WO2020258355A1 - 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 PDF

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WO2020258355A1
WO2020258355A1 PCT/CN2019/094540 CN2019094540W WO2020258355A1 WO 2020258355 A1 WO2020258355 A1 WO 2020258355A1 CN 2019094540 W CN2019094540 W CN 2019094540W WO 2020258355 A1 WO2020258355 A1 WO 2020258355A1
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semi
fluoro
monomer
alternating copolymer
methacrylate
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程振平
成健楠
张丽芬
涂凯
王金英
朱秀林
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Suzhou University
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    • 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
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • 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
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    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/305—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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    • 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
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
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    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
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    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/16—End groups
    • C08G2261/164—End groups comprising organic end groups
    • C08G2261/1642—End groups comprising organic end groups comprising reactive double bonds or triple bonds

Definitions

  • the present invention relates to the technical field of polymer preparation, in particular to a method for photopolymerization of a block copolymer of a main chain type "semi-fluoro" alternating copolymer.
  • topological structure polymers not only expands the performance of polymer materials, but also makes the correlation between polymer structure and performance more obvious. This correlation is of great significance for customizing polymer materials, and the regulation of polymer topology Polymer synthetic chemistry is an important research direction. Common polymer topological structures have linear, star, comb, ring, hyperbranched and dendritic structures, etc., and there are a large number of related literature reports. On the other hand, from the perspective of polymer chain chemical structure, the properties of polymers are closely related to their chain structure composition, and fluoropolymers have always played an important role in the polymer application market, which is due to their outstanding corrosion resistance, The properties of aging resistance, heat resistance, and low surface energy are inseparable.
  • fluorine atoms not only have the characteristics of low polarizability and strong electronegativity, but also have small atomic radius and strong C-F bond energy. Therefore, fluoropolymers are currently widely used in antifouling coatings, hydrophobic materials, surfactants, etc.
  • the fluorine-containing segment it can be divided into side chain type fluoropolymer and main chain type fluoropolymer.
  • the side chain type fluorine-containing polymer is synthesized by directly introducing fluorine-containing monomers (such as pentafluorostyrene, (meth)acrylic acid fluorine-containing ester, etc.) to make it through "living"/controllable free radical polymerization methods such as atom Transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) to obtain side chain type fluoropolymer.
  • fluorine-containing monomers such as pentafluorostyrene, (meth)acrylic acid fluorine-containing ester, etc.
  • ATRP atom Transfer radical polymerization
  • RAFT reversible addition-fragmentation chain transfer
  • the main chain type fluoropolymer is mainly obtained by gaseous fluoromonomers (such as vinylidene fluoride (VDF), etc.) through iodine transfer radical polymerization (ITP).
  • gaseous fluoromonomers such as vinylidene fluoride (VDF), etc.
  • IPP iodine transfer radical polymerization
  • the currently available fluoropolymers are limited by the types of monomers, resulting in a single variety and poor structural designability, making it difficult to meet the requirements of materials for diversified polymer structures.
  • the inventor recently developed a visible light-induced catalyzed polymerization of ⁇ , ⁇ -diiodoperfluoroalkane (as monomer A) and ⁇ , ⁇ -non-conjugated diene (as monomer B) stepwise transfer addition-
  • the new polymerization method of free radical termination (Step Transfer-Addition&Radical-Termination, hereinafter referred to as START)
  • START Step Transfer-Addition&Radical-Termination
  • START Step Transfer-Addition&Radical-Termination
  • n represents the degree of polymerization
  • the purpose of the present invention is to provide a method for photopolymerization of block copolymers of main chain type "semi-fluorine" alternating copolymers.
  • the polymerization method is carried out under visible light irradiation, and the polymerization process is "living". Free radical polymerization characteristics, the prepared polymer has a narrow molecular weight distribution.
  • the first object of the present invention is to provide a method for photopolymerization of a block copolymer of a main chain type "semi-fluoro" alternating copolymer, which includes the following steps:
  • the methacrylate monomers and the "semi-fluorine" alternating copolymer (AB) n macroinitiator under the action of a photocatalyst, in an organic solvent at 20-30 °C light-controlled activity free Base polymerization, the polymerization reaction is carried out under light conditions of 390nm-590nm for at least half an hour to obtain a block copolymer of the main chain type "semi-fluoro" alternating copolymer; wherein,
  • formulas (1)-(4) are as follows:
  • R is selected from C 1 -C 6 alkyl, aryl ether or acyloxy
  • R 1 is selected from a C 1 -C 6 alkyl group, a polyethylene glycol group, an amino group substituted C 1 -C 6 alkyl group, or an epoxy group substituted C 1 -C 6 alkyl group.
  • R is selected from methyl, p-phenylene ether, adipoyloxy or terephthaloyloxy.
  • R 1 is selected from methyl, n-butyl, n-hexyl, polyethylene glycol monomethyl ether, dimethylaminoethyl or glycidyl.
  • the methacrylate monomers are methyl methacrylate, butyl methacrylate, hexyl methacrylate, glycidyl methacrylate, N,N-dimethylaminoethyl methacrylate Or methacrylate polyethylene glycol monomethyl ether ester.
  • the "semi-fluoro" alternating copolymer (AB) n macroinitiator is obtained by polymerizing monomer A and monomer B through START (gradual transfer-addition-termination);
  • the monomer A is selected from 1,4 -Diiodoperfluorobutane, 1,6-diiodoperfluorohexane or 1,8-diiodoperfluorooctane;
  • the monomer B is selected from 1,7-octadiene, 1, 9-decadiene, p-phenylene diallyl ether, terephthalate (1-hexene) ether, diallyl adipate, diallyl terephthalate or bis(1-hexene) En)ester.
  • the preparation method of the "semi-fluoro" alternating copolymer (AB) n macroinitiator refers to the method disclosed in CN107619466A.
  • the molar ratio of monomer A to monomer B is 1-1.2:1.
  • the "semi-fluorine" alternating copolymer (AB) shown in formula (1) n macroinitiator is obtained;
  • the monomer A and monomer B are When the molar ratio is 1.2:1, the "semi-fluoro" alternating copolymer (AB) n macroinitiator represented by formula (3) is obtained.
  • the "semi-fluoro" alternating copolymer macroinitiator used in the present invention is named (AB) n .
  • the "semi-fluoro" alternating copolymers obtained by polymerizing 1,6-diiodoperfluorohexane as monomer A and 1,7-octadiene as monomer B are respectively named (AB 1 ) n And (AB 1 ) n A; the name of the "semi-fluoro" alternating copolymer obtained by using 1,6-diiodoperfluorohexane as monomer A and p-phenylene di(1-hexene) ether as monomer B It is (AB 2 ) n ; the name of the "semi-fluoro” alternating copolymer obtained by using 1,6-diiodoperfluorohexane as monomer A and bis(1-hexene) phthalate as monomer B I
  • the calculation method of the degree of polymerization n of the "semi-fluoro" alternating copolymer (AB) n can be illustrated by taking (AB 1 ) n as an example.
  • the structure of (AB 1 ) n can be characterized by nuclear magnetic 1 H NMR to obtain different polymers.
  • the integral product of) is 16.31.
  • the molecular weight distribution index of the "semi-fluoro" alternating copolymer (AB) n is 1.40 to 1.90.
  • the photocatalyst is tris(2,2'-bipyridine) ruthenium dichloride (Ru(bpy) 3 Cl 2 ) and sodium ascorbate.
  • the concentration of the methacrylate monomer in the organic solvent is 0.002 mol/mL to 0.1 mol/mL.
  • methacrylate monomers "semi-fluorine" alternating copolymer (AB) n macroinitiator, tris(2,2'-bipyridine) ruthenium dichloride (Ru(bpy) 3 Cl 2 )
  • the molar ratio of sodium ascorbate (AsAc-Na) is 30 to 500:1 to 3:0.1 to 0.5:1 to 5, preferably 200 to 500:1 to 2:0.1 to 0.2:1 to 2.
  • the organic solvent is acetone, tetrahydrofuran or N,N-dimethylformamide.
  • acetone tetrahydrofuran or N,N-dimethylformamide.
  • acetone tetrahydrofuran or N,N-dimethylformamide.
  • the 390-590nm light is the light emitted by the LED light source.
  • the light source is a blue LED lamp.
  • the reaction time is 0.5-30h. After 24 hours of reaction, the conversion rate of DMAEMA monomer can reach 99.5%.
  • the methyl methacrylate monomer is methyl methacrylate (MMA), glycidyl methacrylate (GMA), -N,N-dimethylaminoethyl methacrylate (DMAEMA) or methyl methacrylate (MMA).
  • MMA methyl methacrylate
  • GMA glycidyl methacrylate
  • DMAEMA -N,N-dimethylaminoethyl methacrylate
  • MMA methyl methacrylate
  • PEGMA Polyethylene glycol monomethyl ether acrylate
  • the block copolymer of the main chain type "semi-fluoro" alternating copolymer is named (AB 1 ) n -b- PMMA, (AB 1 ) n -b-PGMA, (AB 1 ) n -b-PPEGMA, (AB 1 ) n -b-PDMAEMA; respectively (AB 1 ) n A, (AB 2 ) n or (AB 3 ) n is the main chain type "semi-fluorine" alternating copolymer block copolymer obtained after the macroinitiator initiates MMA polymerization, respectively named PMMA-b-(AB 1 ) n Ab-PMMA, (AB 2 ) n -b-PMMA and (AB 3 ) n -b-PMMA, the structural formulas of the above products are as follows:
  • the second object of the present invention is to provide a block copolymer of the main chain type "semi-fluoro" alternating copolymer of formula (2) or formula (4) prepared by the above light polymerization method, which is a main chain type Block copolymers of polyolefin, polyester or polyether "semi-fluoro" alternating copolymers.
  • the molecular weight distribution index of the block copolymer of the main chain type "semi-fluoro" alternating copolymer of formula (2) or formula (4) is 1.40 to 1.90.
  • the reaction principle is as follows: the "semi-fluorine" alternating copolymer (AB) n is used as the macromolecular initiator to initiate the controllable polymerization of methacrylate monomers under the action of the photocatalyst. As the progress of the block copolymer polymerization degree m gradually increases. At the same time, by designing the structure of the B monomer in the "semi-fluorine" alternating copolymer (AB) n , block copolymers of various main chain polyolefin, polyester or polyether "semi-fluorine" alternating copolymers can be prepared.
  • the present invention has at least the following advantages:
  • the invention utilizes the living radical polymerization method induced by the LED lamp at room temperature (20-30°C), and the operation is simple and safe.
  • the preparation method of the present invention the ln([M] 0 /[M]) of the monomer is in a linear relationship with time, the molecular weight of the polymer increases linearly with the increase of the conversion rate, and the molecular weight distribution is also narrower , In line with the characteristics of "living" radical polymerization, with the design of polymer structure and polymer molecular weight.
  • Figure 1 is the 1 H NMR spectrum of the main chain "semi-fluoro" alternating copolymer (AB 1 ) n ;
  • Figure 2 is a 19 F NMR spectrum of the main chain "semi-fluoro" alternating copolymer (AB 1 ) n ;
  • Example 4 is a GPC elution curve of the block copolymer (AB 1 ) n -b-PMMA of the main chain "semi-fluoro" alternating copolymer obtained at different polymerization times in Example 1;
  • Example 5 is a first-order kinetic diagram of the monomer concentration [M] and reaction time of the block copolymer (AB 1 ) n -b-PMMA of the "semi-fluoro" alternating copolymer in Example 1;
  • FIG. 6 is a graph in FIG. 1 (AB 1) n -b- PMMA of M n and M w / M n with conversion block copolymer of Example "semi-fluoro" alternating copolymer;
  • Figure 7 is a 1 H NMR spectrum of the main chain "semi-fluoro" alternating copolymer (AB 1 ) n A in Example 3;
  • Figure 8 is a 1 H NMR spectrum of the main chain "semi-fluoro" alternating copolymer (AB 2 ) n in Example 3;
  • Testing equipment PL gel permeation chromatograph; INOVA 400MHz nuclear magnetometer.
  • the reaction tube is opened, a small amount of polymer solution is drawn for a hydrogen nuclear magnetic resonance spectrum ( 1 H NMR) test, and the conversion rate of the monomer and the nuclear magnetic molecular weight (Mn , NMR ) are calculated.
  • the rest of the polymer solution is dissolved in a certain amount of tetrahydrofuran, and after passing through a neutral Al 2 O 3 column, a precipitant is added for precipitation, standing, suction filtration, and vacuum drying to obtain a "semi-fluorine" alternating copolymer block copolymer ( AB 1 ) n -b-PMMA.
  • Figure 1-2 shows the 1 H NMR and 19 F NMR test results of (AB 1 ) n , respectively. Its degree of polymerization is 8-9.
  • Figure 3 is the 1 H NMR of the block copolymer (AB 1 ) n -b-PMMA of the "semi-fluoro" alternating copolymer.
  • Figure 4 shows the GPC efflux curve of (AB 1 ) n -b-PMMA obtained at different polymerization times. From right to left, the reaction time corresponding to the curve gradually increases. The polymerization time is 1h, 2h, 4h, 6h, 8h and 10h respectively.
  • the molecular weight and molecular weight distribution index (PDI) of (AB 1 ) n -b-PMMA ) Are 21400g/mol, 1.70; 27800g/mol, 1.44; 32000g/mol, 1.37; 37600g/mol, 1.38; 38100g/mol, 1.34; 46200g/mol, 1.55.
  • PEGMA-300 and PEGMA-400 respectively refer to polyethylene glycol monomethyl ether methacrylate whose molecular weight is 300 g/mol or 400 g/mol.
  • the molecular weight of (AB 1 ) n A, (AB 2 ) n or (AB 3 ) n and PDI are 6400 g/mol, 1.75; 2200 g/mol, 1.28; 9800 g/mol, 1.91, respectively.
  • the reaction tube is opened, a small amount of polymer solution is drawn for a hydrogen nuclear magnetic resonance spectrum ( 1 H NMR) test, and the conversion rate of the monomer and the nuclear magnetic molecular weight (Mn , NMR ) are calculated.
  • the rest of the polymer solution is dissolved in a certain amount of tetrahydrofuran, and after passing through a neutral Al 2 O 3 column, a precipitation agent is added for precipitation, standing, suction filtration, and vacuum drying to obtain a polymer.
  • Figures 7-9 are respectively the 1 H NMR test results of the macroinitiators (AB 1 ) n A, (AB 2 ) n or (AB 3 ) n used in this embodiment.
  • Table 2 shows the polymerization results using different macroinitiators. It can be seen that the polymerization of methyl methacrylate monomer was successfully achieved, and the molecular weight distribution of the obtained polymer was narrow.

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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

主链型“半氟”交替共聚物的嵌段共聚物的光照聚合法 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(Step Transfer-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：
Figure PCTCN2019094540-appb-000001
Figure PCTCN2019094540-appb-000002
其中，x＝4-8；y＝0-3；n＝4-30；m＝100-500；
R选自C 1-C 6烷基、芳醚基或酰氧基；
R 1选自C 1-C 6烷基、聚乙二醇基、胺基取代的C 1-C 6烷基或环氧基取代的C 1-C 6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，R 1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(AB 1) n和(AB 1) 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(AB 2) 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(AB 3) n，上述“半氟”交替共聚物的结构式分别如下：
Figure PCTCN2019094540-appb-000003
Figure PCTCN2019094540-appb-000004
“半氟”交替共聚物(AB) n的聚合度n的计算方法可以以(AB 1) n为例说明，通过核磁 1H NMR对(AB 1) 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(CH 2＝CH-)的积分积为1.00，化学位移a,b(CH 2＝CH-)的积分和为1.83，化学位移h(-CH(I)CH 2CF 2-)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) 3Cl 2)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) 3Cl 2)、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(AB 1) 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(AB 1) n-b-PMMA、(AB 1) n-b-PGMA、(AB 1) n-b-PPEGMA、(AB 1) n-b-PDMAEMA；分别以(AB 1) nA、(AB 2) n或者(AB 3) 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-(AB 1) nA-b-PMMA、 (AB 2) n-b-PMMA以及(AB 3) n-b-PMMA，上述各产物结构式如下：
Figure PCTCN2019094540-appb-000005
Figure PCTCN2019094540-appb-000006
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(AB 1) n的 1H NMR谱图；
图2是主链“半氟”交替共聚物(AB 1) 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(AB 1) n-b-PMMA的 1H NMR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(AB 1) 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(AB 1) 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(AB 1) n-b-PMMA的M n和M w/M n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(AB 1) nA的 1H NMR谱图；
图8是实施例3中主链“半氟”交替共聚物(AB 2) n的 1H NMR谱图；
图9是实施例3中主链“半氟”交替共聚物(AB 3) 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,M n＝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；INOVA 400MHz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(AB 1) n，0.002mmol光催化剂三(2,2'-联吡啶)二氯化钌(Ru(bpy) 3Cl 2)，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(M n,NMR)。其余聚合物溶液溶于一定量的四氢呋喃中，过中性Al 2O 3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(AB 1) n-b-PMMA。图1-2分别是(AB 1) 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(AB 1) 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(AB 1) n-b-PMMA的聚合结果。
图4是不同聚合时间得到的(AB 1) 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(AB 1) 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(AB 1) n-b-PMMA的单体浓度[M]与反应时间的一级动力学图以及(AB 1) n-b-PMMA的M n和M w/M n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M n,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(AB 1) n，0.005mmol光催化剂三(2,2'-联吡啶)二氯化钌(Ru(bpy) 3Cl 2)，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，(AB 1) 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(M n,NMR)。其余聚合物溶液溶于一定量的四氢呋喃中，过中性Al 2O 3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
Figure PCTCN2019094540-appb-000007
表1中，编号为4的实验条件为[M] 0:[(AB 1) n] 0:[Ru(bpy) 3Cl 2] 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(AB 1) nA、(AB 2) n或(AB 3) n，0.002mmol光催化剂三(2,2'-联吡啶)二氯化钌(Ru(bpy) 3Cl 2)，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，(AB 1) nA、(AB 2) n或(AB 3) 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(M n,NMR)。其余聚合物溶液溶于一定量的四氢呋喃中，过中性Al 2O 3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(AB 1) nA、(AB 2) n或(AB 3) 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
Figure PCTCN2019094540-appb-000008
表2中，实验条件为[MMA] 0:[(AB) n] 0:[Ru(bpy) 3Cl 2] 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：
    Figure PCTCN2019094540-appb-100001
    其中，x＝4-8；y＝0-3；n＝4-30；m＝100-500；
    R选自C 1-C 6烷基、芳醚基或酰氧基；
    R 1选自C 1-C 6烷基、聚乙二醇基、胺基取代的C 1-C 6烷基或环氧基取代的C 1-C 6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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