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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- acrylonitrile
- add
- phosphonic acid
- acid copolymer
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims description 22
- GOAJGXULHASQGJ-UHFFFAOYSA-N ethene;prop-2-enenitrile Chemical group C=C.C=CC#N GOAJGXULHASQGJ-UHFFFAOYSA-N 0.000 title 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000012265 solid product Substances 0.000 claims abstract description 5
- 239000012047 saturated solution Substances 0.000 claims abstract 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- -1 alkenyl phosphonic acid Chemical compound 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims 7
- ZTWTYVWXUKTLCP-UHFFFAOYSA-L ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-L 0.000 claims 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims 4
- 235000019394 potassium persulphate Nutrition 0.000 claims 2
- 235000010265 sodium sulphite Nutrition 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 238000004080 punching Methods 0.000 claims 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 24
- 239000003063 flame retardant Substances 0.000 abstract description 24
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 2
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 9
- 239000000835 fiber Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FXYIRRFBFHHNIC-UHFFFAOYSA-N ethenylphosphonic acid;sodium Chemical compound [Na].OP(O)(=O)C=C FXYIRRFBFHHNIC-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种丙烯腈‑乙烯基膦酸共聚物的制备方法，在装有温度计、冷凝管、氮气导入管的三口烧瓶中加入500mL去离子水，通入氮气冲洗25～40min，加热到30～60℃，向三口烧瓶加入1mol的丙烯腈、0.015～0.2mol乙烯基膦酸，同时加入占丙烯腈、乙烯基膦酸总质量1～4％的十二烷基硫醇，再加入占丙烯腈、乙烯基膦酸总质量0.02～0.08％的亚硫酸氢钠，搅拌10min后加入过硫酸钾饱和溶液50mL，在30～50℃下反应2～5h后，过滤产物，以大量去离子水洗涤产物，然后进行真空干燥至恒量，得到白色固体产物即为丙烯腈‑乙烯基膦酸共聚物。本发明的阻燃丙烯腈共聚物不含卤元素，具有阻燃效果好，符合绿色环保要求等特点，且转化率较高，没有污染等特点。The invention discloses a method for preparing an acrylonitrile-vinylphosphonic acid copolymer. Add 500mL of deionized water into a three-neck flask equipped with a thermometer, a condensation tube and a nitrogen gas introduction tube, and then flush with nitrogen gas for 25 to 40 minutes, and heat to 30-60°C, add 1mol of acrylonitrile and 0.015-0.2mol of vinylphosphonic acid to the three-necked flask, and at the same time add dodecyl mercaptan accounting for 1-4% of the total mass of acrylonitrile and vinylphosphonic acid, and then add Acrylonitrile, vinyl phosphonic acid 0.02-0.08% sodium bisulfite, after stirring for 10 minutes, add 50 mL of potassium persulfate saturated solution, react at 30-50 ° C for 2-5 hours, filter the product, and wash with a large amount of deionized water The product was washed, and then vacuum-dried to a constant weight to obtain a white solid product which was an acrylonitrile-vinylphosphonic acid copolymer. The flame-retardant acrylonitrile copolymer of the invention does not contain halogen elements, has the characteristics of good flame-retardant effect, meets the requirements of green environmental protection, and has the characteristics of high conversion rate and no pollution.
Description
【技术领域】【Technical field】
本发明涉及阻燃丙烯腈共聚物制备技术，特别是一种无卤含磷的阻燃丙烯腈共聚物及其制备方法。The invention relates to a preparation technology of a flame-retardant acrylonitrile copolymer, in particular to a halogen-free and phosphorus-containing flame-retardant acrylonitrile copolymer and a preparation method thereof.
【背景技术】【Background technique】
聚丙烯腈及其共聚物是一种良好的成纤成膜聚合物，化学稳定性好，抗氧化，耐溶剂。目前与丙烯腈共聚的单体很多，如醋酸乙烯酯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酰胺、苯乙烯、丁二烯、甲基丙烯磺酸钠、乙烯基吡咯烷酮、衣康酸等，然而这些共聚物以及聚丙烯腈的极限氧指数值较低，属易燃物质。随着人们安全意识的不断增强以及阻燃法规的制定及日益完善，一定程度上限制了聚丙烯腈及丙烯腈共聚物在纤维及膜材料中的应用。聚丙烯腈纤维作为聚丙烯腈及丙烯腈共聚物的主要应用领域，以其良好的强度、低的回潮率、质轻、高蓬松性等类似于羊毛的特性，而成为国内外重点发展的合成纤维品种，在民用及军用方面得到广泛应用。然而由于该纤维极易燃烧，使得该纤维的应用也受到一定程度的限制。Polyacrylonitrile and its copolymers are good fiber-forming and film-forming polymers with good chemical stability, oxidation resistance and solvent resistance. At present, there are many monomers copolymerized with acrylonitrile, such as vinyl acetate, methyl acrylate, methyl methacrylate, acrylamide, styrene, butadiene, sodium methacrylate, vinylpyrrolidone, itaconic acid, etc. However, these copolymers and polyacrylonitrile have low limiting oxygen index values and are flammable substances. With the continuous enhancement of people's safety awareness and the formulation and improvement of flame retardant regulations, the application of polyacrylonitrile and acrylonitrile copolymers in fiber and membrane materials is limited to a certain extent. As the main application field of polyacrylonitrile and acrylonitrile copolymer, polyacrylonitrile fiber has become a synthetic fiber developed mainly at home and abroad because of its good strength, low moisture regain, light weight, high bulkiness and other characteristics similar to wool. Fiber varieties are widely used in civilian and military applications. However, because the fiber is extremely flammable, the application of the fiber is limited to a certain extent.
为开发阻燃聚丙烯腈或阻燃丙烯腈共聚物，国内外主要采用共混阻燃改性、共聚阻燃改性、化学阻燃改性以及后整理阻燃改性。共聚法是一种有效的阻燃聚丙烯腈或阻燃丙烯腈共聚物的制备方法，即采用含有阻燃元素的单体与丙烯腈共聚，从而制备出阻燃聚合物的方法。然而现有的产业化共聚法在制备丙烯腈共聚物时，产物中通常含有较多的卤元素，产品在燃烧时发烟量大，且会释放大量腐蚀性卤化氢气体，既不利于环保，又会给救援人员和逃生人员带来二次危害，极大的限制了丙烯腈聚合物的应用，因此无卤素丙烯腈聚合物成为亟待解决的现实问题，且已成为世界各国关注的问题。In order to develop flame-retardant polyacrylonitrile or flame-retardant acrylonitrile copolymers, blending flame-retardant modification, copolymerization flame-retardant modification, chemical flame-retardant modification and post-finishing flame-retardant modification are mainly used at home and abroad. The copolymerization method is an effective preparation method of flame-retardant polyacrylonitrile or flame-retardant acrylonitrile copolymer, that is, the method of copolymerizing monomers containing flame-retardant elements with acrylonitrile to prepare flame-retardant polymers. However, when the existing industrialized copolymerization method is used to prepare acrylonitrile copolymers, the product usually contains more halogen elements, and the product generates a large amount of smoke when it is burned, and it will release a large amount of corrosive hydrogen halide gas, which is not conducive to environmental protection. It will bring secondary hazards to rescuers and escapees, which greatly limits the application of acrylonitrile polymers. Therefore, halogen-free acrylonitrile polymers have become a practical problem to be solved urgently, and have become a concern of countries all over the world.
【发明内容】【Content of invention】
本发明的目的就是解决现有技术中的问题，提出一种丙烯腈-乙烯基膦酸共聚物的制备方法，本发明的阻燃丙烯腈共聚物不含卤元素，具有阻燃效果好，符合绿色环保要求等特点，且该阻燃丙烯腈共聚物制备方法具有工艺简单，转化率较高，没有污染等特点。The purpose of the present invention is to solve the problems in the prior art, and propose a preparation method of acrylonitrile-vinylphosphonic acid copolymer. The flame-retardant acrylonitrile copolymer of the present invention does not contain halogen elements, has good flame-retardant effect, and conforms to The preparation method of the flame-retardant acrylonitrile copolymer has the characteristics of simple process, high conversion rate and no pollution.
为实现上述目的，本发明提出了一种丙烯腈-乙烯基膦酸共聚物的制备方法，丙烯腈-乙烯基膦酸共聚物的结构式为：In order to achieve the above object, the present invention proposes a kind of preparation method of acrylonitrile-vinyl phosphonic acid copolymer, the structural formula of acrylonitrile-vinyl phosphonic acid copolymer is:
丙烯腈-乙烯基膦酸共聚物的制备方法包括以下步骤：The preparation method of acrylonitrile-vinyl phosphonic acid copolymer comprises the following steps:
a)在装有温度计、冷凝管、氮气导入管的三口烧瓶中加入500mL去离子水，通入氮气冲洗25～40min，加热到30～60℃；a) Add 500mL of deionized water into a three-necked flask equipped with a thermometer, a condenser tube, and a nitrogen inlet tube, flush with nitrogen for 25-40 minutes, and heat to 30-60°C;
b)向三口烧瓶加入1mol的丙烯腈、0.015～0.2mol乙烯基膦酸，同时加入占丙烯腈、乙烯基膦酸总质量1～4％的十二烷基硫醇，再加入占丙烯腈、乙烯基膦酸总质量0.02～0.08％的亚硫酸氢钠，搅拌10min后加入过硫酸钾饱和溶液50mL，在30～50℃下反应2～5h后，过滤产物；b) Add 1 mol of acrylonitrile and 0.015 to 0.2 mol of vinylphosphonic acid to a three-necked flask, and simultaneously add dodecyl mercaptan accounting for 1 to 4% of the total mass of acrylonitrile and vinylphosphonic acid, and then add accounting for acrylonitrile, The total mass of vinylphosphonic acid is 0.02-0.08% sodium bisulfite, after stirring for 10 minutes, add 50 mL of saturated potassium persulfate solution, react at 30-50°C for 2-5 hours, and filter the product;
c)以大量去离子水洗涤产物，然后在60～80℃下真空干燥至恒量，得到白色固体产物即为丙烯腈-乙烯基膦酸共聚物。c) washing the product with a large amount of deionized water, and then vacuum-drying at 60-80° C. to a constant weight to obtain a white solid product which is an acrylonitrile-vinylphosphonic acid copolymer.
作为优选，所述a)步骤中向三口烧瓶中通入氮气冲洗30min，加热到45℃。As a preference, in the step a), the three-necked flask is flushed with nitrogen for 30 minutes and heated to 45°C.
作为优选，所述b)步骤中向三口烧瓶加入占丙烯腈、乙烯基膦酸总质量2％的十二烷基硫醇，再加入占丙烯腈、乙烯基膦酸总质量0.05％的亚硫酸氢钠，搅拌10min后加入过硫酸钾饱和溶液50mL，在40℃下反应3h。As a preference, in the step b), add 2% dodecyl mercaptan accounting for the total mass of acrylonitrile and vinylphosphonic acid to the three-necked flask, and then add 0.05% sulfurous acid accounting for the total mass of acrylonitrile and vinylphosphonic acid Sodium hydrogen, after stirring for 10 minutes, add 50 mL of saturated potassium persulfate solution, and react at 40°C for 3 hours.
本发明的有益效果：本发明的阻燃丙烯腈共聚物不含卤元素，具有阻燃效果好，符合绿色环保要求等特点，且该阻燃丙烯腈共聚物制备方法具有工艺简单，转化率较高，没有污染等特点。Beneficial effects of the present invention: the flame-retardant acrylonitrile copolymer of the present invention does not contain halogen elements, has good flame-retardant effect, meets the requirements of green environmental protection, etc., and the preparation method of the flame-retardant acrylonitrile copolymer has simple process and high conversion rate. High, no pollution and other characteristics.
【具体实施方式】【detailed description】
本发明提出了一种丙烯腈-乙烯基膦酸共聚物的制备方法，丙烯腈-乙烯基膦酸共聚物的结构式为：The present invention proposes a kind of preparation method of acrylonitrile-vinylphosphonic acid copolymer, the structural formula of acrylonitrile-vinylphosphonic acid copolymer is:
丙烯腈-乙烯基膦酸共聚物的制备方法包括以下步骤：The preparation method of acrylonitrile-vinyl phosphonic acid copolymer comprises the following steps:
a)在装有温度计、冷凝管、氮气导入管的三口烧瓶中加入500mL去离子水，通入氮气冲洗25～40min，加热到30～60℃；a) Add 500mL of deionized water into a three-necked flask equipped with a thermometer, a condenser tube, and a nitrogen inlet tube, flush with nitrogen for 25-40 minutes, and heat to 30-60°C;
b)向三口烧瓶加入1mol的丙烯腈、0.015～0.2mol乙烯基膦酸，同时加入占丙烯腈、乙烯基膦酸总质量1～4％的十二烷基硫醇，再加入占丙烯腈、乙烯基膦酸总质量0.02～0.08％的亚硫酸氢钠，搅拌10min后加入过硫酸钾饱和溶液50mL，在30～50℃下反应2～5h后，过滤产物；b) Add 1 mol of acrylonitrile and 0.015 to 0.2 mol of vinylphosphonic acid to a three-necked flask, and simultaneously add dodecyl mercaptan accounting for 1 to 4% of the total mass of acrylonitrile and vinylphosphonic acid, and then add accounting for acrylonitrile, The total mass of vinylphosphonic acid is 0.02-0.08% sodium bisulfite, after stirring for 10 minutes, add 50 mL of saturated potassium persulfate solution, react at 30-50°C for 2-5 hours, and filter the product;
c)以大量去离子水洗涤产物，然后在60～80℃下真空干燥至恒量，得到白色固体产物即为丙烯腈-乙烯基膦酸共聚物。c) washing the product with a large amount of deionized water, and then vacuum-drying at 60-80° C. to a constant weight to obtain a white solid product which is an acrylonitrile-vinylphosphonic acid copolymer.
与现有技术不同，本发明设计的共聚物即是本发明制备方法直接获得的产品，本发明共聚物由于是通过共聚反应的方式制备获得的，阻燃成分通过化学键结合在共聚物中，因而产品具有良好的阻燃性和耐久性；同时所得共聚物中的阻燃成分为磷，不含任何卤元素，适用范围广。Different from the prior art, the copolymer designed in the present invention is the product directly obtained by the preparation method of the present invention. The copolymer of the present invention is prepared through a copolymerization reaction, and the flame retardant components are combined in the copolymer through chemical bonds, so The product has good flame retardancy and durability; at the same time, the flame retardant component in the obtained copolymer is phosphorus, does not contain any halogen elements, and has a wide range of applications.
对比实施例：Comparative example:
制备常规丙烯腈共聚物：Preparation of conventional acrylonitrile copolymers:
三口烧瓶中加入500mL去离子水，以氮气冲洗30min，加热到30℃，加入1mol的丙烯腈和占丙烯腈总质量2％的十二烷基硫醇，再加入占丙烯腈质量0.05％的亚硫酸氢钠，搅拌10min后加入过硫酸钾饱和溶液50mL，在40℃反应进行2h。过滤产物，以大量去离子水洗涤，70℃真空干燥至恒量，得到白色固体丙烯腈共聚物。Add 500mL of deionized water into the three-neck flask, flush with nitrogen for 30min, heat to 30°C, add 1mol of acrylonitrile and 2% of dodecyl mercaptan accounting for the total mass of acrylonitrile, and then add 0.05% of the mass of acrylonitrile. Sodium bisulfate, after stirring for 10 min, 50 mL of saturated potassium persulfate solution was added, and the reaction was carried out at 40° C. for 2 h. The product was filtered, washed with a large amount of deionized water, and vacuum-dried at 70°C to constant weight to obtain a white solid acrylonitrile copolymer.
经检测，该共聚物的LOI值为17.1％。After testing, the LOI value of the copolymer was 17.1%.
实施例一：Embodiment one:
一种丙烯腈-乙烯基膦酸共聚物的制备方法，丙烯腈-乙烯基膦酸共聚物的结构式为：A kind of preparation method of acrylonitrile-vinyl phosphonic acid copolymer, the structural formula of acrylonitrile-vinyl phosphonic acid copolymer is:
丙烯腈-乙烯基膦酸共聚物的制备方法包括以下步骤：The preparation method of acrylonitrile-vinyl phosphonic acid copolymer comprises the following steps:
a)在装有温度计、冷凝管、氮气导入管的三口烧瓶中加入500mL去离子水，通入氮气冲洗30min，加热到30℃；a) Add 500mL of deionized water to a three-necked flask equipped with a thermometer, a condenser tube, and a nitrogen inlet tube, flush with nitrogen for 30 minutes, and heat to 30°C;
b)向三口烧瓶加入1mol的丙烯腈、0.015mol乙烯基膦酸，同时加入占丙烯腈、乙烯基膦酸总质量2％的十二烷基硫醇，再加入占丙烯腈、乙烯基膦酸总质量0.05％的亚硫酸氢钠，搅拌10min后加入过硫酸钾饱和溶液50mL，在40℃下反应2h后，过滤产物；b) Add 1 mol of acrylonitrile and 0.015 mol of vinylphosphonic acid to a three-necked flask, simultaneously add dodecyl mercaptan accounting for 2% of the total mass of acrylonitrile and vinylphosphonic acid, and then add accounting for acrylonitrile and vinylphosphonic acid Sodium bisulfite with a total mass of 0.05%, after stirring for 10 minutes, add 50 mL of saturated potassium persulfate solution, react at 40°C for 2 hours, and filter the product;
c)以大量去离子水洗涤产物，然后在70℃下真空干燥至恒量，得到白色固体产物即为丙烯腈-乙烯基膦酸共聚物。c) The product was washed with a large amount of deionized water, and then vacuum-dried at 70° C. to a constant weight to obtain a white solid product which was an acrylonitrile-vinylphosphonic acid copolymer.
经检测，本实施例所得共聚物的LOI值为26.1％。与阻燃改性反应前对比实施例中共聚物的LOI值17.1％相比，本实施例共聚物的LOI值提高了9％，具有良好的阻燃性。After testing, the LOI value of the copolymer obtained in this embodiment is 26.1%. Compared with the 17.1% LOI value of the copolymer in the comparative example before the flame retardant modification reaction, the LOI value of the copolymer in this example is increased by 9%, and has good flame retardancy.
实施例二：Embodiment two:
本实施例中乙烯基膦酸的添加量为0.02mol，其余制备工艺同于实施例1。经检测，该共聚物的LOI值为28.3％。与对比实施例1相比，本实施例的共聚物LOI值提高了11.2％。The amount of vinylphosphonic acid added in this example is 0.02 mol, and the rest of the preparation process is the same as in Example 1. After testing, the LOI value of the copolymer was 28.3%. Compared with Comparative Example 1, the LOI value of the copolymer of this example was increased by 11.2%.
实施例三：Embodiment three:
本实施例中乙烯基膦酸的添加量为0.2mol，其余制备工艺同于实施例1。In this example, the amount of vinylphosphonic acid added is 0.2 mol, and the rest of the preparation process is the same as in Example 1.
经检测，该共聚物的LOI值为45.6％。与对比实施例1相比，本实施例的共聚物LOI值提高了28.5％。After testing, the LOI value of the copolymer was 45.6%. Compared with Comparative Example 1, the LOI value of the copolymer of this example was increased by 28.5%.
上述实施例是对本发明的说明，不是对本发明的限定，任何对本发明简单变换后的方案均属于本发明的保护范围。The above-mentioned embodiment is an illustration of the present invention, not a limitation of the present invention, and any solution after a simple transformation of the present invention belongs to the protection scope of the present invention.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510157342.9A CN104725562B (en) | 2015-03-30 | 2015-03-30 | A kind of preparation method of acrylonitrile ethylene base phosphonic acid copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510157342.9A CN104725562B (en) | 2015-03-30 | 2015-03-30 | A kind of preparation method of acrylonitrile ethylene base phosphonic acid copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104725562A CN104725562A (en) | 2015-06-24 |
| CN104725562B true CN104725562B (en) | 2017-03-01 |
Family
ID=53450025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510157342.9A Expired - Fee Related CN104725562B (en) | 2015-03-30 | 2015-03-30 | A kind of preparation method of acrylonitrile ethylene base phosphonic acid copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104725562B (en) |
Families Citing this family (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 |
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 |
-
2015
- 2015-03-30 CN CN201510157342.9A patent/CN104725562B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104725562A (en) | 2015-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102040790B (en) | A kind of fireproof polyvinyl acetate emulsion and preparation method thereof | |
| CN102585347A (en) | Halogen-free intumescent flame-retardant polypropylene mixture and preparation method thereof | |
| CN114437366A (en) | Intumescent flame retardant, preparation method and application thereof, flame retardant polyacrylonitrile fiber and preparation method thereof | |
| CN107501566A (en) | A kind of DOPO bases dissaving structure phosphateng halogen-free flame retardant and preparation method thereof | |
| CN114685896B (en) | Preparation method of high-stretch-resistance flame-retardant heat-resistant MPP pipe | |
| CN104846639B (en) | Flame-retardant finishing method of the response type expanding fire retardant to bafta | |
| CN107629248A (en) | A kind of agent of hyperbranched expandable flame retardant containing phosphine oxide and its preparation method and application | |
| CN104388096A (en) | Bagasse composite soil conditioner preparation method | |
| CN104725562B (en) | A kind of preparation method of acrylonitrile ethylene base phosphonic acid copolymer | |
| CN102911505B (en) | Polymer type phosphorus, nitrogen and boron containing flame retardant and preparation method thereof | |
| CN105061666A (en) | Preparation method for organic-phosphorus-modified fluorine-containing polyacrylate flame retarding finishing agent | |
| CN101717469B (en) | Flame-retardant acrylonitrile copolymer and preparation method thereof | |
| CN104558392B (en) | Manufacturing method of highly flame-retardant modified polyacrylonitrile, and flame-retardant fiber | |
| CN103242535B (en) | Linear water-soluble polyphosphazene high-molecular adhesive blended modified fire retardant | |
| CN107973885B (en) | Tough fire retardant agent and preparation method thereof | |
| CN115246859A (en) | A kind of carbamate trimethylol phosphine oxide and its preparation method and application | |
| CN113880981A (en) | Phosphorus-containing polyacrylate adhesive and preparation method and application thereof | |
| CN101457475B (en) | Method for preparing melamine phosphonate flame-retardant-anti-crease integrated dressing agent for cotton | |
| CN103265653B (en) | Fire retardant, preparation method thereof and application thereof in polyvinyl chloride (PVC) wire and cable materials | |
| CN109180881A (en) | A kind of preparation method of highly effective flame-retardant polystyrene | |
| CN110592950B (en) | A kind of method for preparing flame retardant cotton fabric without solvent | |
| CN107686531B (en) | Polyacrylate emulsion for air filter paper and preparation method and application thereof | |
| JP2580724B2 (en) | Manufacturing method of flame retardant fiber | |
| CN112746347A (en) | Preparation method of halogen-free flame-retardant polyacrylonitrile fiber | |
| CN114085337B (en) | Flame retardant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170301 Termination date: 20210330 |