CN104725562B - A kind of preparation method of acrylonitrile ethylene base phosphonic acid copolymer - Google Patents
A kind of preparation method of acrylonitrile ethylene base phosphonic acid copolymer Download PDFInfo
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- CN104725562B CN104725562B CN201510157342.9A CN201510157342A CN104725562B CN 104725562 B CN104725562 B CN 104725562B CN 201510157342 A CN201510157342 A CN 201510157342A CN 104725562 B CN104725562 B CN 104725562B
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- acrylonitrile
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Abstract
The invention discloses a kind of preparation method of acrylonitrile ethylene base phosphonic acid copolymer，Equipped with thermometer、Condensing tube、500mL deionized water is added in the there-necked flask of nitrogen ingress pipe，It is passed through nitrogen and rinse 25～40min，It is heated to 30～60 DEG C，Add the acrylonitrile of 1mol to there-necked flask、0.015～0.2mol vinyl phosphonate，It is simultaneously introduced and account for acrylonitrile、The lauryl mercaptan of vinyl phosphonate gross mass 1～4%，Add and account for acrylonitrile、The sodium sulfite of vinyl phosphonate gross mass 0.02～0.08%，Potassium peroxydisulfate saturated solution 50mL is added after stirring 10min，After reaction 2～5h at 30～50 DEG C，Filtration product，With a large amount of deionized water wash products，Then carry out being dried under vacuum to constant，Obtain white solid product and be acrylonitrile ethylene base phosphonic acid copolymer.The fire resistant acrylonitrile copolymer of the present invention does not contain halogen element, has good flame retardation effect, and the features such as meet environment protection requirement, and conversion ratio is higher, the features such as pollution.
Description
【Technical field】
The present invention relates to fire resistant acrylonitrile copolymer technology of preparing, the fire-retardant acrylonitrile copolymerization of particularly a kind of halogen-free phosphorus-containing
Thing and preparation method thereof.
【Background technology】
Polyacrylonitrile and its copolymer are a kind of good one-tenth fibre film forming polymers, and chemical stability is good, and antioxidation is resistance to molten
Agent.Current and acrylonitrile compolymer monomer is a lot, such as vinylacetate, acrylic acid methyl ester., methyl methacrylate, acryloyl
Amine, styrene, butadiene, methylpropene sodium sulfonate, vinyl pyrrolidone, itaconic acid etc., but these copolymers and poly-
The limited oxygen index value of acrylonitrile is relatively low, belongs to combustible material.Continuous enhancing with people's safety consciousness and flame retardant regulation
Formulate and increasingly perfect, limit the application in fiber and membrane material of polyacrylonitrile and acrylonitrile copolymer to a certain extent.
Polyacrylonitrile fibre as the main application fields of polyacrylonitrile and acrylonitrile copolymer, with its good intensity, low moisture regain
Rate, light weight, high fluffy etc. are similar to the characteristic of Pilus Caprae seu Oviss, and become the synthetic fibers kind given priority to both at home and abroad, civilian
And military aspect is used widely.Easily burn yet with this fiber so that the application of this fiber is also subject to a certain extent
Restriction.
For exploitation fire-retardant polyacrylonitrile or fire resistant acrylonitrile copolymer, mainly adopt blending fire retardant modification, copolymerization both at home and abroad
Flame-retardant modified, chemical flame retardant is modified and after-finishing flame resistant is modified.Copolymerization method is a kind of effective fire-retardant polyacrylonitrile or fire-retardant
The preparation method of acrylonitrile copolymer, that is, adopt the monomer containing ignition-proof element and acrylonitrile compolymer, thus preparing fire-retardant poly-
The method of compound.But existing industrialization copolymerization method is when preparing acrylonitrile copolymer, in product, usually contain more halogen
Element, product amount of being fuming in burning is big, and can discharge a large amount of corrosive hydrogen halides gases, had both been unfavorable for environmental protection, and can have been rescued again
Help personnel and escape personnel brings secondary hazards, significantly limit the application of acrylonitrile polymer, therefore halogen-free acrylonitrile
Polymer becomes realistic problem urgently to be resolved hurrily, and has become the problem of countries in the world concern.
【Content of the invention】
The purpose of the present invention is exactly to solve the problems of the prior art, proposes a kind of acrylonitrile-vinyl base phosphonic acid copolymer
Preparation method, the fire resistant acrylonitrile copolymer of the present invention do not contain halogen element, has good flame retardation effect, meet environment protection requirement
The features such as, and this fire resistant acrylonitrile copolymer preparation method has process is simple, conversion ratio is higher, the features such as pollution.
For achieving the above object, the present invention proposes a kind of preparation method of acrylonitrile-vinyl base phosphonic acid copolymer, propylene
The structural formula of nitrile-vinyl phosphonic acid copolymers is：
The preparation method of acrylonitrile-vinyl base phosphonic acid copolymer comprises the following steps：
A) add 500mL deionized water in equipped with thermometer, condensing tube, the there-necked flask of nitrogen ingress pipe, be passed through nitrogen
Gas flushing 25～40min, is heated to 30～60 DEG C；
B) add acrylonitrile, 0.015～0.2mol vinyl phosphonate of 1mol to there-necked flask, be simultaneously introduced and account for propylene
Nitrile, the lauryl mercaptan of vinyl phosphonate gross mass 1～4%, add account for acrylonitrile, vinyl phosphonate gross mass 0.02～
0.08% sodium sulfite, adds potassium peroxydisulfate saturated solution 50mL after stirring 10min, reacts 2～5h at 30～50 DEG C
Afterwards, filtration product；
C) with a large amount of deionized water wash products, then at 60～80 DEG C, it is dried under vacuum to constant, obtains white solid
Product is acrylonitrile-vinyl base phosphonic acid copolymer.
Preferably, being passed through nitrogen in described a) step in there-necked flask to rinse 30min, it is heated to 45 DEG C.
Preferably, in described b) step to there-necked flask add account for acrylonitrile, vinyl phosphonate gross mass 2% 12
Alkyl hydrosulfide, adds and accounts for acrylonitrile, the sodium sulfite of vinyl phosphonate gross mass 0.05%, adds after stirring 10min
Potassium sulfate saturated solution 50mL, reacts 3h at 40 DEG C.
Beneficial effects of the present invention：The fire resistant acrylonitrile copolymer of the present invention does not contain halogen element, has good flame retardation effect, symbol
The features such as close environment protection requirement, and this fire resistant acrylonitrile copolymer preparation method has process is simple, conversion ratio is higher, does not have
The features such as pollution.
【Specific embodiment】
The present invention proposes a kind of preparation method of acrylonitrile-vinyl base phosphonic acid copolymer, and acrylonitrile-vinyl base phosphonic acids is altogether
The structural formula of polymers is：
The preparation method of acrylonitrile-vinyl base phosphonic acid copolymer comprises the following steps：
A) add 500mL deionized water in equipped with thermometer, condensing tube, the there-necked flask of nitrogen ingress pipe, be passed through nitrogen
Gas flushing 25～40min, is heated to 30～60 DEG C；
B) add acrylonitrile, 0.015～0.2mol vinyl phosphonate of 1mol to there-necked flask, be simultaneously introduced and account for propylene
Nitrile, the lauryl mercaptan of vinyl phosphonate gross mass 1～4%, add account for acrylonitrile, vinyl phosphonate gross mass 0.02～
0.08% sodium sulfite, adds potassium peroxydisulfate saturated solution 50mL after stirring 10min, reacts 2～5h at 30～50 DEG C
Afterwards, filtration product；
C) with a large amount of deionized water wash products, then at 60～80 DEG C, it is dried under vacuum to constant, obtains white solid
Product is acrylonitrile-vinyl base phosphonic acid copolymer.
Unlike the prior art, the copolymer of present invention design is the product that preparation method of the present invention directly obtains, this
Invention copolymer is prepared by the mode then passing through copolyreaction, and flame-retardant composition is combined in copolymer by chemical bonded refractory
In, thus product has good anti-flammability and durability；Flame-retardant composition in gained copolymer is phosphorus simultaneously, without any halogen
Element, applied widely.
Comparative example：
Prepare conventional propylene lonitrile copolymer：
Add 500mL deionized water in there-necked flask, 30min is rinsed with nitrogen, is heated to 30 DEG C, add the propylene of 1mol
Nitrile and the lauryl mercaptan accounting for acrylonitrile gross mass 2%, add the sodium sulfite accounting for acrylonitrile quality 0.05%, stirring
Add potassium peroxydisulfate saturated solution 50mL after 10min, carry out 2h in 40 DEG C of reactions.Filtration product, with a large amount of deionized water wash,
70 DEG C are dried under vacuum to constant, obtain white solid acrylonitrile copolymer.
After testing, the LOI value of this copolymer is 17.1%.
Embodiment one：
A kind of preparation method of acrylonitrile-vinyl base phosphonic acid copolymer, the structural formula of acrylonitrile-vinyl base phosphonic acid copolymer
For：
The preparation method of acrylonitrile-vinyl base phosphonic acid copolymer comprises the following steps：
A) add 500mL deionized water in equipped with thermometer, condensing tube, the there-necked flask of nitrogen ingress pipe, be passed through nitrogen
Gas flushing 30min, is heated to 30 DEG C；
B) add acrylonitrile, the 0.015mol vinyl phosphonate of 1mol to there-necked flask, be simultaneously introduced and account for acrylonitrile, ethylene
The lauryl mercaptan of base phosphonic acids gross mass 2%, adds and accounts for acrylonitrile, the bisulfite of vinyl phosphonate gross mass 0.05%
Sodium, adds potassium peroxydisulfate saturated solution 50mL after stirring 10min, after reaction 2h at 40 DEG C, filtration product；
C) with a large amount of deionized water wash products, then at 70 DEG C, it is dried under vacuum to constant, obtains white solid product
It is acrylonitrile-vinyl base phosphonic acid copolymer.
After testing, the LOI value of the present embodiment gained copolymer is 26.1%.In comparative example before flame-retardant modified reaction
The LOI value 17.1% of copolymer is compared, and the LOI value of the present embodiment copolymer improves 9%, has good anti-flammability.
Embodiment two：
The addition of the present embodiment medium vinyl phosphonic acids is 0.02mol, and remaining preparation technology is same as embodiment 1.After testing,
The LOI value of this copolymer is 28.3%.Compared with comparative example 1, the copolymer 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 remaining preparation technology is same as embodiment 1.
After testing, the LOI value of this copolymer is 45.6%.Compared with comparative example 1, the copolymer LOI of the present embodiment
Value improves 28.5%.
Above-described embodiment is the description of the invention, is not limitation of the invention, any to simple transformation of the present invention after
Scheme belong to protection scope of the present invention.
Claims (3)
1. a kind of preparation method of acrylonitrile-vinyl base phosphonic acid copolymer, including the preparation of acrylonitrile-vinyl base phosphonic acid copolymer
Step is it is characterised in that 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) add 500mL deionized water in equipped with thermometer, condensing tube, the there-necked flask of nitrogen ingress pipe, be passed through nitrogen punching
Wash 25～40min, be heated to 30～60 DEG C；
B) add acrylonitrile, 0.015～0.2mol vinyl phosphonate of 1mol to there-necked flask, be simultaneously introduced and account for acrylonitrile, second
The lauryl mercaptan of alkenyl phosphonic acid gross mass 1～4%, add account for acrylonitrile, vinyl phosphonate gross mass 0.02～
0.08% sodium sulfite, adds potassium peroxydisulfate saturated solution 50mL after stirring 10min, reacts 2～5h at 30～50 DEG C
Afterwards, filtration product；
C) with a large amount of deionized water wash products, then at 60～80 DEG C, it is dried under vacuum to constant, obtains white solid product
It is acrylonitrile-vinyl base phosphonic acid copolymer.
2. as claimed in claim 1 a kind of preparation method of acrylonitrile-vinyl base phosphonic acid copolymer it is characterised in that：Described
A) it is passed through nitrogen in step in there-necked flask and rinses 30min, be heated to 45 DEG C.
3. as claimed in claim 1 a kind of preparation method of acrylonitrile-vinyl base phosphonic acid copolymer it is characterised in that：Described
B) add, to there-necked flask, the lauryl mercaptan accounting for acrylonitrile, vinyl phosphonate gross mass 2% in step, add and account for propylene
Nitrile, the sodium sulfite of vinyl phosphonate gross mass 0.05%, add potassium peroxydisulfate saturated solution 50mL after stirring 10min,
3h is reacted at 40 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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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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| CN104725562B true CN104725562B (en) | 2017-03-01 |
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Families Citing this family (1)
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| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3489706A (en) * | 1967-05-16 | 1970-01-13 | Goodrich Co B F | Bis(beta-chloroethyl)vinyl phosphonate copolymer compositions |
| US3725509A (en) * | 1970-06-23 | 1973-04-03 | Stauffer Chemical Co | Fire retardant thermoplastic polymer compositions of a methyl methacrylate polymer with a copolymer of a halogenated ethylenically unsaturated monomer and a phosphorous containing vinyl monomer |
| 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 |
| CN101717469B (en) * | 2009-12-10 | 2012-01-04 | 天津工业大学 | Flame-retardant acrylonitrile copolymer and preparation method thereof |
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