CN1775821A - Rapid efficient method for preparing acrylonitrile polymer - Google Patents
Rapid efficient method for preparing acrylonitrile polymer Download PDFInfo
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- CN1775821A CN1775821A CN 200510111530 CN200510111530A CN1775821A CN 1775821 A CN1775821 A CN 1775821A CN 200510111530 CN200510111530 CN 200510111530 CN 200510111530 A CN200510111530 A CN 200510111530A CN 1775821 A CN1775821 A CN 1775821A
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Abstract
The invention discloses a fast high efficiency preparation acrylonitrile polymer method. It includes the following steps that the first monomer acrylonitrile, the second monomer acrylic acid methyl ester, the third monomer itaconic acid, and initiator are added into ion liquid orderly. It is churned and done polyreaction for 0.5-4h at 50-80 centigrade degree. Then acrylonitrile copolymer is gained. The benefit effects of the invention are that the polyreaction rate is increased greatly; the conversion is increased greatly; the adopted ion liquid has no volatility; and this is of great advantage to reclaim the ion liquid; the liquid state range of the adopted ion liquid is wide; and this is of great advantage to control reaction temperature.
Description
Technical field
The present invention relates to a kind of preparation method of acrylonitrile polymer, particularly relate to a kind of at [Bmim] BF
4The method that rapidly and efficiently prepares acrylonitrile polymer in the ionic liquid.
Background technology
Vinyl cyanide can carry out mass polymerization, letex polymerization and solution polymerization, solution polymerization is adopted in actual production mostly, generally adopts sodium thiocyanate water solution, dense solder(ing)acid, nitric acid, ethylene carbonate, dimethyl sulfoxide (DMSO), dimethyl formamide or N,N-DIMETHYLACETAMIDE as polymer solvent.Vinyl cyanide again the solution polymerization in these solvents have that polymerization system viscosity is low, mixing and advantages such as heat transfer is easier to, easy temperature control system, but also there are some shortcomings, low as monomer concentration, rate of polymerization slowly causes throughput and plant factor low, and makes molecular weight reduction etc. by the chain transfer that solvent causes.Particularly separated from solvent reclaims the cost increased, and to HUMAN HEALTH, harm that environmental pollution brought, is unfavorable for that the PAN synthetic further develops.Therefore seek the very big concern that speed of reaction is fast, solubleness (increases monomer concentration and throughput) greatly, chain transfer constant is little, novel solvent that be easy to recycle has caused academia and industry member.A kind of solvent that ionic liquid is so just.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method that rapidly and efficiently prepares acrylonitrile polymer, when adopting solution polymerization to remedy vinyl cyanide that prior art exists, speed of reaction slowly reaches solvent for use and has intensive corrodibility and volatility, cause defectives such as serious environmental pollution, satisfy the needs of producing with some field development.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is that a kind of method that rapidly and efficiently prepares acrylonitrile polymer comprises the steps:
The first monomer vinyl cyanide, the second monomer methyl acrylate, the 3rd monomer methylene-succinic acid, initiator are added in the ionic liquid successively, stirring and dissolving, at 50-80 ℃, polyreaction 0.5～4 hour obtains acrylonitrile copolymer.
As optimized technical scheme: described [Bmim] BF
4Ionic liquid is by negatively charged ion and cation composition; Said negatively charged ion is BF
4 -Said positively charged ion is:
Used [Bmim] BF
4Ion liquid liquid scope is :-73 ℃～486 ℃;
Described initiator is a Diisopropyl azodicarboxylate, and consumption is 0.2～1.2% of a total monomer quality;
The mass concentration of total monomer in ionic liquid is 10～35%;
The 11.5～17%, the 3rd monomer mass that 80～88%, second monomer mass that first monomer mass accounts for total monomer quality accounts for total monomer quality accounts for 0.5～3% of total monomer quality;
The viscosity-average molecular weight of prepared acrylonitrile copolymer is 3 * 10
4～8 * 10
4, transformation efficiency reaches more than 70%.
The invention has the beneficial effects as follows:
(1) solvent that is adopted is [Bmim] BF
4Ionic liquid can be accelerated the speed of polyreaction greatly, and 1 hour transformation efficiency can reach more than 70%.
(2) the ionic liquid non-volatility that is adopted helps reaction and finishes ion liquid recovery in back and utilization again.
(3) the liquid wide ranges of the ionic liquid that is adopted in the temperature range of polyreaction, helps the control of temperature of reaction.
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
Embodiment 1
Get 8 gram [Bmim] BF
4Ionic liquid is poured the 0.016 gram initiator Diisopropyl azodicarboxylate that weighs up into, adds the methylene-succinic acid of 0.000308mol again, adds the vinyl cyanide of 0.0236mol and the methyl acrylate of 0.00256mol then successively, the stirring ionic liquid that does not stop when adding.After stirring, heat mixed ionic liquid to 65 ℃, kept this temperature 4 hours, make its abundant polymerization.Measure according to GB, the acrylonitrile copolymer viscosity-average molecular weight of acquisition is 6.46 * 10
4, transformation efficiency reaches 78%.
Embodiment 2
Get 8 gram [Bmim] BF4 ionic liquids, the 0.016 gram initiator Diisopropyl azodicarboxylate that weighs up is poured into, the methylene-succinic acid that adds 0.000154mol again adds the vinyl cyanide of 0.0236mol and the methyl acrylate of 0.00337mol then successively, the stirring ionic liquid that does not stop when adding.After stirring, heat mixed ionic liquid to 70 ℃, kept this temperature 1 hour, make its abundant polymerization.Measure according to GB, the acrylonitrile copolymer viscosity-average molecular weight of acquisition is 5.32 * 10
4, transformation efficiency reaches 80%.
Embodiment 3
Get 8 gram [Bmim] BF4 ionic liquids, the 0.016 gram initiator Diisopropyl azodicarboxylate that weighs up is poured into, the methylene-succinic acid that adds 0.000308mol again adds the vinyl cyanide of 0.0236mol and the methyl acrylate of 0.00256mol then successively, the stirring ionic liquid that does not stop when adding.After stirring, heat mixed ionic liquid to 80 ℃, kept this temperature 0.5 hour, make its abundant polymerization.Measure according to GB, the acrylonitrile copolymer viscosity-average molecular weight of acquisition is 5.32 * 10
4, transformation efficiency reaches 80%.
Claims (7)
1. a method that rapidly and efficiently prepares acrylonitrile polymer is characterized in that, comprises the steps:
The first monomer vinyl cyanide, the second monomer methyl acrylate, the 3rd monomer methylene-succinic acid, initiator are added in the ionic liquid successively, stirring and dissolving, at 50-80 ℃, polyreaction 0.5～4 hour obtains acrylonitrile copolymer.
2. preparation method according to claim 1 is characterized in that, described [Bmim] BF
4Ionic liquid is by negatively charged ion and cation composition; Said negatively charged ion is BF
4 -Said positively charged ion is:
3. preparation method according to claim 1 and 2 is characterized in that, used [Bmim] BF
4Ion liquid liquid scope is :-73 ℃～486 ℃.
4. preparation method according to claim 1 is characterized in that, described initiator is a Diisopropyl azodicarboxylate, and consumption is 0.2～1.2% of a total monomer quality.
5. preparation method according to claim 1 is characterized in that, the quality of total monomer in ionic liquid is 10～35%.
6. preparation method according to claim 1 is characterized in that, the 11.5～17%, the 3rd monomer mass that 80～88%, second monomer mass that first monomer mass accounts for total monomer quality accounts for total monomer quality accounts for 0.5～3% of total monomer quality.
7. according to claim 1,2,4,5,6 each described methods, it is characterized in that the viscosity-average molecular weight of prepared acrylonitrile copolymer is 3 * 10
4～8 * 10
4, transformation efficiency reaches more than 70%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510111530 CN1775821A (en) | 2005-12-15 | 2005-12-15 | Rapid efficient method for preparing acrylonitrile polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510111530 CN1775821A (en) | 2005-12-15 | 2005-12-15 | Rapid efficient method for preparing acrylonitrile polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1775821A true CN1775821A (en) | 2006-05-24 |
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|---|---|---|---|
| CN 200510111530 Pending CN1775821A (en) | 2005-12-15 | 2005-12-15 | Rapid efficient method for preparing acrylonitrile polymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864015A (en) * | 2010-06-25 | 2010-10-20 | 东华大学 | Method for preparing polyacrylonitrile/carbon nano tube composite material by taking ionic liquid as solvent |
| CN101402698B (en) * | 2008-11-10 | 2011-03-16 | 东华大学 | Process for producing high-molecular weight vinyl cyanide polymer in ionic liquid water solution |
-
2005
- 2005-12-15 CN CN 200510111530 patent/CN1775821A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402698B (en) * | 2008-11-10 | 2011-03-16 | 东华大学 | Process for producing high-molecular weight vinyl cyanide polymer in ionic liquid water solution |
| CN101864015A (en) * | 2010-06-25 | 2010-10-20 | 东华大学 | Method for preparing polyacrylonitrile/carbon nano tube composite material by taking ionic liquid as solvent |
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