CN104725562A - Preparation method of acrylonitrile-vinylphosphonic acid copolymer - Google Patents
Preparation method of acrylonitrile-vinylphosphonic acid copolymer Download PDFInfo
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- CN104725562A CN104725562A CN201510157342.9A CN201510157342A CN104725562A CN 104725562 A CN104725562 A CN 104725562A CN 201510157342 A CN201510157342 A CN 201510157342A CN 104725562 A CN104725562 A CN 104725562A
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Abstract
The invention discloses a preparation method of an acrylonitrile-vinylphosphonic acid copolymer, which comprises the following steps: adding 500mL of deionized water into a three-neck flask provided with a thermometer, a condensation tube and a nitrogen guide tube, introducing nitrogen to flush for 25-40 minutes, heating to 30-60 DEG C, adding 1mol of acrylonitrile and 0.015-0.2mol of vinylphosphonic acid into the three-neck flask, adding dodecyl mercaptan which accounts for 1-4% of the total mass of the acrylonitrile and vinylphosphonic acid, adding sodium bisulfite which accounts for 0.02-0.08% of the total mass of the acrylonitrile and vinylphosphonic acid, stirring for 10 minutes, adding 50mL of a potassium persulfate saturated solution, reacting at 30-50 DEG C for 2-5 hours, filtering the product, washing the product with abundant deionized water, and carrying out vacuum drying to constant weight, thereby obtaining the white solid product acrylonitrile-vinylphosphonic acid copolymer. The flame-retardant acrylonitrile copolymer is free of halogen elements, has favorable flame-retardant effect, conforms to the requirement for environmental protection, and has the characteristics of higher conversion rate, no pollution and the like.
Description
[technical field]
The present invention relates to fire resistant acrylonitrile copolymer technology of preparing, particularly a kind of fire resistant acrylonitrile copolymer and preparation method thereof of halogen-free phosphorus-containing.
[background technology]
Polyacrylonitrile and multipolymer thereof are a kind of good fibroblast film-forming polymers, and chemical stability is good, anti-oxidant, solvent resistant.Monomer that is current and acrylonitrile compolymer is a lot, as vinyl acetate, methyl acrylate, methyl methacrylate, acrylamide, vinylbenzene, divinyl, methylpropene sodium sulfonate, vinyl pyrrolidone, methylene-succinic acid etc., but the limiting oxygen index(LOI) value of these multipolymers and polyacrylonitrile is lower, belong to combustible material.Along with the continuous enhancing of people's awareness of safety and the formulation of flame retardant regulation and day by day perfect, limit polyacrylonitrile and the application of acrylonitrile copolymer in fiber and mould material to a certain extent.Polyacrylonitrile fibre is as the main application fields of polyacrylonitrile and acrylonitrile copolymer, the characteristic of wool is similar to its good intensity, low moisture regain, light weight, high fluffy etc., and become the synthon kind given priority to both at home and abroad, civilian and military in be used widely.But very easily burn due to this fiber, make the application of this fiber also by restriction to a certain extent.
For exploitation fire-retardant polyacrylonitrile or fire resistant acrylonitrile copolymer, main adopt that blending fire retardant modification, copolymerization are flame-retardant modified both at home and abroad, chemical flame retardant modification and after-finishing flame resistant modification.Copolymerization method is the preparation method of a kind of effective fire-retardant polyacrylonitrile or fire resistant acrylonitrile copolymer, namely adopts the monomer containing ignition-proof element and acrylonitrile compolymer, thus prepares the method for flame-retardant polymer.But existing industrialization copolymerization method is when preparing acrylonitrile copolymer, usually containing more halogen element in product, product amount of being fuming when burning is large, and macro-corrosion hydrogen halide can be discharged, both be unfavorable for environmental protection, and brought secondary to endanger can to again rescue personnel and escape personnel, significantly limit the application of acrylonitrile polymer, therefore halogen acrylonitrile polymer becomes realistic problem urgently to be resolved hurrily, and has become the problem paid close attention to countries in the world.
[summary of the invention]
Object of the present invention solves the problems of the prior art exactly, a kind of preparation method of acrylonitrile-vinyl base phosphonic acid copolymer is proposed, fire resistant acrylonitrile copolymer of the present invention is not containing halogen element, there is good flame retardation effect, meet the features such as environment protection requirement, and this fire resistant acrylonitrile copolymer preparation method to have technique simple, transformation efficiency is higher, the feature such as not to pollute.
For achieving the above object, the present invention proposes a kind of preparation method of acrylonitrile-vinyl base phosphonic acid copolymer, the structural formula of acrylonitrile-vinyl base phosphonic acid copolymer is:
The preparation method of acrylonitrile-vinyl base phosphonic acid copolymer comprises the following steps:
A) in the there-necked flask that thermometer, prolong, nitrogen ingress pipe are housed, add 500mL deionized water, pass into nitrogen wash 25 ~ 40min, be heated to 30 ~ 60 DEG C;
B) vinyl cyanide, 0.015 ~ 0.2mol vinyl phosphonate of 1mol is added to there-necked flask, add the lauryl mercaptan accounting for vinyl cyanide, vinyl phosphonate total mass 1 ~ 4% simultaneously, add the sodium bisulfite accounting for vinyl cyanide, vinyl phosphonate total mass 0.02 ~ 0.08% again, Potassium Persulphate saturated solution 50mL is added after stirring 10min, react 2 ~ 5h at 30 ~ 50 DEG C after, filtration product;
C) with a large amount of deionized water wash product, then at 60 ~ 80 DEG C, vacuum-drying, to constant, obtains white solid product and is acrylonitrile-vinyl base phosphonic acid copolymer.
As preferably, in there-necked flask, pass into nitrogen wash 30min in described a) step, be heated to 45 DEG C.
As preferably, add the lauryl mercaptan accounting for vinyl cyanide, vinyl phosphonate total mass 2% to there-necked flask in described b) step, add the sodium bisulfite accounting for vinyl cyanide, vinyl phosphonate total mass 0.05% again, add Potassium Persulphate saturated solution 50mL after stirring 10min, at 40 DEG C, react 3h.
Beneficial effect of the present invention: fire resistant acrylonitrile copolymer of the present invention, not containing halogen element, has good flame retardation effect, meets the features such as environment protection requirement, and this fire resistant acrylonitrile copolymer preparation method to have technique simple, transformation efficiency is higher, the feature such as not to pollute.
[embodiment]
The present invention proposes a kind of preparation method of acrylonitrile-vinyl base phosphonic acid copolymer, the structural formula of acrylonitrile-vinyl base phosphonic acid copolymer is:
The preparation method of acrylonitrile-vinyl base phosphonic acid copolymer comprises the following steps:
A) in the there-necked flask that thermometer, prolong, nitrogen ingress pipe are housed, add 500mL deionized water, pass into nitrogen wash 25 ~ 40min, be heated to 30 ~ 60 DEG C;
B) vinyl cyanide, 0.015 ~ 0.2mol vinyl phosphonate of 1mol is added to there-necked flask, add the lauryl mercaptan accounting for vinyl cyanide, vinyl phosphonate total mass 1 ~ 4% simultaneously, add the sodium bisulfite accounting for vinyl cyanide, vinyl phosphonate total mass 0.02 ~ 0.08% again, Potassium Persulphate saturated solution 50mL is added after stirring 10min, react 2 ~ 5h at 30 ~ 50 DEG C after, filtration product;
C) with a large amount of deionized water wash product, then at 60 ~ 80 DEG C, vacuum-drying, to constant, obtains white solid product and is acrylonitrile-vinyl base phosphonic acid copolymer.
Unlike the prior art, namely the multipolymer of the present invention's design is the product that preparation method of the present invention directly obtains, multipolymer of the present invention is owing to being prepared by the mode of copolyreaction, by chemical bonds in the copolymer, thus product has good flame retardant resistance and weather resistance to flame-retardant composition; Flame-retardant composition simultaneously in gained multipolymer is phosphorus, not containing any halogen element, applied widely.
Comparative example:
Prepare conventional propylene lonitrile copolymer:
500mL deionized water is added in there-necked flask, with nitrogen wash 30min, be heated to 30 DEG C, add the vinyl cyanide of 1mol and account for the lauryl mercaptan of vinyl cyanide total mass 2%, add the sodium bisulfite accounting for vinyl cyanide quality 0.05% again, add Potassium Persulphate saturated solution 50mL after stirring 10min, carry out 2h 40 DEG C of reactions.Filtration product, with a large amount of deionized water wash, 70 DEG C of vacuum-dryings, to constant, obtain white solid acrylonitrile copolymer.
After testing, the LOI value of this multipolymer is 17.1%.
Embodiment one:
A preparation method for acrylonitrile-vinyl base phosphonic acid copolymer, the structural formula of acrylonitrile-vinyl base phosphonic acid copolymer is:
The preparation method of acrylonitrile-vinyl base phosphonic acid copolymer comprises the following steps:
A) in the there-necked flask that thermometer, prolong, nitrogen ingress pipe are housed, add 500mL deionized water, pass into nitrogen wash 30min, be heated to 30 DEG C;
B) vinyl cyanide, the 0.015mol vinyl phosphonate of 1mol is added to there-necked flask, add the lauryl mercaptan accounting for vinyl cyanide, vinyl phosphonate total mass 2% simultaneously, add the sodium bisulfite accounting for vinyl cyanide, vinyl phosphonate total mass 0.05% again, Potassium Persulphate saturated solution 50mL is added after stirring 10min, react 2h at 40 DEG C after, filtration product;
C) with a large amount of deionized water wash product, then at 70 DEG C, vacuum-drying, to constant, obtains white solid product and is acrylonitrile-vinyl base phosphonic acid copolymer.
After testing, the LOI value of the present embodiment gained multipolymer is 26.1%.Compared with the LOI value 17.1% of multipolymer in comparative example before flame-retardant modified reaction, the LOI value of the present embodiment multipolymer improves 9%, has good flame retardant resistance.
Embodiment two:
The addition of the present embodiment medium vinyl phosphonic acids is 0.02mol, and all the other preparation technologies are same as embodiment 1.After testing, the LOI value of this multipolymer is 28.3%.Compared with comparative example 1, the multipolymer LOI value of the present embodiment improves 11.2%.
Embodiment three:
The addition of the present embodiment medium vinyl phosphonic acids is 0.2mol, and all the other preparation technologies are same as embodiment 1.
After testing, the LOI value of this multipolymer is 45.6%.Compared with comparative example 1, the multipolymer LOI value of the present embodiment improves 28.5%.
Above-described embodiment is to explanation of the present invention, is not limitation of the invention, anyly all belongs to protection scope of the present invention to the scheme after simple transformation of the present invention.
Claims (3)
1. a preparation method for acrylonitrile-vinyl base phosphonic acid copolymer, the structural formula of acrylonitrile-vinyl base phosphonic acid copolymer is:
The preparation method of acrylonitrile-vinyl base phosphonic acid copolymer comprises the following steps:
A) in the there-necked flask that thermometer, prolong, nitrogen ingress pipe are housed, add 500mL deionized water, pass into nitrogen wash 25 ~ 40min, be heated to 30 ~ 60 DEG C;
B) vinyl cyanide, 0.015 ~ 0.2mol vinyl phosphonate of 1mol is added to there-necked flask, add the lauryl mercaptan accounting for vinyl cyanide, vinyl phosphonate total mass 1 ~ 4% simultaneously, add the sodium bisulfite accounting for vinyl cyanide, vinyl phosphonate total mass 0.02 ~ 0.08% again, Potassium Persulphate saturated solution 50mL is added after stirring 10min, react 2 ~ 5h at 30 ~ 50 DEG C after, filtration product;
C) with a large amount of deionized water wash product, then at 60 ~ 80 DEG C, vacuum-drying, to constant, obtains white solid product and is acrylonitrile-vinyl base phosphonic acid copolymer.
2. the preparation method of a kind of acrylonitrile-vinyl base phosphonic acid copolymer as claimed in claim 1, is characterized in that: in there-necked flask, pass into nitrogen wash 30min in described a) step, be heated to 45 DEG C.
3. the preparation method of a kind of acrylonitrile-vinyl base phosphonic acid copolymer as claimed in claim 1, it is characterized in that: in described b) step, add the lauryl mercaptan accounting for vinyl cyanide, vinyl phosphonate total mass 2% to there-necked flask, add the sodium bisulfite accounting for vinyl cyanide, vinyl phosphonate total mass 0.05% again, add Potassium Persulphate saturated solution 50mL after stirring 10min, at 40 DEG C, react 3h.
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| CN201510157342.9A CN104725562B (en) | 2015-03-30 | 2015-03-30 | A kind of preparation method of acrylonitrile ethylene base phosphonic acid copolymer |
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| CN201510157342.9A CN104725562B (en) | 2015-03-30 | 2015-03-30 | A kind of preparation method of acrylonitrile ethylene base phosphonic acid copolymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708009A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Flame-retardant polyacrylonitrile containing methyl phosphate, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1193572A (en) * | 1967-05-16 | 1970-06-03 | Goodrich Co B F | Ester-Nitrile Addition Copolymers having Improved Resistance to Solvents. |
| US3943085A (en) * | 1970-06-23 | 1976-03-09 | Stauffer Chemical Company | Suspension copolymer composition |
| US3943113A (en) * | 1974-08-09 | 1976-03-09 | Stauffer Chemical Company | Polymer composition of a vinyl compound, a bis (hydrocarbyl)vinylphosphonate and an allyl halide |
| CN101717469A (en) * | 2009-12-10 | 2010-06-02 | 天津工业大学 | Flame-retardant acrylonitrile copolymer and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1193572A (en) * | 1967-05-16 | 1970-06-03 | Goodrich Co B F | Ester-Nitrile Addition Copolymers having Improved Resistance to Solvents. |
| US3943085A (en) * | 1970-06-23 | 1976-03-09 | Stauffer Chemical Company | Suspension copolymer composition |
| US3943113A (en) * | 1974-08-09 | 1976-03-09 | Stauffer Chemical Company | Polymer composition of a vinyl compound, a bis (hydrocarbyl)vinylphosphonate and an allyl halide |
| CN101717469A (en) * | 2009-12-10 | 2010-06-02 | 天津工业大学 | Flame-retardant acrylonitrile copolymer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| PAUL WYMAN ET AL.: "Flame-retarding effects of dialkyl-p-vinylbenzyl phosphonates in copolymers with acrylonitrile", 《POLYMER INTERNATIONAL》 * |
| 赵斯梅: "无卤阻燃聚丙烯腈的合成及性能分析", 《山东纺织经济》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708009A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Flame-retardant polyacrylonitrile containing methyl phosphate, and preparation method and application thereof |
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