CN101402698B - Process for producing high-molecular weight vinyl cyanide polymer in ionic liquid water solution - Google Patents
Process for producing high-molecular weight vinyl cyanide polymer in ionic liquid water solution Download PDFInfo
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- CN101402698B CN101402698B CN2008102025101A CN200810202510A CN101402698B CN 101402698 B CN101402698 B CN 101402698B CN 2008102025101 A CN2008102025101 A CN 2008102025101A CN 200810202510 A CN200810202510 A CN 200810202510A CN 101402698 B CN101402698 B CN 101402698B
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Abstract
The invention discloses a method which takes ionic liquid aqueous solution as a solvent to prepare a high molecular acrylonitrile polymer. The method comprises the following steps: a monomer and an evocating agent are added into the ionic liquid aqueous solution in sequence, stirred and dissolved to carry out polymerization at the temperature of 50 DEG C to 70 DEG C, thus obtaining the acrylonitrile polymer. The method has the advantages of fast reaction speed, high fractional conversion, high molecular weight and small molecular weight distribution of the polymerisate, and the ionic liquid aqueous solution adopted as the solvent is nontoxic without volatility and conducive to environmental protection, and recovery and reuse of the solvent after the reaction.
Description
Technical field
The present invention relates to a kind of preparation method of high-molecular weight vinyl cyanide polymer, particularly the preparation method in ionic liquid aqueous solution belongs to technical field of polymer materials.
Background technology
Polymerization of acrylonitrile adopts solution polymerization and aqueous phase precipitation polymeric method usually, wherein the solvent that is adopted in the solution polymerization process mainly contains N, N-dimethyl formamide, sulphur hydracid sodium water solution, dimethyl sulfoxide (DMSO) etc., the easy volatile of these solvents or severe corrosive, environment is caused very big pressure, limited the development of vinyl cyanide homogeneous solution polymerization to a certain extent.
In recent years, ionic liquid was as a kind of green solvent, because that its vapour pressure approaches is zero, non-volatile, dissolving power is strong, the character of a series of uniquenesses such as recyclable, enlarged day by day in the applied research of polymerization field.Since two thousand four, ionic liquid begins to be applied to the homopolymerization and the copolyreaction of vinyl cyanide.Publication number is that the Chinese patent of CN1560097 discloses the polymerisation process of a kind of vinyl cyanide in ionic liquid, but the related ionic liquid of this method is mainly the hydrophobic nature ionic liquid, and the viscosity-average molecular weight of resulting polymers is all less than 1.0 * 10
5, and high molecular weight polymers for preparation high-performance acrylic fiber be vital (Masson JC.Acrylic fiber technology and application.New York:Macrel Pekker Inc, 1995,37-67).Publication number be the Chinese patent of CN101139412 to disclose a kind of be the method that solvent prepares the distribution of low molecular weight acrylonitrile homopolymer with the ionic liquid, publication number is that CN1752302 and publication number are that to disclose a kind of be the preparation method of the polyacrylonitrile fibre of solvent with the ionic liquid for the Chinese patent of CN101067214.
All having made full use of ionic liquid in the above-mentioned patent is acrylonitrile polymerization or dissolved good solvent, and the ionic liquid characteristics that are easy to recycle, utilizes pure ionic liquid to carry out polyreaction or dissolving for solvent.Yet many ionic liquids all are hydrophilic, in the process of polymer manufacture and shaping, can run into mixing of ionic liquid and water inevitably, for realizing ion liquid recycling, ionic liquid must be separated with water.It is to utilize the not volatile characteristics of ionic liquid and carry out underpressure distillation and remove volatile moisture that wherein the most frequently used ionic liquid and water carry out isolating method; In addition, Scurto etc. (Scurto AM, et al.Carbon dioxideinduced separation of ionic liquids and water.Chem.Commun.2003,572.) have also reported and have used supercritical CO
2Ionic liquid in the flow process recycle-water, but this method and technology requires relatively harshness, is difficult to industrialization.Therefore, no matter be with vacuum distillation method or supercritical CO
2Flow process will realize the method that is separated in of ionic liquid and water fully and technical certain difficulty be arranged, and cost is higher.
Summary of the invention
The purpose of this invention is to provide a kind of is the method that solvent prepares high-molecular weight vinyl cyanide polymer with the ionic liquid aqueous solution, overcomes in ionic liquid the not high and ionic liquid of polyacrylonitrile molecular weight and separates technology and the cost problem of being brought fully with water.
In order to achieve the above object, technical scheme of the present invention provides the preparation method of a kind of high-molecular weight vinyl cyanide polymer in ionic liquid aqueous solution, it is characterized in that, comprises carrying out polymerization procedure in monomer, the initiator adding ionic liquid aqueous solution; Polymeric reaction temperature is 50～70 ℃, and polymerization reaction time is 2～8 hours;
Described monomer is one or more in first monomer, second monomer and the 3rd monomer;
Described first monomer is a vinyl cyanide;
Described second monomer is a kind of in methyl acrylate, methyl methacrylate, methacrylonitrile, vinyl acetate and the acrylamide;
What described the 3rd monomer was methylene-succinic acid, sodium allylsulfonate, methylpropene sodium sulfonate, methacrylic benzene sulfonic acid sodium salt, vinyl pyridine, 2-methyl-5-vinylpyridine and dimethylaminoethyl acrylate methyl in the amino ethyl ester is a kind of;
Described ionic liquid aqueous solution is that 0.1～10% water and mass percent are that 90～99.9% water soluble ion liquid is formed by mass percent;
Wherein, the mass concentration of total monomer in ionic liquid aqueous solution is 5～30%.
Further, described water soluble ion liquid is made up of positively charged ion and negatively charged ion, and wherein, positively charged ion is preferably:
The alkyl imidazol ion
Wherein, R
1, R
2Can be identical, also can be different, they are respectively that H or carbonatoms are the alkyl of 1-8;
Negatively charged ion is preferably Cl
-, Br
-, CF
3COO
-, I
-And NO
3 -In a kind of.
The mass percent of water is preferably 0.5～5% in the described ionic liquid aqueous solution.
The mass percent that first monomer accounts for total monomer is preferably 80～100%, and the mass percent that second monomer accounts for total monomer is preferably 0～17%, and the mass percent that the 3rd monomer accounts for total monomer is preferably 0～3%.
Described initiator is preferably azo class or organo-peroxide class, and consumption is preferably 0.5～1.5% of total monomer quality.
Described azo-initiator is preferably Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
Described organic peroxide initiator is preferably dibenzoyl peroxide, dilauroyl peroxide, peroxidation decoyl or di-isopropyl peroxydicarbonate.
The prepared acrylonitrile homopolymer or the viscosity-average molecular weight of multipolymer are preferably 1.0 * 10
5-2.0 * 10
5, the molecular weight polydispersity index is preferably 1.5-2.0.
The invention has the advantages that:
(1) to adopt ionic liquid aqueous solution be solvent in the present invention, and system viscosity reduces, and the speed of polyreaction is fast, and the transformation efficiency after 2 hours can reach more than 60%.
(2) viscosity-average molecular weight of gained acrylonitrile polymer is big, and molecular weight distribution is little.
(3) adopting ionic liquid aqueous solution is solvent, reduces ion liquid recycling cost.
(4) ionic liquid aqueous solution that adopts is nontoxic, is easy to recycle, and helps environment protection.
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.Be not used in but these embodiment only are used to the present invention is described and limit the scope of the invention.
Embodiment 1
Solvent is 1-butyl-3-Methylimidazole trifluoroacetic acid salt brine solution, is that 99.5% 1-butyl-3-Methylimidazole trifluoroacetate and 0.5% water are formed by mass percent; Monomer is a vinyl cyanide: the mass concentration in ionic liquid aqueous solution is 20%; Initiator is a Diisopropyl azodicarboxylate: the mass percent that accounts for vinyl cyanide is 0.8%.Above-mentioned material is added in the reactor, stir and make it the thorough mixing dissolving, be warming up to 70 ℃, reacted 2 hours, the polyacrylonitrile viscosity-average molecular weight of preparation is 1.35 * 10
5, the molecular weight polydispersity index is 1.53, transformation efficiency is 73.06%.
Embodiment 2
Solvent is 1-alkene ethyl-3-Methylimidazole bromide solution, is that 95% 1-alkene ethyl-3-Methylimidazole bromide and 5% water are formed by mass percent; Monomer is a vinyl cyanide: the mass concentration at ionic liquid aqueous solution is 30%; Initiator is a dibenzoyl peroxide: the mass percent that accounts for acrylonitrile monemer is 1.0%.Above-mentioned material is added in the reactor, stir and make it the thorough mixing dissolving, be warming up to 60 ℃, reacted 3 hours, the polyacrylonitrile viscosity-average molecular weight of preparation is 1.62 * 10
5, the molecular weight polydispersity index is 1.61, transformation efficiency is 80.06%.
Embodiment 3
Solvent is 1-butyl-3-Methylimidazole aqueous chloride solution, is that 99.5% 1-butyl-3-Methylimidazole muriate and 0.5% water are formed by mass percent; Monomer (comprising the first monomer vinyl cyanide and the second monomer methyl acrylate) is 10% in the mass concentration of ionic liquid aqueous solution, and wherein, acrylonitrile content is 98% of a total monomer quality percentage ratio, and methyl acrylate content is 2% of a total monomer quality percentage ratio; Initiator is a 2,2'-Azobis(2,4-dimethylvaleronitrile): account for 1.0% of total monomer quality percentage ratio.Above-mentioned material is added in the reactor, stir and make it the thorough mixing dissolving, be warming up to 65 ℃, reacted 6 hours, the polyacrylonitrile viscosity-average molecular weight of preparation is 1.98 * 10
5, the molecular weight polydispersity index is 1.84, transformation efficiency is 93.06%.
Embodiment 4
Solvent is 1-ethyl-3-Methylimidazole bromide solution, is that 99.9% 1-ethyl-3-Methylimidazole bromide and 0.1% water are formed by mass percent; Monomer (comprising the first monomer vinyl cyanide, second monomers methyl methacrylate and the 3rd monomer methylene-succinic acid) is 15% in the mass concentration of ionic liquid aqueous solution, wherein, acrylonitrile content is 85% of a total monomer quality percentage ratio, methyl methacrylate content is 12% of total monomer quality percentage ratio, and methylene-succinic acid content is 3% of total monomer quality percentage ratio; Initiator is a Diisopropyl azodicarboxylate: account for 0.5% of total monomer quality percentage ratio.Above-mentioned material is added in the reactor, stir and make it the thorough mixing dissolving, be warming up to 55 ℃, reacted 2 hours, the polyacrylonitrile viscosity-average molecular weight of preparation is 1.47 * 10
5, the molecular weight polydispersity index is 1.59, transformation efficiency is 63.06%.
Embodiment 5
Solvent is 1-allyl group-3-Methylimidazole iodide aqueous solution, is that 97% 1-allyl group-3-Methylimidazole iodide and 3% water are formed by mass percent; Monomer (comprising the first monomer vinyl cyanide, the second monomer acrylamide and the 3rd monomer sodium allylsulfonate) is 5% in the mass concentration of ionic liquid aqueous solution, wherein, acrylonitrile content is 90% of a total monomer quality percentage ratio, acrylamide content is 8% of a total monomer quality percentage ratio, and the propene sulfonic acid sodium content is 2% of a total monomer quality percentage ratio; Initiator is a dilauroyl peroxide: account for 1.2% of total monomer quality percentage ratio.Above-mentioned material is added in the reactor, stir and make it the thorough mixing dissolving, be warming up to 50 ℃, reacted 4 hours, the polyacrylonitrile viscosity-average molecular weight of preparation is 1.59 * 10
5, the molecular weight polydispersity index is 1.60, transformation efficiency is 80.34%.
Embodiment 6
Solvent is 1-butyl-3-Methylimidazole nitrate aqueous solution, is that 90% 1-butyl-3-Methylimidazole nitrate and 10% water are formed by mass percent; Monomer (comprising the first monomer vinyl cyanide, the second monomer methacrylonitrile and the 3rd monomer methacrylic benzene sulfonic acid sodium salt) is 10% in the mass concentration of ionic liquid aqueous solution, wherein, acrylonitrile content is 91% of a total monomer quality percentage ratio, methacrylonitrile content is 8% of total monomer quality percentage ratio, and methacrylic benzene sulfonic acid sodium salt content is total monomer quality percentage ratio 1%; Initiator is a di-isopropyl peroxydicarbonate: account for 1.5% of total monomer quality percentage ratio.Above-mentioned material is added in the reactor, stir and make it the thorough mixing dissolving, be warming up to 65 ℃, reacted 8 hours, the polyacrylonitrile viscosity-average molecular weight of preparation is 2.0 * 10
5, the molecular weight polydispersity index is 1.5, transformation efficiency is 94.56%.
Embodiment 7
Solvent is 1,2-dimethyl-3-ethyl imidazol(e) aqueous chloride solution, by mass percent be 99% 1,2-dimethyl-3-ethyl imidazol(e) muriate and 1% water are formed; Monomer (comprising the first monomer vinyl cyanide, the second monomer vinyl acetate and the 3rd monomer ethylene yl pyridines) is 25% in the mass concentration of ionic liquid aqueous solution, wherein, acrylonitrile content is 80% of a total monomer quality percentage ratio, vinyl acetate content is 17% of a total monomer quality percentage ratio, and vinyl pyridine content is 3% of total monomer quality percentage ratio; Initiator is the peroxidation decoyl: account for 1.0% of total monomer quality percentage ratio.Above-mentioned material is added in the reactor, stir and make it the thorough mixing dissolving, be warming up to 65 ℃, reacted 3 hours, the polyacrylonitrile viscosity-average molecular weight of preparation is 1.0 * 10
5, the molecular weight polydispersity index is 2.0, transformation efficiency is 70.56%.
Embodiment 8
Solvent is 1,2-dimethyl-3-ethyl imidazol(e) aqueous chloride solution, by mass percent be 99% 1,2-dimethyl-3-ethyl imidazol(e) muriate and 1% water are formed; Monomer (comprising the first monomer vinyl cyanide, the second monomer vinyl acetate and the 3rd monomer 2-methyl-5-vinylpyridine) is 25% in the mass concentration of ionic liquid aqueous solution, wherein, acrylonitrile content is 80% of a total monomer quality percentage ratio, vinyl acetate content is 17% of a total monomer quality percentage ratio, and 2-methyl-5-vinylpyridine content is 3% of total monomer quality percentage ratio; Initiator is the peroxidation decoyl: account for 1.0% of total monomer quality percentage ratio.Above-mentioned material is added in the reactor, stir and make it the thorough mixing dissolving, be warming up to 65 ℃, reacted 3 hours, the polyacrylonitrile viscosity-average molecular weight of preparation is 1.4 * 10
5, the molecular weight polydispersity index is 1.78, transformation efficiency is 77.83%.
Embodiment 9
Solvent is 1,2-dimethyl-3-ethyl imidazol(e) aqueous chloride solution, by mass percent be 99% 1,2-dimethyl-3-ethyl imidazol(e) muriate and 1% water are formed; Monomer (comprising that the first monomer vinyl cyanide, the second monomer vinyl acetate and the 3rd monomer dimethylaminoethyl acrylate methyl are for amino ethyl ester) is 25% in the mass concentration of ionic liquid aqueous solution, wherein, acrylonitrile content is 80% of a total monomer quality percentage ratio, vinyl acetate content is 17% of a total monomer quality percentage ratio, and dimethylaminoethyl acrylate methyl is 3% of a total monomer quality percentage ratio for amino ethyl ester content; Initiator is the peroxidation decoyl: account for 1.0% of total monomer quality percentage ratio.Above-mentioned material is added in the reactor, stir and make it the thorough mixing dissolving, be warming up to 65 ℃, reacted 3 hours, the polyacrylonitrile viscosity-average molecular weight of preparation is 1.31 * 10
5, the molecular weight polydispersity index is 1.82, transformation efficiency is 68.59%.
Claims (7)
1. the preparation method of high-molecular weight vinyl cyanide polymer in ionic liquid aqueous solution is characterized in that, comprises monomer, initiator are added the step of carrying out polyreaction in the ionic liquid aqueous solution; Polymeric reaction temperature is 50～70 ℃, and polymerization reaction time is 2～8 hours;
Described monomer is more than one in first monomer, second monomer and the 3rd monomer;
Described first monomer is a vinyl cyanide;
Described second monomer is a kind of in methyl acrylate, methyl methacrylate, methacrylonitrile, vinyl acetate and the acrylamide;
What described the 3rd monomer was methylene-succinic acid, sodium allylsulfonate, methylpropene sodium sulfonate, methacrylic benzene sulfonic acid sodium salt, vinyl pyridine, 2-methyl-5-vinylpyridine and dimethylaminoethyl acrylate methyl in the amino ethyl ester is a kind of;
Described ionic liquid aqueous solution is that 0.1～10% water and mass percent are that 90～99.9% water soluble ion liquid is formed by mass percent;
Wherein, the mass concentration of total monomer in ionic liquid aqueous solution is 5～30%, the mass percent that first monomer accounts for total monomer is that mass percent that 80～100%, second monomer accounts for total monomer is that the mass percent that the 0～17%, the 3rd monomer accounts for total monomer is 0～3%.
2. method according to claim 1 is characterized in that, described water soluble ion liquid is made up of positively charged ion and negatively charged ion, and wherein, positively charged ion is:
The alkyl imidazol ion
Wherein, R
1, R
2Can be identical, also can be different, they are respectively that H or carbonatoms are the alkyl of 1-8;
Negatively charged ion is Cl
-, Br
-, CF
3COO
-, I
-And NO
3 -In a kind of.
3. method according to claim 1 is characterized in that, the mass percent of water is 0.5～5% in the described ionic liquid aqueous solution.
4. method according to claim 1 is characterized in that, described initiator is azo class or organo-peroxide class, and consumption is 0.5～1.5% of a total monomer quality.
5. method according to claim 4 is characterized in that, described azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
6. method according to claim 4 is characterized in that, described organic peroxide initiator is dibenzoyl peroxide, dilauroyl peroxide, peroxidation decoyl or di-isopropyl peroxydicarbonate.
7. according to each described method in the claim 1～6, it is characterized in that the prepared acrylonitrile homopolymer or the viscosity-average molecular weight of multipolymer are 1.0 * 10
5-2.0 * 10
5, the molecular weight polydispersity index is 1.5-2.0.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560097A (en) * | 2004-02-17 | 2005-01-05 | 东华大学 | Preparation process of acrylonitrile polymer in ion liquid |
| CN1775821A (en) * | 2005-12-15 | 2006-05-24 | 东华大学 | Rapid efficient method for preparing acrylonitrile polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560097A (en) * | 2004-02-17 | 2005-01-05 | 东华大学 | Preparation process of acrylonitrile polymer in ion liquid |
| CN1775821A (en) * | 2005-12-15 | 2006-05-24 | 东华大学 | Rapid efficient method for preparing acrylonitrile polymer |
Non-Patent Citations (1)
| Title |
|---|
| CN 1560097 A,权利要求1-7. |
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