CN102811999A - Benzophenones macromolecule photoinitiator - Google Patents

Benzophenones macromolecule photoinitiator Download PDF

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CN102811999A
CN102811999A CN2011800124831A CN201180012483A CN102811999A CN 102811999 A CN102811999 A CN 102811999A CN 2011800124831 A CN2011800124831 A CN 2011800124831A CN 201180012483 A CN201180012483 A CN 201180012483A CN 102811999 A CN102811999 A CN 102811999A
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described compound
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赵文超
李家齐
杜西莹
张珏
姚丽秀
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Yingli Science And Technology Development Co Ltd Beijing
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Yingli Science And Technology Development Co Ltd Beijing
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    • 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
    • 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
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated

Abstract

The invention provides a benzophenones macromolecule photoinitiator, as shown in the formula 1. The compound can be used as the photoinitiator suitable for the ultraviolet light curing compositions such as varnish and printing ink. In the fomula 1, n is an integer from 1 to 6, and the R1 represents hydrogen atom, methyl, ethyl. When the n is larger than 1, the groups or the atoms represented by the R1 can be the same or different. The Y representation : <O(CHR2Chr3)a>x-, -<O(CH2)bCO>x-, -<O(CH2)bCO>(X-1)-<O(CHR2CHR3)a>-, wherein one of the R2 and the R3 can represent the hydrogen atom, the methyl, or the ethyl,a is an integer from 1 to 2,b is an integer from 4 to 5,x is an integer from 1 to 10,Q is a residue of an alkoxy or a 2-6 polyol compound without the hydroxyl,m is an integer from 1 to 6, and is not larger than the residue of the alkoxy or the 2-6 polyol compound without the hydroxyl.

Description

The benzophenone macromolecular photoinitiator
Technical field
The present invention relates to a kind of compound that contains the UVNUL MS-40 group, is a kind of novel macromolecular photoinitiator, is used for various coating compositions, comprises varnish and printing-ink etc.It is at least a with the Photocurable composition of compound according to the invention as light trigger that the present invention also provides.
Background technology
UVNUL MS-40 is a kind of light trigger of widespread use in the ultraviolet light polymerization industry, and it has the advantages that surface cure is good, be difficult for yellowing.But the UVNUL MS-40 smell is strong, and very easily migration and being extracted in the food from printed matter, even adopt the packing with barrier film also can't avoid.In order to satisfy the requirement of food safety; Countries in the world especially European Union member countries have been formulated the chemical producting safety Performance Evaluation and the control regime of multiple strictness successively, and many small molecules light trigger products are inhibited in like numerous areas such as food, drug packing materials and use, therefore; Along with continuous increase to low migration light trigger demand; Searching had both had the good solidification performance, had the light trigger than low migration again, was the active demand in market.In order to address this problem, people have developed macromolecular photoinitiator, and it has strong, the advantages such as resin compatible good, functional diversity of low, the anti-transfer ability of volatility, receives much attention in recent years.
The benzophenone macromolecular photoinitiator is to study one type of more macromolecular photoinitiator in recent years; The UVNUL MS-40 molecule is connected with various macromolecular structures with multiple modes such as ether, ester class chemical bonds; So that UVNUL MS-40 is fixed in the macromolecular structure; Reduce benzophenone structural and in prescription, reach the migration after solidifying,, reduce the effect of migration to reach the reduction smell.In WO02003033452; Just disclose a kind of benzophenone macromolecular photoinitiator, this compounds is obtained by 4-carboxyl methoxy benzophenone and polyglycol or other polyvalent alcohol esterifications, and this compounds is for the small molecules light trigger; Have lower stink and mobility after the curing; But the efficiency of initiation of this type of macromolecular photoinitiator obviously reduces than the small molecules light trigger, and because every reduction that restrains chromophore's content; In the practical application of photocuring field; The macromolecular photoinitiator consumption that uses in the prescription is added its manufacturing cost height, so the use cost of macromolecular photoinitiator greatly improves often much larger than the consumption of small molecules light trigger; This also is this environment-friendly and green light trigger kind bigger unfavorable factor in using the popularization process, is an important channel that addresses this problem so improve the reactive behavior of macromolecular photoinitiator.
Summary of the invention
The purpose of this invention is to provide a kind of macromolecular photoinitiator that contains the UVNUL MS-40 group, be used for various Photocurable compositions, comprise varnish, printing-ink etc.This kind compound has higher every gram functionality, in the ultraviolet curing formula system, good solubility is arranged, and reactive behavior is high, low smell, and mobility is low after solidifying.It is at least a with the Photocurable composition of compound according to the invention as light trigger that the present invention also provides.
The macromolecular photoinitiator that contains the UVNUL MS-40 group provided by the present invention is a compound shown in the structural formula 1:
Figure BDA00002100340200021
Structural formula 1
Wherein: n is the integer of 1-6;
R 1Represent Wasserstoffatoms, methyl or ethyl, and at n be R greater than 1 1The group of representative or atom each other can be identical or different;
Y represents Shi-[O (CHR 2CHR 3) a] x-,-[O (CH 2) bCO] x-, or-[O (CH 2) bCO] (x-1)-[O (CHR 2CHR 3) a]-, be wherein:
R 2And R 3One of represent Wasserstoffatoms, another then represents Wasserstoffatoms, methyl or ethyl; A is the integer of 1-2; B is the integer of 4-5; X is the integer of 1-10;
Q is the residue after alkoxyl group or 2-6 unit polyol remove hydroxyl hydrogen; With
M is for greater than 1 but be not more than the contained residue number that removes behind the hydroxyl hydrogen among the Q.
These compounds are adapted at ultraviolet cured paint composition, comprise in varnish and the printing-ink using.
The present invention also provides a kind of Photocurable composition, comprising:
(a) compound shown at least a structural formula (1), with
(b) at least a ethylenically unsaturated compounds that carries out radical polymerization.
In these compounds, we preferred n is 1, R 1Be the Wasserstoffatoms person.
Perhaps when n is the integer of 2-6, select a R 1Be Wasserstoffatoms, methyl or ethyl, other R 1The person that represents the Wasserstoffatoms.
Preferred especially m is 2, and x is the compound of 3-10 integer.
In compound according to the invention, we preferred Y represents Shi-[O (CHR 2CHR 3) a] x-group, wherein a is the integer of 1-2, x is the integer from 3-10; More preferably Y represents Shi-[OCH 2CH 2] x-,
-[O CH 2CH 2CH 2CH 2] x-perhaps-[O CH (CH 3) CH 2] x-group, wherein x is the integer from 3-10.
In the structural formula 1, the preferred terepthaloyl moietie of Q, Ucar 35, butyleneglycol, USP Kosher, TriMethylolPropane(TMP), ditrimethylolpropane, tetramethylolmethane or NSC 65881 remove the residue behind the hydroxyl hydrogen.
Compound according to the invention can be through following two kinds of methods preparation, method 1:
Compound shown in the carboxyl of compound 4-shown in the structural formula 2 alkylidene group sulfenyl UVNUL MS-40 and the formula 3 is carried out esterification obtains The compounds of this invention,
Figure BDA00002100340200031
(HY) m-Q
Structural formula 2 structural formulas 3
Wherein, m, n, R 1, Y, Q are as stated.
Reaction is under normal circumstances preferably carried out under with the situation of solvent, and the place that the character of solvent is also non-key for the present invention is as long as it has no adverse effects to reagent or reaction.The solvent that is fit to comprises: aromatic hydrocarbons, alkane, for example benzene,toluene,xylene or methylcyclohexane.
Reaction is preferably under an acidic catalyst to be carried out, for example sulfonic acid (tosic acid or methylsulfonic acid); Mineral acid (for example sulfuric acid or phosphoric acid).
Reacting by heating, reaction finishes, and adopts ordinary methods such as washing, concentrated solvent that product is separated from reaction mixture.
Method 2:
Adopt 4-sulfydryl UVNUL MS-40 and structural formula 4 compounds to carry out etherification reaction and obtain The compounds of this invention.
Figure BDA00002100340200032
Structural formula 4
Wherein, m, n, R 1, Y, Q are as stated.
4-sulfydryl UVNUL MS-40 and structural formula 4 compounds are joined in organic solvent such as DMF, DMSO, the butanone, add alkali such as salt of wormwood, yellow soda ash etc. again, reacting by heating, reaction finishes, and reaction solution is through washing, and precipitation obtains product.
Employing above-claimed cpd provided by the present invention comprises at least a structural formula 1 compound and at least a ethylenically unsaturated compounds that carries out radical polymerization as the Photocurable composition of light trigger.
Described Photocurable composition, wherein structural formula 1 compound accounts for the 0.05-10% of composition total weight.
The described ethylenically unsaturated compounds that carries out radical polymerization can comprise one or more unsaturated carbon-carbon double bonds, and these compounds can be low-molecular-weight (monomer) or high-molecular weight (oligopolymer).The monomeric example that comprises two keys is the propenoate or the methacrylic ester of alkyl or hydroxyalkyl, methyl acrylate for example, ethyl propenoate; Bing Xisuandingzhi, ethyl acrylate, 2-Hydroxy ethyl acrylate; IBOA, TEB 3K.Also can use the siloxanes propenoate in addition, vinyl cyanide, acrylic amide, vinyl ether such as IVE, vinylbenzene, ring-alkylated styrenes, halogenated styrenes, N-V-Pyrol RC, vinylchlorid or vinylidene chloride.
The example that comprises two or more two keys has terepthaloyl moietie and polyether glycol thereof, Ucar 35 and polyether glycol thereof, NSC 6366; The diacrylate of pinakon or dihydroxyphenyl propane or two (methacrylic ester), and 4,4 '-two (2-acryloyl-oxy oxyethyl group) diphenyl propane; Viscoat 295, pentaerythritol triacrylate or tetraacrylate, and their many ethoxylations or many propoxylated derivative; Vinyl acrylate, divinylbenzene, Succinic Acid divinyl ester; Phthalic acid, diallyl ester, cyanacrylate or three (2-acryloyl ethyl) isocyanuric acid ester.
The example of high-molecular weight polyunsaturated compounds (oligopolymer) is the epoxy resin of acrylated relatively, and the polyester of acrylated comprises the polyester of vinyl ether or epoxide group, and also has urethane and polyethers.The other example of unsaturated oligomer is a unsaturated polyester resin, and said resin passes through by toxilic acid, and phthalic acid makes with one or more divalent alcohol, and its molecular weight 500-3000.In addition, can also use vinyl ether monomers or its oligopolymer, and can also use the end capped oligopolymer of maleic acid ester that has polyester, urethane, polyethers, polyvinyl ether and epoxy main chain.Specially suitable is to have the oligopolymer of vinyl ether group and the mixture of polymers described in the WO90/01512.
Specially suitable example is the ester of two key unsaturated carboxylic acids and polyvalent alcohol or polyepoxide and the polymkeric substance that two key unsaturated groups are arranged in main chain or side chain, for example; Unsaturated polyester, polymeric amide and urethane and multipolymer thereof, Synolac; Polyhutadiene and butadienecopolymer; TR 301 and isoprene copolymer comprise the polymkeric substance and the multipolymer of (methyl) acrylic acid groups in side chain, and also have one or more said mixture of polymers.Wherein the example of unsaturated carboxylic acid is a vinylformic acid, methylacrylic acid, and Ba Dousuan, methylene-succinic acid, styracin, and unsaturated fatty acids are like linolenic acid or oleic acid.Preferred vinylformic acid, methylacrylic acid.Suitable polyvalent alcohol is an aromatic polyol, particularly ester family and cyclic ester family polyvalent alcohol.The example of aromatic polyol has: quinhydrones, 4,4 '-dihydroxybiphenyl, 2,2-two (4-hydroxy phenyl) propane.The example of polyepoxide is for based on above-mentioned polyvalent alcohol being polymer of monomers perhaps comprises oh group in side chain polymkeric substance and multipolymer; Its example is Z 150PH and multipolymer thereof; Or hydroxyalkyl methacrylate or its multipolymer, the polyvalent alcohol that is suitable in addition is the oligomer ester class that has hydroxyl end groups.
The example of aliphatic series and alicyclic polyol is for preferably having the aklylene glycol such as the terepthaloyl moietie of 2-12 carbon atom, 1,2-or 1, ammediol, 1,2-, 1; 3-or 1,4-butyleneglycol, pentanediol, pinakon, ethohexadiol, dodecanediol; Glycol ether, triglycol, molecular weight be preferably from the polyoxyethylene glycol of 200-1500, and 1,3-encircles pentanediol, 1; 2-, 1,3-or 1,4-cyclohexanediol, 1,4-dihydroxyl methylcyclohexane, glycerine; Three (β hydroxyethyl) amine, trihydroxy methyl ethane, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol and sorbyl alcohol.
The described ethylenically unsaturated compounds that carries out radical polymerization also can be, the amides of identical or different unsaturated carboxylic acids and aromatics, alicyclic and aliphatic polyamines, and wherein polyamines preferably has 2-6, especially 2-4 amino group.The example of said polyamines is a quadrol, 1, and 2-or 1,3-tn, 1,5-pentamethylene diamine, octamethylenediamine, phenylenediamine, three second tetramines.Other suitable polyamines are preferred polymkeric substance and the multipolymer that in side chain, has other amino group, and the oligoamide that has amino end group, and the example of said unsaturated amides has methylene diacrylamine, Diethylenetriamine trimethylammonium acrylic amide.
Can be individually or use the ethylenically unsaturated compounds of the above-mentioned radical polymerization carried out, preferred acrylate compounds, allyl ether series compound or its mixture with the form of the mixture of any hope.
Except that formula 1 compound; One or more mixtures that in compsn, can also contain the known light trigger of other types; Known light trigger has UVNUL MS-40,2-isopropyl thioxanthone, 2-hydroxy-2-methyl-phenyl-1-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-(4-methylthio group) phenyl-1-acetone, 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide etc.
In the described Photocurable composition, can add the amine auxiliary compound, for example the tertiary amine compounds; Like triethylamine, trolamine; Dimethyl ethyl aminobenzoate, or reactive amines compounds are like diethylamine and ethoxylated trimethylolpropane triacrylate affixture.Amine auxiliary compound consumption is the 0.05-15% of composition total weight.
In the described Photocurable composition, can also add various auxiliary agents according to Application Areas and the required performance in this field, as: in coloured system (colored paint, printing ink etc.), need to add pigment, for example: titanium oxide, phthalocyanine blue etc.; In order to reach good mobile planarization, need to add flow agent; For the formation of bubble in the inhibition system, often add skimmer; The adding of matting agent then is in order to reduce the gloss of cured film, to obtain low gloss or inferior optical coating, and the addition of various additives in each field also is usual amounts.
Said Photocurable composition can be used for various uses, and it is used to make printing-ink, powder coating; Forme, tackiness agent, dental composition; Optical waveguides, color gluing system, glass cable coating; Electronic circuit board is by the three-dimensional body that stereolithography is produced, image recording material.
Being suitable for the light source that the present invention uses is the equipment of emitted in ultraviolet linear light (UV), and the irradiate light of spectral range 230-450nm of launching sufficient intensity on demand with regard to the ability initiated polymerization, obtains cured film on the Photocurable composition of the present invention that be coated with.
Compound according to the invention is because its particular structural; Sulphur atom directly is connected on the benzophenone phenyl ring; Cause its absorption maximum red shift; From the 250nm red shift to 320nm; Whole absorption band is widened simultaneously, and the efficiency of light energy utilization improves, and therefore compares with the macromolecular photoinitiator that is connected the benzophenone phenyl ring with oxygen atom; Under the equal consumption condition, curing rate is fast again; Simultaneously, this compounds has lower viscosity or fusing point, is convenient to take operation, dissolves faster with acrylate monomer, mixed with resin.As light trigger, compsn can obtain solidification effect faster, enhances productivity with The compounds of this invention.
Description of drawings
Fig. 1 is the temperature-viscosity curve comparison diagram of control Example 2 products and embodiment 5 products.
Specific embodiment
Control Example 1
Figure BDA00002100340200061
Press the method preparation of the comparative example three of patent WO2003033452 description, getting title product is white crystals, fusing point 120-122 ℃.
Control Example 2
Figure BDA00002100340200062
Sample is provided by Tianjin Yingli Technological Development Co., Ltd, analysis of viscosity and test curing speed.
Embodiment 1
In the 100ml there-necked flask, add NSC 6366 10.4g (0.1 mole), Mono Chloro Acetic Acid 19.5g (0.21 mole), tosic acid 0.5g, toluene 100ml.Install the reflux water-dividing device additional, prolong, the stirring and dissolving post-heating is to refluxing, and reflux water-dividing reacted 2 hours, when no moisture is told, stopped reaction.Reaction solution is washed with water to neutrality, and decompression steams toluene, gets the two chloracetates of 24.6g product liquid NSC 6366, yield 95.8%, purity 98.7%.
In the 100ml there-necked flask, add the two chloracetate 3.9g (0.01 mole) of NSC 6366,4-sulfydryl UVNUL MS-40 6.8g (0.032 mole), salt of wormwood 4.4g (0.033 mole) and butanone 40ml; Under the nitrogen protection, be warming up to 50 ℃, stirring reaction 3 hours, decompression steams butanone; Add 100ml toluene, use 30ml0.5% sodium hydroxide successively, 30ml water washing toluene layer, decompression steams toluene; Get faint yellow thickness oily matter 8.7g, yield 94.7%, content 97.7%.1HNMR（300MHz）：δH?0.89（6H，s，CH 3），3.76（4H，s，SCH 2），3.90（4H，s，OCH 2），7.40（4H，d，ArH），7.47（4H，t，ArH），758（2H，t，ArH），772（8H，t，ArH）。
Embodiment 2
Figure BDA00002100340200071
is in the 100ml there-necked flask; Add 1; 4-two butanols 9.0g (0.1 mole); Mono Chloro Acetic Acid 20.8g (0.22 mole), tosic acid 0.5g, toluene 100ml.Install the reflux water-dividing device additional, prolong, the stirring and dissolving post-heating is to refluxing reflux water-dividing reaction 2 hours.Reaction solution is washed with water to neutrality, and decompression steams part toluene, and cooling obtains 1, the two chloracetate white crystals of 4-butyleneglycol, oven-dried weight 20.7g, yield 85.2%, content 99.7%, fusing point 73.2-74.2 ℃.
In the 100ml there-necked flask, add 1, the two chloracetate 2.4g (0.01 mole) of 4-butyleneglycol, 4-sulfydryl UVNUL MS-40 4.5g (0.021 mole), salt of wormwood 3.1g (0.022 mole), DMF30ml, under the nitrogen protection, 50 ℃ of stirring reactions 3 hours.Add 100ml toluene, use 30ml0.5% sodium hydroxide successively, 30ml water washing toluene layer, decompression steams most of toluene, white crystals is separated out in the surplus solution cooling, dry 4.4g, yield 73.5%, content 98.3%, fusing point 89.8-92.5 ℃. 1HNMR（300MHz）：δ H?1.70（4H，s，CH 2），3.75（4H，s，SCH 2），4.14（4H，s，OCH 2），7.41（4H，d，ArH），7.50（4H，t，ArH），7.58（2H，t，ArH），7.75（8H，t，ArH）。
Embodiment 3
is in the 100ml there-necked flask; Add glycol ether 10.6g (0.1 mole); Mono Chloro Acetic Acid 20.0g (0.21 mole); Tosic acid 0.5g, toluene 100ml.Install the reflux water-dividing device additional, prolong, stirring and dissolving post-heating divide water reaction 2 hours to refluxing.Reaction solution is used 1% sodium carbonate solution 30ml successively, water 30ml washing, decompression steams toluene, gets the two chloracetate 23.7g of glycol ether, yield 91.5%, content 97.6%.
In 100ml single port bottle, add the two chloracetate 3.9g (0.015 mole) of glycol ether, 4-sulfydryl UVNUL MS-40 6.75g (0.032 mole); Salt of wormwood 4.4g (0.032 mole), butanone 40ml is under the nitrogen protection; Be warming up to 50 ℃, stirring reaction 3 hours.Remove by filter insolubles, decompression steams butanone, adds 100ml toluene, uses 30ml0.5% sodium hydroxide successively, 30ml water washing toluene layer, and decompression steams toluene, gets faint yellow thickness oily matter 9.0g, yield 97.7%, dibasic acid esters content 98.1%. 1HNMR（300MHz）：
δ H?3.66（4H，t，OCH? 2），3.78(4H，s，SCH 2），4.29（4H，t，OOCH? 2），7.40（4H，d，ArH），7.47（4H，t，ArH），7.58（2H，t，ArH），7.73（8H，t，ArH）。
Embodiment 4
Figure BDA00002100340200081
In the 100ml there-necked flask, add TriMethylolPropane(TMP) 13.4g (0.1 mole), Mono Chloro Acetic Acid 31.9g (0.33 mole), tosic acid 0.7g, toluene 150ml.Install the reflux water-dividing device additional, prolong, the stirring and dissolving post-heating reacted 4 hours and reflux water-dividing to refluxing, when no moisture is told, stopped reaction.Reaction solution is used 1% sodium carbonate solution 30ml successively, water 30ml, water 30ml washing, decompression steams toluene, trimethylolpropane tris (Mono Chloro Acetic Acid) ester 34.5g, yield 95.0, three ester contents 95.4% wherein, dibasic acid esters 3.1%.
In the 100ml there-necked flask, add trimethylolpropane tris (Mono Chloro Acetic Acid) ester 3.6g (0.01 mole), 4-sulfydryl UVNUL MS-40 7.0g (0.033 mole); Salt of wormwood 4.7g (0.034 mole), DMF40ml is under the nitrogen protection; Be warming up to 50 ℃, stirring reaction 3 hours, underpressure distillation DMF.Add 100ml toluene, use 30ml0.5% sodium hydroxide successively, 30ml water, 30ml water washing toluene layer, decompression steams toluene, gets faint yellow thickness oily matter 8.8g, yield 98.0%. 1HNMR（300MHz）：δ H0.73（3H，t，CH 3），1.27（2H，m，CH 2），3.72（6H，s，SCH 2），3.96（6H，s，OCH 2），7.23（6H，d，ArH），7.38（6H，t，ArH），7.57（3H，t，ArH），7.71（12H，t，ArH）
Embodiment 5
Figure BDA00002100340200082
In the 100ml there-necked flask, add Macrogol 200 sample 20.1g (0.1 mole), Mono Chloro Acetic Acid 20.0g (0.21 mole), tosic acid 0.5g, toluene 100ml.Install the reflux water-dividing device additional, prolong, stirring and dissolving post-heating divide water reaction 2 hours to refluxing.Reaction solution is used 1% sodium carbonate solution 30ml successively, water 30ml washing, decompression steams toluene, gets the two chloracetate 31.8g of liquid Macrogol 200, yield 90.2%, content 98.1%.
In the 100ml there-necked flask, add the two chloracetate 16.1g (0.04 mole) of Macrogol 200,4-sulfydryl UVNUL MS-40 18g (0.084 mole), DMF 40ml after the stirring and dissolving, adds 13.2g (0.095 mole) Anhydrous potassium carbonate.Under the nitrogen protection, be warming up to 50 ℃ of stirring reactions 3 hours.Decompression steams N, and N '-N 80-100ml adds 100ml toluene; Use 30ml0.5% sodium hydroxide successively, 30ml water, 30ml water washing toluene layer; Decompression steams toluene; Get the faint yellow oily product of 27.0g, all dibasic acid esters of high pressure liquid chromatographic analysis add up to content 97.81%, yield 94.5%.Together with control Example 2 sample viscosimetrics.
Table 1 viscosity test result
Figure BDA00002100340200091
Table 2 embodiment 5 product liquid chromatograph mass spectrography analytical resultss
Figure BDA00002100340200092
Figure BDA00002100340200101
Embodiment 6
Figure BDA00002100340200102
4-chlorobenzophenone 10.8g, Thiovanic acid 4.6g, sodium hydroxide 4.1g; DMF20ml, 80 ℃ of reaction 5h drop in the 50ml water; Be neutralized to acidity with hydrochloric acid, separate out white solid, filter out solid; Filter cake dries quantity 12.2g, 4-Benzoylbenzene ethyl thioglycollic acid yield 90%, fusing point 130-131.5 ℃.
In 100ml single port bottle, add THF homopolymer 250 sample 2.5g (0.01 mole), 4-Benzoylbenzene ethyl thioglycollic acid 5.7g (0.021 mole), toluene 100ml after the stirring and dissolving, adds the 0.3g tosic acid.Under the nitrogen protection, reflux dewatering reaction 8 hours.Cooling reaction liquid is used 30ml0.5% sodium hydroxide successively, 30ml water, and 30ml water washing toluene layer, decompression steams toluene, gets the faint yellow oily product of 6.9g, and all dibasic acid esters of high pressure liquid chromatographic analysis add up to content 97.30%, yield 95.8%.
Table 3 embodiment 6 product liquid chromatograph mass spectrography analytical resultss
Figure BDA00002100340200103
Figure BDA00002100340200111
Embodiment 7 compsn curing performances are estimated
To process corresponding ultraviolet curing clear coat composition as light trigger by prepared product of the foregoing description and UVNUL MS-40 (BP).The prescription of said composition sees Table 4.
Table 4
System component Per-cent (%)
Light trigger 4
Amino acrylates synergistic agent (P115, the special company of cyanogen) 6
Epoxy acrylate oligomer (6210G, Changxing company) 30
GPTA (EM2385 propoxylation USP Kosher triacrylate, Changxing company) 60
The clear coat composition of preparation gained executed printing on the tinplate with the excellent spreader of 10 micro wires, using a power is that the medium pressure mercury Jupiter is cured with 100 meters/component velocity in 60 watts/centimetre.Record obtains surface of good and thoroughly solidifies number of pass times under the needed lamp, and last cured film is carried out the smell assessment and tested pencil hardness by standard GB/T6739-1996, and its result is as shown in table 5.Wherein staging is adopted in smell assessment, and tasteless is 1 grade, is 5 grades strongly, with many people as a result MV represent.
Table 5 performance evaluation result
Compound Number of times Pencil hardness Smell
Embodiment 4 3 H 1
Embodiment 5 3 H 1
Embodiment 6 3 H 1
Control Example 2 6 H 1
BP 4 H 5
The result shows that the light-initiated speed of The compounds of this invention is more fast again than control Example 2, and use properties significantly improves.
Embodiment 2 product fusing points are than low about 30 ℃ of control Example 1 product, and the viscosity of viscosity ratio control Example 2 products of embodiment 5 products significantly reduces, and The compounds of this invention has better processing property.Their temperature-viscosity curve is seen Figure of description 1.

Claims (12)

1. the compound shown in the formula 1
Figure FDA00002100340100011
Structural formula 1
Wherein: n is the integer of 1-6;
R 1Represent Wasserstoffatoms, methyl or ethyl, and at n greater than 1 o'clock, R 1The group of representative or atom each other can be identical or different;
Y represents Shi-[O (CHR 2CHR 3) a] x-,-[O (CH 2) bCO] x-,-[O (CH 2) bCO] (x-1)-[O (CHR 2CHR 3) a]-, be wherein: R 2And R 3One of represent Wasserstoffatoms, another then represents Wasserstoffatoms, methyl or ethyl; A is the integer of 1-2; B is the integer of 4-5; X is the integer of 1-10;
Q is the residue after alkoxyl group or 2-6 unit polyol remove hydroxyl hydrogen; With
M is the integer of 1-6, but is not more than the contained residue number that removes behind the hydroxyl hydrogen among the Q;
2. the described compound of claim 1, wherein n is 1.
3. the described compound of claim 2, wherein R 1Represent Wasserstoffatoms.
4. the described compound of claim 1, wherein n is the integer of 2-6, a R 1Represent Wasserstoffatoms, methyl or ethyl, and another or other R 1Represent Wasserstoffatoms.
5. the described compound of claim 1, wherein m is 2, x is the integer of 3-10.
6. the described compound of claim 1, wherein Y represents Shi-[O (CHR 2CHR 3) a] x-group, wherein a is the integer of 1-2, x is the integer of 3-10.
7. any described compound among the claim 1-6, wherein Y represents Shi-[OCH 2CH 2] x-,-[O CH 2CH 2CH 2CH 2] x-perhaps-[O CH (CH 3) CH 2] x-group.
8. each described compound among aforesaid right requires, wherein x is the integer from 3-6.
9. each described compound among aforesaid right requires, wherein Q is the residue after terepthaloyl moietie, Ucar 35, butyleneglycol, USP Kosher, TriMethylolPropane(TMP), ditrimethylolpropane, tetramethylolmethane or NSC 65881 remove hydroxyl hydrogen.
10. Photocurable composition, comprising:
(a) each said structural formula (1) compound among at least a aforesaid right requires, with
(b) at least a ethylenically unsaturated compounds that carries out radical polymerization.
11. according to the said Photocurable composition of claim 10, also contain other known light trigger as component (c) and other additives as component (d),
Wherein component (c) is one of benzophenone, Alpha-hydroxy ketone, alpha-amino group ketone or acylphosphine oxide class or its miscellany.
12. according to the said compsn of claim 10, the weight content 0.05-10% of component (a) wherein.
CN2011800124831A 2011-10-24 2011-10-24 Benzophenones macromolecule photoinitiator Pending CN102811999A (en)

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