WO2021128473A1 - 近红外光热转化下的乙烯基类单体的"活性"自由基聚合方法 - Google Patents

近红外光热转化下的乙烯基类单体的"活性"自由基聚合方法 Download PDF

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WO2021128473A1
WO2021128473A1 PCT/CN2020/070786 CN2020070786W WO2021128473A1 WO 2021128473 A1 WO2021128473 A1 WO 2021128473A1 CN 2020070786 W CN2020070786 W CN 2020070786W WO 2021128473 A1 WO2021128473 A1 WO 2021128473A1
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cavity
infrared light
atrp
reaction
radical polymerization
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French (fr)
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张丽芬
高群
程振平
涂凯
李海辉
姚澜
朱秀林
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苏州大学
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    • C08F120/00—Homopolymers 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
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    • C08F2438/00—Living radical polymerisation
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    • 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]

Definitions

  • the invention relates to the technical field of polymer preparation, in particular to a "living" radical polymerization method under near-infrared photothermal conversion of vinyl monomers.
  • polymerization can be controlled by controlling reaction conditions such as temperature, light, mechanical force, applied voltage, and chemical redox.
  • reaction conditions such as temperature, light, mechanical force, applied voltage, and chemical redox.
  • the light source used for photopolymerization can be roughly divided into ultraviolet light (UV, ⁇ 400nm, ⁇ 6eV), visible light (vis, 400-700nm, ⁇ 2eV) and near-infrared light (NIR, 670-1100nm, ⁇ 1.5eV) and so on.
  • NIR near-infrared
  • Boyer et al. used bacterial chlorophyll a as a catalyst for PET-RAFT polymerization to obtain polymers with controllable molecular weight and narrow molecular weight distribution.
  • this catalyst is difficult to synthesize and expensive, which is not conducive to large-scale production.
  • the purpose of the present invention is to provide a "living" free radical polymerization method under near-infrared photothermal conversion of vinyl monomers, which utilizes near-infrared photo-responsive substances through photothermal conversion, that is, under light irradiation
  • the heat energy generated under the polymerization reaction is used for the energy required for the "living"/controllable free radical polymerization.
  • the method of the present invention has mild conditions, a wide range of monomers, and the adopted near-infrared dye solution has stable photothermal properties and can be recycled for a long time. use.
  • the present invention adopts the following technical solutions:
  • the purpose of the present invention is to provide a "living" radical polymerization method under near-infrared photothermal conversion of vinyl monomers.
  • the reaction vessel is irradiated with near-infrared light with a wavelength of 750-850nm, and the reaction vessel used has mutual A first cavity and a second cavity that are not connected, wherein the organic solution of the near-infrared light-responsive dye is placed in the first cavity, and the second cavity is used to place a closed reaction flask containing the reaction liquid, The reaction flask is filled with protective gas; the near-infrared light is irradiated into the near-infrared light-responsive dye solution in the first cavity to convert the near-infrared light into heat, and the reaction flask in the second cavity is heated to the polymerization site
  • a variety of "living" radical polymerization techniques for vinyl monomers are constructed at a temperature of 50-100°C according to the composition of the reaction solution to obtain polymers represented by formulas (4)-(6);
  • the near-infrared light-responsive dyes include the croton acid cyanine compounds represented by formulas (1)-(3):
  • n 1 and n 2 are independently selected from 1-10;
  • the reaction solution includes vinyl monomers, organic solvents, ATRP initiators, ATRP ligands and ATRP catalysts; or
  • the reaction liquid includes vinyl monomers, organic solvents, RAFT reagents and thermal initiators; or
  • the reaction liquid includes vinyl monomers, organic solvents, ATRP initiators and additives; the additives include organic amines and/or iodine-containing compounds;
  • n 1 , m 2 and m 3 are independently selected from 10-300;
  • R 1 , R 1 ′ and R 1 ′′ are each independently selected from isobutyl cyano group, 4-cyanovaleric acid group, 2-phenylacetate group or 2-isobutyric acid ethyl group;
  • R 2 , R 2 ′ and R 2 ′′ are each independently selected from hydrogen or methyl
  • R 3 , R 3 ′ and R 3 ′′ are each independently selected from phenyl, 2-naphthyl, bromine, chlorine or iodine;
  • R 4 is selected from methyl, butyl, polyethylene glycol monomethyl ether, hydroxyethyl, hydroxypropyl or N,N-dimethylaminoethyl;
  • R 5 is selected from hydrogen, methyl, ethyl or hydroxymethyl
  • R 6 is selected from hydrogen, methyl, ethyl or hydroxymethyl.
  • "living" radical polymerization includes atom transfer radical polymerization (ATRP), bromoiodine conversion "living” radical polymerization, and reversible addition-fragmentation chain transfer polymerization (RAFT).
  • ATRP atom transfer radical polymerization
  • RAFT reversible addition-fragmentation chain transfer polymerization
  • the reaction liquid includes vinyl monomers, organic solvents, ATRP initiators, ATRP ligands and ATRP catalysts
  • vinyl monomers undergo ATRP polymerization.
  • the reaction liquid includes vinyl monomers, organic solvents, RAFT reagents and In the case of thermal initiators, the vinyl monomers undergo RAFT polymerization.
  • the reaction solution includes vinyl monomers, organic solvents, ATRP initiators and additives
  • the vinyl monomers undergo bromine-iodine conversion "living" radical polymerization.
  • the concentration of the near-infrared light-responsive dye is 1.0-10.0 mg/mL, and the power of the near-infrared light is 0.05-1.0 W/cm 2 . Preferably, it is 0.1-0.3 W/cm 2 .
  • the vinyl monomers are methyl acrylate, methyl methacrylate (MMA), butyl acrylate, butyl methacrylate, polyethylene glycol monomethyl ether acrylate, and polyethylene glycol methacrylate.
  • Methyl ether ester hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N,N-dimethylaminoethyl methacrylate, glycidyl methacrylate, styrene , N,N-dimethylacrylamide, N,N-diethylacrylamide, N-dihydroxyethylacrylamide.
  • the ATRP initiator is one or more of ethyl 2-bromophenylacetate, ethyl 2-bromoisobutyrate and 2-iodo-2-methylpropionitrile;
  • the ATRP ligand is bipyridine, One or more of pentamethyldivinyltriamine, hexamethyltrivinyltetraamine and triphenylphosphine;
  • ATRP catalyst is one or more of CuBr, CuCl, FeBr 2 and FeCl 2 .
  • the RAFT reagent is isobutyronitrile dithionaphthoate or 4-cyano-4-(thiobenzoyl)valeric acid;
  • the thermal initiator is azobisisobutyronitrile and/or benzyl peroxide Acyl.
  • the RAFT reagent is isobutyronitrile dithionaphthoate (CPDN); when R 1 is 4-cyanovaleric acid group, the RAFT reagent is 4-cyano-4 -(Thiobenzoyl)valeric acid (CPADB).
  • CPADB is selected.
  • the additive is one or more of NaI, KI, triethylamine, triethanolamine and tetrabutylammonium iodide.
  • the organic solvent is one or more of toluene, acetone, ethanol, methanol, N,N-dimethylformamide and dimethyl sulfoxide.
  • the molar ratio of vinyl monomer, RAFT reagent and thermal initiator is 50-1000:2:1-0.5; the molar ratio of vinyl monomer, ATRP initiator, ATRP catalyst and ATRP ligand is 50 -1000:1:0.01-1.5:0.3-4.5; the molar ratio of vinyl monomer, ATRP initiator and additives is 50-1000:1:1-10.
  • the molar ratio of vinyl monomer, RAFT reagent and thermal initiator is 300-500:2:1; the molar ratio of vinyl monomer, ATRP initiator, ATRP catalyst and ATRP ligand is 100-500 :1:0.05-1:0.3-3; the molar ratio of vinyl monomer, ATRP initiator and additives is 50-500:1:1-2.
  • the concentration of the vinyl monomer in the reaction solution is 1.0-8.0 mol/L, preferably 1.0-4.0 mol/L.
  • reaction time is 1-20h.
  • the first cavity surrounds the outside of the second cavity
  • the device for generating near-infrared light surrounds the outside of the first cavity.
  • reaction container is a glass jacketed reaction flask
  • second cavity provides a water bath environment for the sealed reaction flask.
  • the solvent of the organic solution of the near-infrared light-responsive dye is toluene.
  • the light source used for illumination of the present invention is a near-infrared LED lamp.
  • the light wavelength is 810 nm.
  • the present invention also discloses a polymerization reaction device under near-infrared photothermal conversion, which comprises a reaction container, the reaction container is used for receiving near-infrared light irradiation, and the reaction container has a first cavity and a second cavity that are not connected to each other.
  • the first cavity contains the organic solution of the near-infrared light-responsive dye
  • the second cavity is equipped with a reaction flask containing the reaction liquid; the near-infrared light is irradiated into the first cavity, and the near-infrared light-responsive dye is near infrared
  • the light is converted into heat energy, and the reaction liquid in the second cavity is heated to 50-100°C.
  • the first cavity surrounds the outside of the second cavity, and the outside of the first cavity is surrounded by an illumination unit, and the illumination unit is used to emit near-infrared light.
  • the present invention is based on a polymerization reaction device under near-infrared photothermal conversion, which uses near-infrared photo-responsive dyes to convert near-infrared light into heat, and the generated heat heats the reaction vessel, and uses near-infrared photothermal conversion to generate heat energy required for polymerization, avoiding This solves the problems of uneven light irradiation and low penetration of short-wavelength light.
  • the method of the invention has mild conditions, a wide range of monomers, and the adopted near-infrared dye solution has stable photothermal properties and can be recycled for a long time.
  • the molecular weight of the polymer increases linearly with the increase of the conversion rate, and the molecular weight distribution is also narrow (M w /M n ⁇ 1.20), which conforms to the characteristics of "living" radical polymerization.
  • Figure 3 is the 1 H NMR test result of the polymer PMMA in Example 2;
  • Figure 5 shows the chain extension of the polymer PMMA in Example 2.
  • Figure 6 is the 1 H NMR test result of the polymer PDMA in Example 3.
  • Figure 7 is the 1 H NMR test result of the polymer PGMA in Example 4.
  • Figure 9 is the 1 H NMR test result of the polymer PS in Example 6;
  • Figure 10 is the 1 H NMR test result of the polymer PMMA in Example 7.
  • FIG. 11 is the 1 H NMR test result of the polymer PMMA in Example 8.
  • the used raw material MMA needs to be passed through a neutral alumina column to remove the polymerization inhibitor, and then placed in the upper layer of the refrigerator for storage.
  • the ketone acid cyanine near-infrared dyes were synthesized in the laboratory according to the methods in the literature "Dyes Pigments, 2008, 78, 60.” and “J. Am. Chem. Soc., 2017, 139, 11333.”. Other reagents can be used directly after they are obtained commercially.
  • test methods are used:
  • the number average molecular weight (M n, GPC ) and molecular weight distribution (M w /M n ) of the obtained polymer are measured by TOSOH HLC-8320 gel permeation chromatography (GPC), which is equipped with a TOSOH refractive index detector.
  • GPC gel permeation chromatography
  • One guard column (4.6 ⁇ 20mm, TSKgel guard column SuperMP-N) and two test columns (4.6 ⁇ 150mm, TSKgelSupermultiporeHZ-N)
  • the testable molecular weight ranges from 5 ⁇ 10 2 to 5 ⁇ 10 5 g/mol.
  • THF was used as the mobile phase
  • the temperature was 40°C
  • the flow rate was 0.35 mL/min.
  • the sample is drawn through the TOSOH autosampler for testing.
  • the linear PMMA purchased from TOSOH is selected as the standard sample.
  • the preparation process of the sample for testing GPC is as follows: take 20 ⁇ L of polymer mixed solution, freeze-dry, remove the solvent, then dissolve the polymer with THF, pass the polymer solution through a small column of neutral alumina and filter with 0.45 ⁇ m Head the syringe, and finally inject the pure polymer solution into the test bottle.
  • NMR spectra of the obtained product and the polymer were measured by Bruker 300MHz nuclear magnetic resonance instrument, using CDCl 3 as the deuterated reagent, tested at room temperature (25° C.), and tetramethylsilane (TMS) as the internal standard.
  • UV-vis is measured by Shimadzu UV-2600 ultraviolet-visible spectrophotometer, with toluene as the solvent.
  • Figure 2 is the temperature rise test results of 6.4 mg/mL ketocyanine dyes under near-infrared light at different powers.
  • a water bath environment is set in the inner layer of the glass jacketed reaction flask, in which an ampoule containing the reaction liquid (ie, the second cavity) is placed.
  • MMA polymerization system monomer methyl methacrylate
  • CPADB 4-cyano-4-(thiobenzoyl)pentanoic acid
  • AIBN thermal initiator azo Diisobutyronitrile
  • the mixed solution is a pink homogeneous solution.
  • Thaw and inflate repeat this process three times, and seal the ampoule.
  • Place the sealed ampoule in the inner water bath of the jacket of the glass jacket reaction flask, and then place the glass jacket reaction flask in the center of the ring-shaped near-infrared ring light source ( ⁇ 810nm, 100mW/cm 2 ) ,
  • the glass jacket reaction flask is placed on the magnetic stirrer, and the constant temperature of the photothermal conversion at this time is 59.8°C.
  • Table 1 shows the test results of product polymerization under different polymerization times.
  • the polymerized monomers used can also be selected from other monomers other than MMA, such as methyl acrylate, butyl (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, (meth) Hydroxyethyl acrylate and N,N-dimethylaminoethyl (meth)acrylate can also be used to obtain "living"/controllable polymers using the above-mentioned polymerization methods.
  • monomers other than MMA such as methyl acrylate, butyl (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, (meth) Hydroxyethyl acrylate and N,N-dimethylaminoethyl (meth)acrylate can also be used to obtain "living"/controllable polymers using the above-mentioned polymerization methods.
  • a water bath environment is set in the inner layer of the glass jacketed reaction flask, in which an ampoule containing the reaction liquid (ie, the second cavity) is placed.
  • DMA monomer N,N-dimethylacrylamide
  • CPADB water-soluble initiator azobiscyanovaleric acid
  • V-501 water-soluble initiator azobiscyanovaleric acid
  • the polymerization method of the present invention can also realize the "living" radical polymerization of N,N-dimethylacrylamide monomer, and has good controllability and polymerization speed.
  • a water bath environment is set in the inner layer of the glass jacketed reaction flask, in which an ampoule containing the reaction liquid (ie, the second cavity) is placed.
  • GMA polymerization system monomer glycidyl methacrylate
  • CPDN RAFT reagent isobutyronitrile dithionaphthoate
  • AIBN initiator AIBN molar ratio
  • [GMA] 0 / [CPDN] 0 /[AIBN] 0 300/2
  • Table 3 shows the test results of GMA monomer polymerization under the above conditions.
  • R represents [GMA] 0 /[CPDN] 0 /[AIBN] 0 ; the monomer conversion rate (Conv.%) is calculated by nuclear magnetism;
  • M n,GPC represents the molecular weight obtained by GPC;
  • M w /M n represents the molecular weight distributed.
  • the polymerization method of the present invention can also carry out the "living" radical polymerization of glycidyl methacrylate monomer, and has good controllability and polymerization speed.
  • a water bath environment is set in the inner layer of the glass jacketed reaction flask, in which an ampoule containing the reaction liquid (ie, the second cavity) is placed.
  • MA polymerization system monomer methyl acrylate
  • RAFT reagent CPDN initiator AIBN mole ratio
  • AIBN amino acid methyl acrylate
  • Table 4 shows the test results of the MA monomer polymerization under the above polymerization conditions.
  • R represents [MA] 0 /[CPDN] 0 /[AIBN] 0 ; the monomer conversion rate (Conv.%) is calculated by nuclear magnetism;
  • M n,GPC represents the molecular weight obtained by GPC;
  • M w /M n represents The molecular weight distribution.
  • the polymerization method of the present invention can also "living" polymerization of methyl acrylate monomers, and has good controllability.
  • a water bath environment is set in the inner layer of the glass jacketed reaction flask, in which an ampoule containing the reaction liquid (ie, the second cavity) is placed.
  • the polymerization method of the present invention can also "living" free radical polymerization of styrene monomer, and has good controllability.
  • a water bath environment is set in the inner layer of the glass jacketed reaction flask, in which an ampoule containing the reaction liquid (ie, the second cavity) is placed.
  • the preparation method of the reaction solution is as follows: Use ethyl 2-bromoisobutyrate (EBiB) as the ATRP initiator to initiate the polymerization of monomer MMA.
  • EBiB ethyl 2-bromoisobutyrate
  • Table 6 shows the test results of product polymerization under different polymerization conditions
  • R represents [MMA] 0 /[I] 0 /[CuBr] 0 /[bpy] 0
  • the monomer conversion rate (Conv.%) is calculated by the weight method
  • M n,GPC represents the molecular weight obtained by GPC
  • M w / M n represents the molecular weight distribution.
  • a water bath environment is set in the inner layer of the glass jacketed reaction flask, in which an ampoule containing the reaction liquid (ie, the second cavity) is placed.
  • MMA monomer MMA
  • BNI catalyst tetrabutylammonium iodide
  • the croconocyanine dyes represented by formulas (2) and (3) above in the specification of different structures were investigated in place of formula (1) for photothermal conversion. At this time, they also have high-efficiency photothermal conversion capabilities. Realize the "living" radical polymerization of vinyl monomers. Dissolve 35.0 mg of the ketone acid cyanine dyes represented by formulas (2) and (3) with two different structures in 7 mL of toluene solution, respectively, and transfer them to the designed device jacket, that is, the first cavity. A water bath environment is set in the inner layer of the glass jacketed reaction flask, in which an ampoule containing the reaction liquid (ie, the second cavity) is placed.
  • MMA polymerization system monomer methyl methacrylate
  • CPADB 4-cyano-4-(thiobenzoyl)pentanoic acid
  • AIBN thermal initiator azo azobisisobutyronitrile
  • the mixed solution is a pink homogeneous solution. Place the ampoule in liquid nitrogen to freeze the solution, and then pump for 20-30 seconds, then add argon to thaw and dissolve at room temperature, and then freeze and pump. Thaw and inflate, this process is repeated three times to remove the oxygen in the ampoule. After deoxygenation, quickly move the ampoule to the nozzle of the spray gun, and seal the ampoule with an outer flame.
  • Table 8 shows the test results of product polymerization using crotonocyanine dyes of different structures for photothermal conversion and RAFT polymerization.
  • R represents [MMA] 0 /[CPADB] 0 /[AIBN] 0 ; monomer conversion rate (Conv %) is calculated from the hydrogen nuclear magnetic spectrum; T represents the temperature of the reaction liquid in the ampoule.
  • M n,GPC represents the molecular weight obtained by GPC;
  • M w / M n represents the molecular weight distribution.
  • the polymerized monomers used can also be selected in addition to methyl methacrylate (MMA), methyl acrylate (MA), N,N-dimethylacrylamide (DMA), glycidyl methacrylate ( GMA) and other monomers other than styrene (St) such as butyl (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, hydroxyethyl (meth)acrylate, (methyl) Hydroxypropyl acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethyl acrylamide, N-dihydroxyethyl acrylamide, etc. can also be "active" by the above polymerization method. /Controllable polymer.
  • Living" free radical polymerization shows very good characteristics of "living"/controllable polymerization. For example, the conversion rate reaches 81.9% in 7 hours, and the molecular weight distribution is narrow (M w /M n ⁇ 1.20).
  • the GPC molecular weight of the obtained polymer is closer to the theoretical molecule, indicating that the polymer has a high degree of terminal functionalization.

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Abstract

近红外光热转化下乙烯基类单体的"活性"自由基聚合方法，采用波长为750-850nm的近红外光照射反应容器，所采用的反应容器具有互不连通的第一腔体和第二腔体，所述第一腔体中容置有克酮酸菁类近红外光响应染料的有机溶液，所述第二腔体中用于放置容置反应液的密闭反应瓶；反应液包括乙烯基类单体，ATRP引发剂、ATRP配体、ATRP催化剂、RAFT试剂、热引发剂和添加剂中的二种以上，以及有机溶剂；近红外光由第一腔体照射入第二腔体中；近红外光响应染料将近红外光转换成热能，并将反应容器加热至50-100℃，使得反应液中的单体发生聚合得到分子量及分子量分布可控的聚合物。

Description

近红外光热转化下的乙烯基类单体的“活性”自由基聚合方法 技术领域
本发明涉及聚合物制备技术领域，尤其涉及乙烯基类单体的近红外光热转化下的“活性”自由基聚合方法。
背景技术
在“活性”/可控自由基聚合(LRP)中，可以通过控制温度、光照、机械力、外加电压、化学氧化还原等反应条件来调控聚合。根据光的波长可以把用于光聚合反应的光源大致分为紫外光(UV，<400nm，～6eV)、可见光(vis，400-700nm，～2eV)以及近红外光(NIR，670-1100nm，～1.5eV)等。近年来科研工作者使用紫外光、可见光等光源开发出了多种光控LRP技术，比如引发-转移-终止聚合(Iniferter)、氮氧稳定自由基聚合(NMP)、原子转移自由基聚合(ATRP)、碘存在下的可逆络合聚合(RCMP)、溴碘转换活性自由基聚合、光诱导电子转移-可逆加成-断裂链转移聚合(PET-RAFT)等。但是通过调研可以发现大多数光控LRP是在蓝色波段或者更短波长的UV下进行，这种短波长光源能量高，易发生副反应；同时，短波长光在穿透过程中会发生折射、散射，造成其穿透能力降低等不足。近红外(NIR)光源的特点是长波长、低能量，根据相关理论计算显示，近红外光渗透进入组织的深度能达到7-14cm，并且对生命体的荧光背景几乎可完全消除。但是用近红外光调控的聚合有着各种阻碍，比如相比于UV和可见光，NIR能量较低，通常条件下很难有效刺激化学反应的发生。到目前为止用近红外光调控的LRP的文献数量很有限。如Boyer等人将细菌叶绿素a作为PET-RAFT聚合的催化剂，得到了分子量可控、分子量分布窄的聚合物，然而这种催化剂合成困难，且价格昂贵，不利于规模化生产。
发明内容
为解决上述技术问题，本发明的目的提供一种乙烯基类单体的近红外光热转化下的“活性”自由基聚合方法，利用近红外光响应物质通过光热转换，即在光的照射下产生的热能用于聚合反应所需要能量实现“活性”/可控自由基聚合，本发明的方法条件温和，单体使用范围广，所采用的近红外染料溶液光热性能稳定，可长期循环使用。
为解决上述技术问题，本发明采用以下技术方案：
本发明的目的是提供一种乙烯基类单体的近红外光热转化下的“活性”自由基聚合方法，采用波长为750-850nm的近红外光照射反应容器，所采用的反应容器具有互不连通的第一腔 体和第二腔体，所述第一腔体中置有近红外光响应染料的有机溶液，所述第二腔体中用于放置容置反应液的密闭反应瓶，反应瓶中填充有保护气体；近红外光照射至所述第一腔体中的近红外光响应染料溶液中将近红外光转换成热量，并将第二腔体中的反应容瓶加热至聚合所需温度50-100℃，根据反应液的组份不同构建乙烯基类单体的多种“活性”自由基聚合技术，得到式(4)-(6)所示的聚合物；
所述近红外光响应染料包括式(1)-(3)所示的克酮酸菁类化合物：
Figure PCTCN2020070786-appb-000001
其中，n 1和n 2分别独立地选自1-10；
所述反应液包括乙烯基类单体、有机溶剂、ATRP引发剂、ATRP配体及ATRP催化剂；或
所述反应液包括乙烯基类单体、有机溶剂、RAFT试剂及热引发剂；或
所述反应液包括乙烯基类单体、有机溶剂、ATRP引发剂及添加剂；所述添加剂包括有机胺和/或含碘化合物；
式(4)-(6)所示的聚合物的结构式如下：
Figure PCTCN2020070786-appb-000002
其中，m 1、m 2和m 3分别独立地选自10-300；
R 1、R 1’和R 1”分别独立地选自异丁氰基、4-氰基戊酸基、2-苯乙酸乙酯基或2-异丁酸乙酯基；
R 2、R 2’和R 2”分别独立地选自氢或甲基；
R 3、R 3’和R 3”分别独立地选自苯基、2-萘基、溴、氯或者碘；
R 4选自甲基、丁基、聚乙二醇单甲醚基、羟乙基、羟丙基或N,N-二甲氨基乙基；
R 5选自氢、甲基、乙基或羟甲基；
R 6选自氢、甲基、乙基或羟甲基。
进一步地，“活性”自由基聚合包括原子转移自由基聚合(ATRP)、溴碘转换“活性”自由基聚合以及可逆加成-断裂链转移聚合(RAFT)。当反应液包括乙烯基类单体、有机溶剂、ATRP引发剂、ATRP配体及ATRP催化剂时，乙烯基类单体发生ATRP聚合，当反应液包括乙烯基类单体、有机溶剂、RAFT试剂及热引发剂时，乙烯基类单体发生RAFT聚合，当反应液包括乙烯基类单体、有机溶剂、ATRP引发剂及添加剂时，乙烯基类单体发生溴碘转换“活性”自由基聚合。
进一步地，近红外光响应染料的有机溶液中，近红外光响应染料的浓度为1.0-10.0mg/mL，所述近红外光的功率为0.05-1.0W/cm 2。优选地，为0.1-0.3W/cm 2。
进一步地，乙烯基类单体为丙烯酸甲酯、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸聚乙二醇单甲醚酯、甲基丙烯酸聚乙二醇单甲醚酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、甲基丙烯酸N,N-二甲氨基乙酯、甲基丙烯酸缩水甘油酯、苯乙烯、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、N-二羟乙基丙烯酰胺。
进一步地，ATRP引发剂为2-溴苯乙酸乙酯、2-溴异丁酸乙酯以及2-碘-2-甲基丙腈中的一种或几种；ATRP配体为二联吡啶、五甲基二乙烯基三胺、六甲基三乙烯基四胺和三苯基膦中的一种或几种；ATRP催化剂为CuBr、CuCl、FeBr 2和FeCl 2中的一种或几种。
进一步地，RAFT试剂为二硫代萘甲酸异丁腈酯或4-氰基-4-(硫代苯甲酰)戊酸；热引发 剂为偶氮二异丁腈和/或过氧化苯甲酰。
进一步地，当R 1为异丁氰基时，RAFT试剂为二硫代萘甲酸异丁腈酯(CPDN)；R 1为4-氰基戊酸基时，RAFT试剂为4-氰基-4-(硫代苯甲酰)戊酸(CPADB)。优选地，选择CPADB。
进一步地，添加剂为NaI、KI、三乙胺、三乙醇胺和四丁基碘化铵中的一种或几种。
进一步地，有机溶剂为甲苯、丙酮、乙醇、甲醇、N,N-二甲基甲酰胺和二甲基亚砜中的一种或几种。
进一步地，乙烯基类单体、RAFT试剂和热引发剂的摩尔比为50-1000:2:1-0.5；乙烯基类单体、ATRP引发剂、ATRP催化剂和ATRP配体的摩尔比为50-1000:1:0.01-1.5:0.3-4.5；乙烯基类单体、ATRP引发剂和添加剂的摩尔比为50-1000:1:1-10。优选地，乙烯基类单体、RAFT试剂和热引发剂的摩尔比为300-500:2:1；乙烯基类单体、ATRP引发剂、ATRP催化剂和ATRP配体的摩尔比为100-500:1:0.05-1:0.3-3；乙烯基类单体、ATRP引发剂和添加剂的摩尔比为50-500:1:1-2。
进一步地，反应液中，乙烯基类单体的浓度为1.0-8.0mol/L，优选为1.0-4.0mol/L。
进一步地，反应时间为1-20h。
进一步地，第一腔体环绕于第二腔体外部，产生近红外光的装置环绕于第一腔体外部。
进一步地，反应容器为玻璃夹套反应瓶，第二腔体为密闭反应瓶提供水浴环境。
进一步地，近红外光响应染料的有机溶液的溶剂为甲苯。
进一步地，本发明光照所使用的光源为近红外LED灯。优选地，光照波长为810nm。
本发明还公开了一种近红外光热转化下的聚合反应装置，其包括反应容器，反应容器用于接收近红外光照射，反应容器具有互不连通的第一腔体和第二腔体，第一腔体中容置有近红外光响应染料的有机溶液，第二腔体中设有容置反应液的反应瓶；近红外光照射至第一腔体中，近红外光响应染料将近红外光转换成热能，并将第二腔体中的反应液加热至50-100℃。
进一步地，第一腔体环绕于第二腔体外部，第一腔体外部环绕有光照单元，该光照单元用于发出近红外光。
借由上述方案，本发明至少具有以下优点：
本发明基于近红外光热转化下的聚合反应装置，利用近红外光响应染料将近红外光转换成热量，所产生的热量对反应容器进行加热，利用近红外光热转换产生聚合所需热能，避免了光辐照不均，短波长的光穿透性低等问题。本发明的方法条件温和，单体使用范围广，所采用的近红外染料溶液光热性能稳定可长期循环使用。采用本发明的制备方法，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(M w/M n<1.20)，符合“活性”自由基聚合 的特征。
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是不同浓度的克酮酸菁类近红外染料在近红外光照(λ＝810nm,100mW/cm 2)下的升温测试结果；
图2是浓度为6.4mg/mL的近红外染料在不同功率下近红外光照(λ＝810nm)下的升温测试结果；
图3是实施例2中聚合物PMMA的 1H NMR测试结果；
图4是实施例2中聚合物PMMA制备过程中的聚合动力学图以及GPC流出曲线；
图5是实施例2中聚合物PMMA的扩链情况；
图6是实施例3中聚合物PDMA的 1H NMR测试结果；
图7是实施例4中聚合物PGMA的 1H NMR测试结果；
图8是实施例5中聚合物PMA的 1H NMR测试结果；
图9是实施例6中聚合物PS的 1H NMR测试结果；
图10是实施例7中聚合物PMMA的 1H NMR测试结果；
图11是实施例8中聚合物PMMA的 1H NMR测试结果。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
本发明以下实施例中，所使用的原料MMA需过中性氧化铝柱子去除阻聚剂，然后放置于冰箱上层保存。克酮酸菁类近红外染料按照文献“Dyes Pigments,2008,78,60.”与“J.Am.Chem.Soc.,2017,139,11333.”中的方法在实验室中合成得到。其他试剂均可通过商业途径获得后直接使用。
本发明中，采用以下测试方法：
1、所得聚合物的数均分子量(M n,GPC)和分子量分布(M w/M n)通过TOSOH HLC-8320凝胶渗透色谱仪(GPC)测得，该仪器配备TOSOH示差折光检测器，一根保护柱(4.6×20mm,TSKgel guard column SuperMP-N)和两根测试柱(4.6×150mm,TSKgelSupermultiporeHZ-N)，可测试的分子量范围从5×10 2到5×10 5g/mol。测试时以THF为流动相，温度为40℃，流 速为0.35mL/min。样品是通过TOSOH自动进样器吸取进行测试，分析数据时选择从TOSOH购买的线型PMMA作为标样。测试GPC的样品的制备过程如下：取20μL的聚合物混合溶液，经过冷冻干燥，除去溶剂，然后用THF将聚合物溶解，将聚合物溶液通过一中性氧化铝的小柱子和装有0.45μm滤头的注射器，最后将纯净的聚合物溶液注入测试瓶中。
2、所得产物和聚合物的核磁谱图通过Bruker 300MHz核磁共振仪测试得到，以CDCl 3为氘代试剂，在室温条件下(25℃)测试的，四甲基硅烷(TMS)为内标。
3、UV-vis通过Shimadzu UV-2600紫外-可见分光光度计测得，甲苯为溶剂。
实施例1克酮酸菁类近红外染料的光热转换效率研究
将说明书中式(1)所示的克酮酸菁类染料溶于7mL甲苯中，配成不同浓度(2.0mg/mL、5.0mg/mL、6.0mg/mL)并依次加入到玻璃夹套反应瓶的外层夹套即第一腔体中，将玻璃夹套反应瓶放置到近红外环形光源(λ＝810nm)中，利用型号为鑫思特HT-18的红外成像仪测试不同浓度的染料每分钟的升温情况。
图1是不同浓度(0mg/mL、2.0mg/mL、5.0mg/mL、6.0mg/mL)的克酮酸菁类近红外染料(式(1)所示)在近红外光照(λ＝810nm,100mW/cm 2)下的升温测试结果。
按照上述方法，测定浓度为6.4mg/mL克酮酸菁类染料在不同功率(0.10W/cm 2、0.15W/cm 2、0.22W/cm 2、0.34W/cm 2)下近红外光(λ＝810nm)照射下的的升温情况。
图2是浓度为6.4mg/mL克酮酸菁类染在不同功率下近红外光照下的升温测试结果。
实施例2通过可逆-加成断裂链转移聚合制备聚甲基丙烯酸甲酯
取35.0mg克酮酸菁染料(1)溶解到7.0mL的甲苯中，然后转移到玻璃夹套反应瓶的外层夹套即第一腔体中，以其作为光热转换热源。在玻璃夹套反应瓶的内层中设置水浴环境，其中放置盛有反应液的安瓿瓶(即第二腔体)。其中，反应液的配制方法如下：将聚合体系单体甲基丙烯酸甲酯(MMA)、RAFT试剂4-氰基-4-(硫代苯甲酰)戊酸(CPADB)以及热引发剂偶氮二异丁腈(AIBN)按摩尔比[MMA] 0/[CPADB] 0/[AIBN] 0＝500:2:1，分别将MMA(0.20mL,1.88mmol)，CPADB(2.10mg,7.53×10 -3mmol)，AIBN(0.62mg,3.76×10 -3mmol)，甲苯(0.30mL)，加入一2mL洁净的安瓿瓶中，放入一粒洁净的搅拌子。混合溶液为粉色的均相溶液，将安瓿瓶置于液氮中使溶液冻住，然后抽气20-30秒，再通入氩气，在室温下使其解冻溶解，然后再冷冻抽气，解冻充气，此过程重复三次，将安瓿瓶封管。将封好口的安瓿瓶放置在玻璃夹套反应瓶的夹套内层水浴中，再将玻璃夹套反应瓶放置在呈环形的近红外环形光源(λ＝810nm，100mW/cm 2)的中央，玻璃夹套反应瓶置于磁力搅拌器上，此时光热转换的恒定温度为59.8℃。反应至一定时间，将安瓿瓶降温，破管，用移液枪移取20μL聚合物(PMMA) 溶液溶于CDCl 3进行 1H NMR测试，计算转化率。以上方法所制备的产物聚合物PMMA的结构式如下：
Figure PCTCN2020070786-appb-000003
在上述反应条件下，测定不同的反应时间下单体的转化率，得到如图4所示的聚合动力学图。从图4(a)中可以看出，在0到7小时，ln([M] 0/[M])随着时间符合一级动力学，从图4(b)中可以看出，聚合物的分子量随着转化率的增加，基本上呈现线型增长的趋势，分子量分布也较窄(M w/M n<1.20)。通过GPC得到的分子量与理论分子量较为接近，也说明了聚合物具有较高的末端官能化度。聚合动力学表明，以CPADB为链转移试剂，在近红外环形光源带辐照下引发MMA的RAFT聚合符合“活性”聚合的特征。图4(c)中，自右向左，曲线依次对应表1中编号为1、2、3、4、5、6、7的聚合产物，从图4(c)中可以看出，聚合物的分子量从较长的流出时间到较短的流出时间的变化表明聚合物的分子量从小变大的过程。
表1为不同聚合时间下的产物聚合情况测试结果，单体转化率(Conv.％)由核磁氢谱计，R表示[MMA] 0/[CPADB] 0/[AIBN] 0；M n,th表示按照公式M n,th＝M CPADB+[Monomer] 0/[CPADB] 0×M monomer×Conv.(％)计算得到的分子量；M n,GPC表示GPC得到的分子量；M w/M n表示分子量分布。
表1：不同聚合时间下的产物聚合情况测试结果
Figure PCTCN2020070786-appb-000004
选取聚合一小时，分子量为12300g/mol，分子量分布为1.10(图5中曲线a)的PMMA 作为大分子RAFT试剂进行扩链，将其与单体、引发剂以[MMA] 0:[PMMA] 0:[AIBN] 0＝600:1:0.5的比例混合，按照前述的方式处理，在近红外光照(λ＝810nm，100mW/cm 2)下3.5小时后，以相同的方式后处理，得到分子量为21600g/mol，分子量分布为1.10的聚合物(图5中曲线b)，这证明所合成的聚合物具有“活性”特征。
本发明中，所使用的聚合单体还可选择除MMA之外的其他单体如丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸聚乙二醇单甲醚酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸N,N-二甲氨基乙酯，采用上述的聚合方法也可得到“活性”/可控的聚合物。
实施例3通过RAFT聚合制备聚合物聚N,N-二甲基丙烯酰胺(PDMA)
将式(1)所示的近红外克酮酸菁类染料35.0mg溶于7mL的甲苯中，转移到玻璃夹套反应瓶的外层夹套即第一腔体中，以其作为光热转换热源。在玻璃夹套反应瓶的内层中设置水浴环境，其中放置盛有反应液的安瓿瓶(即第二腔体)。其中，反应液的配制方法如下，将聚合体系中单体N,N-二甲基丙烯酰胺(DMA)、RAFT试剂CPADB以及水溶性引发剂偶氮二氰基戊酸(V-501)按摩尔比[DMA] 0/[CPADB] 0/[V-501] 0＝500/2/0.8，分别将DMA(0.20mL,1.80mmol)，CPADB(1.17mg,7.20×10 -3mmol)，V-501(0.48mg,2.88×10 -3mmol)，甲苯(0.30mL)，加入一2mL洁净的安瓿瓶中，放入一粒洁净的搅拌子。将安瓿瓶置于液氮中使溶液冻住，然后抽气20-30秒，再通入氩气，在室温下使其解冻溶解，然后再冷冻抽气，解冻充气，此过程重复三次，将安瓿瓶封管。将封好口的安瓿瓶放置在玻璃夹套反应瓶的夹套内层水浴中，再将玻璃夹套反应瓶放置在呈环形的近红外环形光源(λ＝810nm，100mW/cm 2)的中央，玻璃夹套反应瓶置于磁力搅拌器上，此时光热转换的温度为60.0℃。反应至一定时间，将安瓿瓶降温，破管，用移液枪移取20μL聚合物(PDMA)溶液溶于CDCl 3进行 1H NMR测试，计算转化率。以上方法所制备的产物聚合物PDMA的结构式如下：
Figure PCTCN2020070786-appb-000005
表2：不同聚合时间下的产物聚合情况测试结果
Figure PCTCN2020070786-appb-000006
表2为不同聚合时间下的产物聚合情况测试结果，R表示[DMA] 0/[CPADB] 0/[V-501] 0；单体转 化率(Conv.％)由核磁计算得到；M n,th表示按照公式M n,th＝M CPADB+[Monomer] 0/[CPADB] 0×M monomer×Conv.(％)计算得到的分子量；M n,GPC表示GPC得到的分子量；M w/M n表示分子量分布。
通过上述的聚合结果，可以看到本发明的聚合方法同样可以实现N,N-二甲基丙烯酰胺单体的“活性”自由基聚合，并且具有良好的调控性与聚合速度。
实施例4通过RAFT聚合制备聚合物聚甲基丙烯酸缩水甘油酯(PGMA)
将式(1)所示的近红外克酮酸菁类染料35.0mg溶于7mL的甲苯中，转移到玻璃夹套反应瓶的外层夹套即第一腔体中，以其作为光热转换热源。在玻璃夹套反应瓶的内层中设置水浴环境，其中放置盛有反应液的安瓿瓶(即第二腔体)。其中，反应液的配制方法如下，将聚合体系单体甲基丙烯酸缩水甘油酯(GMA)、RAFT试剂二硫代萘甲酸异丁腈酯(CPDN)以及引发剂AIBN按摩尔比[GMA] 0/[CPDN] 0/[AIBN] 0＝300/2/1，分别将GMA(0.20mL,1.50mmol)，CPDN(2.70mg,0.01mmol)，AIBN(0.80mg,5.00×10 -3mmol)，甲苯(0.30mL)，加入到2mL洁净的安瓿瓶中，放入一粒洁净的搅拌子。将安瓿瓶置于液氮中使溶液冻住，然后抽气20-30秒，再通入氩气，在室温下使其解冻溶解，然后再冷冻抽气，解冻充气，此过程重复三次，将安瓿瓶封管。将封好口的安瓿瓶放置在玻璃夹套反应瓶的夹套内层水浴中，再将玻璃夹套反应瓶放置在呈环形的近红外环形光源(λ＝810nm，100mW/cm 2)的中央，玻璃夹套反应瓶置于磁力搅拌器上，此时光热转换的温度为58.8℃。反应至一定时间，将安瓿瓶降温，破管，用移液枪移取20μL聚合物(PGMA)溶液溶于CDCl 3进行 1H NMR测试，计算转化率。以上方法所制备的产物聚合物PGMA的结构式如下：
Figure PCTCN2020070786-appb-000007
表3：GMA单体聚合情况测试结果
Figure PCTCN2020070786-appb-000008
表3为以上条件下GMA单体聚合情况测试结果，R表示[GMA] 0/[CPDN] 0/[AIBN] 0；单体转化率(Conv.％)由核磁计算得到；M n,th表示按照公式M n,th＝M CPDN+ [Monomer] 0/[CPDN] 0×M monomer×Conv.(％)计算得到的分子量；M n,GPC表示GPC得到的分子量；M w/M n表示分子量分布。
通过上述的聚合结果，可以看到本发明的聚合方法同样可以进行甲基丙烯酸缩水甘油酯单体的“活性”自由基聚合，并且具有良好的调控性与聚合速度。
实施例5通过RAFT制备聚丙烯酸甲酯(PMA)
将式(1)所示的近红外克酮酸菁类染料35.0mg溶于7mL的甲苯中，转移到玻璃夹套反应瓶的外层夹套即第一腔体中，以其作为光热转换热源。在玻璃夹套反应瓶的内层中设置水浴环境，其中放置盛有反应液的安瓿瓶(即第二腔体)。其中，反应液的配制方法如下，将聚合体系单体丙烯酸甲酯(MA)、RAFT试剂CPDN以及引发剂AIBN按摩尔比[MA] 0/[CPDN] 0/[AIBN] 0＝300/2/1，分别将MA(0.30mL,3.31mmol)，CPDN(5.97mg,0.02mmol)，AIBN(1.81mg,0.01mmol)，甲苯(0.20mL)，加入到2mL洁净的安瓿瓶中，放入一粒洁净的搅拌子。将安瓿瓶置于液氮中使溶液冻住，然后抽气20-30秒，再通入氩气，在室温下使其解冻溶解，然后再冷冻抽气，解冻充气，此过程重复三次，将安瓿瓶封管。将封好口的安瓿瓶放置在玻璃夹套反应瓶的夹套内层水浴中，再将玻璃夹套反应瓶放置在呈环形的近红外环形光源(λ＝810nm，100mW/cm 2)的中央，玻璃夹套反应瓶置于磁力搅拌器上，此时光热转换的温度为60.0℃。反应至一定时间，将安瓿瓶降温，破管，用移液枪移取20μL聚合物(PGMA)溶液溶于CDCl 3进行 1H NMR测试，计算转化率。以上方法所制备的产物聚合物PMA的结构式如下：
Figure PCTCN2020070786-appb-000009
表4：MA单体聚合情况测试结果
Figure PCTCN2020070786-appb-000010
表4为以上聚合条件下MA单体聚合情况测试结果，R表示[MA] 0/[CPDN] 0/[AIBN] 0；单体转化率(Conv.％)由核磁计算得到；M n,th表示按照公式M n,th＝M CPDN+[Monomer] 0/[CPDN] 0×M monomer×Conv.(％)计算得到的分子量；M n,GPC表示GPC得到的分子量； M w/M n表示分子量分布。
通过上述的聚合结果，可以看到本发明聚合方法同样可以丙烯酸甲酯单体的“活性”聚合，并且具有良好的调控性。
实施例6通过RAFT聚合制备聚苯乙烯(PS)
将式(1)所示的近红外克酮酸菁类染料35.0mg溶于7mL的甲苯中，转移到玻璃夹套反应瓶的外层夹套即第一腔体中，以其作为光热转换热源。在玻璃夹套反应瓶的内层中设置水浴环境，其中放置盛有反应液的安瓿瓶(即第二腔体)。其中，反应液的配制方法如下，将聚合体系单体苯乙烯(St)、RAFT试剂CPDN以及引发剂AIBN按摩尔比[St] 0/[CPDN] 0/[AIBN] 0＝400/2/1，分别将St(0.20mL,1.71mmol)，CPDN(2.40mg,8.60×10 -3mmol)，AIBN(0.70mg,4.26×10 -3mmol)，甲苯(0.30mL)，加入到2mL洁净的安瓿瓶中，放入一粒洁净的搅拌子。将安瓿瓶置于液氮中使溶液冻住，然后抽气20-30秒，再通入氩气，在室温下使其解冻溶解，然后再冷冻抽气，解冻充气，此过程重复三次，将安瓿瓶封管。将封好口的安瓿瓶放置在玻璃夹套反应瓶的夹套内层水浴中，再将玻璃夹套反应瓶放置在呈环形的近红外环形光源(λ＝810nm，300mW/cm 2)的中央，玻璃夹套反应瓶置于磁力搅拌器上，此时光热转换的温度为90.2℃。反应至一定时间，将安瓿瓶降温，破管，采取重量法测试转化率。以上方法所制备的产物聚合物PS的结构式如下：
Figure PCTCN2020070786-appb-000011
表5：St单体聚合情况测试结果
Figure PCTCN2020070786-appb-000012
表5为以上条件下St单体聚合情况测试结果，R表示[St] 0/[CPDN] 0/[AIBN] 0；单体转化率(Conv.％)由重量法计算得到；M n,th表示按照公式M n,th＝M CPDN+[Monomer] 0/[CPDN] 0×M monomer×Conv.(％)计算得到的分子量；M n,GPC表示GPC得到的分子量；M w/M n表示分子量分布。
通过上述的聚合结果，可以看到本发明聚合方法同样可以苯乙烯单体的“活性”自由基 聚合，并且具有良好的调控性。
实施例7通过原子转移自由基聚合(ATRP)制备聚合物PMMA
将式(1)所示的近红外克酮酸菁类染料35.0mg溶于7mL的甲苯中，转移到玻璃夹套反应瓶的外层夹套即第一腔体中，以其作为光热转换热源。在玻璃夹套反应瓶的内层中设置水浴环境，其中放置盛有反应液的安瓿瓶(即第二腔体)。其中，反应液的配制方法如下：使用2-溴异丁酸乙酯(EBiB)作为ATRP引发剂引发单体MMA聚合，聚合体系中单体MMA、引发剂EBiB、催化剂CuBr以及配体二联吡啶(bpy)按摩尔比[MMA] 0/[EBiB] 0/[CuBr] 0/[bpy] 0＝400/1/1/2，分别将MMA(0.25mL,2.35mmol)，EBiB(3.40μL,5.87×10 -3mmol),CuBr(3.40mg,5.87×10 -3mmol)，bpy(7.3mg,1.17×10 -2mmol)，甲苯(0.25mL)，加入到2mL洁净的安瓿瓶中，放入一粒洁净的搅拌子。此外作几组平行实验，选择同样的单体、催化剂和配体，更换ATRP引发剂为2-碘-2-甲基丙腈(CP-I)，按摩尔比[MMA] 0/[CP-I] 0/[CuBr] 0/[bpy] 0＝200/1/1/2，将MMA(0.25mL,2.35mmol)，CP-I(2.70μL,1.17×10 -2mmol)，CuBr(3.40mg,1.17×10 -2mmol),bpy(7.3mg,2.35×10 -2mmol)，甲苯(0.25mL)，加入到2mL洁净的安瓿瓶中，放入一粒洁净的搅拌子。将安瓿瓶置于液氮中使溶液冻住，然后抽气20～30秒，再通入氩气，在室温下使其解冻溶解，然后再冷冻抽气，解冻充气，此过程重复三次，将安瓿瓶中的氧气除尽。除氧后，迅速将安瓿瓶移至喷枪口处，用外焰将安瓿瓶封死。将封好口的安瓿瓶放置在玻璃夹套反应瓶的夹套内层水浴中，再将玻璃夹套反应瓶放置在呈环形的近红外环形光源(λ＝810nm，100mW/cm 2)的中央，玻璃夹套反应瓶置于磁力搅拌器上，此时光热转换的温度为60.0℃。反应至一定时间，将安瓿瓶降温，破管，采取重量法计算单体转化率。以上方法所制备的产物聚合物PMMA的结构式分别如下，其 1H NMR测试结果分别如图10a、b所示：
Figure PCTCN2020070786-appb-000013
表6：不同引发剂、不同聚合时间下的产物聚合情况测试结果
Figure PCTCN2020070786-appb-000014
表6为不同聚合条件下的产物聚合情况测试结果，R表示[MMA] 0/[I] 0/[CuBr] 0/[bpy] 0；单体转化率(Conv.％)由重量法计算得到；M n,th表示按照公式M n,th＝M I+[Monomer] 0/[I] 0×M monomer×Conv.(％)计算得到的分子量；M n,GPC表示GPC得到的分子量；M w/M n表示分子量分布。
结果表明，采用ATRP方法所得到的聚合物同样具有可控的分子量及窄分子量分布。
实施例8通过原位溴碘转换“活性”自由基聚合制备聚合物PMMA
将式(1)所示的近红外克酮酸菁类染料35.0mg溶于7mL的甲苯中，转移到玻璃夹套反应瓶的外层夹套即第一腔体中，以其作为光热转换热源。在玻璃夹套反应瓶的内层中设置水浴环境，其中放置盛有反应液的安瓿瓶(即第二腔体)。其中，反应液的配制方法如下：单体MMA、ATRP引发剂2-溴苯乙酸乙酯(EBPA)、NaI以及催化剂四丁基碘化铵(BNI)按摩尔比[MMA] 0/[EBPA] 0/[NaI] 0/[BNI] 0＝800/8/9/9，分别将MMA(1mL,9.4mmol)，EBPA(17μL,9.4×10 -2mmol),NaI(15mg,0.106mmol)，BNI(37mg,0.106mmol)，加入到2mL洁净的安瓿瓶中，放入一粒洁净的搅拌子。将安瓿瓶置于液氮中使溶液冻住，然后抽气20～30秒，再通入氩气，在室温下使其解冻溶解，然后再冷冻抽气，解冻充气，此过程重复三次，将安瓿瓶中的氧气除尽。除氧后，迅速将安瓿瓶移至喷枪口处，用外焰将安瓿瓶封死。将封好口的安瓿瓶放置在玻璃夹套反应瓶的夹套内层水浴中，再将玻璃夹套反应瓶放置在呈环形的近红外环形光源(λ＝810nm，100mW/cm 2)的中央，玻璃夹套反应瓶置于磁力搅拌器上，此时光热转换的温度为60.0℃。反应至一定时间，将安瓿瓶降温，破管，采取重量法计算转化率。以上方法所制备的产物聚合物PMMA的结构式如下：
Figure PCTCN2020070786-appb-000015
表7：溴碘转换“活性”自由基聚合情况测试结果
Figure PCTCN2020070786-appb-000016
表7为以上条件下的聚合情况测试结果，R表示[MMA] 0/[EBPA] 0/[NaI] 0/[BNI] 0；单体转化率(Conv.％)由重量法计算得到；M n,th表示按照公式M n,th＝M EBP-I+[Monomer] 0/[EBPA] 0×M monomer×Conv.(％)计算得到的分子量；M n,GPC表示GPC得到的分子量；M w/M n表示分子量分布。
结果表明，采用原位溴碘转换“活性”自由基聚合方法所得到的聚合物同样具有可控的分子量及窄分子量分布。
实施例9通过不同的克酮酸菁染料进行光热转换制备聚合物PMMA
本实施例考察了不同结构的说明书上文中式(2)、(3)所示的克酮酸菁染料替代式(1)进行光热转换，此时它们同样具有高效的光热转换能力，来实现乙烯基类单体的“活性”自由基聚合。分别取两种不同结构的式(2)、(3)所示的克酮酸菁染料各35.0mg溶于7mL的甲苯溶液中，分别转移到设计的装置夹套即第一腔体中，在玻璃夹套反应瓶的内层中设置水浴环境，其中放置盛有反应液的安瓿瓶(即第二腔体)。将玻璃夹套反应瓶放置在呈环形的近红外环形光源(λ＝810nm，100mW/cm 2)的中央，玻璃夹套反应瓶置于磁力搅拌器上。
其中，反应液的配制方法如下：将聚合体系单体甲基丙烯酸甲酯(MMA)、RAFT试剂4-氰基-4-(硫代苯甲酰)戊酸(CPADB)以及热引发剂偶氮二异丁腈(AIBN)按摩尔比[MMA] 0/[CPADB] 0/[AIBN] 0＝500/2/1，将MMA(0.20mL,1.88mmol)，CPADB(2.10mg,7.53×10 -3mmol)，AIBN(0.62mg,3.76×10 -3mmol)，甲苯(0.30mL)，加入到2mL洁净的安瓿瓶中，放入一粒洁净的搅拌子。混合溶液为粉色的均相溶液，将安瓿瓶置于液氮中使溶液冻住，然后抽气20～30秒，再通入氩气，在室温下使其解冻溶解，然后再冷冻抽气，解冻充气，此过程重复三次，将安瓿瓶中的氧气除尽。除氧后，迅速将安瓿瓶移至喷枪口处，用外焰将安瓿瓶封管。将封好口的安瓿瓶放置在玻璃夹套反应瓶的夹套内层水浴中，再将玻璃夹套反应瓶放置在呈环形的近红外环形光源(λ＝810nm，100mW/cm 2)的中央，玻璃夹套反应瓶置于磁力搅拌器上，此时光热转换的温度如表8所示。反应至一定时间，将安瓿瓶降温，破管，用移液枪移取20μL聚合物溶液溶于CDCl 3进行 1H NMR测试，计算转化率。以上方法所制备的产物聚合物PMMA的结构式与实施例1中的相同。
表8：不同染料光热转换下的产物聚合情况测试结果
Figure PCTCN2020070786-appb-000017
表8是使用了不同结构的克酮酸菁染料进行光热转换进行RAFT聚合的产物聚合情况测试结果，R表示[MMA] 0/[CPADB] 0/[AIBN] 0；单体转化率(Conv.％)由核磁氢谱计算得到；T表示安瓿瓶内反应液的温度。M n,th表示按照公式M n,th＝M CPADB+[Monomer] 0/[CPADB] 0×M monomer×Conv.(％)计算得到的分子量；M n,GPC表示GPC得到的分子量；M w/M n表示分子量分布。
从表8可分析，不同结构的克酮酸菁染料(2)、(3)仍有高效的光热转换效率，并且可以通过本发明设计的装置通过光热转换来实现乙烯基类单体的“活性”自由基聚合。
本发明中，所使用的聚合单体还可选择除甲基丙烯酸甲酯(MMA)、丙烯酸甲酯(MA)、N,N-二甲基丙烯酰胺(DMA)、甲基丙烯酸缩水甘油酯(GMA)以及苯乙烯(St)之外的其他单体如(甲基)丙烯酸丁酯、(甲基)丙烯酸聚乙二醇单甲醚酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸N,N-二甲氨基乙酯、N,N-二乙基丙烯酰胺、N-二羟乙基丙烯酰胺等采用上述的聚合方法也可得到“活性”/可控的聚合物。
综上，本发明通过利用不同结构的克酮酸菁类近红外染料的光热转换特性，在近红外环形光源(λ＝810nm)的照射下通过光热转换实现了乙烯基类单体的“活性”自由基聚合，表现出了很好的“活性”/可控聚合特征。如7个小时转化率达到81.9％，分子量分布也较窄(M w/M n<1.20)，得到的聚合物GPC分子量与理论分子较为接近，说明了聚合物的末端官能化度高。从聚合动力学来看，符合一级动力学特征，通过对低分子量的聚合物进行扩链实验，得到高分子量的聚合物，从而证明了该聚合方式为“活性”/可控自由基聚合。
以上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. 近红外光热转化下的乙烯基类单体的“活性”自由基聚合方法，其特征在于，
    采用波长为750-850nm的近红外光照射反应容器，所采用的反应容器具有互不连通的第一腔体和第二腔体，所述第一腔体中容置有近红外光响应染料的有机溶液，所述第二腔体中用于放置容置反应液的密闭反应瓶；近红外光照射至所述第一腔体中，所述近红外光响应染料将所述近红外光转换成热能，并将第二腔体中的反应液加热至50-100℃，使得反应液中的乙烯基类单体发生“活性”自由基聚合，得到式(4)-(6)所示的聚合物；
    所述近红外光响应染料包括式(1)-(3)所示的克酮酸菁类化合物中的一种或几种：
    Figure PCTCN2020070786-appb-100001
    其中，n 1和n 2分别独立地选自1-10；
    所述反应液包括乙烯基类单体、有机溶剂、ATRP引发剂、ATRP配体及ATRP催化剂；或
    所述反应液包括乙烯基类单体、有机溶剂、RAFT试剂及热引发剂；或
    所述反应液包括乙烯基类单体、有机溶剂、ATRP引发剂及添加剂；所述添加剂包括有机胺和/或含碘化合物；
    式(4)-(6)所示的聚合物的结构式如下：
    Figure PCTCN2020070786-appb-100002
    其中，m 1、m 2和m 3分别独立地选自10-300；
    R 1、R 1’和R 1”分别独立地选自异丁氰基、4-氰基戊酸基、2-苯乙酸乙酯基或2-异丁酸乙酯基；
    R 2、R 2’和R 2”分别独立地选自氢或甲基；
    R 3、R 3’和R 3”分别独立地选自苯基、2-萘基、溴、氯或者碘；
    R 4选自甲基、丁基、聚乙二醇单甲醚基、羟乙基、羟丙基或N,N-二甲氨基乙基；
    R 5选自氢、甲基、乙基或羟甲基；
    R 6选自氢、甲基、乙基或羟甲基。
  2. 根据权利要求1所述的“活性”自由基聚合方法，其特征在于，所述近红外光响应染料的有机溶液中，近红外光响应染料的浓度为1.0-10.0mg/mL，所述近红外光的功率为0.05-1.0W/cm 2。
  3. 根据权利要求1所述的“活性”自由基聚合方法，其特征在于，所述乙烯基类单体为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸聚乙二醇单甲醚酯、甲基丙烯酸聚乙二醇单甲醚酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、甲基丙烯酸N,N-二甲氨基乙酯、甲基丙烯酸缩水甘油酯、苯乙烯、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、N-二羟乙基丙烯酰胺。
  4. 根据权利要求1所述的“活性”自由基聚合方法，其特征在于，所述ATRP引发剂为2-溴苯乙酸乙酯、2-溴异丁酸乙酯以及2-碘-2-甲基丙腈中的一种或几种；所述ATRP配体为二联吡啶、五甲基二乙烯基三胺、六甲基三乙烯基四胺和三苯基膦中的一种或几种；所述ATRP催化剂为CuBr、CuCl、FeBr 2和FeCl 2中的一种或几种。
  5. 根据权利要求1所述的“活性”自由基聚合方法，其特征在于，所述RAFT试剂为二硫代萘甲酸异丁腈酯或4-氰基-4-(硫代苯甲酰)戊酸；所述热引发剂为偶氮二异丁腈和/或过氧化苯甲酰。
  6. 根据权利要求1所述的“活性”自由基聚合方法，其特征在于，所述添加剂为NaI、KI、三乙胺、三乙醇胺和四丁基碘化铵中的一种或几种；所述有机溶剂为甲苯、丙酮、乙醇、 甲醇、N,N-二甲基甲酰胺和二甲基亚砜中的一种或几种。
  7. 根据权利要求1所述的所述的“活性”自由基聚合方法，其特征在于，所述乙烯基类单体、RAFT试剂和热引发剂的摩尔比为50-1000:2:1-0.5；所述乙烯基类单体、ATRP引发剂、ATRP催化剂和ATRP配体的摩尔比为50-1000:1:0.01-1.5:0.3-4.5；所述乙烯基类单体、ATRP引发剂和添加剂的摩尔比为50-1000:1:1-10。
  8. 根据权利要求1所述的“活性”自由基聚合方法，其特征在于，所述反应液中，乙烯基类单体的浓度为1.0-8.0mol/L。
  9. 根据权利要求1所述的“活性”自由基聚合方法，其特征在于，所述第一腔体环绕于所述第二腔体外部，产生近红外光的装置环绕于第一腔体外部。
  10. 一种近红外光热转化下的聚合反应装置，其特征在于：包括反应容器，所述反应容器用于接收近红外光照射，所述反应容器具有互不连通的第一腔体和第二腔体，所述第一腔体中容置有近红外光响应染料的有机溶液，所述第二腔体中设有容置反应液的反应瓶；所述近红外光照射至所述第一腔体中，所述近红外光响应染料将所述近红外光转换成热能，并将第二腔体中的反应液加热至50-100℃。
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