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CN105669924A - Organic-inorganic linear-dendritic hybrid copolymer containing POSS structure and synthetic method of organic-inorganic linear-dendritic hybrid copolymer - Google Patents

  • ️Wed Jun 15 2016
Organic-inorganic linear-dendritic hybrid copolymer containing POSS structure and synthetic method of organic-inorganic linear-dendritic hybrid copolymer Download PDF

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CN105669924A
CN105669924A CN201610250752.2A CN201610250752A CN105669924A CN 105669924 A CN105669924 A CN 105669924A CN 201610250752 A CN201610250752 A CN 201610250752A CN 105669924 A CN105669924 A CN 105669924A Authority
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China
Prior art keywords
organic
block copolymer
inorganic hybrid
poss
hybrid block
Prior art date
2016-04-21
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CN201610250752.2A
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CN105669924B (en
Inventor
许一婷
黄佳美
柳超
孙晓晴
侯培鑫
曾碧榕
戴李宗
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Xiamen University
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Xiamen University
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2016-04-21
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2016-06-15
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2016-04-21 Priority to CN201610250752.2A priority Critical patent/CN105669924B/en
2016-06-15 Publication of CN105669924A publication Critical patent/CN105669924A/en
2018-08-21 Application granted granted Critical
2018-08-21 Publication of CN105669924B publication Critical patent/CN105669924B/en
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2036-04-21 Anticipated expiration legal-status Critical

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  • 238000010189 synthetic method Methods 0.000 title claims description 10
  • 229920001577 copolymer Polymers 0.000 title description 3
  • 229920001400 block copolymer Polymers 0.000 claims abstract description 35
  • 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 18
  • 239000000178 monomer Substances 0.000 claims abstract description 17
  • 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 16
  • 238000006243 chemical reaction Methods 0.000 claims abstract description 16
  • 239000002904 solvent Substances 0.000 claims abstract description 16
  • XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 15
  • XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
  • 238000007872 degassing Methods 0.000 claims abstract description 12
  • 239000003999 initiator Substances 0.000 claims abstract description 12
  • YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims abstract description 8
  • IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
  • 239000003054 catalyst Substances 0.000 claims abstract description 8
  • 229910052786 argon Inorganic materials 0.000 claims abstract description 6
  • 238000000502 dialysis Methods 0.000 claims abstract description 6
  • 239000002253 acid Substances 0.000 claims abstract description 5
  • 239000011230 binding agent Substances 0.000 claims abstract description 5
  • PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
  • 239000007788 liquid Substances 0.000 claims abstract description 4
  • 230000007935 neutral effect Effects 0.000 claims abstract description 4
  • 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
  • 239000012300 argon atmosphere Substances 0.000 claims abstract description 3
  • 239000007789 gas Substances 0.000 claims abstract description 3
  • 239000012528 membrane Substances 0.000 claims abstract description 3
  • WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
  • SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 15
  • YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
  • YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
  • YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
  • XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
  • 230000035484 reaction time Effects 0.000 claims description 8
  • 230000015572 biosynthetic process Effects 0.000 claims description 7
  • 238000003786 synthesis reaction Methods 0.000 claims description 7
  • ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
  • 239000000843 powder Substances 0.000 claims description 6
  • RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
  • -1 methacryloxypropyl Chemical group 0.000 claims description 5
  • SVYHMICYJHWXIN-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethyl 2-methylprop-2-enoate Chemical compound CC(C)N(C(C)C)CCOC(=O)C(C)=C SVYHMICYJHWXIN-UHFFFAOYSA-N 0.000 claims description 4
  • JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
  • JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 3
  • 239000003795 chemical substances by application Substances 0.000 claims description 3
  • 239000008367 deionised water Substances 0.000 claims description 3
  • 229910021641 deionized water Inorganic materials 0.000 claims description 3
  • 238000001556 precipitation Methods 0.000 claims description 3
  • 239000000047 product Substances 0.000 claims description 3
  • 239000012141 concentrate Substances 0.000 claims description 2
  • 238000001035 drying Methods 0.000 claims description 2
  • 239000002244 precipitate Substances 0.000 claims description 2
  • 230000001376 precipitating effect Effects 0.000 claims description 2
  • 238000002360 preparation method Methods 0.000 claims description 2
  • UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
  • 238000010257 thawing Methods 0.000 claims description 2
  • 238000001291 vacuum drying Methods 0.000 claims description 2
  • 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
  • 238000001308 synthesis method Methods 0.000 abstract description 4
  • 239000003153 chemical reaction reagent Substances 0.000 abstract 1
  • 239000000243 solution Substances 0.000 description 13
  • 229920000642 polymer Polymers 0.000 description 9
  • 238000000034 method Methods 0.000 description 7
  • 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
  • 238000001338 self-assembly Methods 0.000 description 4
  • 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 description 3
  • 239000003814 drug Substances 0.000 description 3
  • 229940079593 drug Drugs 0.000 description 3
  • 238000006116 polymerization reaction Methods 0.000 description 3
  • 230000004043 responsiveness Effects 0.000 description 3
  • 238000001228 spectrum Methods 0.000 description 3
  • 239000000126 substance Substances 0.000 description 3
  • ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
  • VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
  • 229920000469 amphiphilic block copolymer Polymers 0.000 description 2
  • 239000007864 aqueous solution Substances 0.000 description 2
  • 238000007334 copolymerization reaction Methods 0.000 description 2
  • 238000002329 infrared spectrum Methods 0.000 description 2
  • 239000000693 micelle Substances 0.000 description 2
  • 229920005604 random copolymer Polymers 0.000 description 2
  • 125000001424 substituent group Chemical group 0.000 description 2
  • 230000002194 synthesizing effect Effects 0.000 description 2
  • SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
  • NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
  • NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
  • 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
  • LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical class COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
  • CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
  • 239000004698 Polyethylene Substances 0.000 description 1
  • 229910004298 SiO 2 Inorganic materials 0.000 description 1
  • 125000000217 alkyl group Chemical group 0.000 description 1
  • 125000003118 aryl group Chemical group 0.000 description 1
  • QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
  • 230000001588 bifunctional effect Effects 0.000 description 1
  • 239000000969 carrier Substances 0.000 description 1
  • 239000012986 chain transfer agent Substances 0.000 description 1
  • 238000013270 controlled release Methods 0.000 description 1
  • 229920006037 cross link polymer Polymers 0.000 description 1
  • 239000003431 cross linking reagent Substances 0.000 description 1
  • KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
  • 238000012377 drug delivery Methods 0.000 description 1
  • 230000002209 hydrophobic effect Effects 0.000 description 1
  • 238000001727 in vivo Methods 0.000 description 1
  • 239000003446 ligand Substances 0.000 description 1
  • 238000010550 living polymerization reaction Methods 0.000 description 1
  • 229920002521 macromolecule Polymers 0.000 description 1
  • 239000000463 material Substances 0.000 description 1
  • 239000011259 mixed solution Substances 0.000 description 1
  • 238000005580 one pot reaction Methods 0.000 description 1
  • 239000001301 oxygen Substances 0.000 description 1
  • 229910052760 oxygen Inorganic materials 0.000 description 1
  • 229920000573 polyethylene Polymers 0.000 description 1
  • 229920001296 polysiloxane Polymers 0.000 description 1
  • 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
  • 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
  • 238000000926 separation method Methods 0.000 description 1
  • 235000012239 silicon dioxide Nutrition 0.000 description 1
  • 239000000377 silicon dioxide Substances 0.000 description 1
  • 229920002050 silicone resin Polymers 0.000 description 1
  • 150000003512 tertiary amines Chemical group 0.000 description 1
  • 229920003169 water-soluble polymer Polymers 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • 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
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/04—End-capping
    • C—CHEMISTRY; METALLURGY
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    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
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    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
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Abstract

含POSS结构的有机无机杂化嵌段共聚物及其合成方法，涉及嵌段共聚物。所述含POSS结构的有机无机杂化嵌段共聚物，记为PEG-b-P(POSS-co-DEA)。合成方法：将聚乙二醇单甲醚、缚酸剂溶于溶剂中得聚乙二醇单甲醚溶液，在冰浴条件下，将2－溴代异丁酰溴溶于溶剂中再滴入聚乙二醇单甲醚溶液中反应后，撤去冰浴，再在常温条件下反应，将所得到的溶液用透析膜透析后，冻干，即得大分子引发剂；将所得大分子引发剂、第二单体、第三单体溶于溶剂中，经连续冻融脱气并在氩气氛下加入催化剂后，再继续冻融脱气并充入氩气后密封反应，再液氮冷冻，所得产物通过中性氧化铝柱子除去催化剂后，浓缩，沉淀，干燥，即得嵌段共聚物。An organic-inorganic hybrid block copolymer containing a POSS structure and a synthesis method thereof relate to a block copolymer. The organic-inorganic hybrid block copolymer containing POSS structure is denoted as PEG-b-P (POSS-co-DEA). Synthesis method: Dissolve polyethylene glycol monomethyl ether and acid-binding agent in a solvent to obtain a polyethylene glycol monomethyl ether solution. Dissolve 2-bromoisobutyryl bromide in a solvent in an ice bath and then drop After reacting in a polyethylene glycol monomethyl ether solution, remove the ice bath, and then react at room temperature, dialyze the obtained solution with a dialysis membrane, freeze-dry to obtain a macromolecular initiator; Dissolve the reagent, the second monomer and the third monomer in the solvent, after continuous freeze-thaw degassing and adding the catalyst under the argon atmosphere, then continue the freeze-thaw degassing and fill it with argon gas, seal the reaction, and then freeze in liquid nitrogen , the obtained product is passed through a neutral alumina column to remove the catalyst, concentrated, precipitated, and dried to obtain a block copolymer.

Description

含POSS结构的有机无机杂化嵌段共聚物及其合成方法Organic-inorganic hybrid block copolymer containing POSS structure and its synthesis method

技术领域technical field

本发明涉及嵌段共聚物，尤其是涉及一种含POSS结构的有机无机杂化嵌段共聚物及其合成方法。The invention relates to a block copolymer, in particular to an organic-inorganic hybrid block copolymer containing a POSS structure and a synthesis method thereof.

背景技术Background technique

笼型多面体低聚倍半硅氧烷(POSS)是近年来出现的一种新型有机-无机杂化材料，POSS经典的结构式为(RSiO1.5)n(n≥4，R＝H、烷基、芳基或其他有机官能基团)，介于二氧化硅(SiO2)和硅树脂(R2SiO)n之间。其笼型骨架具有良好的尺寸稳定性及耐热性，有机取代基也具有可设计性。通过设计POSS的取代基，使其与不同性质的单体共聚，可以合成结构和性能丰富的嵌段共聚物。Cage polyhedral oligomeric silsesquioxane (POSS) is a new type of organic-inorganic hybrid material that has emerged in recent years. The classic structural formula of POSS is (RSiO 1.5 )n(n≥4, R=H, alkyl, aryl or other organofunctional groups), between silicon dioxide (SiO 2 ) and silicone resin (R 2 SiO)n. Its cage-shaped skeleton has good dimensional stability and heat resistance, and the organic substituents are also designable. By designing the substituents of POSS to copolymerize with monomers of different properties, block copolymers with rich structures and properties can be synthesized.

双亲性共聚物是一类在选择性溶剂中，能够发生微相分离，从而形成自组装结构的聚合物。其自组装形成丰富的形态，如线形、球形、囊泡状、层状等，且具有较好的可控性，因而一直是高分子领域的研究热点。目前合成双亲嵌段共聚物主要方法为可控/活性聚合，可实现分子设计的可控性。Amphiphilic copolymers are a class of polymers that can undergo microphase separation in selective solvents to form self-assembled structures. Its self-assembly forms rich shapes, such as linear, spherical, vesicular, layered, etc., and has good controllability, so it has always been a research hotspot in the field of polymers. At present, the main method of synthesizing amphiphilic block copolymers is controlled/living polymerization, which can realize the controllability of molecular design.

多面体齐聚倍半硅氧烷(POSS)中硅氧形成笼形结构，可通过分子设计，将POSS引入到聚合物中，制备POSS基聚合物。为了利用其诸多的优异特性，已经有许多人在POSS基嵌段共聚物的合成上做了大量的研究工作。WZhang等(WZhang,BFang,AWalther,AHEMüller.Macromolecules,2009.42.2563-2569.)使用氨基POSS合成了一种带POSS的三硫酯链转移剂，加入丙烯酸合成一种包含POSS双亲性聚合物，并研究了其在水中自组装行为；HussainH等(HussainH,TanBH,SeahGL,etal.Langmuir,2010,26(14):11763-11773.)选用双官能度引发剂，采用原子转移自由基聚合(ATRP)方法，合成了聚甲基丙烯酰氧丙基POSS-聚乙二醇-聚甲基丙烯酰氧丙基POSS(P(MA-POSS)-b-PEG-b-P(MA-POSS))ABA型嵌段聚合物。Silicone and oxygen in polyhedral oligosilsesquioxane (POSS) form a cage structure, and POSS can be introduced into polymers through molecular design to prepare POSS-based polymers. In order to take advantage of its many excellent properties, many people have done a lot of research work on the synthesis of POSS-based block copolymers. (WZhang, BFang, AWalther, AHEMüller.Macromolecules, 2009.42.2563-2569.) used amino POSS to synthesize a trithioester chain transfer agent with POSS, added acrylic acid to synthesize a kind of amphiphilic polymer comprising POSS, and Its self-assembly behavior in water was studied; HussainH et al. (HussainH, TanBH, SeahGL, etal.Langmuir, 2010, 26(14): 11763-11773.) selected a bifunctional initiator and used atom transfer radical polymerization (ATRP) method, synthesized polymethacryloxypropyl POSS-polyethylene glycol-polymethacryloxypropyl POSS (P(MA-POSS)-b-PEG-b-P(MA-POSS)) ABA-type embedded segment polymer.

聚甲基丙烯酸二乙基氨基乙酯(PDEA)是研究与应用得较为广泛的水溶性高分子之一，由于其叔胺基团的存在,PDEA是一种同时对溶液pH、温度敏感的双重刺激响应性高聚物。ZengJ等(ZengJ,DuP,LiuP.RSCAdvances,2013,3(42):19492-19500.)选用聚乙二醇大分子引发剂、甲基丙烯酸二乙基氨基乙酯(DEA)以及交联剂采用一锅法合成了核交联的聚合物，并研究了聚合物胶束的药物释放。Polydiethylaminoethyl methacrylate (PDEA) is one of the most widely studied and applied water-soluble polymers. Due to the existence of its tertiary amine groups, PDEA is a dual-purpose polymer that is sensitive to the pH and temperature of the solution. Stimuli-responsive polymers. ZengJ etc. (ZengJ, DuP, LiuP.RSCAdvances, 2013,3(42):19492-19500.) select polyethylene glycol macroinitiator, diethylaminoethyl methacrylate (DEA) and crosslinking agent to adopt Core-crosslinked polymers were synthesized in a one-pot method and drug release from polymeric micelles was studied.

单纯依靠PEG和POSS共聚得到的嵌段共聚物或无规共聚物在水溶液自组装形成的纳米胶束，由于缺乏响应性，无法作为药物的运输及控制释放的载体。另一方面单纯依靠DEA或者其他响应性的物质和PEG共聚得到嵌段共聚物或无规共聚物在水溶液自组装形成的纳米胶束，由于形成胶束的高分子链间隙导致药物在体内运输过程中无法避免的出现泄漏。本发明合成的嵌段共聚物既具有响应性，同时又由于POSS基团的笼型结构可以降低药物在体内运输过程中泄露的可能性。Nanomicelles formed by the self-assembly of block copolymers or random copolymers in aqueous solution solely relying on the copolymerization of PEG and POSS cannot be used as carriers for drug delivery and controlled release due to lack of responsiveness. On the other hand, relying solely on DEA or other responsive substances and PEG copolymerization to obtain nanomicelles formed by the self-assembly of block copolymers or random copolymers in aqueous solution, the drug transport process in the body is caused by the gap between the polymer chains forming the micelles. Leaks are unavoidable. The block copolymer synthesized by the invention not only has responsiveness, but also can reduce the possibility of drug leakage during in vivo transportation due to the cage structure of the POSS group.

发明内容Contents of the invention

本发明的目的是提供一种具温敏性和pH响应性的含POSS结构的有机无机杂化嵌段共聚物及其合成方法。The object of the present invention is to provide a temperature-sensitive and pH-responsive organic-inorganic hybrid block copolymer containing a POSS structure and a synthesis method thereof.

所述含POSS结构的有机无机杂化嵌段共聚物，记为PEG-b-P(POSS-co-DEA)，其结构式如下：The organic-inorganic hybrid block copolymer containing POSS structure is denoted as PEG-b-P (POSS-co-DEA), and its structural formula is as follows:

其中，R＝CH3或H；R1＝CH3，C2H5或CH(CH3)2。Wherein, R=CH 3 or H; R 1 =CH 3 , C 2 H 5 or CH(CH 3 ) 2 .

所述含POSS结构的有机无机杂化嵌段共聚物的合成路线如下：The synthetic route of the organic-inorganic hybrid block copolymer containing POSS structure is as follows:

1)大分子引发剂PEG-Br的制备1) Preparation of macromolecular initiator PEG-Br

2)PEG-b-P(POSS-co-DEA)的合成2) Synthesis of PEG-b-P (POSS-co-DEA)

其中，R＝CH3或H；R1＝CH3，C2H5或CH(CH3)2；m＝135。Wherein, R=CH 3 or H; R 1 =CH 3 , C 2 H 5 or CH(CH 3 ) 2 ; m=135.

所述含POSS结构的有机无机杂化嵌段共聚物的合成方法，包括以下步骤：The synthetic method of the organic-inorganic hybrid block copolymer containing POSS structure, comprises the following steps:

1)大分子引发剂的合成1) Synthesis of macroinitiators

将聚乙二醇单甲醚、缚酸剂溶于溶剂中得聚乙二醇单甲醚溶液，在冰浴条件下，将2－溴代异丁酰溴(BiBB)溶于溶剂中再滴入聚乙二醇单甲醚溶液中反应后，撤去冰浴，再在常温条件下反应，将所得到的溶液用透析膜透析后，冻干，即得大分子引发剂，呈白色粉末；Dissolve polyethylene glycol monomethyl ether and acid-binding agent in a solvent to obtain a polyethylene glycol monomethyl ether solution. Under ice bath conditions, dissolve 2-bromoisobutyryl bromide (BiBB) in a solvent and drop After reacting in a polyethylene glycol monomethyl ether solution, remove the ice bath, and then react at normal temperature, dialyze the obtained solution with a dialysis membrane, freeze-dry to obtain a macromolecular initiator, which is a white powder;

在步骤1)中，所述聚乙二醇单甲醚的平均分子量可为600、1000、2000、5000；所述缚酸剂可选自三乙胺、吡啶等中的一种；所述溶剂可选自重蒸二氯甲烷、甲苯等中的一种；所述将2－溴代异丁酰溴(BiBB)溶于溶剂中再滴入聚乙二醇单甲醚溶液中反应的时间可至少2h；所述在常温条件下反应的时间可至少24h；所述透析可将反应溶液在去离子水中透析48h。In step 1), the average molecular weight of the polyethylene glycol monomethyl ether can be 600, 1000, 2000, 5000; the acid-binding agent can be selected from one of triethylamine, pyridine, etc.; the solvent It can be selected from one of redistilled dichloromethane, toluene, etc.; the reaction time of dissolving 2-bromoisobutyryl bromide (BiBB) in a solvent and dropping it into the polyethylene glycol monomethyl ether solution can be at least 2h; the reaction time at room temperature may be at least 24h; and the dialysis may be dialysis of the reaction solution in deionized water for 48h.

2)嵌段共聚物的合成2) Synthesis of block copolymers

将步骤1)得到的大分子引发剂、第二单体、第三单体溶于溶剂中，经连续冻融脱气并在氩气氛下加入催化剂后，再继续冻融脱气并充入氩气后密封反应，再液氮冷冻，将所得的产物通过中性氧化铝柱子以除去催化剂后，浓缩，沉淀，干燥，即得含POSS结构的有机无机杂化嵌段共聚物，呈淡黄色粉末。Dissolve the macromolecular initiator, the second monomer, and the third monomer obtained in step 1) in a solvent, and after continuous freeze-thaw degassing and adding a catalyst under an argon atmosphere, continue freeze-thawing and degassing and fill with argon Seal the reaction after gas, then freeze with liquid nitrogen, pass the obtained product through a neutral alumina column to remove the catalyst, concentrate, precipitate, and dry to obtain an organic-inorganic hybrid block copolymer containing a POSS structure, which is a light yellow powder .

在步骤2)中，所述第二单体可选自甲基丙烯酰氧丙基七异丁基笼形倍半硅氧烷(MAPOSS)、丙烯酰氧丙基七异丁基笼形倍半硅氧烷(APOSS)等中的一种；所述第三单体可选自甲基丙烯酸二乙基氨基乙酯(DEA)、甲基丙烯酸-N,N-二甲基氨基乙酯(DMAEMA)、2-(二异丙基氨基)甲基丙烯酸乙酯(DPA)等中的一种；所述溶剂可选自重蒸四氢呋喃、甲苯等中的一种；所述经连续冻融脱气后聚合，可经连续冻融脱气3～5次后在氩气保护下聚合；所述反应的温度可为60～70℃，反应的时间可至少24h；所述沉淀可采用无水乙醚作为沉淀剂反复沉淀2次；所述干燥可采用真空干燥。In step 2), the second monomer can be selected from methacryloxypropyl heptaisobutyl cage silsesquioxane (MAPOSS), acryloyloxypropyl heptaisobutyl cage silsesquioxane One of siloxane (APOSS) and the like; the third monomer can be selected from diethylaminoethyl methacrylate (DEA), N,N-dimethylaminoethyl methacrylate (DMAEMA ), 2-(diisopropylamino) ethyl methacrylate (DPA), etc.; the solvent can be selected from one of redistilled tetrahydrofuran, toluene, etc.; after the continuous freeze-thaw degassing Polymerization, which can be polymerized under the protection of argon after continuous freeze-thaw degassing for 3 to 5 times; the reaction temperature can be 60-70°C, and the reaction time can be at least 24h; the precipitation can be anhydrous ether as the precipitation The agent was repeatedly precipitated twice; the drying can be vacuum drying.

所述大分子引发剂、第一单体、第二单体的摩尔比可为(10～20)∶(50～100)∶(150～300)。The molar ratio of the macroinitiator, the first monomer and the second monomer may be (10-20):(50-100):(150-300).

本发明选用不同分子量的聚乙二醇单甲醚合成大分子引发剂PEG-Br，以甲基丙烯酰氧丙基POSS和甲基丙烯酸二乙基氨基乙酯(DEA)作为共聚单体，利用ATRP聚合，成功合成了含POSS结构的有机无机杂化嵌段共聚物PEG-b-P(POSS-co-DEA)。The present invention selects polyethylene glycol monomethyl ethers of different molecular weights to synthesize the macromolecular initiator PEG-Br, uses methacryloxypropyl POSS and diethylaminoethyl methacrylate (DEA) as comonomers, utilizes ATRP polymerization successfully synthesized organic-inorganic hybrid block copolymer PEG-b-P (POSS-co-DEA) with POSS structure.

本发明的目标产物为含POSS结构的双亲性嵌段共聚物，且疏水嵌段为含POSS侧基的丙烯酸酯嵌段，亲水嵌段为聚乙二醇单甲醚。其中甲基丙烯酸二乙基氨基乙酯(DEA)、甲基丙烯酸-N,N-二甲基氨基乙酯(DMAEMA)、2-(二异丙基氨基)甲基丙烯酸乙酯(DPA)随着pH值或温度变化改变其亲疏水性，体现出温度或pH响应性。该反应采用ATRP聚合法，可控性好，可以较简便地合成有机-无机杂化的嵌段共聚物。The target product of the present invention is an amphiphilic block copolymer containing a POSS structure, and the hydrophobic block is an acrylate block containing POSS side groups, and the hydrophilic block is polyethylene glycol monomethyl ether. Among them, diethylaminoethyl methacrylate (DEA), N, N-dimethylaminoethyl methacrylate (DMAEMA), 2-(diisopropylamino) ethyl methacrylate (DPA) Change its hydrophilicity and hydrophobicity with the change of pH value or temperature, reflecting temperature or pH responsiveness. The reaction adopts the ATRP polymerization method, which has good controllability and can easily synthesize organic-inorganic hybrid block copolymers.

附图说明Description of drawings

图1为大分子引发剂mPEG-Br的1HNMR谱图。在图1中，横坐标为化学位移chemicalshift(ppm)。Figure 1 is the 1 HNMR spectrum of the macromolecular initiator mPEG-Br. In Fig. 1, the abscissa is the chemical shift (ppm).

图2为含POSS结构的有机无机杂化嵌段共聚物，记为PEG-b-P(POSS-co-DEA)的1HNMR谱图。在图2中，横坐标为化学位移chemicalshift(ppm)。Fig. 2 is the 1 H NMR spectrum of an organic-inorganic hybrid block copolymer containing a POSS structure, denoted as PEG-bP (POSS-co-DEA). In FIG. 2, the abscissa is the chemical shift (ppm).

图3为大分子引发剂mPEG-Br的红外光谱谱图。在图3中，横坐标为波数。Fig. 3 is the infrared spectrogram of the macromolecular initiator mPEG-Br. In Fig. 3, the abscissa is the wave number.

图4为含POSS结构的有机无机杂化嵌段共聚物，记为PEG-b-P(POSS-co-DEA)的红外光谱谱图。在图4中，横坐标为波数。Fig. 4 is the infrared spectrogram of the organic-inorganic hybrid block copolymer containing POSS structure, denoted as PEG-b-P (POSS-co-DEA). In Fig. 4, the abscissa is the wave number.

具体实施方式detailed description

本发明是一种含POSS结构的有机无机杂化嵌段共聚物的合成方法。具体实施方式由以下实施例详细给出，但本发明不限于以下实施例；本发明可在其它更广的方面解释，不受这些实施例的限制。The invention is a method for synthesizing an organic-inorganic hybrid block copolymer containing a POSS structure. The specific embodiment is given in detail by the following examples, but the present invention is not limited to the following examples; the present invention can be interpreted in other broader aspects without being limited by these examples.

实施例1Example 1

将6gPEG，2.2gTEA溶于20ml的DCM中。用冰浴将反应体系冷却至0℃。滴加0.198ml的BiBB和2ml的DCM混合溶液。滴加后撤去冰浴使体系升至室温，继续反应24h。反应溶液在去离子水中透析48h后冻干，得到白色粉末PEG-Br。相应的1HNMR谱图如图1所示，IR谱图如图3所示。6gPEG, 2.2gTEA were dissolved in 20ml of DCM. The reaction system was cooled to 0°C with an ice bath. A mixed solution of 0.198 ml of BiBB and 2 ml of DCM was added dropwise. After the dropwise addition, the ice bath was removed to allow the system to rise to room temperature, and the reaction was continued for 24 hours. The reaction solution was dialyzed in deionized water for 48 h and then freeze-dried to obtain PEG-Br as a white powder. The corresponding 1 HNMR spectrum is shown in FIG. 1 , and the IR spectrum is shown in FIG. 3 .

称取0.4315g步骤(1)得到的大分子引发剂、量取0.233g第二单体MAPOSS、0.15mL第三单体DEA、0.015g配体2，2'－联吡啶(Bpy)溶于1.5mL四氢呋喃中。即按计量比配制PEG-Br∶MAPOSS∶DEA＝1∶5∶15四氢呋喃溶液体系，经连续冻融脱气3～5次后氩气保护下加入0.007gCuBr催化剂，再继续连续冻融脱气3～5次，反应在65℃聚合。反应固定时间后液氮猝冷停止反应，反应样品通过中性氧化铝柱子以除去催化剂。选择无水乙醚为沉淀剂反复离心沉淀2次，真空干燥得到淡黄色嵌段共聚物粉末。相应的1HNMR谱图如图2所示，IR谱图如图4所示。Weigh 0.4315g of the macroinitiator obtained in step (1), measure 0.233g of the second monomer MAPOSS, 0.15mL of the third monomer DEA, and 0.015g of the ligand 2,2'-bipyridine (Bpy) in 1.5 mL tetrahydrofuran. That is to prepare PEG-Br:MAPOSS:DEA=1:5:15 tetrahydrofuran solution system according to the metering ratio, after continuous freeze-thaw degassing for 3 to 5 times, add 0.007g CuBr catalyst under the protection of argon, and then continue to freeze-thaw degassing continuously for 3 ~5 times, the reaction was polymerized at 65°C. After a fixed reaction time, liquid nitrogen was quenched to stop the reaction, and the reaction sample was passed through a neutral alumina column to remove the catalyst. Anhydrous diethyl ether was selected as the precipitating agent, centrifuged and precipitated twice, and vacuum-dried to obtain a light yellow block copolymer powder. The corresponding 1 HNMR spectrum is shown in FIG. 2 , and the IR spectrum is shown in FIG. 4 .

实施例2Example 2

步骤1反应时间为36h，其余同实施例1。Step 1 reaction time is 36h, all the other are the same as embodiment 1.

实施例3Example 3

步骤2配制PEG-Br∶MAPOSS∶DEA＝1∶3∶15四氢呋喃溶液体系，其余同实施例1。Step 2 prepare PEG-Br:MAPOSS:DEA=1:3:15 tetrahydrofuran solution system, the rest is the same as Example 1.

实施例4Example 4

步骤2配制PEG-Br∶MAPOSS∶DEA＝1∶7∶15四氢呋喃溶液体系，其余同实施例1。Step 2 prepare PEG-Br:MAPOSS:DEA=1:7:15 tetrahydrofuran solution system, the rest is the same as Example 1.

实施例5Example 5

步骤2配制PEG-Br∶MAPOSS∶DEA＝1∶9∶15四氢呋喃溶液体系，其余同实施例1。Step 2 prepare PEG-Br:MAPOSS:DEA=1:9:15 tetrahydrofuran solution system, the rest is the same as Example 1.

实施例6Example 6

步骤2反应时间为36h，其余同实施例1。Step 2 reaction time is 36h, all the other are the same as embodiment 1.

实施例7Example 7

步骤2反应在70℃聚合，其余同实施例1。The step 2 reaction was polymerized at 70° C., and the others were the same as in Example 1.

实施例8Example 8

步骤2配制PEG-Br∶MAPOSS∶DMAEMA＝1∶7∶15四氢呋喃溶液体系，其余同实施例1。Step 2 prepare PEG-Br:MAPOSS:DMAEMA=1:7:15 tetrahydrofuran solution system, the rest is the same as Example 1.

实施例9Example 9

步骤2配制PEG-Br∶MAPOSS∶DPA＝1∶7∶15四氢呋喃溶液体系，其余同实施例1。Step 2 prepare PEG-Br:MAPOSS:DPA=1:7:15 tetrahydrofuran solution system, the rest is the same as Example 1.

Claims (10)

1.含POSS结构的有机无机杂化嵌段共聚物，其特征在于记为PEG-b-P(POSS-co-DEA)，其结构式如下：1. The organic-inorganic hybrid block copolymer containing POSS structure is characterized in that it is recorded as PEG-b-P (POSS-co-DEA), and its structural formula is as follows: 其中，R＝CH3或H；R1＝CH3，C2H5或CH(CH3)2。Wherein, R=CH 3 or H; R 1 =CH 3 , C 2 H 5 or CH(CH 3 ) 2 . 2.如权利要求1所述含POSS结构的有机无机杂化嵌段共聚物的合成路线如下：2. the synthetic route of the organic-inorganic hybrid block copolymer containing POSS structure as claimed in claim 1 is as follows: 1)大分子引发剂PEG-Br的制备1) Preparation of macromolecular initiator PEG-Br 2)PEG-b-P(POSS-co-DEA)的合成2) Synthesis of PEG-b-P (POSS-co-DEA) 其中，R＝CH3或H；R1＝CH3，C2H5或CH(CH3)2；m＝135。Wherein, R=CH 3 or H; R 1 =CH 3 , C 2 H 5 or CH(CH 3 ) 2 ; m=135. 3.如权利要求1所述含POSS结构的有机无机杂化嵌段共聚物的合成方法，其特征在于包括以下步骤：3. the synthetic method that contains the organic-inorganic hybrid block copolymer of POSS structure as claimed in claim 1, is characterized in that comprising the following steps: 1)大分子引发剂的合成1) Synthesis of macroinitiators 将聚乙二醇单甲醚、缚酸剂溶于溶剂中得聚乙二醇单甲醚溶液，在冰浴条件下，将2－溴代异丁酰溴溶于溶剂中再滴入聚乙二醇单甲醚溶液中反应后，撤去冰浴，再在常温条件下反应，将所得到的溶液用透析膜透析后，冻干，即得大分子引发剂，呈白色粉末；Dissolve polyethylene glycol monomethyl ether and acid-binding agent in a solvent to obtain a polyethylene glycol monomethyl ether solution. Under ice bath conditions, dissolve 2-bromoisobutyryl bromide in a solvent and drop into polyethylene glycol monomethyl ether solution. After reacting in the glycol monomethyl ether solution, remove the ice bath, and then react under normal temperature conditions, dialyze the obtained solution with a dialysis membrane, freeze-dry to obtain the macromolecular initiator, which is a white powder; 2)嵌段共聚物的合成2) Synthesis of block copolymers 将步骤1)得到的大分子引发剂、第二单体、第三单体溶于溶剂中，经连续冻融脱气并在氩气氛下加入催化剂后，再继续冻融脱气并充入氩气后密封反应，再液氮冷冻，将所得的产物通过中性氧化铝柱子以除去催化剂后，浓缩，沉淀，干燥，即得含POSS结构的有机无机杂化嵌段共聚物，呈淡黄色粉末。Dissolve the macromolecular initiator, the second monomer, and the third monomer obtained in step 1) in a solvent, and after continuous freeze-thaw degassing and adding a catalyst under an argon atmosphere, continue freeze-thawing and degassing and fill with argon Seal the reaction after gas, then freeze with liquid nitrogen, pass the obtained product through a neutral alumina column to remove the catalyst, concentrate, precipitate, and dry to obtain an organic-inorganic hybrid block copolymer containing a POSS structure, which is a light yellow powder . 4.如权利要求3所述含POSS结构的有机无机杂化嵌段共聚物的合成方法，其特征在于在步骤1)中，所述聚乙二醇单甲醚的平均分子量为600、1000、2000、5000。4. the synthetic method that contains the organic-inorganic hybrid block copolymer of POSS structure as claimed in claim 3 is characterized in that in step 1) in, the average molecular weight of described polyethylene glycol monomethyl ether is 600,1000, 2000, 5000. 5.如权利要求3所述含POSS结构的有机无机杂化嵌段共聚物的合成方法，其特征在于在步骤1)中，所述缚酸剂选自三乙胺、吡啶中的一种。5. the synthetic method that contains the organic-inorganic hybrid block copolymer of POSS structure as claimed in claim 3 is characterized in that in step 1), described acid-binding agent is selected from the one in triethylamine, pyridine. 6.如权利要求3所述含POSS结构的有机无机杂化嵌段共聚物的合成方法，其特征在于在步骤1)中，所述溶剂选自重蒸二氯甲烷、甲苯中的一种；所述将2－溴代异丁酰溴溶于溶剂中再滴入聚乙二醇单甲醚溶液中反应的时间可至少2h；所述在常温条件下反应的时间可至少24h；所述透析可将反应溶液在去离子水中透析48h。6. as claimed in claim 3 containing the synthetic method of the organic-inorganic hybrid block copolymer of POSS structure, it is characterized in that in step 1) in, described solvent is selected from the one in redistilling methylene chloride, toluene; The reaction time of dissolving 2-bromoisobutyryl bromide in a solvent and then dripping it into the polyethylene glycol monomethyl ether solution can be at least 2h; the reaction time at normal temperature can be at least 24h; the dialysis can be The reaction solution was dialyzed against deionized water for 48 h. 7.如权利要求3所述含POSS结构的有机无机杂化嵌段共聚物的合成方法，其特征在于在步骤2)中，所述大分子引发剂、第二单体、第三单体的摩尔比为(10～20)∶(50～100)∶(150～300)。7. as claimed in claim 3 containing the synthetic method of the organic-inorganic hybrid block copolymer of POSS structure, it is characterized in that in step 2) in, described macromolecular initiator, the second monomer, the third monomer The molar ratio is (10～20):(50～100):(150～300). 8.如权利要求3所述含POSS结构的有机无机杂化嵌段共聚物的合成方法，其特征在于在步骤2)中，所述第二单体选自甲基丙烯酰氧丙基七异丁基笼形倍半硅氧烷、丙烯酰氧丙基七异丁基笼形倍半硅氧烷中的一种；所述第三单体可选自甲基丙烯酸二乙基氨基乙酯、甲基丙烯酸-N,N-二甲基氨基乙酯、2-(二异丙基氨基)甲基丙烯酸乙酯中的一种。8. the synthetic method that contains the organic-inorganic hybrid block copolymer of POSS structure as claimed in claim 3 is characterized in that in step 2) in, described second monomer is selected from the group consisting of methacryloxypropyl heptaiso One of butyl cage silsesquioxane, acryloxypropyl heptaisobutyl cage silsesquioxane; the third monomer can be selected from diethylaminoethyl methacrylate, One of N,N-dimethylaminoethyl methacrylate and 2-(diisopropylamino)ethyl methacrylate. 9.如权利要求3所述含POSS结构的有机无机杂化嵌段共聚物的合成方法，其特征在于在步骤2)中，所述溶剂选自重蒸四氢呋喃、甲苯中的一种；所述经连续冻融脱气后聚合，可经连续冻融脱气3～5次后在氩气保护下聚合。9. as claimed in claim 3 containing the synthetic method of the organic-inorganic hybrid block copolymer of POSS structure, it is characterized in that in step 2) in, described solvent is selected from the one in distilling tetrahydrofuran (THF), toluene; Polymerize after continuous freeze-thaw degassing, and polymerize under the protection of argon after continuous freeze-thaw degassing for 3 to 5 times. 10.如权利要求3所述含POSS结构的有机无机杂化嵌段共聚物的合成方法，其特征在于在步骤2)中，所述反应的温度为60～70℃，反应的时间至少24h；所述沉淀可采用无水乙醚作为沉淀剂反复沉淀2次；所述干燥可采用真空干燥。10. the synthetic method of the organic-inorganic hybrid block copolymer containing POSS structure as claimed in claim 3, is characterized in that in step 2), the temperature of described reaction is 60～70 ℃, the time of reaction is at least 24h; The precipitation can be precipitated twice using anhydrous ether as a precipitating agent; the drying can be vacuum drying.

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