CN106008756B - A kind of polymerizable water-soluble silicon ether block ion liquid type photoinitiator and preparation method thereof - Google Patents

A kind of polymerizable water-soluble silicon ether block ion liquid type photoinitiator and preparation method thereof Download PDF

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CN106008756B
CN106008756B CN201610542521.9A CN201610542521A CN106008756B CN 106008756 B CN106008756 B CN 106008756B CN 201610542521 A CN201610542521 A CN 201610542521A CN 106008756 B CN106008756 B CN 106008756B
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CN106008756A (en
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孙芳
张国伟
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Beijing University of Chemical Technology
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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
    • 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
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/10—Esters
    • C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate

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Abstract

The invention discloses a kind of polymerizable water-soluble silicon ether block ion liquid type photoinitiators and preparation method thereof, it is characterized in that small molecule photoinitiator, polymerizable carbon-carbon double bond group and silicon ether segmented structure are introduced into ionic liquid, to synthesize polymerizable water-soluble silicon ether block ion liquid type photoinitiator.The preparation method of polymerizable water-soluble silicon ether block ion liquid type photoinitiator of the present invention has following the utility model has the advantages that (1) has good water solubility, so as to be used to prepare to the smaller material of environment and human body harm.(2) it is volatile to successfully solve traditional small molecule photoinitiator for polymerizable water-soluble silicon ether block ion liquid type photoinitiator, decomposes that fragment is easy to migrate and incompatible or poor compatibility with system disadvantage.(3) polymerizable water-soluble silicon ether block ion liquid type photoinitiator, unique ionic liquid structure can be used for preparing photocuring anti-biotic material, provide a kind of new approaches to prepare photocuring anti-biotic material.

Description

A kind of polymerizable water-soluble silicon ether block ion liquid type photoinitiator and its preparation Method
Technical field
The present invention relates to a kind of Polymerizable ionic liquid type photoinitiators, and specifically a kind of polymerizable water-soluble silicon ether is embedding Section ion liquid type photoinitiator, the synthetic method and application of the polymerizable photoinitiator, belong to Ionic liquids technologies field and Synthesis of polymer material field.
Background technique
Ionic liquid refers in room temperature and close to being in a liquid state at room temperature, the organic salt that is made of completely zwitterion, because Its with low-steam pressure, fusing point is low, electrochemical window is big, noninflammability, acid adjustable and good solubility, viscosity and density etc. Feature is applied successfully to organic synthesis, electrochemistry, separation and Extraction and material science etc. as catalyst/reaction medium Field.Into 21st century, the research to ionic liquid is even more to advance by leaps and bounds, a series of stable ionic liquid of performances at Function synthesis keeps it very active with the application study of organic synthesis field in catalysis.At present the study on the synthesis of ionic liquid into The third generation, i.e. functionalized ion liquid are entered.Called function ionic liquid refers to matching by various structure anions and canons It is right, or different functional groups is introduced in yin or cation so as to adjust the chemical composition of ionic liquid, realize ionic liquid object The change for changing property, to obtain the function-specific ionic liquid with required property.Functionalized ion liquid not only has The general character of general ionic liquid, and catalysis, chiral synthesis, antibacterial, drug delivery and in terms of have oneself again significantly Superiority.The huge potential using value of functionalized ion liquid has been recognized, for functionalized ion liquid synthesis with Application study is also simply placed in the exploratory stage, designs with unique physical and chemical functionalized ion liquid and adapts to various special need It will be the important directions of ionic liquid future development.By small molecule photoinitiator be introduced into ionic liquid cation or yin from In the structure of son, preparation synthesis can be applied to the functional ion liquid of aqueous light initiation system, for ionic liquid in photopolymerization The research in field has great importance with application.
One of an important factor for photoinitiator is influence photopolymerization, it can absorb ultraviolet light or visible optical radiation energy, make low Polymers and diluent are transformed into rapidly the compound of solid matter by liquid.Traditional small molecule radical photopolymerization initiator with And the photolysis debris remained in system is easy migration and volatilization, makes material aging xanthochromia after solidification, smell and toxicity occurs, makes About photocuring system food and in terms of application.In addition, traditional Photopolymer System is there are still many disadvantages, Such as activity dilution body has volatility, has certain harm etc. to environment and human body.Therefore the water solubility with active group can Polymerization photoinitiator causes monomer and oligomer polymerization in aqueous systems becomes the important development direction in this field.Water solubility can It is connected to optical active group and double bond on polymerization photoinitiator main chain or side chain, generates living radical initiation after absorbing radiation energy Aqueous monomers, oligomer and photoinitiator fragment crosslink solidification, to reduce moving for the photolysis debris remained in system It moves and volatilizees.And ionic liquid has good dissolubility, fixedness, designability, the ionic liquid of special construction has again There is good antibacterial action, therefore ionic liquid structure and double bond can be introduced into photoinitiator, prepares silicon ether block ion Liquid-type polymerizable photoinitiator.The photoinitiator that can be used for curing field and there is functionalized ion liquid performance this at present Report it is also more rare.This photoinitiator not only has good water solubility, but also introduces alkyl quaternaries with tradition Water-soluble photoinitiator, which is compared, has higher thermal stability；It is aqueous light-initiated with the Sulfonates that cannot use in acid condition Agent is compared, and ionic liquid can change the type of its anion by design, realizes that it can normally make within the scope of wide soda acid With.In addition, the functional ion liquid with anti-microbial property is introduced into photoinitiator, provided to prepare photocuring anti-biotic material A kind of new thinking.
Summary of the invention
The present invention provides a kind of polymerizable water-soluble silicon ether block ion liquid type light for aqueous Photopolymer System Initiator, preparation method and its application in photocuring anti-biotic material.The present inventor by extensively and profoundly studying, from point Minor structure is set out, and small molecule photoinitiator, double bond group and silicon ether segmented structure are introduced into ionic liquid by MOLECULE DESIGN, To synthesize polymerizable water-soluble silicon ether block ion liquid type photoinitiator.This method, which can substantially reduce, to be remained in system The migration and volatilization of photolysis debris, while to realize that the photocuring anti-biotic material of water-based system provides new approaches, and safety collar It protects, is simple and easy.
Specifically, the present invention relates to following aspects:
1. a kind of polymerizable water-soluble silicon ether block ion liquid type photoinitiator general formula is as follows:
M is benzoin class, styrax ethers, alkylacetophenone class, alkylamino radical acetophenones, benzophenone, thioxanthene The residue of ketone, tonka-bean ketone or camphorone micromolecular photoinitiator compound, wherein the small molecule photoinitiator compound Selected from hydroxyl, amino, carboxyl, halogen or epoxy group；
A is、、、、、With；Wherein the value range of q can be 1~12, preferably 1~6；R1' ' and R2' ' identical or different, and independently select From singly-bound,、、、、With, Wherein the value range of q' can be 1~12, preferably 1~6；；R7And R8It is identical or different, and independently selected from hydrogen atom, C1-12 Alkyl, C1-12Alkoxy, C2-12Alkenyl, halogen atom, cyano, C6-10Aryl, C6-10Aryloxy group, C6-10Aralkoxy, C8-12 Aromatic yl alkenyl, C3-8Naphthenic base, carboxyl, carboxyl C1-12Poly- (the C of alkyl ester group, carboxyl1-4) alkylene glycol ether ester group, C2-7Carboxyl Alkoxy, C1-12Alkyl ester group, C2-7Poly- (the C of Carboxyalkoxy1-4) alkylene glycol ether ester group, C2-7Alkoxy carbonyl；
B is represented:
Wherein the value range of n can be 1~50, preferably 1~15, most preferably 1~8；The value of m can be 1~10, excellent Select 1~5, most preferably 1 or 3；R9And R10It is identical or different, and independently selected from C1-12Alkyl, N, O, S hetero atom replace C1-12Alkyl, C1-12Alkoxy；R11Selected from C1-12Alkyl, C1-12Alkoxy；
E is represented:
Wherein the value range of p can be 1-20, preferably 1-10, most preferably 1-5；R12And R13It is identical or different, and solely On the spot it is selected from C1-12Alkyl, C1-12Alkoxy or H；
R1、R2And R3It is identical or different, and independently selected from H, C1~4Alkyl, C1~4Alkoxy or halogen；
R4、R5And R6It is identical or different, and independently selected from hydrogen atom, C1-12Alkyl, C1-12Alkoxy, C2-12Alkenyl, Halogen atom, cyano, C6-10Aryl, C6-10Aryloxy group, C6-10Aralkoxy, C8-12Aromatic yl alkenyl, C3-8Naphthenic base, carboxyl, Carboxyl C1-12Poly- (the C of alkyl ester group, carboxyl1-4) alkylene glycol ether ester group, C2-7Carboxyalkoxy, C1-12Alkyl ester group, C2-7Carboxyl Poly- (the C of alkoxy1-4) alkylene glycol ether ester group；
X-For anionic group, it is selected from chloride ion, bromide ion, iodide ion, nitrate ion, sulfite ion, tetrafluoro Borate ion, hexafluorophosphoricacid acid ions, p-methyl benzenesulfonic acid radical ion, benzenesulfonate ion, dodecyl sodium sulfonate radical ion, three Fluorine tosylate ion, tetraphenyl borate radical ion, isocyano ion, C1-12Alkyl carboxylic acid radical ion, trifluoroacetic acid radical ion, Double trifluoromethanesulfonic acid imines ions.
2. according to the polymerizable water-soluble silicon ether block ion liquid type photoinitiator of item 1, it is characterised in that the M For the residue of alkylacetophenone class and the small molecule photoinitiator compound of benzophenone, the small molecule photoinitiator compound With selected from hydroxyl, halogen, amino and carboxyl.
3. according to the polymerizable water-soluble silicon ether block ion liquid type photoinitiator of any one of item 1-2, it is characterised in that The R7And R8It is identical, and it is independently selected from hydrogen atom, C1-C10Alkyl, C1-C10Alkoxy, halogen atom, more preferably hydrogen are former Son；R9And R10It is identical, and it is independently selected from C1-6Alkyl, C1-6Alkoxy；Preferably C1-6Alkyl, more preferably methyl；Institute State R11Selected from C1-6Alkyl, preferably normal-butyl.
4. according to the polymerizable water-soluble silicon ether block ion liquid type photoinitiator of any one of item 1-3, it is characterised in that The R12And R13It is identical, and independently selected from methyl or H.
5. according to the polymerizable water-soluble silicon ether block ion liquid type photoinitiator of any one of item 1-4, it is characterised in that The R1、R2And R3It is identical, and independent it is selected as H；R4、R5And R6It is identical, and independent it is selected as methyl or H.
6. according to the polymerizable water-soluble silicon ether block ion liquid type photoinitiator of any one of item 1-5, it is characterised in that The X–Selected from bromide ion, nitrate ion, p-methyl benzenesulfonic acid radical ion, hexafluorophosphoricacid acid ions, preferably to toluene sulphur Acid ion.
7. a kind of method of the polymerizable water-soluble silicon ether block ion liquid type photoinitiator of any one of preparation 1-6, It is characterized in that being reacted using the mixture of substance I and substance II:
Substance I is the imidazole intermediates with silicon ether block chain, general formula are as follows:
Wherein n, m, p, R9、R10、R11、R12And R13Definition as described in item 1；
II general formula of substance are as follows:
Wherein M, A, R4、R5And R6Definition as described in item 1；
R1' be independently selected from O,、、、 -NH-、、 Or；
X is chlorine, bromine, iodine, nitric acid group, sulfate group, sulfurous acid group, tetrafluoro boric acid group, hexafluorophosphoric acid group, right Tosylat group, benzene sulfonic acid group, dodecyl sodium sulfonate group, trifluoromethanesulfonic acid group, tetraphenyl borate group, isocyanate group Group, C1-12Alkyl carboxylic acid groups, trifluoroacetic acid group, double trifluoromethanesulfonic acid imine groups, preferably bromine, nitric acid group, to first Benzene sulfonic acid group, hexafluorophosphoric acid group, more preferably tosate.
8. according to the method for item 7, wherein the reaction is that substitution reaction, hydrolysis, oxidation reaction, acid-base neutralization are anti- It answers, esterification and quaternization reaction.
9. according to the described in any item methods of item 7-8, it is characterised in that the substance I has the imidazoles of silicon ether block chain The molar ratio of II compound of intermediate and the substance is 1:(1 ~ 2).
10. according to the described in any item methods of item 7-9, it is characterised in that the mixture also include can dissolve it is described The anhydrous solvent of imidazole intermediates and the substance II of the substance I with silicon ether block chain, preferably anhydrous acetonitrile.
11. according to any one of item 7-10 the method, it is characterised in that the substance I has the imidazoles of silicon ether block chain Intermediate and II reaction temperature of the substance are not particularly limited, can be this field any temperature, preferably 50-90 DEG C.
12. a kind of composition of free redical photocuring, it is characterised in that described in any item polymerizable comprising item 1-6 Water-soluble silicon ether block ion liquid type photoinitiator.
13. according to the composition of item 12, it is characterised in that the composition includes the polymerizable water-soluble of 0.2%-3% Silicon ether block ion liquid type photoinitiator, the water-soluble tree of the photopolymerization of the deionized water and 14.8%-72% of 25%-85% Rouge or water-soluble monomer, the total weight based on the composition.
14. according to the composition of item 13, it is characterised in that the photopolymerization water-soluble resin is selected from water-base epoxy (first Base) acrylic resin, aqueous polyurethane (methyl) acrylic resin, waterborne polyester (methyl) acrylic resin, aqueous polyethers (first Base) acrylic resin, poly- (methyl) acrylic resin of water soluble acrylic acid esterification；The water-soluble monomer is simple function group, double One of functional group or polyfunctional group (methyl) acrylate monomer, (methyl) acrylic acid or (methyl) acrylamide are more Kind.
15. according to composition described in item 14, it is characterised in that the water-soluble monomer is acrylamide and acrylic acid hydroxyl Ethyl ester.
16. the described in any item polymerizable water-soluble silicon ether block ion liquid type photoinitiators of 1-6, feature exist Cause water-soluble resin in polymerizable water-soluble silicon ether block ion liquid type photoinitiator or monomer polymerization prepares photocuring and applies The purposes of the materials such as material, ink, adhesive, photoresist, printed circuit board and optical fiber.
17. according to the purposes of item 16, it is characterised in that the water-soluble resin is selected from water-base epoxy (methyl) acrylic acid tree Rouge, aqueous polyurethane (methyl) acrylic resin, waterborne polyester (methyl) acrylic resin, aqueous polyethers (methyl) acrylic acid tree Rouge, water soluble acrylic acid are esterified poly- (methyl) acrylic resin；The hydrophilic monomer is simple function group, difunctional or more officials One of (methyl) acrylate monomer, (methyl) acrylic acid or (methyl) acrylamide or a variety of can be rolled into a ball.
Detailed description of the invention
Below in the description of this invention, except as otherwise clearly stating, the numerical value in the application can be considered " big by word About " modify.But the present inventor has reported the numerical value in embodiment as accurately as possible, although these numerical value are inevitable Ground includes certain error.
In this application, unless expressly excluded, specific or preferred embodiment of the invention can combine.In addition, this Every element of application embodiment is specifically preferably selecting for corresponding upper technical characteristic.If the upper technology Feature can be combined with other upper features, then the element of embodiment, i.e., described specifically to preferably select, can also be with It is combined with other upper features.These combinations should be considered as a part of the application original description content.
Synthetic method
Synthetic route is explained with preferred embodiment below, with water-soluble silicon ether block ion liquid type macromolecular Photoinitiator Si-E3For the synthesis of -2959-A:
Step 1: anion occurs at room temperature for n-BuLi, hexamethyl cyclotrisiloxane (D3) and dimethylchlorosilane Ring-opening polymerization synthesizes single-ended hydrogen containing polysiloxane, i.e. compound 1.
Step 2: nucleophilic substitution occurs at room temperature for allyl hydroxyethyl ether and excessive p-methyl benzene sulfonic chloride, Synthetic product 2.
Step 3: product 2, diglycol and sodium hydride react synthetic product 3 under conditions of 60-80 DEG C.
Step 4: single-ended hydrogen containing polysiloxane reacts synthetic product under the catalysis of catalyst chloroplatinic acid with product 3 4。
Step 5: nucleophilic substitution, synthetic product 5 occur at room temperature for product 4 and p-methyl benzenesulfonic acid chlorine.
Step 6: product 5 reacts synthetic product 6 for 60-80 DEG C under the action of NaH with imidazoles.
Step 7: 2- hydroxyl -4- (2- hydroxy ethoxy) -2- methyl phenyl ketone (photoinitiator 2959) and p-methyl benzenesulfonic acid Nucleophilic substitution, synthetic product 7 occur at room temperature for chlorine.
Step 8: product 7 reacts at room temperature with acryloyl chloride, synthetic product 8.
Step 9: product 6 and product 8 are heated to reflux in acetonitrile and quaternization reaction occurs synthesize final product Si- for 80 DEG C E3-2959-A。
Some embodiments according to the present invention provide water-soluble silicon ether block ion liquid type macromolecular photoinitiator Preparation method, this method comprises: (1) by n-BuLi, hexamethyl cyclotrisiloxane (D3) and dimethylchlorosilane occur yin Cationic ring opening polymerization reaction, synthesizes single-ended hydrogen containing polysiloxane, this reaction is reacted 8-15 hours at room temperature；(2) allyl Base hydroxyethyl ether is reacted with excessive p-methyl benzene sulfonic chloride, the allyl hydroxyethyl ether that synthesis p-methyl benzenesulfonic acid replaces, this Reaction is reacted 4-15 hours at room temperature；(3) the allyl hydroxyethyl ether and polyethylene glycol that p-methyl benzenesulfonic acid replaces are hydrogenating It is reacted in the presence of sodium and allyloxy polyoxyethylene ether is made, this reaction is reacted 5-20 hours at 40-90 DEG C；(4) single-ended hydrogeneous Polymethyl siloxane reacts synthesis single-ended hydroxyl containing polyether chain with allyloxy polyoxyethylene ether under the catalysis of catalyst chloroplatinic acid Base silicone oil, this reaction are reacted 2-20 hours at 60-90 DEG C, and catalyst amount is 10-100 ppm；(5) single-ended containing polyether chain Hydroxy silicon oil is reacted with excessive p-methyl benzene sulfonic chloride, and synthesis p-methyl benzenesulfonic acid replaces silicone oil containing polyether chain, this reaction exists It reacts 4-15 hours at room temperature；(6) p-methyl benzenesulfonic acid replaces silicone oil containing polyether chain and imidazoles to synthesize under the action of NaH siliceous The imidazole intermediates of ether block, this reaction are reacted 20 hours at 60-90 DEG C；(7) small molecule photoinitiator with to methylbenzene sulphur Nucleophilic substitution, the small molecule photoinitiator that synthesis p-methyl benzenesulfonic acid replaces occur for sour chlorine.(8) p-methyl benzenesulfonic acid takes Small molecule photoinitiator and the acryloyl chloride in generation react, and synthesis p-methyl benzenesulfonic acid replaces the photoinitiator of small molecule containing double bond (9) imidazole intermediates of siliceous ether block replace the photoinitiator of small molecule containing double bond to react to obtain polymerizable water with p-methyl benzenesulfonic acid Dissolubility silicon ether block ion liquid type photoinitiator, the reaction are reacted 10-72 hours at 50-100 DEG C.
The polymerizable water-soluble silicon ether block ion liquid type photoinitiator of synthesis not only possesses excellent light-initiated characteristic, Simultaneously compared with traditional oil-soluble small molecule photoinitiator, that is, improve its solubility in aqueous systems significantly reduce again it is residual Stay in the migration and volatilization of the photolysis debris in system.
Alkane used in synthesizing water-solubility silicon ether block ion liquid type macromolecular photoinitiator in the present invention, with active The raw materials such as photoinitiator, D3, polyether chain, the imidazoles of group are not limited to the substance enumerated in the present invention, are also possible to other similar The compound of type.
In the present invention, the active group of the photoinitiator containing reactive group includes, but are not limited to hydroxyl, amino, carboxyl Or mixtures thereof, the photoinitiator containing reactive group includes, but are not limited to benzoin class, styrax ethers, alkylbenzene second In ketone, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone or camphorone micromolecular photoinitiator It is one or more.
In the present invention, polyether chain includes, but are not limited to one of polyethylene glycol, polypropylene glycol, polytetramethylene glycol or more Kind.
In the present invention, used catalyst can use catalyst commonly used in the art, and to them without spy Other restriction.
The preparation method of the invention polymerizable water-soluble silicon ether block ion liquid type photoinitiator has following beneficial One of effect is a variety of: (1) having good water solubility, endanger smaller material to environment and human body so as to be used to prepare Material.(2) polymerizable water-soluble silicon ether block ion liquid type photoinitiator, unique ionic liquid structure can be used for preparing light Curing antibiotic material provides a kind of new approaches to prepare photocuring anti-biotic material.(3) polymerizable water-soluble silicon ether block ionic liquid It is volatile that figure photoinitiator solves traditional small molecule photoinitiator, decompose fragment it is easy to migrate and incompatible with system or The disadvantage of poor compatibility.
Using ultraviolet-uisible spectrophotometer to polymerizable water-soluble silicon ether block ion liquid type photoinitiator ultraviolet light Absorption is studied, as schemed shown in attached 3；And its light degradation behavior is tracked, under UV illumination, polymerizable ionic liquid Figure photoinitiator photosensitive group occur light degradation, as scheme the characteristic absorption shown in attached 4,267 nm at light application time extension and It reduces.
Detailed description of the invention
Fig. 1 is polymerizable water-soluble silicon ether block ion liquid type photoinitiator infrared spectrogram prepared by embodiment 1.
Fig. 2 is polymerizable water-soluble silicon ether block ion liquid type photoinitiator prepared by embodiment 11HNMR spectrogram.
Fig. 3 is polymerizable water-soluble silicon ether block ion liquid type photoinitiator UV absorption spectrogram prepared by embodiment 1.
Fig. 4 be embodiment 1 prepare polymerizable water-soluble silicon ether block ion liquid type photoinitiator ultraviolet absorption peak with Light application time changes spectrogram.
Fig. 5 is polymerizable water-soluble silicon ether block ion liquid type photoinitiator Si-E prepared by embodiment 11-2959-A The high-efficient liquid phase chromatogram of cured film extract liquor.
Fig. 6 is polymerizable water-soluble silicon ether block ion liquid type photoinitiator the anti-bacterial result figure prepared by embodiment 1.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below.In the specification of the present application, unless otherwise It clearly states, all parts and percentage are based on weight.
Embodiment 1:
Water-soluble polymerizable water-soluble silicon ether block ion liquid type photoinitiator Si-E1The synthesis of -2959-A:
Step 1: the synthesis of single-ended hydrogeneous dimethyl silicone polymer is leaked under the conditions of nitrogen protection to equipped with constant pressure addition 18 mL dry toluenes are separately added into the three-necked flask of bucket and condenser pipe, 12 mL (19.2 mmol) n-BuLi n-hexane is molten Liquid (1.6 M), is slowly added dropwise 5.811g(26.1mmol) toluene solution (12mL) of D3, after being added dropwise, it is stirred at room temperature 0.5 24 mL anhydrous tetrahydro furans are added in h, continue to stir 8 h, 2.29 g(24.2 mmol of end-capping reagent dimethylchlorosilane is added), Stir 2 h.To the end of reacting, solvent is removed in rotation, is centrifugated lithium chloride, obtains the single-ended hydrogeneous polydimethylsiloxanes of colourless transparent liquid Alkane, yield 95%.Reaction equation is as follows:
Step 2: the synthesis for the allyl hydroxyethyl ether that p-methyl benzenesulfonic acid replaces: to the three-necked flask that condenser pipe is housed In be separately added into 10 g(98 mmol) allyl hydroxyethyl ether, 70 mL anhydrous methylene chlorides, ice-water bath is cooled to 0 DEG C, point The potassium hydroxide powder after 21.96 g (392 mmol) grinding is added is criticized, 0.5 h is stirred, 22.4 g(118 mmol are added) it is right Toluene sulfonyl chloride is warmed to room temperature, and continues to stir 4 h, and TLC is monitored after reaction, washes liquid separation, organic phase anhydrous slufuric acid Sodium is dry, and revolving removes solvent, the Methods For Purification that obtained crude product is chromatographed by column, and solvent is V(ethyl acetate): V(petroleum ether)=1:6 mixed solution, obtain light yellow transparent liquid p-methyl benzenesulfonic acid substitution allyl hydroxyethyl ether, produce Rate 98%.Reaction equation is as follows:
Step 3: (the Si-E of silicone oil containing polyether chain1- TsO) synthesis: under the conditions of nitrogen protection, to be equipped with constant pressure addition 10.27 g(24.9 mmol are separately added into the three-necked flask of funnel and condenser pipe) single-ended hydrogen containing polysiloxane, 20 mL Dry toluene, the aqueous isopropanol of (40-80 ppm) 2 % chloroplatinic acid are warming up to 50-60 DEG C of stirring 0.5 after mixing 7.65 g (29.9 mmol) p-methyl benzenesulfonic acid substituted allyl hydroxyethyl ether is added dropwise dropwise, is added dropwise and is warming up to 80 by h DEG C, continue to stir 2-8 h, infrared monitoring to Si -- H bond completely disappears, and washes liquid separation, and organic phase is dry with anhydrous sodium sulfate, rotation Solvent is evaporated off, the Methods For Purification that obtained crude product is chromatographed by column, solvent is V(ethyl acetate): V(petroleum ether) The mixed solution of=1:6 obtains light yellow transparent liquid p-methyl benzenesulfonic acid and replaces silicone oil containing polyether chain, yield 92%.Reaction equation It is as follows:
Step 4: imidazole intermediates (the Si-E of siliceous ether block1- IM) synthesis: under the conditions of nitrogen protection, to being equipped with 5 mL anhydrous tetrahydro furans, 0.295 g(4.3 mmol are separately added into the three-necked flask of constant pressure funnel and condenser pipe) miaow Azoles, ice-water bath are cooled to 0 DEG C, and 0.24 g (6 mmol) sodium hydride (60% mineral oil dispersed) is added portionwise, is to slowly warm up to 50 DEG C, 1 h is stirred, 2.89g(4.3 mmol is added dropwise dropwise) Si-E1Reflux 12 h, TLC monitoring reaction is added dropwise in-TsO After, it filters, obtains brown liquid, after being dissolved with methanol, then use petroleum ether, liquid separation takes methanol phase, and revolving removing is molten Agent, the Methods For Purification that obtained crude product is chromatographed by column, solvent are V(methylene chloride): V(methanol)=1:20 it is mixed Solution is closed, the imidazole intermediates of amber transparent liquid silicon-containing ether block, yield 83% are obtained.Reaction equation is as follows:
Step 5: p-methyl benzenesulfonic acid replaces the synthesis of photoinitiator (Tso-2959): to three mouthfuls of burnings equipped with condenser pipe 26.9 g(120 mmol are separately added into bottle) 2- hydroxyl -4- (2- hydroxy ethoxy) -2- methyl phenyl ketone, 300 mL anhydrous two Chloromethanes, ice-water bath are cooled to 0 DEG C, the potassium hydroxide powder after 22.4 g (400 mmol) grinding is added portionwise, stirring 0.5 19.0 g(100 mmol are added in h) p-methyl benzene sulfonic chloride, it is warmed to room temperature, continues to stir 4 h, TLC is monitored after reaction, Liquid separation is washed, organic phase is dry with anhydrous sodium sulfate, and revolving removes solvent, the method that obtained crude product is chromatographed by column Purification, solvent be V(ethyl acetate): V(petroleum ether)=1:6 mixed solution, obtain white solid p-methyl benzenesulfonic acid substitution Small molecule photoinitiator 2959, yield 90%.Reaction equation is as follows:
Step 6: p-methyl benzenesulfonic acid replaces the synthesis of photoinitiator containing double bond (Tso-2959-A): to equipped with condenser pipe Three-necked flask in be separately added into 50 mL methylene chloride, 1.89 g(5 mmol) 2959-TsO, 0.808 g (8 mmol) three 0.5 h is stirred at room temperature in ethamine, and 0.54 g (6 mmol) acryloyl chloride is added dropwise, and continues to stir 19 h, TLC monitoring reaction terminates Afterwards, liquid separation is washed, organic phase is dry with anhydrous sodium sulfate, and revolving removes solvent, and obtained crude product is chromatographed by column Methods For Purification, solvent be V(ethyl acetate): V(petroleum ether)=1:6 mixed solution, obtain white solid p-methyl benzenesulfonic acid Replace the photoinitiator of small molecule containing double bond (Tso-2959-A), yield 87.3%.Reaction equation is as follows:
Step 7: silicon ether block ion liquid type macromolecular photoinitiator (Si-E1- 2959) synthesis: in nitrogen protection Under the conditions of, 3 mL anhydrous acetonitriles, 1 g (1.77 mmol) siliceous ether block are separately added into the reaction tube equipped with condenser pipe Imidazole intermediates (Si-E1- IM), 0.91 g(2.13 mmol) the p-methyl benzenesulfonic acid substitution photoinitiator of small molecule containing double bond (TsO-2959-A), 85 DEG C after mixing, are warming up to, reflux 48-72 h is protected from light, after reaction, revolving removes solvent, will Obtained crude product is washed three times with 10 mL anhydrous ethers, and obtaining light yellow viscous liquid silicon ether block ion liquid type can Polymerization photoinitiator (Si-E1- 2959-A), yield 91%.Reaction equation is as follows:
Product Si-E1For the infrared spectrum and nuclear magnetic spectrogram of -2959-A referring to attached drawing 1 and attached drawing 2, infrared data is as follows: IR (KBr, cm-1): 3146cm-1(=CH), 3060 cm-1(Ar-H), 2952 cm-1 (-CH3, -CH2), 1720 cm-1 (> C=O), 1602 cm-1 (-C=CH2), 1573 cm-1,1396 cm-1(- C=N-), 1320 cm-1 ,1160 cm-1(S=O) 1170 cm-1(C-O-C), 1020-1092 cm-1(Si-O-Si), 800-804 cm-1(Si-CH3).Its nuclear magnetic data is such as Under:1H-NMR (CD3OD, ppm): δ 9.12 (- N=CH-) δ 6.90-8.30 (Ar-H), δ 7.660-7.760 (- N-CH= CH-N-), δ 5.80-6.70 (- CH=CH2), δ 3.35-4.80 (- CH2CH2- O-), δ 3.35-4.80 (N-CH2), δ 2.38 (Ar-CH3), δ 1.00-1.50 (C-CH3), δ 0.80-1.00 (- CH2CH2), δ 0.53-0.80 (- Si-CH2), δ 0.05- 0.10 (-Si-CH3)。
Embodiment 2:
Water-soluble polymerizable water-soluble silicon ether block ion liquid type photoinitiator Si-E3The synthesis of -2959-A.
Step 1: the synthesis of single-ended hydrogen containing polysiloxane, method such as 1 first step of embodiment, reaction equation is as follows:
Step 2: the synthesis of p-methyl benzenesulfonic acid substituted allyl ethylether, method such as 1 second step of embodiment, reaction equation It is as follows:
Step 3: the synthesis of allyloxy polyethylene oxygen ether: under the conditions of nitrogen protection, to equipped with constant pressure funnel and 30 mL anhydrous tetrahydro furans, 12.4 g(117 mmol are separately added into the three-necked flask of condenser pipe) diglycol, ice Water-bath cooling is added portionwise 1.87 g (46.8 mmol) sodium hydride (60% mineral oil dispersed), after mixing, stirs to 0 DEG C 2 h are mixed, 10 g(39.1 mmol are added dropwise dropwise) p-methyl benzenesulfonic acid substituted allyl ethylether, 16 h of reflux are added dropwise, TLC is monitored after reaction, and adding water is reaction quenching, and with chloroform extraction liquid separation, organic phase is dry with anhydrous sodium sulfate, rotation Solvent is evaporated off, the Methods For Purification that obtained crude product is chromatographed by column, solvent is V(ethyl acetate): V(petroleum ether) The mixed solution of=8:1 obtains light yellow transparent liquid allyloxy polyethylene oxygen ether, yield 65.2%.Reaction equation is as follows:
Step 4: single-ended polyether chain hydroxy silicon oil (Si- E3- OH) synthesis: under the conditions of nitrogen protection, to equipped with perseverance 10.27 g(24.9 mmol are separately added into the three-necked flask of pressure dropping funel and condenser pipe) single-ended hydrogen containing polysiloxane, The aqueous isopropanol of 20 mL dry toluenes, (40-80 ppm) 2 % chloroplatinic acid is warming up to 50-60 DEG C and stirs after mixing 0.5 h is mixed, 4.43 g (29.9 mmol) allyloxy polyethylene oxygen ether is added dropwise dropwise, is added dropwise and is warming up to 80oC, after Continuous stirring 2-8 h, infrared monitoring to Si -- H bond completely disappear, and wash liquid separation, and organic phase is dry with anhydrous sodium sulfate, and revolving removes Solvent, the Methods For Purification that obtained crude product is chromatographed by column, solvent are V(ethyl acetate): V(petroleum ether)=1:6 Mixed solution obtains light yellow transparent liquid one-ended hydroxy silicone oil (Si- E3- OH), yield 92.3%.Reaction equation is as follows:
Step 5: p-methyl benzenesulfonic acid replaces single-ended polyether chain silicone oil (Si-E3- TsO) synthesis: to equipped with condenser pipe 7.28 g(12.1 mmol are separately added into three-necked flask) Si-E3- OH, 25 mL anhydrous methylene chlorides, ice-water bath are cooled to 0 DEG C, the potassium hydroxide powder after 2.71 g (48.4 mmol) grinding is added portionwise stirs 0.5 h, 2.77 g(14.5 is added Mmol) p-methyl benzene sulfonic chloride is warmed to room temperature, and continues to stir 4 h, TLC is monitored after reaction, washes liquid separation, and organic phase is used Anhydrous sodium sulfate is dry, and revolving removes solvent, the Methods For Purification that obtained crude product is chromatographed by column, and solvent is V(second Acetoacetic ester): V(petroleum ether)=1:6 mixed solution, obtain light yellow transparent liquid p-methyl benzenesulfonic acid and replace single-ended polyether chain Silicone oil, yield 85%.Reaction equation is as follows:
Step 6: imidazole intermediates (the Si-E of siliceous ether block3- IM) synthesis: under the conditions of nitrogen protection, to being equipped with 5 mL anhydrous tetrahydro furans, 0.295 g(4.3 mmol are separately added into the three-necked flask of constant pressure funnel and condenser pipe) miaow Azoles, ice-water bath are cooled to 0 DEG C, and 0.24 g (6 mmol) sodium hydride (60% mineral oil dispersed) is added portionwise, is to slowly warm up to 50 DEG C, 1 h is stirred, 3.27 g(4.3 mmol are added dropwise dropwise) Si-E3Reflux 12 h, TLC monitoring reaction is added dropwise in-TsO After, it filters, obtains brown liquid, after being dissolved with methanol, then use petroleum ether, liquid separation takes methanol phase, and revolving removing is molten Agent, the Methods For Purification that obtained crude product is chromatographed by column, solvent are V(methylene chloride): V(methanol)=1:20 it is mixed Solution is closed, the imidazole intermediates (Si-E of amber transparent liquid silicon-containing ether block is obtained3- IM), yield 83%.Reaction equation is as follows:
Step 7: p-methyl benzenesulfonic acid replace photoinitiator 2959(Tso-2959) synthesis: method such as embodiment 1 the 5th Step, reaction equation are as follows:
Step 8: p-methyl benzenesulfonic acid replaces the synthesis of photoinitiator containing double bond (Tso-2959-A): method such as embodiment 1 6th step, reaction equation are as follows:
Step 9: silicon ether block ion liquid type polymerizable photoinitiator (Si-E3- 2959) synthesis: in nitrogen protection Under the conditions of, 3 mL anhydrous acetonitriles, 1 g (1.77 mmol) siliceous ether block are separately added into the reaction tube equipped with condenser pipe Imidazole intermediates (Si-E3- IM), 0.74 g(1.7 mmol) p-methyl benzenesulfonic acid substitution photoinitiator containing double bond 2959 (2959-TsO-A) is warming up to 85 DEG C after mixing, is protected from light reflux 48-72 h, and after reaction, revolving removes solvent, will Obtained crude product is washed three times with 10 mL anhydrous ethers, and obtaining light yellow viscous liquid silicon ether block ion liquid type can Polymerization photoinitiator (Si-E3- 2959-A), yield 88.7%.Reaction equation is as follows:
Embodiment 3-4:
The step of repeating embodiment 2, the difference is that the molecular weight of polyethylene glycol used is different, it is as shown in the table:
In embodiment 1-4, Si represents PolydimethylsiloxaneChain Chain section；A represents acryloyl group；Ao represents allyloxy；E Represent polyether segment；TsO represents p-methyl benzenesulfonic acid group；IM represents imidazole group.
Embodiment 5
The purpose of the present embodiment is that polymerizable water-soluble silicon ether block ion prepared by embodiment 1 can be used in explanation Liquid-type photoinitiator can significantly reduce the migration for remaining in the photolysis debris in system compared to small molecule photoinitiator.
Weighing 0.05g(3.5mmol) polymerizable water-soluble silicon ether block ion liquid type prepared by embodiment 1 is light-initiated Agent and 4.95g tri (propylene glycol) diacrylate (TPGDA), are sufficiently mixed, are added drop-wise on homemade mold, make it spontaneously After diffusing into the liquid film of 20 × 5 × 0.3 mm, another clean coverslip is covered above it, is placed in wavelength 365 Nm, light intensity are 5 mW cm-2Ultraviolet lamp under irradiate 5 min, obtain polymer film (Si-E1- 2959-A-TPGDA)；It weighs 0.013g(3.5mmol) photoinitiator (2959) and 4.987g tri (propylene glycol) diacrylate (TPGDA) are uniformly mixed, The polymer film (2959-TPGDA) obtained according to the above method is used as reference；Respectively by 0.5g Si-E1- 2959-A-TPGDA and 2959-TPGDA obtained extract liquor with 15.0g acetonitrile extraction seven days, was analyzed with the ultraviolet combination of high performance liquid chromatography, as a result As shown in Fig. 5, it is respectively 0.95 and 0.65 minute that TPGDA and photoinitiator 2959, which decompose fragment retention time, with small molecule Photoinitiator 2959 compares polymerizable water-soluble silicon ether block ion liquid type photoinitiator (Si-E1- 2959-A) it can significantly drop The migration of photolysis debris of the low-residual in system.
Embodiment 6
The purpose of the present embodiment is that polymerizable water-soluble silicon ether block ion prepared by embodiment 1 can be used in explanation Liquid-type photoinitiator can be used for preparing photocuring anti-biotic material.
Choose Gram-negative bacteria (Escherichia coli-E.coliATCC25922) bacterium is used for experiment.By 0.5 wt% of beef extract, 0.5 wt% of sodium chloride and 1 wt% of peptone is uniformly mixed, and adds the deionized water of certain mass, and 15 min of ultrasound make it Even dissolution, acquired solution are bacteriotrophy meat soup.Liquid nutrient broth is put into steam sterilizer 120 min that sterilize.It takes out The above-mentioned nutrient broth of certain mass and the agar that 1.5 ~ 2.0 wt% are added in it, dissolve by heating, and resulting liquid is nutrition Agar medium.Fluid nutrient medium is put into steam sterilizer, sterilize 120 min at 121 DEG C.Fluid nutrient medium after sterilizing It pours into culture dish rapidly, it is cooling in super-clean bench, obtain solid medium.In super-clean bench, with the inoculation to sterilize in advance Ring scrapes a small amount of Fresh bacterial, and is quickly transferred in nutrient broth, at 37 DEG C, cultivates 24 h, obtained liquid is mother Liquid.
Weigh polymerizable water-soluble silicon ether block ion liquid type macromolecular photoinitiator prepared by 0.04 g embodiment 1 (Si-E1- 2959-A) and 1.96 g tri (propylene glycol) diacrylates (TPGDA), it is sufficiently mixed, being added drop-wise to self-control size is On the mold of 50 × 50 mm, after so that it is spontaneously diffused into the liquid film of 40 × 40 × 3 mm, another is covered above it Polyethylene film, is placed in 365 nm of wavelength, and light intensity is 5 mW cm-2Ultraviolet lamp under irradiate 5 min, obtain polymer film Si- E1-2959-A-TPGDA；Weigh polymerizable water-soluble silicon ether block ion liquid type macromolecular prepared by 0.04 g embodiment 1 Photoinitiator (Si-E1- 2959-A), 0.6 g distilled water and 1.96 g acrylic acid 2- hydroxyl ethyl esters (HEA) are sufficiently mixed, and are added dropwise It is after so that it is spontaneously diffused into the liquid film of 40 × 40 × 3 mm, to be put into baking on the mold of 50 × 50 mm to self-control size Distilled water is removed in 50 DEG C of bakings in case, covers another polyethylene film above it, is placed in 365 nm of wavelength, and light intensity is 5 mW cm-2 Ultraviolet lamp under irradiate 5 min, obtain polymer film Si-E1-2959-A-HEA；Same method prepares small molecule photoinitiator 2959 polymer film 2959-TPGDA and 2959-HEA.
Before testing, sterilization treatment is carried out to all stand-by instruments.Contained with the mother liquor addition that liquid-transfering gun draws 0.2 mL In the test tube of 1.8 mL aqua sterilisas.It repeats from upper method, bacterium solution is diluted 10 times.Select bacterial content for 105~5×105 CFU/mL Test tube as inoculation sample bacterium solution.According to national standard GB/T4789.2-2003, the inoculation bacterium solution of 0.4 mL is taken to drop evenly right According on group sample and antibacterial film coating group sample, polyethylene film is covered on sample surfaces, and is put into blank culture dish, it will It is placed in the super-clean bench of natural light irradiation, at 37 DEG C, cultivates 1 h.Each film does 3 groups in parallel, is averaged.To training The sample for supporting 1 h uses the multiple washing sample of aqua sterilisa and polyethylene film of 10 mL, the liquid after collecting washing.Take out 0.2 The liquid of mL is coated in the solid agar medium previously obtained, 24 h is cultivated in 37 DEG C of climatic chambers, on sample Bacterial plaque count.As a result as shown in Fig. 6, compared with polymer film 2959-TPGDA and 2959-HEA, polymer film Si-E1- 2959-A-TPGDA and Si-E1- 2959A-HEA has apparent antibacterial action.
Raw material sources
Methylene chloride: Tianjin Fu Chen Chemical Co., Ltd.
Toluene: Tianjin Fu Chen Chemical Co., Ltd.
Tetrahydrofuran: Tianjin Fu Chen Chemical Co., Ltd.
Acetonitrile: Tianjin Fu Chen Chemical Co., Ltd.
P-methyl benzene sulfonic chloride: Tianjin Fu Chen Chemical Co., Ltd.
Allyl hydroxyethyl ether: Beijing is coupled Science and Technology Ltd.
N-BuLi: Beijing lark prestige Science and Technology Ltd.
Hexamethyl cyclotrisiloxane: Beijing lark prestige Science and Technology Ltd.
Dimethylchlorosilane: Tianjin Heowns Biochemical Technology Co., Ltd.
Chloroplatinic acid: Sa En chemical technology (Shanghai) Co., Ltd.
Sodium hydride: Beijing lark prestige Science and Technology Ltd.
Imidazoles: Tianjin Fu Chen Chemical Co., Ltd.
2- hydroxyl -4- (2- hydroxy ethoxy) -2- methyl phenyl ketone (photoinitiator 2959): the abundant Photar fine chemistry industry in Qingdao has Limit company
Ethylene glycol: Tianjin Fu Chen Chemical Co., Ltd.
Diglycol: Beijing Yi Nuokai Science and Technology Ltd.
Triethylene-glycol: Beijing Yi Nuokai Science and Technology Ltd.
Tetraethylene-glycol: Beijing Yi Nuokai Science and Technology Ltd.
Allyloxy polyoxyethylene ether: Beijing Yi Nuokai Science and Technology Ltd.
Acryloyl chloride: Beijing is coupled Science and Technology Ltd.
Triethylamine: Tianjin Fu Chen Chemical Co., Ltd..

Claims (13)

1. a kind of polymerizable water-soluble silicon ether block ion liquid type photoinitiator general formula is as follows:
M be benzoin class, styrax ethers, alkylacetophenone class, alkylamino radical acetophenones, benzophenone, thioxanthones, The residue of tonka-bean ketone or camphorone micromolecular photoinitiator compound, wherein the small molecule photoinitiator compound has hydroxyl Base, amino, carboxyl, halogen or epoxy group；
A is Wherein the value range of q is 1~12；R1" and R2" identical or different, and independently Selected from singly-bound, The value range of q' is 1~12；
R7And R8It is identical or different, and independently selected from hydrogen atom, C1-12Alkyl, C1-12Alkoxy, C2-12Alkenyl, halogen are former Son, cyano, C6-10Aryl, C6-10Aryloxy group, C6-10Aralkoxy, C8-12Aromatic yl alkenyl, C3-8Naphthenic base, carboxyl, carboxyl C1-12 The poly- C of alkyl ester group, carboxyl1-4Alkylene glycol ether ester group, C2-7Carboxyalkoxy, C1-12Alkyl ester group, C2-7Carboxyalkoxy is poly- C1-4Alkylene glycol ether ester group, C2-7Alkoxy carbonyl；
B is represented:
Wherein the value range of n is 1~50；The value of m is 1~10；R9And R10It is identical or different, and independently selected from C1-12's Alkyl, N, O, the C that S hetero atom replaces1-12Alkyl, C1-12Alkoxy；R11Selected from C1-12Alkyl, C1-12Alkoxy；
E is represented:
Wherein the value range of p is 1-20；R12And R13It is identical or different, and independently selected from C1-12Alkyl, C1-12Alcoxyl Base or H；
R1、R2And R3It is identical or different, and independently selected from H, C1-4Alkyl, C1-4Alkoxy or halogen；
R4、R5And R6It is identical or different, and independently selected from hydrogen atom, C1-12Alkyl, C1-12Alkoxy, C2-12Alkenyl, halogen Atom, cyano, C6-10Aryl, C6-10Aryloxy group, C6-10Aralkoxy, C8-12Aromatic yl alkenyl, C3-8Naphthenic base, carboxyl, carboxyl C1-12The poly- C of alkyl ester group, carboxyl1-4Alkylene glycol ether ester group, C2-7Carboxyalkoxy, C1-12Alkyl ester group, C2-7Carboxyalkoxy Poly- C1-4Alkylene glycol ether ester group；
X-For anionic group, it is selected from chloride ion, bromide ion, iodide ion, nitrate ion, sulfite ion, tetrafluoroborate Ion, hexafluorophosphoricacid acid ions, p-methyl benzenesulfonic acid radical ion, benzenesulfonate ion, dodecyl sodium sulfonate radical ion, trifluoro methylsulphur Acid ion, tetraphenyl borate radical ion, isocyano ion, C1-12Alkyl carboxylic acid radical ion, trifluoroacetic acid radical ion, double trifluoros Methanesulfonic acid imines ion.
2. polymerizable water-soluble silicon ether block ion liquid type photoinitiator according to claim 1, wherein the M is alkylbenzene The residue of the small molecule photoinitiator compound of ethyl ketone class and benzophenone, the small molecule photoinitiator compound have hydroxyl Base, halogen, amino and carboxyl；The value range of the q is 1~6；The value range of the q' is 1~6；The value model of the n Enclose is 1~15；The value of the m is 1~5；The value range of the p is 1~10；
The X- is p-methyl benzenesulfonic acid radical ion；The R1、R2And R3It is identical, and it is selected from H；The R4、R5And R6It is identical, and select For methyl or H；The R7And R8It is identical, and it is selected from hydrogen atom, C1-C10Alkyl, C1-C10Alkoxy, halogen atom；The R9With R10It is identical, and it is selected from C1-6Alkyl；The R11For normal-butyl；R12And R13It is identical, and it is selected from C1-12Alkyl or H.
3. polymerizable water-soluble silicon ether block ion liquid type photoinitiator according to claim 2, wherein the M is alkylbenzene The residue of the small molecule photoinitiator compound of ethyl ketone class and benzophenone, the small molecule photoinitiator compound have hydroxyl Base；The value range of the n is 1~8；The value of the m is 1 or 3；
The value range of the p is 1~5；The R7And R8It is identical, and it is selected from hydrogen atom；The R9And R10It is identical, and select From methyl；R12And R13It is identical, and it is selected from methyl or H.
4. a kind of method for the polymerizable water-soluble silicon ether block ion liquid type photoinitiator for preparing claim 1, feature It is to be reacted using the mixture of substance I and substance II:
Substance I is the imidazole intermediates with silicon ether block chain, general formula are as follows:
Wherein n, m, p, R9、R10、R11、R12And R13Definition it is as described in claim 1；
II general formula of substance are as follows:
Wherein M, A, R4、R5And R6Definition it is as described in claim 1；
R1' be independently selected from-O-,-NH-、
X be chlorine, bromine, iodine, nitric acid group, sulfate group, sulfurous acid group, tetrafluoro boric acid group, hexafluorophosphoric acid group, to toluene Sulfonic acid group, benzene sulfonic acid group, dodecyl sodium sulfonate group, trifluoromethanesulfonic acid group, tetraphenyl borate group, isocyanate group, C1-12Alkyl carboxylic acid groups, trifluoroacetic acid group, double trifluoromethanesulfonic acid imine groups.
5. method according to claim 4, it is characterised in that the X is tosate.
6. method according to claim 4, wherein the reaction is that substitution reaction, hydrolysis, oxidation reaction, acid-base neutralization are anti- It answers, esterification and quaternization reaction.
7. method according to claim 4, it is characterised in that the mixture also includes that can dissolve the substance I with silicon ether The anhydrous solvent of the imidazole intermediates of block chain and the substance II；The substance I has the imidazole intermediates of silicon ether block chain Molar ratio with II compound of substance is 1:(1~2)；Imidazole intermediates and institute of the substance I with silicon ether block chain It states II reaction temperature of substance to be not particularly limited, is this field any temperature.
8. method according to claim 7, it is characterised in that the anhydrous solvent is anhydrous acetonitrile；The substance I has silicon ether The imidazole intermediates of block chain and II reaction temperature of the substance are 50-90 DEG C.
9. a kind of composition of free redical photocuring, it is characterised in that include polymerizable water-soluble silicon described in claim 1 Ether block ion liquid type photoinitiator；The composition includes the polymerizable water-soluble silicon ether block ion of 0.2%-3% Liquid-type photoinitiator, the water-soluble resin or water-soluble of the photopolymerization of the deionized water and 14.8%-72% of 25%-85% Property monomer, the total weight based on the composition.
10. composition according to claim 9, it is characterised in that the photopolymerization water-soluble resin is selected from water-base epoxy (methyl) acrylic resin, aqueous polyurethane (methyl) acrylic resin, waterborne polyester (methyl) acrylic resin, aqueous polyethers (methyl) acrylic resin, water soluble acrylic acid are esterified poly- (methyl) acrylic resin；The water-soluble monomer be simple function group, One of difunctional or polyfunctional group (methyl) acrylate monomer, (methyl) acrylic acid or (methyl) acrylamide are more Kind.
11. composition according to claim 10, it is characterised in that the water-soluble monomer is acrylamide and propylene Sour hydroxyl ethyl ester.
12. polymerizable water-soluble silicon ether block ion liquid type photoinitiator according to any one of claim 1-3 Purposes, it is characterised in that polymerizable water-soluble silicon ether block ion liquid type photoinitiator causes water-soluble resin or monomer polymerization Prepare the purposes of photocureable coating, ink, adhesive, photoresist, printed circuit board and fiber optic materials.
13. purposes according to claim 12, it is characterised in that the water-soluble resin is selected from water-base epoxy (methyl) acrylic acid Resin, aqueous polyurethane (methyl) acrylic resin, waterborne polyester (methyl) acrylic resin, aqueous polyethers (methyl) acrylic acid Resin, water soluble acrylic acid are esterified poly- (methyl) acrylic resin；The water-soluble monomer is simple function group, difunctional or more One of functional group (methyl) acrylate monomer, (methyl) acrylic acid or (methyl) acrylamide are a variety of.
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