CN110183598A - 主链型“半氟”交替共聚物的嵌段共聚物的光照聚合法 - Google Patents
主链型“半氟”交替共聚物的嵌段共聚物的光照聚合法 Download PDFInfo
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- CN110183598A CN110183598A CN201910579630.1A CN201910579630A CN110183598A CN 110183598 A CN110183598 A CN 110183598A CN 201910579630 A CN201910579630 A CN 201910579630A CN 110183598 A CN110183598 A CN 110183598A
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- monomer
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 34
- 239000011737 fluorine Substances 0.000 title claims abstract description 30
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 29
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 28
- 238000005286 illumination Methods 0.000 title claims abstract description 6
- 229920001577 copolymer Polymers 0.000 title abstract description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract 4
- 239000000178 monomer Substances 0.000 claims abstract description 49
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 229920005603 alternating copolymer Polymers 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 239000011941 photocatalyst Substances 0.000 claims description 8
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 7
- 229960005055 sodium ascorbate Drugs 0.000 claims description 7
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 7
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 7
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical group C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 claims description 6
- HMLSBRLVTDLLOI-UHFFFAOYSA-N 1-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)C(C)OC(=O)C(C)=C HMLSBRLVTDLLOI-UHFFFAOYSA-N 0.000 claims description 6
- -1 bis (1-hexene) terephthalate Chemical compound 0.000 claims description 6
- JOQDDLBOAIKFQX-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I JOQDDLBOAIKFQX-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
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- SRDQTCUHAMDAMG-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro-1,8-diiodooctane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I SRDQTCUHAMDAMG-UHFFFAOYSA-N 0.000 claims description 2
- JILAKKYYZPDQBE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)I JILAKKYYZPDQBE-UHFFFAOYSA-N 0.000 claims description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
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- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000008378 aryl ethers Chemical class 0.000 claims description 2
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 claims description 2
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical group C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 claims description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 3
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- 238000006243 chemical reaction Methods 0.000 description 16
- 239000004926 polymethyl methacrylate Substances 0.000 description 16
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
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- 239000000243 solution Substances 0.000 description 8
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- BZSVVCFHMVMYCR-UHFFFAOYSA-N 2-pyridin-2-ylpyridine;ruthenium Chemical compound [Ru].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 BZSVVCFHMVMYCR-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- WWZSWFPFBCVCJQ-UHFFFAOYSA-N 1,4-bis(hex-5-enyl)benzene Chemical compound C=CCCCCC1=CC=C(CCCCC=C)C=C1 WWZSWFPFBCVCJQ-UHFFFAOYSA-N 0.000 description 1
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 description 1
- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 description 1
- DUGLMATUSUVYMV-UHFFFAOYSA-N 7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical group C1=C(O2)C=CC2=C1 DUGLMATUSUVYMV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
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- 125000003651 hexanedioyl group Chemical group C(CCCCC(=O)*)(=O)* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 1
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- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
本发明涉及一种主链型“半氟”交替共聚物的嵌段共聚物的光照聚合法，包括以下步骤：在保护气氛中，将甲基丙烯酸酯类单体和“半氟”交替共聚物(AB)n大分子引发剂在光催化剂作用下，在有机溶剂中于20‑30℃下发生光控活性自由基聚合，该聚合反应在390nm‑590nm的光照条件下进行至少半小时，得到主链型聚烯烃、聚酯或者聚醚“半氟”交替共聚物的嵌段共聚物。该聚合方法在可见光照射条件下进行，聚合过程具有“活性”自由基聚合特性，所制备的聚合物分子量分布较窄。
Description
技术领域
本发明涉及聚合物制备技术领域，尤其涉及一种主链型“半氟”交替共聚物的嵌段共聚物的光照聚合法。
背景技术
拓扑结构聚合物的出现不仅拓展了高分子材料的性能，而且使聚合物结构与性能的相关性更加明显，这一相关性对于定制高分子材料具有重要的意义，而聚合物拓扑结构的调控在高分子合成化学中是一个重要的研究方向。常见的聚合物拓扑结构有线形、星形、梳形、环形、超支化及树枝状结构等，并有大量的相关文献报道。另一方面从聚合物链化学结构来看，聚合物的性能与其链结构组成密切相关，而含氟聚合物在聚合物应用的市场中一直有着很重要的地位，这与其突出的耐腐蚀性、耐老化性、耐热性、低表面能等性能密不可分。究其原因，主要是因为氟原子不仅有着低极化率和强电负性的特征，并且它的原子半径小，C-F键键能强。因此，目前关于含氟聚合物在防污涂料、疏水材料、表面活性剂等方面有着很广泛应用。
按照含氟链段位置的不同，可将其分为侧链型含氟聚合物和主链型含氟聚合物。其中侧链型含氟聚合物的合成采用直接引入含氟单体(如五氟苯乙烯、(甲基)丙烯酸含氟酯等)，使其通过“活性”/可控自由基聚合方法如原子转移自由基聚合(ATRP)、可逆加成-断裂链转移(RAFT)得到侧链型含氟聚合物。而主链型含氟聚合物主要采用气态氟单体(如偏氟乙烯(VDF)等)通过碘转移自由基聚合(ITP)的方法得到。总体而言，目前所能得到的含氟聚合物由于受单体种类的限制而使其品种单一、结构可设计性不强，难于满足材料对聚合物结构多样化的要求。发明人最近发展了一种可见光诱导催化聚合的α,ω-二碘代全氟烷烃(作为单体A)和α,ω-非共轭双烯(作为单体B)的逐步转移加成-自由基终止(StepTransfer-Addition&Radical-Termination,以下简称START)的新型聚合方法，通过非共轭双烯单体B的结构设计可得到聚合物结构多样、分子量可调控的新型“半氟”交替共聚物(AB)n(注：由于这类交替共聚物中A单体链节为全氟碳，为了和其它类型的含氟聚合物相区别，因此称之为“半氟”交替共聚物，其中n表示聚合度)，这为解决上述提到的目前存在的含氟聚合物品种单一的问题打开了新的思路并提供了一种可行的聚合方法。为了进一步充分利用含氟聚合物的优越性能，以这类独特的新型“半氟”交替共聚物(AB)n为构筑单元合成出具有各种拓扑结构的全新含氟聚合物，不仅可以开拓出一个新的研究方向，还将有利于进一步丰富含氟聚合物的种类及其应用范围。
发明内容
为解决上述技术问题，本发明的目的是提供一种主链型“半氟”交替共聚物的嵌段共聚物的光照聚合法，该聚合方法在可见光照射条件下进行，聚合过程具有“活性”自由基聚合特性，所制备的聚合物分子量分布较窄。
本发明的第一个目的是提供一种主链型“半氟”交替共聚物的嵌段共聚物的光照聚合法，包括以下步骤：
在保护气氛中，将甲基丙烯酸酯类单体和“半氟”交替共聚物(AB)n大分子引发剂在光催化剂作用下，在有机溶剂中于20-30℃下发生光控活性自由基聚合，该聚合反应在390nm-590nm的光照条件下进行至少半小时，得到主链型“半氟”交替共聚物的嵌段共聚物；其中，
“半氟”交替共聚物(AB)n大分子引发剂的结构为式(1)时，得到的主链型“半氟”交替共聚物的嵌段共聚物如式(2)所示；
“半氟”交替共聚物(AB)n大分子引发剂的结构为式(3)时，得到的主链型“半氟”交替共聚物的嵌段共聚物如式(4)所示；
其中，式(1)-(4)如下：
其中，x＝4-8；y＝0-3；n＝4-30；m＝100-500；
R选自C1-C6烷基、芳醚基或酰氧基；
R1选自C1-C6烷基、聚乙二醇基、胺基取代的C1-C6烷基或环氧基取代的C1-C6烷基。
优选地，R选自甲基、对苯醚基、己二酰氧基或者对苯二甲酰氧基。
优选地，R1选自甲基、正丁基、正己基、聚乙二醇单甲醚基、二甲胺基乙基或环氧丙基。
优选地，x＝4、6或8；y＝0或1；n＝4-15；m＝200-500。
进一步地，甲基丙烯酸酯类单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸己酯、甲基丙烯酸环氧丙酯、甲基丙烯酸-N,N-二甲氨基乙酯或甲基丙烯酸聚乙二醇单甲醚酯。
进一步地，“半氟”交替共聚物(AB)n大分子引发剂由单体A与单体B通过START(逐步转移-加成-终止)聚合得到；所述单体A选自1,4-二碘代全氟丁烷，1,6-二碘代全氟己烷或1,8-二碘代全氟辛烷；所述单体B选自1,7-辛二烯、1,9-葵二烯、对苯二烯丙基醚、对苯二(1-己烯)醚、己二酸二烯丙酯、对苯二甲酸二丙烯酯或对苯二甲酸二(1-己烯)酯。
进一步地，“半氟”交替共聚物(AB)n大分子引发剂的制备方法参考CN107619466A中所公开的方法。
进一步地，单体A与单体B的摩尔比为1-1.2:1。当单体A与单体B的摩尔比为1:1时，得到式(1)所示的“半氟”交替共聚物(AB)n大分子引发剂；当单体A与单体B的摩尔比为1.2:1时，得到式(3)所示的“半氟”交替共聚物(AB)n大分子引发剂。
本发明所使用的“半氟”交替共聚物大分子引发剂命名为(AB)n。具体地，以1,6-二碘代全氟己烷为单体A以及1,7-辛二烯为单体B所聚合得到的“半氟”交替共聚物分别命名为(AB1)n和(AB1)nA；以1,6-二碘代全氟己烷为单体A以及对苯二(1-己烯)醚为单体B所得到的“半氟”交替共聚物命名为(AB2)n；以1,6-二碘代全氟己烷为单体A以及苯二甲酸二(1-己烯)酯为单体B所得到的“半氟”交替共聚物命名为(AB3)n，上述“半氟”交替共聚物的结构式分别如下：
“半氟”交替共聚物(AB)n的聚合度n的计算方法可以以(AB1)n为例说明，通过核磁1H NMR对(AB1)n进行结构的表征能够得出聚合物不同位置氢(H)的化学位移。其中将化学位移c(CH2＝CH-)的积分积为1.00，化学位移a,b(CH2＝CH-)的积分和为1.83，化学位移h(-CH(I)CH2CF2-)的积分积为16.31。通过对聚合物的化学结构式进行分析，h＝2n-1，n＝(h+1)/2，所以聚合物的聚合度n≈8～9。
进一步地，“半氟”交替共聚物(AB)n的分子量分布指数为1.40～1.90。
进一步地，光催化剂为三(2,2′-联吡啶)二氯化钌(Ru(bpy)3Cl2)和抗坏血酸钠。
进一步地，甲基丙烯酸酯类单体在有机溶剂中的浓度为0.002mol/mL～0.1mol/mL。
进一步地，甲基丙烯酸酯类单体、“半氟”交替共聚物(AB)n大分子引发剂、三(2,2'-联吡啶)二氯化钌(Ru(bpy)3Cl2)、抗坏血酸钠(AsAc-Na)的摩尔比30～500:1～3:0.1～0.5:1～5，优选为200～500:1～2:0.1～0.2:1～2。
进一步地，有机溶剂为丙酮、四氢呋喃或者N,N-二甲基甲酰胺。优选为丙酮。
进一步地，390-590nm光为采用LED灯光源发出的光。优选地，光源为蓝色LED灯。
优选地，反应时间为0.5-30h。反应24h时，DMAEMA单体转化率可达99.5％。
优选地，甲基丙烯酸甲酯类单体为甲基丙烯酸甲酯(MMA)、甲基丙烯酸环氧丙酯(GMA)、甲基丙烯酸-N,N-二甲氨基乙酯(DMAEMA)或者甲基丙烯酸聚乙二醇单甲醚酯(PEGMA)。以(AB1)n为大分子引发剂分别引发MMA、GMA、PEGMA、DMAEMA聚合后所得到的主链型“半氟”交替共聚物的嵌段共聚物命名为(AB1)n-b-PMMA、(AB1)n-b-PGMA、(AB1)n-b-PPEGMA、(AB1)n-b-PDMAEMA；分别以(AB1)nA、(AB2)n或者(AB3)n为大分子引发剂引发MMA聚合后所得到的主链型“半氟”交替共聚物的嵌段共聚物分别命名为PMMA-b-(AB1)nA-b-PMMA、(AB2)n-b-PMMA以及(AB3)n-b-PMMA，上述各产物结构式如下：
其中，n＝4-30；m＝100-500。优选地，n＝4-15，m＝200-500。
本发明的第二个目的是提供一种采用上述光照聚合法所制备的式(2)或式(4)的主链型“半氟”交替共聚物的嵌段共聚物，其为主链型聚烯烃、聚酯或者聚醚类“半氟”交替共聚物的嵌段共聚物。
进一步地，式(2)或式(4)的主链型“半氟”交替共聚物的嵌段共聚物的分子量分布指数为1.40-1.90。
本发明制备方法中，反应原理如下：采用“半氟”交替共聚物(AB)n为大分子引发剂，在光催化剂的作用下引发甲基丙烯酸酯类单体可控聚合，随着聚合反应的进行，嵌段共聚物聚合度m逐渐增大。同时通过设计“半氟”交替共聚物(AB)n中B单体的结构可制备各种主链型聚烯烃、聚酯或者聚醚类“半氟”交替共聚物的嵌段共聚物。
借由上述方案，本发明至少具有以下优点：
本发明利用室温(20-30℃)下LED灯诱导的活性自由基聚合方法，操作简便安全。采用本发明的制备方法，单体的ln([M]0/[M])随着时间的延长呈一级线性关系，聚合物的分子量随着转化率的增加线性增长，分子量分布也较窄，符合“活性”自由基聚合的特征，具有聚合物结构和聚合物分子量的可设计性。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
图1是主链“半氟”交替共聚物(AB1)n的1H NMR谱图；
图2是主链“半氟”交替共聚物(AB1)n的19F NMR谱图；
图3是实施例1中制备的主链“半氟”交替共聚物的嵌段共聚物(AB1)n-b-PMMA的1HNMR谱图；
图4是实施例1中不同聚合时间得到的主链“半氟”交替共聚物的嵌段共聚物(AB1)n-b-PMMA的GPC流出曲线；
图5是实施例1中“半氟”交替共聚物的嵌段共聚物(AB1)n-b-PMMA的单体浓度[M]与反应时间的一级动力学图；
图6是实施例1中“半氟”交替共聚物的嵌段共聚物(AB1)n-b-PMMA的Mn和Mw/Mn与转化率的关系曲线；
图7是实施例3中主链“半氟”交替共聚物(AB1)nA的1H NMR谱图；
图8是实施例3中主链“半氟”交替共聚物(AB2)n的1H NMR谱图；
图9是实施例3中主链“半氟”交替共聚物(AB3)n的1H NMR谱图。
具体实施方式
下面结合附图及实施案例对本发明作进一步描述。下文中的描述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围。
本发明以下实施例中所使用的化学试剂：甲基丙烯酸甲酯(95％)购于Aladdin公司；甲基丙烯酸缩水甘油酯(>95％)购于TCI公司；甲基丙烯酸2-(二甲氨基)乙酯(>98.5％)购于TCI公司；聚(乙二醇)甲基丙烯酸甲酯(PEGMA,Mn＝300g mol-1)购于Aldrich公司；三(2,2'-联吡啶)二氯化钌(98％)购于安耐吉化学公司；抗坏血酸钠购于百灵威科技有限公司；丙酮，AR；四氢呋喃，AR；甲醇，工业级。
测试仪器：PL凝胶渗透色谱仪；INOVA400MHz核磁仪。
测定条件：HR1、HR3和HR4三柱串联使用，示差检测器，流动相为四氢呋喃(1mL/min)，柱温30℃，用聚苯乙烯或聚甲基丙烯酸甲酯标样做校正标样进行校正。1H NMR在INOVA300MHz核磁仪上以TMS为内标测定。
实施例1.
在光反应管中加入拟聚合的5mmol单体甲基丙烯酸甲酯，0.01mmol交替含氟聚合物大分子引发剂(AB1)n，0.002mmol光催化剂三(2,2'-联吡啶)二氯化钌(Ru(bpy)3Cl2)，0.01mmol抗坏血酸钠(AsAc-Na)，0.5mL丙酮，通过除氧操作后，选择在485nm的LED蓝光照射下进行室温聚合反应。当反应达到预定的时间后，打开反应管，抽取少量的聚合物溶液进行核磁共振氢谱(1H NMR)测试并计算单体的转化率及核磁分子量(Mn,NMR)。其余聚合物溶液溶于一定量的四氢呋喃中，过中性Al2O3柱后，加入沉淀剂沉淀、静置、抽滤、真空干燥后得到“半氟”交替共聚物的嵌段共聚物(AB1)n-b-PMMA。图1-2分别是(AB1)n的1H NMR和19F NMR测试结果。其聚合度为8-9。图3是“半氟”交替共聚物的嵌段共聚物(AB1)n-b-PMMA的1H NMR。
按照上述步骤做多组平行实验，聚合时间分别为1h、2h、4h、6h、8h和10h，测试不同时间下(AB1)n-b-PMMA的聚合结果。
图4是不同聚合时间得到的(AB1)n-b-PMMA的GPC流出曲线。自右向左，曲线所对应的反应时间逐渐延长，聚合时间分别为1h、2h、4h、6h、8h和10h，所得到的(AB1)n-b-PMMA的分子量及分子量分布指数(PDI)依次为21400g/mol、1.70；27800g/mol、1.44；32000g/mol、1.37；37600g/mol、1.38；38100g/mol、1.34；46200g/mol、1.55。
图5-6分别是(AB1)n-b-PMMA的单体浓度[M]与反应时间的一级动力学图以及(AB1)n-b-PMMA的Mn和Mw/Mn与转化率的关系曲线。结果表明，聚合物分子量及其分布的变化曲线表示分子量Mn,GPC随着单体转化率线性增长，聚合物可控性较好，分子量分布较窄。
实施例2
在光反应管中加入拟聚合的不同单体(5mmol)，0.025mmol交替含氟聚合物大分子引发剂(AB1)n，0.005mmol光催化剂三(2,2'-联吡啶)二氯化钌(Ru(bpy)3Cl2)，0.025mmol抗坏血酸钠(AsAc-Na)，0.5mL丙酮，通过除氧操作后，选择在485nm的LED蓝光照射下进行室温聚合反应。其中，(AB1)n的分子量为4000g/mol，PDI为1.40。当反应达到预定的时间后，打开反应管，抽取少量的聚合物溶液进行核磁共振氢谱(1H NMR)测试并计算单体的转化率及核磁分子量(Mn,NMR)。其余聚合物溶液溶于一定量的四氢呋喃中，过中性Al2O3柱后，加入沉淀剂沉淀、静置、抽滤、真空干燥后得到聚合物，结果如表1所示。
表1不同聚合体系的聚合结果
表1中，编号为4的实验条件为[M]0:[(AB1)n]0:[Ru(bpy)3Cl2]0:[AsAc-Na]0＝100:1:0.2:1。上表中，PEGMA-300、PEGMA-400分别指的是甲基丙烯酸聚乙二醇单甲醚酯中，聚乙二醇的分子量为300g/mol或400g/mol。
实施例3
在光反应管中加入拟聚合的5mmol单体甲基丙烯酸甲酯，0.01mmol不同的交替含氟聚合物大分子引发剂(AB1)nA、(AB2)n或(AB3)n，0.002mmol光催化剂三(2,2'-联吡啶)二氯化钌(Ru(bpy)3Cl2)，0.01mmol抗坏血酸钠(AsAc-Na)，0.5mL丙酮，通过除氧操作后，选择在485nm的LED蓝光照射下进行室温聚合反应。其中，(AB1)nA、(AB2)n或(AB3)n的分子量以及PDI分别为6400g/mol、1.75；2200g/mol、1.28；9800g/mol、1.91。
当反应达到预定的时间后，打开反应管，抽取少量的聚合物溶液进行核磁共振氢谱(1H NMR)测试并计算单体的转化率及核磁分子量(Mn,NMR)。其余聚合物溶液溶于一定量的四氢呋喃中，过中性Al2O3柱后，加入沉淀剂沉淀、静置、抽滤、真空干燥后得到聚合物。
图7-9分别是本实施例使用的大分子引发剂(AB1)nA、(AB2)n或(AB3)n的1H NMR测试结果。
表2是使用不同大分子引发剂的聚合结果，可看出成功实现了甲基丙烯酸甲酯单体的聚合，且所得聚合物分子量分布较窄。
表2不同大分子引发剂对聚合体系的影响结果
表2中，实验条件为[MMA]0:[(AB)n]0:[Ru(bpy)3Cl2]0:[AsAc-Na]0＝500:1:0.2:1。
以上所述仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。
Claims (10)
1.一种主链型“半氟”交替共聚物的嵌段共聚物的光照聚合法，其特征在于，包括以下步骤：
在保护气氛中，将甲基丙烯酸酯类单体和“半氟”交替共聚物(AB)n大分子引发剂在光催化剂作用下，在有机溶剂中于20-30℃下发生光控活性自由基聚合，该聚合反应在390nm-590nm的光照条件下进行至少半小时，得到主链型“半氟”交替共聚物的嵌段共聚物；其中，
“半氟”交替共聚物(AB)n大分子引发剂的结构为式(1)时，得到的主链型“半氟”交替共聚物的嵌段共聚物如式(2)所示；
“半氟”交替共聚物(AB)n大分子引发剂的结构为式(3)时，得到的主链型“半氟”交替共聚物的嵌段共聚物如式(4)所示；
其中，式(1)-(4)如下：
其中，x＝4-8；y＝0-3；n＝4-30；m＝100-500；
R选自C1-C6烷基、芳醚基或酰氧基；
R1选自C1-C6烷基、聚乙二醇基、胺基取代的C1-C6烷基或环氧基取代的C1-C6烷基。
2.根据权利要求1所述的光照聚合法，其特征在于：所述甲基丙烯酸酯类单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸己酯、甲基丙烯酸环氧丙酯、甲基丙烯酸-N,N-二甲氨基乙酯或甲基丙烯酸聚乙二醇单甲醚酯。
3.根据权利要求1所述的光照聚合法，其特征在于：所述“半氟”交替共聚物(AB)n大分子引发剂由单体A与单体B通过START聚合得到；所述单体A选自1,4-二碘代全氟丁烷，1,6-二碘代全氟己烷或1,8-二碘代全氟辛烷；所述单体B选自1,7-辛二烯、1,9-葵二烯、对苯二烯丙基醚、对苯二(1-己烯)醚、己二酸二烯丙酯、对苯二甲酸二丙烯酯或对苯二甲酸二(1-己烯)酯。
4.根据权利要求3所述的光照聚合法，其特征在于：所述单体A与单体B的摩尔比为1～1.2:1。
5.根据权利要求1所述的光照聚合法，其特征在于：x＝4、6或8。
6.根据权利要求1所述的光照聚合法，其特征在于：y＝0或1。
7.根据权利要求1所述的光照聚合法，其特征在于：所述光催化剂为三(2,2′-联吡啶)二氯化钌和抗坏血酸钠。
8.根据权利要求1所述的光照聚合法，其特征在于：所述甲基丙烯酸酯类单体在有机溶剂中的浓度为0.002mol/mL～0.1mol/mL。
9.根据权利要求1所述的光照聚合法，其特征在于：所述甲基丙烯酸酯类单体和“半氟”交替共聚物(AB)n大分子引发剂的摩尔比为30-500:1-3。
10.一种权利要求1-9中任一项所述的光照聚合法所制备的式(2)或式(4)的主链型“半氟”交替共聚物的嵌段共聚物。
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| US16/965,716 US20220033557A1 (en) | 2019-06-28 | 2019-07-03 | Photopolymerization method for preparing block copolymer with main-chain semi-fluorinated alternating copolymer |
| PCT/CN2019/094540 WO2020258355A1 (zh) | 2019-06-28 | 2019-07-03 | 主链型"半氟"交替共聚物的嵌段共聚物的光照聚合法 |
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| CN115010869A (zh) * | 2022-06-10 | 2022-09-06 | 苏州大学 | 一种含氟接枝共聚物及其制备方法 |
| CN115043968A (zh) * | 2022-05-24 | 2022-09-13 | 苏州大学 | 一种半氟化交替共聚物反相胶束及其制备方法 |
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| CN115124670B (zh) * | 2022-06-07 | 2023-09-29 | 苏州大学 | 一种氟硅氧烷嵌段共聚物及其制备方法与应用 |
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