CN115141297A - 一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法 - Google Patents
一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法 Download PDFInfo
- Publication number
- CN115141297A CN115141297A CN202210803822.8A CN202210803822A CN115141297A CN 115141297 A CN115141297 A CN 115141297A CN 202210803822 A CN202210803822 A CN 202210803822A CN 115141297 A CN115141297 A CN 115141297A
- Authority
- CN
- China
- Prior art keywords
- functional group
- disulfide
- nitrobenzyl
- synthesizing
- epoxy
- 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.)
- Granted
Links
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 40
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 39
- 239000003999 initiator Substances 0.000 title claims abstract description 34
- -1 pyridinium ester Chemical class 0.000 title claims abstract description 17
- KTDBRQXHEDDCIW-UHFFFAOYSA-N [N+](=O)([O-])C(C1=CC=CC=C1)SSC(C1=CC=CC=C1)[N+](=O)[O-] Chemical compound [N+](=O)([O-])C(C1=CC=CC=C1)SSC(C1=CC=CC=C1)[N+](=O)[O-] KTDBRQXHEDDCIW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000001308 synthesis method Methods 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims abstract description 27
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- PTMBWNZJOQBTBK-UHFFFAOYSA-N pyridin-4-ylmethanol Chemical compound OCC1=CC=NC=C1 PTMBWNZJOQBTBK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 7
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 4
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims abstract description 4
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 3
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical group 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 238000001782 photodegradation Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YJIHPMSQOPZABY-UHFFFAOYSA-N 2-nitrosobenzaldehyde Chemical compound O=CC1=CC=CC=C1N=O YJIHPMSQOPZABY-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
本发明涉及可降解聚苯乙烯合成技术领域，且公开了一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法，通过4，4′‑偶氮双(4‑氰基戊酸)的羧酸官能团与4‑吡啶甲醇的醇羟基官能团发生脱水缩合反应，得到吡啶化中间单体M1，中间单体M1的吡啶官能团与环氧溴丙烷的溴官能团发生烷基化反应，得到环氧化中间单体M2，中间单体M2的环氧官能团与2‑硝基‑1，4‑苄二硫醇的巯基官能团发生环氧开环反应，得到大分子偶氮引发剂P，大分子偶氮引发剂P引发苯乙烯的自由基聚合，制备得到主链上含有紫外光光降解基团硝基苄二硫醚、可见光光降解基团不对称烷基吡啶鎓酯的聚苯乙烯。
Description
技术领域
本发明涉及可降解聚苯乙烯合成技术领域，具体为一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法。
背景技术
聚苯乙烯(PS)是由苯乙烯单体通过聚合而形成的线性高分子，由于聚苯乙烯物理机械性能良好，能适应多种加工方式且性价比较高，因此，此类制品在我们的日常生活中随处可见，聚苯乙烯塑料被应用于一次性快餐饭盒、电子器件如仪表外壳、建筑板材等制品中，虽然聚苯乙烯拥有很多的优点，但在自然条件下不易降解，废弃后易造成环境污染。聚苯乙烯难以降解的主要原因是其主链由稳定性高的碳碳键构成，在自然条件下不易断裂。如果在聚苯乙烯主链引入易断裂的化学键，使聚苯乙烯在特定条件下降解成为低聚物，低聚物进一步被微生物生物分解，就可以实现聚苯乙烯的降解。
研究发现：2-硝基-1，4-苄二硫醚类物质在紫外光照条件下，硝基被异构化后，苯环上a位上的氢均可以产生自由基，导致物质会按照两种方式进行降解，一是与硝基邻位上的取代基变成醛基，生成邻亚硝基苯甲醛类的产物，另一种是硝基间位上的取代基变成醛基；不对称烷基吡啶鎓酯结构是类可见光光裂解基团，其在可见光触发下可以通过与联吡啶钌/抗坏血酸之间发生间接电子转移过程实现C-O键断裂；
本发明引用下述参考文献：温州大学的硕士学位论文《光敏性2-硝基-1-4-苄二硫醇在高分子合成中的应用及其光降解机理研究》公开了2-硝基-1，4-苄二硫醇的结构和制备方法。
发明内容
(一)解决的技术问题
针对现有技术聚苯乙烯在自然条件下不易降解，废弃后易造成环境污染的不足，本发明提供一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法。
(二)技术方案
为实现上述目的，本发明提供如下技术方案：
一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法，包括以下步骤：
步骤Step1，合成主链上含有紫外光光降解基团硝基苄二硫醚和可见光光降解基团吡啶鎓酯的大分子偶氮引发剂P；
步骤Step2，将1份的苯乙烯，0.2-0.4份的大分子偶氮引发剂P溶解于N，N-二甲基甲酰胺中，并将其置于封管当中，经过冷冻-抽真空-通氮气解冻后，在抽真空的条件下进行封管反应得到可降解聚苯乙烯。
优选的，所述步骤Step1，大分子偶氮引发剂P的合成方法如下：
步骤Step1-1，4，4′-偶氮双(4-氰基戊酸)的羧酸官能团与4-吡啶甲醇的醇羟基官能团发生脱水缩合反应，得到吡啶化中间单体M1；
步骤Step1-2，中间单体M1的吡啶官能团与环氧溴丙烷的溴官能团发生烷基化反应，得到环氧化中间单体M2；
步骤Step1-3，中间单体M2的环氧官能团与2-硝基-1，4-苄二硫醇的巯基官能团发生环氧开环反应，得到大分子偶氮引发剂P。
优选的，所述步骤Step1-1，吡啶化中间单体M1的合成过程采用催化剂4-二甲氨基吡啶。
优选的，所述步骤Step1-3，大分子偶氮引发剂P的合成过程采用催化剂一水氢氧化锂。
优选的，所述步骤Step2，经过三次冷冻-抽真空-通氮气解冻后，在抽真空的条件下进行封管，在80-100℃下反应4-6h，得到可降解聚苯乙烯。
(三)有益的技术效果
与现有技术相比，本发明具备以下有益的技术效果：
本发明通过：4，4′-偶氮双(4-氰基戊酸)的羧酸官能团与4-吡啶甲醇的醇羟基官能团发生脱水缩合反应，得到吡啶化中间单体M1，中间单体M1的吡啶官能团与环氧溴丙烷的溴官能团发生烷基化反应，得到环氧化中间单体M2，中间单体M2的环氧官能团与2-硝基-1，4-苄二硫醇的巯基官能团发生环氧开环反应，得到大分子偶氮引发剂P，大分子偶氮引发剂P引发苯乙烯的自由基聚合，制备得到主链上含有紫外光光降解基团硝基苄二硫醚、可见光光降解基团不对称烷基吡啶鎓酯的聚苯乙烯，渗透凝胶色谱(GPC)的测试结果证明利用该主链上的光降解基团可以实现聚苯乙烯的降解。
附图说明
图1为合成吡啶化中间单体M1的反应式；
图2为合成环氧化中间单体M2的反应式；
图3为合成大分子偶氮引发剂P的反应式；
图4为基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯的结构式。
具体实施方式
实施例1：
吡啶化中间单体M1的合成：
取280mg4，4′-偶氮双(4-氰基戊酸)、218mg4-吡啶甲醇和50mg4-二甲氨基吡啶催化剂溶解在100mL二氯甲烷中，室温条件下搅拌24h，反应完毕之后依次用饱和碳酸氢钠以及饱和氯化钠溶液洗涤，有机相用无水硫酸镁干燥，收集有机相旋蒸，得到吡啶化中间单体M1；
环氧化中间单体M2的合成：
称取277mg中间单体M1溶于5mL二甲基亚砜，之后加入163mg环氧溴丙烷，将反应体系置于85℃油浴中反应24h，反应液在二氯甲烷中沉淀，得到中间单体M2；
大分子偶氮引发剂P的合成：
称取103mg2-硝基-1，4-苄二硫醇于含有6mL四氢呋喃的50mL的圆底烧瓶中，之后加入353mg中间单体M2，2mg一水氢氧化锂催化剂，在室温条件下磁力搅拌反应24h，反应结束后调节pH值至中性，加入无水硫酸镁干燥3h，过滤，收集滤液，旋蒸，将产物溶解于二氯甲烷中、沉淀在环己烷中，之后于40℃真空干燥24h，得到大分子偶氮引发剂P；
可降解聚苯乙烯的合成：
将1g苯乙烯，332mg大分子偶氮引发剂P溶解于1mL的N，N-二甲基甲酰胺中，并将其置于5mL的封管当中，经过三次冷冻-抽真空-通氮气解冻后，在抽真空的条件下进行封管，80℃下反应6h，反应物在甲醇中沉淀三次后，在真空烘箱中干燥得到可降解聚苯乙烯；
称取本实施例1制备的样品6mg-10mg之间的质量于2mL的四氢呋喃中，样品完全溶解后，转移至玻璃表面皿上，测试其渗透凝胶色谱(GPC)，之后于蓝色LED光(452nm，6W)和紫外光(365nm，2W)下同时辐照10h，再次测试其渗透凝胶色谱(GPC)，其具体方法如下：采用高效液相色谱(HPLC)分离单元e2695，以聚苯乙烯作为参比标准，流动相为四氢呋喃，流速设定为1mL/min，柱温设为35℃，流动相需预先通过保护预柱以及规格为7.8＊300mm的分离柱，检测器为2414示差检测器；测样时，取5mg待测样于1.0mL的色谱级四氢呋喃中，震荡2min，，加速物质溶解，然后将其经过粉色0.22um的聚四氟乙烯滤头，过滤至2mL的玻璃样品瓶中，除去不溶物和大颗粒的物质，防止阻塞GPC内部的注射针头，最后，将样品瓶上样，测样，其测试结果如下：
光照前渗透凝胶色谱(GPC)的测试结果为：数均分子量Mn＝27150g/moL，重均分子量Mw＝46427，PDI＝Mw/Mn＝1.71；
光照后渗透凝胶色谱(GPC)的测试结果为：数均分子量Mn＝6981g/moL；
由此可知，实施例1制备的聚苯乙烯具有光降解功能。
实施例2：
可降解聚苯乙烯的合成：
将1g苯乙烯，238mg大分子偶氮引发剂P溶解于1mL的N，N-二甲基甲酰胺中，并将其置于5mL的封管当中，经过三次冷冻-抽真空-通氮气解冻后，在抽真空的条件下进行封管，90℃下反应6h，反应物在甲醇中沉淀三次后，在真空烘箱中干燥得到可降解聚苯乙烯；
其中，大分子偶氮引发剂P采用实施例1的制备方法制备得到；
实施例3：
可降解聚苯乙烯的合成：
将1g苯乙烯，380mg大分子偶氮引发剂P溶解于1mL的N，N-二甲基甲酰胺中，并将其置于5mL的封管当中，经过三次冷冻-抽真空-通氮气解冻后，在抽真空的条件下进行封管，100℃下反应4h，反应物在甲醇中沉淀三次后，在真空烘箱中干燥得到可降解聚苯乙烯；
其中，大分子偶氮引发剂P采用实施例1的制备方法制备得到。
Claims (5)
1.一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法，其特征在于，包括以下步骤：
步骤Step1，合成主链上含有紫外光光降解基团硝基苄二硫醚和可见光光降解基团吡啶鎓酯的大分子偶氮引发剂P；
步骤Step2，将1份的苯乙烯，0.2-0.4份的大分子偶氮引发剂P溶解于N，N-二甲基甲酰胺中，并将其置于封管当中，经过冷冻-抽真空-通氮气解冻后，在抽真空的条件下进行封管反应得到可降解聚苯乙烯。
2.根据权利要求1所述的一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法，其特征在于，所述步骤Step1，大分子偶氮引发剂P的合成方法如下：
步骤Step1-1，4，4′-偶氮双(4-氰基戊酸)的羧酸官能团与4-吡啶甲醇的醇羟基官能团发生脱水缩合反应，得到吡啶化中间单体M1；
步骤Step1-2，中间单体M1的吡啶官能团与环氧溴丙烷的溴官能团发生烷基化反应，得到环氧化中间单体M2；
步骤Step1-3，中间单体M2的环氧官能团与2-硝基-1，4-苄二硫醇的巯基官能团发生环氧开环反应，得到大分子偶氮引发剂P。
3.根据权利要求2所述的一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法，其特征在于，所述步骤Step1-1，吡啶化中间单体M1的合成过程采用催化剂4-二甲氨基吡啶。
4.根据权利要求2所述的一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法，其特征在于，所述步骤Step1-3，大分子偶氮引发剂P的合成过程采用催化剂一水氢氧化锂。
5.根据权利要求1-4任一项所述的一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法，其特征在于，所述步骤Step2，经过三次冷冻-抽真空-通氮气解冻后，在抽真空的条件下进行封管，在80-100℃下反应4-6h，得到可降解聚苯乙烯。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210803822.8A CN115141297B (zh) | 2022-07-07 | 2022-07-07 | 一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210803822.8A CN115141297B (zh) | 2022-07-07 | 2022-07-07 | 一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115141297A true CN115141297A (zh) | 2022-10-04 |
| CN115141297B CN115141297B (zh) | 2024-02-20 |
Family
ID=83412217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210803822.8A Active CN115141297B (zh) | 2022-07-07 | 2022-07-07 | 一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115141297B (zh) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0466026A2 (en) * | 1990-07-07 | 1992-01-15 | Mitsubishi Rayon Co., Ltd | Biodegradable polymers |
| US5206371A (en) * | 1990-08-10 | 1993-04-27 | Georgia Tech Research Corporation | Quaternary pyridinium compounds |
| WO2004087777A2 (en) * | 2003-03-28 | 2004-10-14 | Carnegie Mellon University | Degradable polymers |
| EP2018847A1 (fr) * | 2007-07-24 | 2009-01-28 | L'Oreal | Composition capillaire comprenant au moins un colorant direct disulfure et au moins un agent alcalin hydroxyde et procédé de mise en forme et de coloration simultanées. |
| WO2012015481A1 (en) * | 2010-07-28 | 2012-02-02 | University Of Akron | Functional biodegradable polymers |
| WO2012054456A1 (en) * | 2010-10-20 | 2012-04-26 | Schlumberger Canada Limited | Degradable latex and method |
| CN103826467A (zh) * | 2011-09-22 | 2014-05-28 | 洲际大品牌有限责任公司 | 光可降解的胶基糖基础剂、包括所述光可降解的胶基糖基础剂的咀嚼型胶基糖及其制作方法 |
| CN104177516A (zh) * | 2014-09-11 | 2014-12-03 | 青岛方达化工有限公司 | 一种溴化脂肪族烯烃/乙烯基芳香族共聚物阻燃剂及其制备方法 |
| CN104953034A (zh) * | 2015-04-22 | 2015-09-30 | 电子科技大学 | 可降解的柔性光电子器件用基板及其制备方法 |
| CN110066355A (zh) * | 2019-04-29 | 2019-07-30 | 南京工程学院 | 可降解聚苯乙烯及其制备方法 |
| CN113087659A (zh) * | 2020-01-09 | 2021-07-09 | 中国科学院长春应用化学研究所 | Dmap-硫脲催化剂及其制备方法和高分子量生物降解聚酯及其制备方法 |
| CN115028760A (zh) * | 2022-07-19 | 2022-09-09 | 李旭东 | 一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法 |
| CN115322314A (zh) * | 2022-07-18 | 2022-11-11 | 王兵 | 一种含有硝基苄二硫醚和吡啶鎓酯嵌段两端带溴可降解聚苯乙烯的合成方法 |
-
2022
- 2022-07-07 CN CN202210803822.8A patent/CN115141297B/zh active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0466026A2 (en) * | 1990-07-07 | 1992-01-15 | Mitsubishi Rayon Co., Ltd | Biodegradable polymers |
| US5206371A (en) * | 1990-08-10 | 1993-04-27 | Georgia Tech Research Corporation | Quaternary pyridinium compounds |
| WO2004087777A2 (en) * | 2003-03-28 | 2004-10-14 | Carnegie Mellon University | Degradable polymers |
| EP2018847A1 (fr) * | 2007-07-24 | 2009-01-28 | L'Oreal | Composition capillaire comprenant au moins un colorant direct disulfure et au moins un agent alcalin hydroxyde et procédé de mise en forme et de coloration simultanées. |
| WO2012015481A1 (en) * | 2010-07-28 | 2012-02-02 | University Of Akron | Functional biodegradable polymers |
| WO2012054456A1 (en) * | 2010-10-20 | 2012-04-26 | Schlumberger Canada Limited | Degradable latex and method |
| CN103826467A (zh) * | 2011-09-22 | 2014-05-28 | 洲际大品牌有限责任公司 | 光可降解的胶基糖基础剂、包括所述光可降解的胶基糖基础剂的咀嚼型胶基糖及其制作方法 |
| CN104177516A (zh) * | 2014-09-11 | 2014-12-03 | 青岛方达化工有限公司 | 一种溴化脂肪族烯烃/乙烯基芳香族共聚物阻燃剂及其制备方法 |
| CN104953034A (zh) * | 2015-04-22 | 2015-09-30 | 电子科技大学 | 可降解的柔性光电子器件用基板及其制备方法 |
| CN110066355A (zh) * | 2019-04-29 | 2019-07-30 | 南京工程学院 | 可降解聚苯乙烯及其制备方法 |
| CN113087659A (zh) * | 2020-01-09 | 2021-07-09 | 中国科学院长春应用化学研究所 | Dmap-硫脲催化剂及其制备方法和高分子量生物降解聚酯及其制备方法 |
| CN115322314A (zh) * | 2022-07-18 | 2022-11-11 | 王兵 | 一种含有硝基苄二硫醚和吡啶鎓酯嵌段两端带溴可降解聚苯乙烯的合成方法 |
| CN115028760A (zh) * | 2022-07-19 | 2022-09-09 | 李旭东 | 一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法 |
Non-Patent Citations (6)
| Title |
|---|
| KOOHMAREH, GA 等: "Synthesis and characterization of some new thermally stable polyimides and copolyimides bearing bipyridine side-chain groups", 《JOURNAL OF POLYMER RESEARCH》, vol. 18, no. 5, pages 983 - 991, XP019928635, DOI: 10.1007/s10965-010-9498-x * |
| PENG, XH 等: "Preparation and biodegradability of polystyrene having pyridinium group in the main chain", 《EUROPEAN POLYMER JOURNAL》, vol. 35, no. 9, pages 1599 - 1605, XP004362341, DOI: 10.1016/S0014-3057(98)00253-5 * |
| 周桐桐: "吡啶鎓酯类可见光降解型聚合物的合成与应用探索", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, pages 014 - 1942 * |
| 张涵之: "基于间接电子转移过程的含吡啶鎓酯可见光降解聚合物功能调控及应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, pages 016 - 852 * |
| 李大爱: "光敏性2-硝基-1, 4-苄二硫醇在高分子合成中的应用及其光降解机理研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, pages 016 - 907 * |
| 胡晓倩: "可光、化学降解聚苯乙烯的合成与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, pages 014 - 264 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115141297B (zh) | 2024-02-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pei et al. | Synthesis of water-soluble, fully biobased cellulose levulinate esters through the reaction of cellulose and alpha-angelica lactone in a DBU/CO 2/DMSO solvent system | |
| Sui et al. | Suzuki–Miyaura catalyst-transfer polycondensation with Pd (IPr)(OAc) 2 as the catalyst for the controlled synthesis of polyfluorenes and polythiophenes | |
| Zhang et al. | Terminal functional glycopolymers via a combination of catalytic chain transfer polymerisation (CCTP) followed by three consecutive click reactions | |
| CN115028760B (zh) | 一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法 | |
| Zhao et al. | Water soluble hyperbranched polymers from controlled radical homopolymerization of PEG diacrylate | |
| Memon et al. | Syntheses and binding properties of polymeric calix [4] crown-4 | |
| Ma et al. | BINOLs as visible light photocatalysts for metal-free atom transfer radical polymerization | |
| CN115322314B (zh) | 一种含有硝基苄二硫醚和吡啶鎓酯嵌段两端带溴可降解聚苯乙烯的合成方法 | |
| Yang et al. | Self-condensing reversible complexation-mediated copolymerization for highly branched polymers with in situ formed inimers | |
| CN115141297A (zh) | 一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子偶氮引发剂的可降解聚苯乙烯合成方法 | |
| Nonque et al. | Study on polymerization of bio-based isosorbide monomethacrylate for the formation of low-Tg and high-Tg sustainable polymers | |
| CN103965384B (zh) | 聚甲基丙烯酸甲酯的制备方法 | |
| CN114957573A (zh) | 一种含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的合成方法 | |
| CN112876665B (zh) | 以稀土催化剂合成含多不饱和侧基聚酯或聚醚酯及其后修饰的方法 | |
| US11905378B2 (en) | High-grafting density cyclic comb shaped polymer and preparation method therefor | |
| Yong et al. | Branched polystyrenes from suspension “Strathclyde” polymerization using a vulcanization accelerator as a chain transfer agent | |
| Kim et al. | Synthesis and photocrosslinking of poly (vinylbenzyl abietate) | |
| US9724686B2 (en) | Sulfonated polyethylene | |
| CN116789875B (zh) | 一种分子量可控的窄分布的聚甲基丙烯酸甲酯的制备方法 | |
| JP5283107B2 (ja) | 機能化された新規直鎖状重合体及びその製造方法 | |
| CN113402644B (zh) | 一种水溶性活性酯聚合物及其合成方法和应用 | |
| Thibaud et al. | Synthesis of well-defined soluble polystyrene supports: Impact of polymer chain on grafted organotin reagent activity | |
| RU2671564C1 (ru) | Способ получения аддитивных полимеров на основе норборненов, содержащих двойную связь в заместителе | |
| Guliev et al. | Synthesis and polymerization of (p-Vinylphenyl) cyclopropylmethyl cinnamate | |
| Buffagni | Reazioni Radicaliche a Trasferimento di Atomo: Polimerizzazione dello Stirene e Sintesi di γ-Lattoni |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240112 Address after: 515000 No.17, middle section of Jinsheng Road, Jinping District, Shantou City, Guangdong Province Applicant after: Guangdong Blue Ocean Packaging New Technology Co.,Ltd. Address before: No. 341, Unit 3, Building 30, Building 30, Hope Garden, Regiment 148, Xiying Town, Shihezi City, Xinjiang Uygur Autonomous Region 832000 Applicant before: Li Xudong |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |