer powder, yield 92.4%.Analytical test the results are shown in Table 1.
Table 1 polymer analysis test result
| The test sequence number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Outward appearance | White powder | White powder | White powder | White powder |
| Apparent density, g/cm 3 | 0.31 | 0.31 | 0.31 | 0.31 |
| Number-average molecular weight | 187,000 | 200,000 | 208,000 | 185,000 |
| Tg，℃ | 151 | 152 | 152 | 151 |
| Yield, % | 96.4 | 95.1 | 93.7 | 95.2 |
Continuous table 1
| The test sequence number | Embodiment 5 | Embodiment 6 |
| Outward appearance | White powder | White powder |
| Apparent density, g/cm 3 | 0.31 | 0.31 |
| Number-average molecular weight | 218,000 | 220,000 |
| Tg，℃ | 153 | 153 |
| Yield, % | 95.1 | 92.4 |
Claims (7)
1, the solution copolymerization method of preparation maleic anhydride-alkyl vinyl ether alternating copolymer, it is characterized in that maleic anhydride and alkyl vinyl ether by the mol ratio of 1:1 in mixed solvent, initiator causes and carries out the solution copolymerization reaction, polymerization temperature is 81 ℃～90 ℃, reaction times is 5～7 hours, obtain the pulpous state copolymer solution, filtration, vacuum-drying finally obtain the white polymer powder.
2, method according to claim 1, alkyl vinyl ether are the mixture that methylvinylether and IVE are formed, and the mol ratio of IVE and methylvinylether is 0.03:1～0.1:1.
3, according to right 1 described method, it is characterized in that described solvent is the mixture of alkane and ketone, the weight ratio of the two is 3～5, wherein, alkane is selected from normal hexane, octane, octane-iso; Ketone is selected from acetone, methylethylketone, pimelinketone.
4,, it is characterized in that described solvent is normal hexane and methylethylketone mixed solvent according to right 3 described methods.
5, according to right 3 described methods, the weight ratio of solvent in polymerization system is 60%～80%.
6, according to right 1 described method,, it is characterized in that described initiator is organo-peroxide or azo-compound, initiator concentration is 0.04%～0.16% of a reaction monomers in the reaction system.
7, according to right 6 described methods,, it is characterized in that described initiator is peroxy dicarbonate two (2-ethyl-hexyl) ester.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101875202A CN101456932A (en) | 2008-12-25 | 2008-12-25 | Method for preparing maleic anhydride-alkyl vinyl ether co-polymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030856B (en) * | 2009-09-25 | 2012-05-30 | 博爱新开源制药股份有限公司 | Method for devolatilizing vinyl methyl ether/maleic anhydride copolymer |
| CN107805290A (en) * | 2017-12-05 | 2018-03-16 | 博爱新开源制药股份有限公司 | A kind of tert-Butyl vinyl ether/copolymer-maleic anhydride and preparation method thereof |
-
2008
- 2008-12-25 CN CNA2008101875202A patent/CN101456932A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030856B (en) * | 2009-09-25 | 2012-05-30 | 博爱新开源制药股份有限公司 | Method for devolatilizing vinyl methyl ether/maleic anhydride copolymer |
| CN107805290A (en) * | 2017-12-05 | 2018-03-16 | 博爱新开源制药股份有限公司 | A kind of tert-Butyl vinyl ether/copolymer-maleic anhydride and preparation method thereof |
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Open date: 20090617 |