CN110615866B - 一种可逆加成-断裂链转移聚合体系及其在制备嵌段环化共聚物中的应用 - Google Patents
一种可逆加成-断裂链转移聚合体系及其在制备嵌段环化共聚物中的应用 Download PDFInfo
- Publication number
- CN110615866B CN110615866B CN201910959048.8A CN201910959048A CN110615866B CN 110615866 B CN110615866 B CN 110615866B CN 201910959048 A CN201910959048 A CN 201910959048A CN 110615866 B CN110615866 B CN 110615866B
- Authority
- CN
- China
- Prior art keywords
- monomer
- chain transfer
- polymerization
- methyl
- initiator
- 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.)
- Active
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 33
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000000178 monomer Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 230000001588 bifunctional effect Effects 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 229910052710 silicon Chemical group 0.000 claims description 8
- 239000010703 silicon Chemical group 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000012986 chain transfer agent Substances 0.000 claims description 4
- -1 dithiobenzoic acid cyano isopropyl ester Chemical class 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 238000013467 fragmentation Methods 0.000 claims description 2
- 238000006062 fragmentation reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 9
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- IDSLBLWCPSAZBL-UHFFFAOYSA-N 2-cyanopropan-2-yl benzenecarbodithioate Chemical group N#CC(C)(C)SC(=S)C1=CC=CC=C1 IDSLBLWCPSAZBL-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 4
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 4
- 241000953555 Theama Species 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920005565 cyclic polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F222/00—Copolymers 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
本发明涉及一种可逆加成‑断裂链转移聚合体系及其在制备嵌段环化共聚物中的应用，由聚合介质、双官能团单体、单官能团单体、链转移试剂、引发剂构成的聚合体系本发明通过碳或硅上的偕二甲基效应，设计双官能团呈相互接近构象的单体分子，通过可逆加成‑断裂链转移聚合体系，引发双官能团单体及单官能团环化共聚得到主链上序列具有有序结构的新型嵌段环化共聚物。本发明方法所设计的单体合成简便，克服了因发生交联反应而不能得到目标产物的困难，通过本方法容易合成具有不同大小环的线性环化共聚物。
Description
技术领域
本申请属于高分子化合物技术领域，具体涉及一种可逆加成-断裂链转移聚合(RAFT)体系及其在制备嵌段环化共聚物中的应用。
背景技术
主链含有大环的线性环化聚合物(Linear cyclopolymer)[Sakai,R.；Satoh,T.；Kakuchi,R.；Kaga,H.；Kakuchi,T.Macromolecules 2004,37,3996]是一类通过双官能团单体由分子内/分子间链增长交替进行而得到的新型聚合物。这种聚合物中的大环可以通过设计而作为金属离子、有机小分子、手性分子(如氨基酸)等识别主体，因而这种聚合物有望作为金属离子分离、手性分离等的固定相分离材料。环化聚合(Cyclopolymerization)是通过单体分子中的两个反应官能团经引发，先进行分子内环化、再分子间反应的这两种链传递反应交替进行的聚合反应，环化聚合是合成线性环化聚合物的一种主要方法。环化聚合的方法有自由基聚合、阴离子聚合、过渡金属催化聚合、基团转移聚合(GTP)、原子转移自由基聚合(ATRP)等。由于环化反应热力学稳定性的影响，成功合成的环化聚合物主要是含五元环、六元环的线性环化聚合物[Coluccini,C.；Metrangolo,P.；Parachini,M.；Pasini,D.；Resnati,G.；Righetti,P.J.Polym.Sci.Part A:Polym Chem.2008,46,5202]，合成大环线性环化聚合物比较困难。
有效合成大环线性环化聚合物关键在于所设计的双官能团单体分子的反应官能团呈相互接近的构象，这种构象有利于降低分子内环化反应的活化能，提高分子内成环反应活性。利用环己烷环张力和分子内相邻氨基的氢键作用，Endo首次设计了双官能团呈相互接近构象的单体分子，并顺利合成了含十九元大环的线性环化聚合物[Ochiai,B.；Ootani,Y.；Endo,T.J.Am.Chem.Soc.2008,130,10832]。由于单体设计方法的限制，用于合成大环线性环化聚合物的例子则较少。
本发明希望利用偕二甲基(Thorpe-Ingold)效应设计大环环化聚合单体，利用所设计的单体克服单体分子中双官能团活性相对低而导致合成大环环化聚合物困难的难题，通过环化共聚合成新型嵌段环化共聚物。
发明内容
为了克服现有技术存在的不足，本发明利用全新的环化单体设计方法，即通过碳或硅上的偕二甲基效应，设计反应双官能团呈相互接近的构象环化聚合单体，这种设计提高了单体的反应双官能团的反应活性，再利用RAFT技术合成新型嵌段环化共聚物。
为实现上述目的，本发明所采取的技术方案为：
一种可逆加成-断裂链转移聚合体系，由聚合介质、双官能团单体、单官能团单体、链转移试剂、引发剂构成的聚合体系，
所述双官能团单体的结构式如(I)所示：
式(I)中，Y为碳或硅，R1为甲基、苯基或异丙基；R2为甲基、苯基或异丙基；R3为氢原子或甲基，n为2、3或4；
所述单官能团单体的结构式如(II)所示：
式(II)中R4为甲基或乙基，R5为氢原子或甲基。
本发明通过可逆加成-断裂链转移聚合体系，引发双官能团单体及单官能团环化共聚得到主链上序列具有有序结构的新型嵌段环化共聚物。其中可逆加成-断裂链转移聚合体系的通式为S/M1/M2/R/I，式中S表示聚合介质，M1是双官能团单体，M2是单官能团单体，R是链转移试剂，I是引发剂。
作为优选，所述聚合介质为二甲亚砜、N，N-二甲基甲酰胺、甲苯中的一种。
作为优选，所述链转移试剂为二硫代苯甲酸氰基异丙酯(CPDB)。
作为优选，所述引发剂为偶氮二异丁腈(AIBN)。
作为优选，所述双官能团单体、单官能团单体、链转移试剂、引发剂的摩尔比为100：100：4：1。
作为优选，聚合体系中双官能团单体或单官能团单体的浓度为0.0375mol/L～0.075mol/L。本发明通过控制聚合介质(溶剂)的添加量来配置M1和M2的浓度，浓度的控制是制备有序结构的嵌段环化共聚物的一个重要因素。
上述可逆加成-断裂链转移聚合体系在制备嵌段环化共聚物中的应用，包括下述步骤：
(1)在氮气保护下，将链转移试剂加入聚合介质中，搅拌溶解；
(2)加入通氮除氧的双官能团单体和单官能团单体，继续通氮除氧气；
(3)在氮气保护下加入引发剂，升温到设定温度，恒温反应；
(4)反应结束后，用甲醇沉淀聚合液得共聚物。
作为优选，聚合体系的反应温度为75～90℃。
作为优选，所述聚合介质为二甲亚砜、N，N-二甲基甲酰胺、甲苯中的一种；所述链转移试剂为二硫代苯甲酸氰基异丙酯；所述引发剂为偶氮二异丁腈。
作为优选，所述双官能团单体、单官能团单体、链转移试剂、引发剂的摩尔比为100：100：4：1；聚合体系中双官能团单体或单官能团单体的浓度为0.0375mol/L～0.075mol/L。
发明所设计的聚合单体中的双官能团呈相互接近的构象，该构象提高了分子内环化反应的活性，有利于反应按生成大环线性环化聚合物的方向进行，克服了因发生交联反应而不能得到目标产物的困难。
本发明与现有技术术相比，本发明方法所设计的单体合成简便，通过本方法容易合成具有不同大小环的线性环化共聚物。
具体实施方式
下面通过实施例，对本发明的技术方案作进一步具体的说明，这些实施例是对本发明的说明而作，不是对本发明的限制。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。实施例中的物质份数都为摩尔份数。
实施例1
M1单体(式(I)中Y为硅，R1为苯基，R2为苯基；R3为甲基，n为2)和M2单体(通式中R4为甲基，R5为氢)的环化共聚
称取二硫代苯甲酸氰基异丙酯(CPDB)4份，溶解在相应体积量的甲苯中，通氮除氧气。称取100份的M1单体和M2单体，通氮除氧气后，加入甲苯溶液中，继续通氮除氧，加入1份的偶氮二异丁腈(AIBN)引发剂，加热到80℃温度下恒温反应。3小时后，用甲醇处理聚合液，得新型嵌段环化共聚物，Mn＝3000，PDI＝1.27。所得共聚物经水解处理后，核磁分析，δ＝0.98ppm，1.14ppm处出现MMA序列的峰，其主链结构为MAM-MAM-MAM序列MAM为重复单元有序结构的嵌段环化共聚物。
实施例2
M1单体(通式中Y为硅，R1为甲基，R2为苯基；R3为甲基，n为3)和M2单体(通式中R4为乙基，R5为氢)的环化共聚
称取二硫代苯甲酸氰基异丙酯(CPDB)4份，溶解在相应体积量的二甲亚砜中，通氮除氧气。称取100份的M1单体和M2单体，通氮除氧气后，加入甲苯溶液中，继续通氮除氧，加入1份的偶氮二异丁腈(AIBN)引发剂，加热到80℃温度下恒温反应。4小时后，用甲醇处理聚合液，得新型嵌段环化共聚物，Mn＝3200，PDI＝1.30。所得共聚物经水解处理后，核磁分析，δ＝0.98ppm，1.14ppm处出现MMA序列的峰，其主链结构为MAM-MAM-MAM序列MAM为重复单元有序结构的嵌段环化共聚物。
实施例3
M1单体(通式中Y为硅，R1为异丙基，R2为异丙基；R3为甲基，n为4)和M2单体(通式中R4为甲基，R5为氢)的环化共聚
称取二硫代苯甲酸氰基异丙酯(CPDB)4份，溶解在相应体积量的N，N-二甲基甲酰胺中，通氮除氧气。称取100份的M1单体和M2单体，通氮除氧气后，加入甲苯溶液中，继续通氮除氧，加入1份的偶氮二异丁腈(AIBN)引发剂，加热到80℃温度下恒温反应。4小时后，用甲醇处理聚合液，得新型嵌段环化共聚物，Mn＝3500，PDI＝1.23。所得共聚物经水解处理后，核磁分析，δ＝0.98ppm，1.14ppm处出现MMA序列的峰，其主链结构为MAM-MAM-MAM序列MAM为重复单元有序结构的嵌段环化共聚物。
实施例4
M1单体(通式中Y为碳，R1为异丙基，R2为异丙基；R3为甲基，n为3)和M2单体(通式中R4为甲基，R5为氢)的环化共聚
称取二硫代苯甲酸氰基异丙酯(CPDB)4份，溶解在相应体积量的甲苯中，通氮除氧气。称取100份的M1单体和M2单体，通氮除氧气后，加入甲苯溶液中，继续通氮除氧，加入1份的偶氮二异丁腈(AIBN)引发剂，加热到80℃温度下恒温反应。4小时后，用甲醇处理聚合液，得新型嵌段环化共聚物，Mn＝3400，PDI＝1.20。所得共聚物经水解处理后，核磁分析，δ＝0.98ppm，1.14ppm处出现MMA序列的峰，其主链结构为MAM-MAM-MAM序列MAM为重复单元有序结构的嵌段环化共聚物。
实施例5
M1单体(通式中Y为硅，R1为苯基，R2为苯基；R3为氢，n为3)和M2单体(通式中R4为甲基，R5为甲基)的环化共聚
称取二硫代苯甲酸氰基异丙酯(CPDB)4份，溶解在相应体积量的甲苯中，通氮除氧气。称取100份的M1单体和M2单体，通氮除氧气后，加入甲苯溶液中，继续通氮除氧，加入1份的偶氮二异丁腈(AIBN)引发剂，加热到80℃温度下恒温反应。4小时后，用甲醇处理聚合液，得新型嵌段环化共聚物，Mn＝2800，PDI＝1.25。所得共聚物经水解处理后，核磁分析，δ＝1.02ppm，1.09ppm，1.14ppm处出现AMA序列的峰，其主链结构为AMA-MAM-AMA序列AMA为重复单元有序结构的嵌段环化共聚物。
实施例6
M1单体(通式中Y为硅，R1为苯基，R2为苯基；R3为氢，n为3)和M2单体(通式中R4为乙基，R5为甲基)的环化共聚
称取二硫代苯甲酸氰基异丙酯(CPDB)4份，溶解在相应体积量的甲苯中，通氮除氧气。称取100份的M1单体和M2单体，通氮除氧气后，加入甲苯溶液中，继续通氮除氧，加入1份的偶氮二异丁腈(AIBN)引发剂，加热到80℃温度下恒温反应。4小时后，用甲醇处理聚合液，得新型嵌段环化共聚物，Mn＝2900，PDI＝1.25。所得共聚物经水解处理后，核磁分析，δ＝1.02ppm，1.09ppm，1.14ppm处出现AMA序列的峰，其主链结构为AMA-MAM-AMA序列AMA为重复单元有序结构的嵌段环化共聚物。
实施例7
M1单体(通式中Y为碳，R1为苯基，R2为苯基；R3为氢，n为3)和M2单体(通式中R4为乙基，R5为甲基)的环化共聚
称取二硫代苯甲酸氰基异丙酯(CPDB)4份，溶解在相应体积量的甲苯中，通氮除氧气。称取100份的M1单体和M2单体，通氮除氧气后，加入二甲亚砜溶液中，继续通氮除氧，加入1份的偶氮二异丁腈(AIBN)引发剂，加热到80℃温度下恒温反应。5小时后，用甲醇处理聚合液，得新型嵌段环化共聚物，Mn＝3100，PDI＝1.29。所得共聚物经水解处理后，核磁分析，δ＝1.02ppm，1.09ppm，1.14ppm处出现AMA序列的峰，其主链结构为AMA-MAM-AMA序列AMA为重复单元有序结构的嵌段环化共聚物。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。
Claims (2)
1.一种可逆加成-断裂链转移聚合体系，其特征在于由聚合介质、双官能团单体、单官能团单体、链转移试剂、引发剂构成的聚合体系，
所述双官能团单体的结构式如（I）所示：
（I）
式（I）中，Y为碳或硅，R1为甲基、苯基或异丙基；R2为甲基、苯基或异丙基；R3为氢原子或甲基，n为2、3或4；
所述单官能团单体的结构式如（II）所示：
（II）
式（II）中R4为甲基或乙基，R5为氢原子或甲基；
所述聚合介质为二甲亚砜、N，N-二甲基甲酰胺、甲苯中的一种；
所述链转移试剂为二硫代苯甲酸氰基异丙酯；
所述引发剂为偶氮二异丁腈；
所述双官能团单体、单官能团单体、链转移试剂、引发剂的摩尔比为100：100：4：1；聚合体系中双官能团单体或单官能团单体的浓度为0.0375mol/L~ 0.075mol/L；
聚合体系的反应温度为75~90℃。
2.一种权利要求1所述可逆加成-断裂链转移聚合体系在制备嵌段环化共聚物中的应用，其特征在于包括下述步骤：
（1）在氮气保护下，将链转移试剂加入聚合介质中，搅拌溶解；
（2）加入通氮除氧的双官能团单体和单官能团单体，继续通氮除氧气；
（3）在氮气保护下加入引发剂，升温到设定温度，恒温反应；
（4）反应结束后，用甲醇沉淀聚合液得共聚物。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910959048.8A CN110615866B (zh) | 2019-10-10 | 2019-10-10 | 一种可逆加成-断裂链转移聚合体系及其在制备嵌段环化共聚物中的应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910959048.8A CN110615866B (zh) | 2019-10-10 | 2019-10-10 | 一种可逆加成-断裂链转移聚合体系及其在制备嵌段环化共聚物中的应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110615866A CN110615866A (zh) | 2019-12-27 |
| CN110615866B true CN110615866B (zh) | 2021-10-08 |
Family
ID=68925299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910959048.8A Active CN110615866B (zh) | 2019-10-10 | 2019-10-10 | 一种可逆加成-断裂链转移聚合体系及其在制备嵌段环化共聚物中的应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110615866B (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044595A (zh) * | 2012-11-09 | 2013-04-17 | 杭州师范大学 | 一种大环线性环化聚合物的制备方法 |
| CN109988261A (zh) * | 2019-04-03 | 2019-07-09 | 南华大学 | 一种含脲基大环的环化聚合物及其制备方法和应用 |
-
2019
- 2019-10-10 CN CN201910959048.8A patent/CN110615866B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044595A (zh) * | 2012-11-09 | 2013-04-17 | 杭州师范大学 | 一种大环线性环化聚合物的制备方法 |
| CN109988261A (zh) * | 2019-04-03 | 2019-07-09 | 南华大学 | 一种含脲基大环的环化聚合物及其制备方法和应用 |
Non-Patent Citations (1)
| Title |
|---|
| Acid-cleavable polymeric core–shell particles for delivery of hydrophobic drugs;Yannie Chan,et al.,;《Journal of Controlled Release》;20061010;197-207页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110615866A (zh) | 2019-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mbarushimana et al. | Polymerizations of nitrophenylsulfonyl-activated aziridines | |
| Janoschka et al. | Polymerization of free secondary amine bearing monomers by RAFT polymerization and other controlled radical techniques | |
| Hong et al. | Synthesis and characterization of well‐defined diblock and triblock copolymers of poly (N‐isopropylacrylamide) and poly (ethylene oxide) | |
| Amalin Kavitha et al. | A tailor‐made polymethacrylate bearing a reactive diene in reversible diels–alder reaction | |
| Roy et al. | RAFT polymerization of methacrylates containing a tryptophan moiety: controlled synthesis of biocompatible fluorescent cationic chiral polymers with smart pH-responsiveness | |
| Wendler et al. | Amphiphilic cationic block copolymers via controlled free radical polymerization | |
| Nagasaki et al. | Primary amino-terminal heterobifunctional poly (ethylene oxide). Facile synthesis of poly (ethylene oxide) with a primary amino group at one end and a hydroxyl group at the other end | |
| Audouin et al. | Star polymers by cross‐linking of linear poly (benzyl‐l‐glutamate) macromonomers via free‐radical and RAFT polymerization. A simple route toward peptide‐stabilized nanoparticles | |
| Li et al. | Precise synthesis of poly (N-acryloyl amino acid) through photoinduced living polymerization | |
| Yakimanskii et al. | Grafting copolymerization of vinyl monomers on polyimide macroinitiators by the method of atom transfer radical polymerization | |
| Zhou et al. | Enzyme mimetic-catalyzed ATRP and its application in block copolymer synthesis combined with enzymatic ring-opening polymerization | |
| Pan et al. | Dual thermo‐and pH‐sensitive network‐grafted hydrogels formed by macrocrosslinker as drug delivery system | |
| Ling et al. | Deprotonation Reaction of α‐Amino acid N‐Carboxyanhydride at 4‐CH Position by Yttrium Tris [bis (trimethylsilyl) amide] | |
| Liu et al. | Controlled polymerization of 2‐(diethylamino) ethyl methacrylate and its block copolymer with N‐isopropylacrylamide by RAFT polymerization | |
| Max et al. | Double Hydrophilic Poly (ethylene oxide)‐block‐Poly (dehydroalanine) Block Copolymers: Comparison of Two Different Synthetic Routes | |
| Sanda et al. | Helical Polymer Carrying Helical Grafts from Peptide‐Based Acetylene Macromonomers: Synthesis | |
| CN112961278A (zh) | 一种功能化乙烯基吡咯烷酮共聚物及其制备方法 | |
| CN110615866B (zh) | 一种可逆加成-断裂链转移聚合体系及其在制备嵌段环化共聚物中的应用 | |
| Chen et al. | Ultrafast organocatalytic ring‐opening polymerization of N‐sulfonyl aziridine in the melt | |
| Yamamoto et al. | Synthesis and functionalities of poly (N‐vinylalkylamide). XII. Synthesis and thermosensitive property of poly (vinylamine) copolymer prepared from poly (N‐vinylformamide‐co‐N‐vinylisobutyramide) | |
| JP5250641B2 (ja) | ｐＨ感受性ポリエチレンオキシドコポリマー及びそれらの合成方法 | |
| WO2018197885A1 (en) | Branched polymers | |
| Karatzas et al. | Synthesis of well-defined functional macromolecular chimeras based on poly (ethylene oxide) or poly (N-vinyl pyrrolidone) | |
| Wang et al. | Preparation and characterization of novel hyperbranched poly (amido amine) s from Michael addition polymerizations of trifunctional amines with diacrylamides | |
| Ekinci et al. | Preparation and Characterization of an Aromatic Polyimide and Its Use as a Selective Membrane for H_2O_2 |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |