CN103073659A - Water-soluble organic silicon macromolecular photoinitiator and preparation method thereof - Google Patents
Water-soluble organic silicon macromolecular photoinitiator and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种水溶性有机硅大分子光引发剂及其制备方法，其特点在于采用有机硅聚合物与小分子光引发剂反应，制得水溶性有机硅大分子光引发剂。本发明所述的水溶性有机硅大分子光引发剂的制备方法有以下有益效果：(1)在水体系当中具有一定的溶解度，从而可以引发水溶性光聚合体系的光聚合，制备对环境和人体危害更小的环保材料。(2)有机硅大分子光引发剂，由于具有突出的低表面张力和低表面能而赋予其的自动上浮能力，使其在水体系中自发向体系表面迁移，最终在体系中形成浓度的梯度分布，进而引发梯度聚合，获得分子量梯度聚合物。(3)制备成本低，操作简单，产率高。大分子光引发剂解决了传统小分子光引发剂易挥发，易黄变等弊病。The invention discloses a water-soluble organic silicon macromolecular photoinitiator and a preparation method thereof, which is characterized in that the water-soluble organic silicon macromolecular photoinitiator is prepared by reacting an organic silicon polymer with a small molecular photoinitiator. The preparation method of the water-soluble organic silicon macromolecular photoinitiator of the present invention has the following beneficial effects: (1) has a certain solubility in the middle of the water system, thereby can initiate the photopolymerization of the water-soluble photopolymerization system, and the preparation is environmentally friendly Environmentally friendly materials with less harm to the human body. (2) Silicone macromolecular photoinitiator, due to its outstanding low surface tension and low surface energy, it has the self-floating ability, so that it spontaneously migrates to the surface of the system in the water system, and finally forms a concentration gradient in the system distribution, and then initiate gradient polymerization to obtain molecular weight gradient polymers. (3) The preparation cost is low, the operation is simple, and the yield is high. Macromolecular photoinitiators solve the disadvantages of traditional small molecule photoinitiators such as volatilization and yellowing.
Description
Technical field
The present invention relates to a kind of macromolecular photoinitiator, particularly a kind of water-soluble organic silicon macromolecular photoinitiator, the synthetic method of this macromolecular photoinitiator and the purposes in the aqueous systems gradient polymeric thereof.
Background technology
The key element (for example, form or structure) that gradient polymer refers to consist of polymkeric substance is along one party to a kind of type material that is continuous gradient variation, material character and function by a side direction opposite side and also changes in gradient.Molecular weight is a fundamental of polymkeric substance, and it all has a great impact use properties and the processing characteristics of polymkeric substance.When the molecular weight of polymkeric substance changed, one or more can change thereupon in the performance of polymkeric substance such as mechanical property (intensity etc.), optical property (specific refractory power etc.), thermal property (second-order transition temperature etc.), electric property (specific conductivity etc.), the processing characteristics (rheological etc.) etc.When the molecular weight of polymkeric substance along one party when being changed by a side direction opposite side continuous gradient, can make the performance of polymkeric substance the continuous gradient variation also occur, this molecular weight is molecular weight gradient polymer along one party to the polymkeric substance that is the continuous gradient variation by a side direction opposite side.
Light trigger is one of photopolymerisable important factor of impact, and its energy absorbing ultraviolet light or visible radiation energy makes oligopolymer and thinner are transformed into rapidly the compound of solid matter by liquid state.Traditional small molecules radical photopolymerization initiator and the photolysis debris that remains in the system move and volatilization easily, make and solidify rear material aging xanthochromia, smell and toxicity occur, have restricted the application of photocuring system at aspects such as food and drug packages.In addition, still there are many shortcomings in traditional Photopolymer System, and for example active dilution body has volatility, and environment and human body are had certain harm etc.Therefore become the important development direction in this field with the water-soluble macromolecule light trigger of active group trigger monomer and oligopolymer polymerization in aqueous systems.Be connected to optical active group on water-soluble macromolecule light trigger main chain or the side chain, produce living radical behind the absorbing radiation energy and cause water-based Photopolymer System crosslinking curing.And in photopolymerization, when if water-soluble light trigger is the Gradient distribution of successively decreasing successively from the upper layer to the deep layer in polymerization system, under photoirradiation, graded can occur in the polymerization degree from the top layer of system to deep layer, the molecular weight distribution gradient of material realizes gradient polymeric after namely solidifying.Simultaneously, the upper layer initiator concentration is maximum, can effectively reduce Surface Oxygen inhibition in the photopolymerization.For reaching this purpose, need to carry out special molecular designing to water-soluble light trigger.Still there is not the macromolecular photoinitiator that can be applicable to the aqueous systems gradient polymeric in this area.
Summary of the invention
The invention provides a kind of water-soluble organic silicon macromolecular photoinitiator for the aqueous systems gradient polymeric, its preparation method and in the purposes of aqueous systems gradient polymeric.The inventor from molecular structure, is incorporated into small molecules light trigger organo-siloxane chain on and generation hydrophilic radical by molecular designing by studying extensively and profoundly, thus synthesizing water-solubility silicone macromolecule light trigger.The method provides new approaches for the gradient polymeric of realizing water-based system, and safety and environmental protection, simple.
Particularly, the present invention relates to following aspect:
1. water-soluble organic silicon macromolecular photoinitiator that general formula is (I):
Wherein, the q value is 1 or 2, p=3-q;
M is the residue of bitter almond oil camphor class, st-yrax ethers, alkylacetophenone class, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone or camphorphorone micromolecular photoinitiator compound, wherein this small molecules photoinitiator compound is selected from hydroxyl, amino, carboxyl, halogen or epoxide group;
The A representative:
Wherein the span of n can be 2～50, and is preferred 2～15, most preferably 2～8; The value of m can be 1～10, and is preferred 1～5, most preferably 1 or 2; R
7And R
8Identical or different, and be independently selected from C
1-12Alkyl, N, the C that O, S heteroatoms replace
1-12Alkyl, C
1-12Alkoxyl group or H;
R
1Independently be selected from o,
R
2Be C
3-12Alkylidene group or optional C from being replaced by alkyl, aryl and alkoxyl group
1-10Alkylidene group, preferred C
3-6Alkylidene group, propylidene most preferably;
R
3Independently be selected from H, C
1-12Alkyl or C
1-12Aralkyl;
X
-Be selected from halogen anion, preferred halogen anion X
-Be Br
-
2. according to the water-soluble organic silicon macromolecular photoinitiator of item 1, it is characterized in that described M is the residue of the small molecules photoinitiator compound of alkylacetophenone class and benzophenone, this small molecules photoinitiator compound is with being selected from hydroxyl, halogen, the group of amino and carboxyl.
3. according to each water-soluble organic silicon macromolecular photoinitiator of item 1-2, it is characterized in that described R
7And R
8Identical, and be C independently
1-12Alkyl, preferred C
1-6Alkyl, methyl more preferably.
4. according to each water-soluble organic silicon macromolecular photoinitiator of item 1-3, it is characterized in that described R
1Be O.
5. according to each water-soluble organic silicon macromolecular photoinitiator of item 1-4, it is characterized in that described R
3Be H.
6. according to the water-soluble organic silicon macromolecular photoinitiator of item 2, it is characterized in that described this small molecules photoinitiator compound is with hydroxyl.
7. each the method for water-soluble organic silicon macromolecular photoinitiator of a preparation 1-6 is characterized in that so that comprise the mixture of following substance A and B and react:
Substance A is that general formula is the organosilicon polymer of (II):
Wherein the span of n ' can be 2～50, and is preferred 2～15, most preferably 2～8; The value of m ' can be 1～10, and is preferred 1～5, most preferably 1 or 2;
R
4And R
5Identical or different, and be independently selected from H, C
1-12Alkyl or C
1-12Aralkyl;
R
7' and ' R
8' identical or different, and be independently selected from C
1-12Alkyl, N, the C that O, S heteroatoms replace
1-12Alkyl, C
1-12Alkoxyl group or H;
Substance B is that general formula is shown in (III):
X-R
2′-R
1′-M
(III)
Wherein the definition of M is as described in the item 1;
R
1' independently be selected from o,
R
2' be C
3-12Alkylidene group or optional C from being replaced by alkyl, aryl and alkoxyl group
1-10Alkylidene group, preferred C
3-6Alkylidene group, propylidene most preferably;
X independently is selected from halogen atom F, Cl, Br and I, is preferably Cl and Br, more preferably Br.
8. according to item 7 described methods, it is characterized in that described R
7' and R
8' identical, and be C independently
1-12Alkyl, preferred C
1-6Alkyl, methyl more preferably.
9. according to each described method of item 7-8, it is characterized in that described mixture also comprises the solvent that can dissolve described organosilicon polymer.
10. according to each described method of item 7-9, the mol ratio that it is characterized in that described organosilicon polymer and described substance B compound is 1: (1～4).
11. according to each described method of item 7-10, it is characterized in that organosilicon polymer and described substance B temperature of reaction do not have particular restriction, can be any temperature in this area, preferred 40-90 ℃.
12. the composition of a free redical photocuring is characterized in that comprising each described water-soluble organic silicon macromolecular photoinitiator of a 1-6.
13. the composition according to item 12, it is characterized in that said composition comprises the described water-soluble organic silicon macromolecular photoinitiator of 0.2%-3%, photoresponse water soluble resin or the water-soluble monomer of the deionized water of 25%-85% and 14.8%-72% are based on the gross weight of said composition.
14. according to the composition of item 13, it is characterized in that described photoresponse water soluble resin is selected from water-base epoxy (methyl) acrylic resin, aqueous polyurethane (methyl) acrylic resin, waterborne polyester (methyl) acrylic resin, water-based polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of water soluble acrylic acid esterification; Described water-soluble monomer is simple function group, one or more in bifunctional or polyfunctional group (methyl) acrylate monomer, vinylformic acid or the acrylamide.
15. according to item 14 described methods, it is characterized in that preferred described water-soluble monomer is acrylamide.
16. each described water-soluble organic silicon macromolecular photoinitiator of 1-6 is characterized in that causing water soluble resin or water-soluble monomer and prepares purposes in the gradient polymer.
17. the purposes of item 16 is characterized in that described water soluble resin is selected from water-base epoxy (methyl) acrylic resin, aqueous polyurethane (methyl) acrylic resin, waterborne polyester (methyl) acrylic resin, water-based polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of water soluble acrylic acid esterification; Described hydrophilic monomer is simple function group, one or more in bifunctional or polyfunctional group (methyl) acrylate monomer, vinylformic acid or the acrylamide.
Detailed Description Of The Invention
In the description of this invention, except other offers some clarification on, the numerical value among the application all can be considered by word " approximately " to be modified hereinafter.But the inventor has as far as possible accurately reported the numerical value among the embodiment, although these numerical value comprise certain error inevitably.
In this application, unless clearly get rid of, concrete or preferred embodiment of the present invention can make up.In addition, every key element of the embodiment of the present application is the concrete preferred selection of the upper technical characterictic corresponding with it.If described upper technical characterictic can make up with other upper feature, the described key element of embodiment then, namely described concrete preferred selection also can be made up with described other upper feature.These combinations should be regarded as the part of the original record content of the application.
Synthetic method
The below explains synthetic route with preferred specific embodiments, with difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
2-A synthesizes example:
The first step: 4-dihydroxy benaophenonel (HBP) is with excessive 1, and the 3-dibromopropane under the katalysis of sodium ethylate nucleophilic substitution reaction occurs, synthetic product HBP-Br.
Second step: product HBP-Br and aminoalkyl silicone oil KF-8010 react synthetic product W-Si-HBP
2-A.
Product W-Si-HBP
2The molecular weight result of-A is as follows:
According to embodiments more of the present invention, the preparation method of water-soluble organic silicon macromolecular photoinitiator is provided, the method comprises: the alkane reaction that (1) contains halogen with small molecules light trigger and the two ends of hydroxyl reaction group, generation contains the small molecules light trigger product of halogen, and this reaction was 20～80 ℃ of lower reactions 2～30 hours; (2) the small molecules light trigger and the aminoalkyl silicone oil that contain halogen react, and obtain difunctionality water-soluble organic silicon macromolecular photoinitiator end product, and this reaction was 20～90 ℃ of lower reactions 3～24 hours.
Synthetic water-soluble organic silicon macromolecular photoinitiator not only has excellent light-initiated characteristic, compares with traditional oils dissolubility small molecules light trigger simultaneously, has significantly improved its solubleness in aqueous systems.
The used alkane of synthesizing water-solubility silicone macromolecule light trigger among the present invention, with raw materials such as the light trigger of active group, organosilicon polymers, the material that is not limited to enumerate among the present invention also can be other compound of the same type.
In the present invention, the active group that contains the light trigger of reactive group comprises, but be not limited to, hydroxyl, amino, carboxyl or its mixture, the described light trigger that contains reactive group comprises, but be not limited to one or more in bitter almond oil camphor class, st-yrax ethers, alkylacetophenone class, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone or the camphorphorone micromolecular light trigger.
In the present invention, employed catalyzer can adopt this area catalyzer commonly used, and there is no particular limitation to them.
The preparation method who invents described water-soluble organic silicon macromolecular photoinitiator has one or more in the following beneficial effect: (1) can water-soluble system, thereby can be used for preparing to environment and the less material of harm.(2) outstanding low surface tension and the low surface energy of silicone macromolecule light trigger has from the ability that is sent to the migration of diagram of system face it, the final Gradient distribution that in system, forms concentration, and then cause gradient polymeric, obtain molecular weight gradient polymer.(3) preparation cost is low, and is simple to operate, and productive rate is high.It is volatile that macromolecular photoinitiator has solved traditional small molecules light trigger, decomposes fragment easily migration and disadvantage incompatible with system or that consistency is poor.
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.In present specification, unless expressly stated otherwise,, all parts and per-cent are all based on weight.
Raw material sources
Methylene dichloride: Huai’an great chemical industry company limited in morning
Trolamine: Beijing chemical reagents corporation
Sodium Metal 99.5: sea, Nanjing Tonghua worker company limited
Ethanol: Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing
4-dihydroxy benaophenonel (HBP): the abundant Photar in Qingdao Fine Chemical Co., Ltd
1,3-dibromopropane: Li Deshi (Beijing) chemical technology company limited
Aminoalkyl silicone oil (KF-8010, Mn=414): chemical company limited of Shanghai SHIN-ETSU HANTOTAI
Aminoalkyl silicone oil (X-22-161A, Mn=784): chemical company limited of Shanghai SHIN-ETSU HANTOTAI
Aminoalkyl silicone oil (X-22-161B, Mn=1450): chemical company limited of Shanghai SHIN-ETSU HANTOTAI
Acrylamide: Tianjin good fortune chemical industry in morning company limited
Triphenyl phosphorus: river, Shanghai Lay bio tech ltd
Bromine: the blue or green limitless blessing in Beijing Science and Technology Ltd.
Deionized water: Beijing University of Chemical Technology
Embodiment 1:
Hydrogen-abstraction difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
2-A's is synthetic
The first step: HBP-Br small molecules light trigger synthetic, in agitator, temperature are housed take into account the four-hole boiling flask of prolong, add respectively 0.69g (0.03mol) sodium and 25ml dehydrated alcohol, stir under the room temperature condition, dissolve rear adding 5.94g (0.03mol) 4-dihydroxy benaophenonel (HBP) fully until sodium, continue to stir 40 minutes, add 6.06g (0.03mol) 1, be warming up to 60 ℃ of reactions 4 hours under the 3-dibromopropane stirs.Filtered while hot after question response finishes, revolve steam remove alcohol solvent after, with the Methods For Purification of resulting crude product by column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 20, obtain pure white crystal HBP-Br productive rate 86.50%, reaction formula is as follows:
Second step: hydrogen-abstraction difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
2-A's is synthetic, in the four-hole boiling flask that agitator, prolong and thermometer are housed, add respectively 7.38g (0.01mol) aminoalkyl silicone oil KF-8010,6.38g (0.02mol) HBP-Br and 20ml anhydrous acetonitrile are warming up to 60 ℃ under the agitation condition, reacted 20 hours.Revolve after question response finishes and steam solvent, with the Methods For Purification of resulting crude product by column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 20, obtains hydrogen-abstraction difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
2-A, productive rate 56.80%, reaction formula is as follows:
1H-NMR (the CDCl of the first step end product HBP-Br wherein
3, 600MH
Z): δ=6.99-7.86 (9H, phenyl ring), δ=4.20 (2H ,-O-C
H 2), δ=3.65 (2H, Br-C
H 2), δ=2.39 (2H ,-CH
2-C
H 2-CH
2-); Second step end product W-Si-HBP
21H-NMR (the CDCl of-A
3, 600MH
Z): 8=6.99-7.80 (18H, phenyl ring), δ=4.22 (4H ,-O-C
H 2-CH
2-CH
2-NH
2-), δ=3.30 (4H ,-O-CH
2-CH
2-C
H 2-NH
2-), δ=3.10 (4H ,-Si-CH
2-C
H 2-NH
2-), δ=2.50 (4H, O-CH
2-C
H 2-CH
2-NH
2-), δ=0.5 (4H, Si-C
H 2-), δ=0.00 (61H, C
H 3-Si-C
H 3).
Embodiment 2:
Cracking type difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-(2959)
2Synthetic
The first step: 2959-Br small molecules light trigger synthetic, in round-bottomed flask, add respectively 2.62g (0.01mol) triphenyl phosphorus and 15ml methylene dichloride, under the ice-water bath agitation condition, slowly be added drop-wise in round-bottomed flask with constant pressure funnel the mixture of 1.6g (0.01mol) bromine and 10ml methylene dichloride, add 2.24g (0.01mol) 2959 small molecules light triggers after 10 minutes, continue to stir one hour.Revolve after reaction finishes and steam solvent.With the Methods For Purification of resulting crude product by column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 8, obtains pure faint yellow product 2959-Br, productive rate 78.65%, and reaction formula is as follows:
Second step: cracking type difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-(2959)
2Synthetic, in the four-hole boiling flask that agitator, prolong and thermometer are housed, add respectively 7.38g (0.01mol) aminoalkyl silicone oil KF-8010,5.74g (0.02mol) 2959-Br and 20ml anhydrous acetonitrile are warming up to 70 ℃ under the agitation condition, reacted 24 hours.Question response finishes, revolve and steam solvent, with the Methods For Purification of resulting crude product by column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 5, obtains cracking type difunctionality water-soluble organic silicon macromolecular photoinitiator W-Si-(2959)
2, productive rate 62.30%, reaction formula is as follows:
Embodiment 3:
Hydrogen-abstraction four functionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
4-A's is synthetic.
The first step: E-Si-HBP
2Synthesizing of-A macromolecular photoinitiator is with before synthetic W-Si-HBP
2-A leaves standstill with adding methylene dichloride behind the NaOH solution washing of 0.01mol/L three times, discards water layer after the solution layering, revolves to steam methylene chloride, obtains product E-Si-HBP
2-A, reaction formula is as follows:
Second step: hydrogen-abstraction four functionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
4-A's is synthetic, adds 12g (0.01mol) E-Si-HBP in the four-hole boiling flask that agitator, prolong and thermometer are housed
2-A (Mn is about 1200), 6.38g (0.02mol) HBP-Br and 20ml anhydrous acetonitrile are warming up to 60 ℃ under stirring, and react 20 hours.Revolve after question response finishes and steam solvent, with the Methods For Purification of resulting crude product by column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 10, obtains hydrogen-abstraction four functionality water-soluble organic silicon macromolecular photoinitiator W-Si-HBP
4-A, productive rate 80.75%, reaction formula is as follows:
Embodiment 4:
Composite water dissolubility silicone macromolecule light trigger W-Si-HBP
2-(2959)
2Synthetic.
The first step: E-Si-HBP
2Synthesizing of-A macromolecular photoinitiator, method such as embodiment 3 the first steps, reaction formula is as follows:
Second step: composite water dissolubility silicone macromolecule light trigger W-Si-HBP
2-(2959)
2Synthetic, in the four-hole boiling flask that agitator, prolong and thermometer are housed, add 12g (0.01mol) E-Si-HBP
2-A (Mn is about 1200), 5.74g (0.02mol) 2959-Br and 20ml anhydrous acetonitrile are warming up to 70 ℃ under stirring, and react 24 hours.Revolve after question response finishes and steam solvent, with the Methods For Purification of resulting crude product by column chromatography, developping agent is the mixing solutions of V (ethyl acetate): V (sherwood oil)=1: 8, obtains composite water dissolubility silicone macromolecule light trigger W-Si-HBP
2-(2959)
2Productive rate is 49%, and reaction formula is as follows:
Embodiment 5-6:
Repeat the step of embodiment 1, difference is that the molecular weight of used raw material silicone oil is different, is shown in Table 1:
Embodiment 7
The purpose of present embodiment is to illustrate can use embodiment 1 prepared water-soluble organic silicon macromolecular photoinitiator to cause polymerisation in aqueous systems, the preparation molecular weight gradient polymer.
Take by weighing the water-soluble organic silicon macromolecular photoinitiator W-Si-HBP among the 0.01g embodiment 1
2It is 6mm that-A fully mixes rear immigration diameter with water-soluble monomer acrylamide (AM) 0.4g, deionized water 0.6g and trolamine 0.01g, height is in the cylindrical glass bottle of 40mm, left standstill 60 minutes, then, the cylindrical glass bottle that the mixture of clear is housed placed under 1000 watts of UV curing machines expose, make it that photochemical reaction occur, exposed 50 minutes, AM is polymerized to polyacrylamide (PAM) and Precipitation in water, the vacuum drying oven oven dry is inserted in its taking-up.
The right cylinder PAM that the present invention will obtain before, vertically cut into slices in the different heights place from top to bottom, XPS test and molecular weight test have been carried out in the surface of the PAM thin slice that is positioned at the different vertical height that again section is obtained, and the Si element ratio that accounts for all elements is respectively 14.31%, 12.86%, 11.00% and 8.53% from top to bottom.The PAM thin slice that is positioned at the different vertical height that section is obtained passes through its molecular weight of gel liquid phase Studies by Chromatography, and number-average molecular weight is followed successively by 0.2 * 10 from top to bottom
5, 0.5 * 10
5, 0.8 * 10
5, 1.2 * 10
5
The invention has the beneficial effects as follows: a few class water-soluble organic silicon macromolecular photoinitiators that synthesized have kept himself preferably photosensitivity, and have had good water-soluble.Go for photocuring environment and the preparation molecular weight gradient polymeric material of aqueous systems, belong to the environmental friendliness shaped material.Synthetic method is simple, easy handling, the raw material cheapness that is easy to get.
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| CN105885053A (en) * | 2016-04-22 | 2016-08-24 | 中山大学 | Phosphonate photoinitiator and preparation method thereof |
| CN106065076A (en) * | 2016-07-08 | 2016-11-02 | 北京化工大学 | A kind of water-soluble silicon ether block ion liquid type macromolecular photoinitiator and preparation method thereof |
| CN106146852A (en) * | 2016-07-08 | 2016-11-23 | 北京化工大学 | A kind of siliceous macromole cation light initiator and preparation method thereof |
| CN114656591A (en) * | 2020-12-23 | 2022-06-24 | 北京化工大学 | Water-soluble macromolecular photoinitiator and preparation method and application thereof |
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| CN105885053A (en) * | 2016-04-22 | 2016-08-24 | 中山大学 | Phosphonate photoinitiator and preparation method thereof |
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| CN106065076A (en) * | 2016-07-08 | 2016-11-02 | 北京化工大学 | A kind of water-soluble silicon ether block ion liquid type macromolecular photoinitiator and preparation method thereof |
| CN106146852A (en) * | 2016-07-08 | 2016-11-23 | 北京化工大学 | A kind of siliceous macromole cation light initiator and preparation method thereof |
| CN106065076B (en) * | 2016-07-08 | 2020-05-19 | 北京化工大学 | Water-soluble silyl ether block ionic liquid type macromolecular photoinitiator and preparation method thereof |
| CN114656591A (en) * | 2020-12-23 | 2022-06-24 | 北京化工大学 | Water-soluble macromolecular photoinitiator and preparation method and application thereof |
| CN114656591B (en) * | 2020-12-23 | 2023-06-13 | 北京化工大学 | Water-soluble macromolecular photoinitiator and preparation method and application thereof |
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