CN100372877C - High molecular type diphenyl ketone light initiator and its preparing method - Google Patents
High molecular type diphenyl ketone light initiator and its preparing method Download PDFInfo
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Abstract
The present invention discloses a high molecular type diphenyl ketone light initiator represented by the following formula and a preparing method thereof. Halogenated diphenyl ketone and para-aminophenol or para-amino thiophenol are used as raw material to generate benzophenone with an amino group. Then, a maleimide group is introduced by the amino group. The benzophenone containing the maleimide group and tertiary amine with unsaturated double bonds are further copolymerized by free groups to obtain the high molecular type diphenyl ketone light initiator containing the structure of a hydrogen donor of the tertiary amine. Because the structure contains a phenoxy group or a thiophenyl group, the ultraviolet absorption of the high molecular type diphenyl ketone light initiator has a great red shift relatively to the benzophenone. After the hydrogen donor of the tertiary amine is introduced into the high molecular chain of the benzophenone, polymerization can be initiated under the condition of not being required to additionally add the hydrogen donor. Relatively to a small molecular photo initiation system, the high molecular type diphenyl ketone light initiator overcomes the defects of toxicity and migration of a small molecular photoinitiator and has wide application in the fields of ultraviolet light solidification, etc.
Description
Technical field: the invention belongs to a kind of functional high molecule material and preparation method thereof, particularly high molecular benzophenone photoinitiator and preparation method thereof.
Background technology: UV-curing technology has widely at industrial circles such as photo-cured coating, photoresist material, light-curable ink, electronic package material, tackiness agent, optical media replication, paper glazings to be used, particularly after the nineties, shown its bright development prospect more.In the technical progress process of photocuring system, the research and development of photoinitiator system are all the time in occupation of crucial position.
Traditional small molecules photocuring system, in long process of preservation, light trigger has reduced the photopolymerization efficiency of initiation and has caused product smell and toxicity to occur owing to volatilizing easily with photocuring system consistency difference and moving.Therefore research and development efficient, become the focus that people pay close attention to good polymerizable or the polymer type light trigger of system consistency.Commercial a large amount of benzophenone as the efficiency light initiator is not only poor with the photocuring system consistency, and must could use at aided initiating amine.This has not only reduced the light-initiated efficient of benzophenone, and the field of having limited its application.The acrylate chloride group that will contain unsaturated double-bond as (101 pages of nineteen eighty-three periodical Polymer the 24th volumes) such as C.Carlini is incorporated in the 4-dihydroxy benaophenonel structure, prepared polymerisable diphenyl ketone photo initiator, further copolymerization obtains benzophenone polymer light trigger; R.Stephen etc. (75 pages of nineteen ninety-five periodical Journal of Photochemistry and Photob iology the 89th volumes) make high molecular benzophenone photoinitiator by polycondensation.These polymer systems are compared uv-absorbing very big red shift are not taken place with benzophenone, and do not contain coinitiator amine, cannot use as light trigger separately.
Summary of the invention: the objective of the invention is from Molecular Structure Design, be incorporated into benzene oxygen or thiophenyl group and maleimide base group in the benzophenone structural simultaneously by molecular designing, it is further passed through radical copolymerization with unsaturated tertiary amine monomers, prepared the high molecular benzophenone photoinitiator that contains coinitiator amine.With respect to benzophenone, big red shift takes place in its uv-absorbing, has simultaneously and causes effect preferably; And need not to add again in addition coinitiator amine, promptly can be used as light trigger and use.
High molecular benzophenone photoinitiator structural formula of the present invention is as follows:
In the formula: R
1Be selected from hydrogen, fluorine, chlorine, methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, nitro, dimethylin or diethylin; R2 is selected from hydrogen, methyl, ethyl or propyl group;
R
3Be selected from
X is selected from oxygen or sulphur; 1＜a＜10000,1＜b＜10000.
The 4-[(4-dimaleoyl imino is wherein arranged) phenoxy group] multipolymer of benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-chloro-4 '-[(4-dimaleoyl imino) phenoxy group] benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-fluoro-4 '-[(4-dimaleoyl imino) phenoxy group] benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-methyl-4 '-[(4-dimaleoyl imino) phenoxy group] benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-nitro-4 '-[(4-dimaleoyl imino) phenoxy group] benzophenone and dimethylaminoethyl methacrylate, the 4-[(4-dimaleoyl imino) thiophenyl] multipolymer of benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-chloro-4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-fluoro-4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-methyl-4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-nitro-4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-methoxyl group-4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone and dimethylaminoethyl methacrylate, the 4-[(4-dimaleoyl imino) phenoxy group] multipolymer of benzophenone and dimethylamino-propyl Methacrylamide, the multipolymer of 4-chloro-4 '-[(4-dimaleoyl imino) phenoxy group] benzophenone and dimethylamino-propyl Methacrylamide, the 4-[(4-dimaleoyl imino) thiophenyl] multipolymer of benzophenone and dimethylamino-propyl Methacrylamide, the multipolymer of 4-chloro-4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone and dimethylamino-propyl Methacrylamide, the multipolymer of 4-fluoro-4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone and dimethylamino-propyl Methacrylamide, 4-methyl-4-[(4-dimaleoyl imino) thiophenyl] multipolymer of benzophenone and dimethylamino-propyl Methacrylamide, the 4-[(4-dimaleoyl imino) phenoxy group] multipolymer of benzophenone and dimethylamino propyl acrylamide, the 4-[(4-dimaleoyl imino) thiophenyl] multipolymer of benzophenone and dimethylamino propyl acrylamide, the multipolymer of 4-chloro-4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone and dimethylamino propyl acrylamide, the 4-[(4-dimaleoyl imino) thiophenyl] multipolymer of benzophenone and diallyl methylamine, the multipolymer or the 4-[(4-dimaleoyl imino of 4-chloro-4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone and diallyl methylamine) thiophenyl] multipolymer of benzophenone and diene butyl methylamine.
The preparation method of high molecular benzophenone photoinitiator of the present invention is as follows: followingly all represent that with mass parts (a) at room temperature is dissolved in 1 part of halogenated benzophenone and 0.3～3 part of p-aminophenol or p-aminophenyl thiophenol in 40～150 parts the organic solvent, at potassium hydroxide, salt of wormwood, sodium hydroxide or yellow soda ash exist down, reacted between 100～140 ℃ 1～5 hour, be warming up to then between 140～185 ℃, reacted 1～10 hour, reaction finishes postcooling to room temperature, then reaction solution is poured into to 10～100 parts 5～30% aqueous hydrochloric acid and precipitated, obtain containing the benzophenone hydrochloride of aniline structure, the mixed solution of using Virahol and water is to its recrystallization; The benzophenone hydrochloride structural formula that wherein contains the aniline structure is as follows:
(b) 1 part of benzophenone hydrochloride that contains the aniline structure is slowly joined to stir in 20 parts of saturated aqueous sodium acetate solutions sloughed hydrochloride in two hours, to consider cake behind the suction filtration at room temperature is dissolved in 40～150 parts the organic solvent, other gets 0.5～5 part maleic anhydride, be dissolved in 10～100 parts the organic solvent, under vigorous stirring, slowly drip and contain the solution of maleic anhydride in the benzophenone solution that contains the aniline structure, reacted 0.5～5 hour down at 0～30 ℃ then, again reaction soln is poured in 20～200 parts the mixture of ice and water or in the ice-cold ether, filters the benzophenone that precipitation obtains containing the maleinamic acid structure; The benzophenone structural formula that wherein contains the maleinamic acid structure is as follows:
(c) 1 part of benzophenone that contains the maleinamic acid structure is dissolved in 5～50 parts the diacetyl oxide, the anhydrous sodium acetate that adds 0.1～part, nitrogen protection slowly heats up down, reacted 0.5～5 hour down at 60～120 ℃, reaction naturally cools to room temperature with reaction solution after finishing, then it is slowly poured in the mixture of ice and water of 20～100 parts of vigorous stirring, stirred 0.5～2 hour, ice bath cooling back suction filtration, recrystallization in hexanaphthene, chloroform alcohol, methyl alcohol, ethyl acetate or its mixture again obtains containing the benzophenone of maleimide base group; The benzophenone structural formula that wherein contains the maleimide amine structure is as follows:
(d) contain the benzophenone of maleimide base group, 0.1～10 part unsaturated tertiary amine and 0.005～0.22 part Diisopropyl azodicarboxylate with 1 part and place long-neck single port flask, add 5～40 parts organic solvent dissolution; Be placed in the liquid nitrogen and cool off, vacuumize after 20 minutes and led to nitrogen 5 minutes, circulate and with gaslight glass single port flask is sealed under three final vacuum states, place 50～100 ℃ to react down after 1～96 hour then, product is inserted in 50～400 parts of methyl alcohol obtain high molecular benzophenone photoinitiator after precipitation, suction filtration, the drying.
Halogenated benzophenone structural formula used in the present invention is as follows:
In the formula: R
1Be selected from hydrogen, fluorine, chlorine, methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, nitro, dimethylin or diethylin; R4 is selected from fluorine, chlorine or bromine; Wherein have 4-chlorobenzophenone, 4-methyl-4 '-chlorobenzophenone, 4-fluorine benzophenone, 4-bromine benzophenone, 4-methyl-4 '-fluorine benzophenone, 4-methyl-4 '-bromine benzophenone, 4-fluoro-4 '-methoxy benzophenone, 4-chloro-4 '-nitro benzophenone, 4-ethyl-4 '-bromine benzophenone, 4,4 '-difluoro benzophenone, 4,4 '-dichloro benzophenone or 4-chloro-4 '-nitro benzophenone.
The present invention uses the organic solvent in (a) to be selected from pimelinketone, butanone, N, dinethylformamide, N,N-dimethylacetamide or N-methyl-2-pyridine alkane ketone; (b) organic solvent in is selected from acetone, chloroform, butanone, N, N-dimethyl formamide, N, N-N,N-DIMETHYLACETAMIDE or N-methyl-2-pyridine alkane ketone; (d) organic solvent in is selected from tetrahydrofuran (THF), butanone, 1,4-dioxane, N, N-dimethyl formamide, N, N-N,N-DIMETHYLACETAMIDE or N-methyl-2-pyridine alkane ketone.
The structural formula of employed unsaturated tertiary amine is as follows among the present invention:
R
2Be selected from hydrogen, methyl, ethyl or propyl group;
R
3Be selected from
Dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate methyl amine propyl ester, dimethylamino propyl acrylamide, dimethylamino-propyl Methacrylamide, diallyl methylamine or diene butyl methylamine are wherein arranged.
The entire reaction equation that the present invention prepares high molecular benzophenone photoinitiator can be expressed as:
High molecular benzophenone photoinitiator of the present invention is by benzene oxygen or thiophenyl group and maleimide base group being incorporated in the benzophenone molecule simultaneously, it further being obtained high molecular benzophenone photoinitiator with unsaturated tertiary amine copolymerization.The introducing of benzene oxygen or thiophenyl group makes benzophenone produce big red shift, more helps the absorption of UV-light.Because it contains the coinitiator amine structure, need not to add micromolecular coinitiator amine in addition uses, this will significantly reduce the toxicity and the migration of small molecules light trigger, improve the small molecules tertiary amine for detrimentally affects such as photocuring system xanthochromias, the application of diphenyl ketone photo initiator will be expanded greatly, so it will have a wide range of applications at the ultraviolet light polymerization industrial circle.
Description of drawings:
Fig. 1 is the 4-[(4-dimaleoyl imino) thiophenyl] the high molecular benzophenone photoinitiator infrared spectrogram of benzophenone and dimethylaminoethyl methacrylate copolymerization.
Fig. 2 is the 4-[(4-dimaleoyl imino) thiophenyl] the hydrogen nuclear magnetic resonance spectrogram of high molecular benzophenone photoinitiator of benzophenone and dimethylaminoethyl methacrylate copolymerization.
Fig. 3 is the 4-[(4-dimaleoyl imino) thiophenyl] the high molecular benzophenone photoinitiator uv absorption spectra of benzophenone and dimethylaminoethyl methacrylate copolymerization.
Concrete embodiment: following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1:
(a) in the there-necked flask that water trap, prolong and nitrogen protection device are housed; add 1-Methyl-2-Pyrrolidone, 3.60 gram potassium hydroxide, 12.96 4-chlorobenzophenone and the 30mL toluene that restrain of 7.50 gram p-aminophenyl thiophenols, 50mL under the nitrogen protection successively, stirring makes system evenly mixed.Slowly be warmed up to 130～135 ℃ under the oil bath, reacted 3 hours, during moisture in the system go out with methylbenzene azeotropic.Slowly be warmed up to 170～175 ℃ once more, reacted 3 hours.Slowly reduce to suction filtration after the room temperature, remove insolubles.In 1 hour, slowly join in the 100mL concentrated hydrochloric acid and 500mL mixture of ice and water of vigorous stirring considering liquid.Suction filtration, washing, petroleum ether is inserted the vacuum drying oven drying with filter cake, gets 18.35 gram products.The mixing solutions recrystallization of water, concentrated hydrochloric acid and Virahol gets 13.42 gram 4-[(4-amino) thiophenyl] the benzophenone hydrochloride.Fusing point: 101～103 ℃.M/z:305 (removing HCl), FT-IR (KBr): 3460,3368 (NH
2), 1648 (C=O), 1084 (C-S).
1H NMR ([D6] DMSO, 400MHz): δ=7.70-7.63 (5H, phenyl ring), 7.54-7.51 (2H, phenyl ring), 7.49-7.45 (2H, phenyl ring), 7.26-7.23 (2H, phenyl ring), 7.19-7.17 (2H, phenyl ring).C19H16ClNOS (341.5gmol
-1): ultimate analysis, theoretical value: C66.75, H4.72, N4.10, S9.38; Actual value: C65.29, H4.93, N3.76, S9.02.
(b) with the 4-[(4-amino of 4.44 grams) thiophenyl] the benzophenone hydrochloride places the saturated anhydrous acetic acid sodium water solution of 40mL, stirs suction filtration after 2 hours, and the worry cake is dissolved in the acetone of 40mL, and it is inserted in the there-necked flask stir then.Other gets 1-35 gram maleic anhydride, be dissolved in the 15mL acetone, it is inserted in the constant pressure funnel, drip slowly in 15 minutes and contain the acetone soln of maleic anhydride to there-necked flask, stirring at room 2 hours, be poured in the 250mL frozen water, vigorous stirring 0.5 hour, suction filtration gets garnet to yellow mercury oxide.Vacuum-drying gets 4.25 gram 4-[(4-maleinamide acidic groups) thiophenyl] benzophenone.Productive rate: 73.8%.Fusing point: 158～159 ℃.FT-IR(KBr)：3473(NH)，3281(COOH)，
1632(C=O?ofCOOH)，1588(CH=CH)，1085(C-S)。
1H NMR ([D6] DMSO, 400MHz): b=12.95 (1H, COOH), 10.57 (1H, NH), 7.77-7.74 (2H, phenyl ring), 7.70-7.64 (5H, phenyl ring), (7.54-7.50 4H, phenyl ring), 7.22-7.20 (2H, phenyl ring) 6.49-6.46 (1H,-CH=), 6.32-6.27 (1H ,-CH=).(c) with 3.78 gram 4-[(4-maleinamide acidic groups) thiophenyl] benzophenone, 0.75 restrains anhydrous sodium acetate and the 30mL diacetyl oxide joins in the there-necked flask, slowly is warmed up to 95～100 ℃ under the nitrogen protection, react to naturally cool to room temperature after 0.5 hour.Reaction solution is poured in the 100mL icy water, outwells the part supernatant liquid after leaving standstill, added 150mL frozen water vigorous stirring again 1 hour, washing, petroleum ether is used the dissolve with methanol product after the vacuum-drying, and heat filtering is removed insolubles.Separate out the glassy yellow crystal behind the naturally cooling, suction filtration.Vacuum-drying gets 2.79 gram xanchromatic 4-[(4-dimaleoyl iminos) benzene sulphur clump] benzophenone, productive rate: 77.7%, fusing point: 63～64 ℃, m/z:385.FT-IR(KBr)：
1588(CH＝CH)，1080(C-S)。
1H NMR (CDCl
3, 400MHz): δ=7.79-7.72 (4H, phenyl ring), 7.59-7.57 (3H, phenyl ring), 7.50-7.47 (2H, phenyl ring), 7.43-7.41 (2H, phenyl ring), 7.34-7.32 (2H, phenyl ring), 6.89 (2H, CH=CH).C
23H
15NO
3S (385gmol
-1): ultimate analysis, theoretical value: C71.67, H3.92, N3.63, S8.32: actual value: C71.74, H3.91, N3.51, S8.15.
(d) with 1.925 gram 4-[(4-dimaleoyl iminos) thiophenyl] benzophenone, the dimethylaminoethyl methacrylates of 1.572 grams and 34.97 milligrams Diisopropyl azodicarboxylate place long-neck single port flask, adds the N of 15mL, dissolve in the dinethylformamide; Be placed in the liquid nitrogen and cool off, vacuumize after 20 minutes and led to nitrogen 5 minutes, circulate and with gaslight glass single port flask is sealed under three final vacuum states, place 90 ℃ of oil bath reactions after 72 hours then, product is inserted obtain the bolarious high molecular benzophenone photoinitiator of 1.67 grams in the 150mL methyl alcohol after precipitation, suction filtration, the drying.Fig. 1 is the 4-[(4-dimaleoyl imino) thiophenyl] the high molecular benzophenone photoinitiator infrared spectrogram of benzophenone and dimethylaminoethyl methacrylate copolymerization, FT-IR (KBr, cm
-1): 3472 (OH, hydrogen bonds), 1714 (C=O of
With
), 1652 (
), 1588 (Ar), 1081 (C-S).Fig. 2 is the 4-[(4-dimaleoyl imino) thiophenyl] the hydrogen nuclear magnetic resonance spectrogram of high molecular benzophenone photoinitiator of benzophenone and dimethylaminoethyl methacrylate copolymerization,
1H NMR (CDCl
3, 400MHz): δ=7.77-7.03 (13H, phenyl ring), 4.32-3.80 (3H, CH, CH
2Of-CH-CH
2-), 2.73-2.41 (2H ,-OCH
2-), 2.41-1.50 (8H ,-CH
2-N-(CH
3)
2), 1.41-0.40 (CH
3Of-C-CH
3).Fig. 3 is the 4-[(4-dimaleoyl imino) thiophenyl] uv absorption spectra of high molecular benzophenone photoinitiator in chloroform of benzophenone and dimethylaminoethyl methacrylate copolymerization, its corresponding maximum absorption is λ
Max: 263nm and 316nm.With N, dinethylformamide is an eluent, the 4-[(4-dimaleoyl imino) thiophenyl] its number-average molecular weight of gel chromatography gained M of high molecular benzophenone photoinitiator of benzophenone and dimethylaminoethyl methacrylate copolymerization
nBe 3068, molecular weight distribution width: M
w/ M
n=1.296.Ultimate analysis: S7.00,4-[(4-dimaleoyl imino) thiophenyl] benzophenone and dimethylaminoethyl methacrylate mol ratio in polymkeric substance be 1: 0.4371.
Embodiment 2:
(a) in the there-necked flask that water trap, prolong and nitrogen protection device are housed; the 1-Methyl-2-Pyrrolidone, 2.60 gram potassium hydroxide, 30mL toluene and 8.80 grams 4 that add 4.40 gram p-aminophenyl thiophenols, 40mL under the nitrogen protection successively, 4 '-dichloro benzophenone.Slowly heating up was warmed up between 130～135 ℃ in 30 minutes, reacted 3 hours, during have moisture to go out with methylbenzene azeotropic.Slowly heating up once more rises between 170～175 ℃ system temperature, and toluene is all told, and reacts 3 hours.Naturally cool to room temperature, suction filtration removes insolubles.Filtrate slowly is poured in 75mL concentrated hydrochloric acid and the 250mL mixture of ice and water, stirs, suction filtration, washing.Vacuum-drying gets dark yellow 4-chloro-4 '-[(4-amino) thiophenyl] the benzophenone hydrochloride to light coffee color of 12.71 grams, the mixing solutions recrystallization of water, concentrated hydrochloric acid, ethanol and Virahol.Fusing point: 107～109 ℃.FT-IR(KBr)：3406(NH)，1646(C＝O)，1588(C＝C)，1083(C-S)，752(Cl)。
1H NMR ([D6] DMSO, 400MHz): δ=7.73-7.69 (2H, phenyl ring), 7.66-7.58 (4H, phenyl ring), 7.40-7.38 (2H, phenyl ring), 7.20-7.18 (2H, phenyl ring), 7.01-6.99 (2H, phenyl ring), 4.24 (2H, NH2).C
19H
15C
L2NOS (376gmol
-1): ultimate analysis, theoretical value: C60.64, H4.02, N3.72, S8.52; Actual value: C60.84, H4.21, N3.43, S7.53.
(b) 4-chloro-4 '-[(4-amino) thiophenyl] the benzophenone hydrochloride with 3.76 grams is dissolved in the saturated aqueous sodium acetate solution of 120mL, stirs 2 hours, and suction filtration is dissolved in filter cake in the 40mL acetone, and funnel filters out insolubles.Considering liquid inserts in the there-necked flask, other gets 1.20 gram maleic anhydrides, be dissolved in the 10mL acetone, it is inserted in the constant pressure funnel, the acetone soln that dropping slowly contains maleic anhydride in 15 minutes is to there-necked flask, and stirring at room 2 hours is poured into the 150mL frozen water, vigorous stirring 0.5 hour, suction filtration get grass green to yellow mercury oxide.Vacuum-drying gets 3.53 gram 4-chloro-, 4 '-[(4-maleinamide acidic group) thiophenyl] benzophenone.Productive rate: 80.7%.Fusing point: 153～155 ℃.FT-IR(KBr)：3480(NH)，3294(COOH)，1717(C＝O?of
)，1646(
)，1589(CH＝CH)，1084(C-S)，753(Cl)。1H NMR ([D6] DMSO, 400MHz): δ=12.90 (1H, COOH), 10.54 (1H, NH), 7.76-7.69 (4H, phenyl ring), 7.67-7.57 (4H, phenyl ring), (7.54-7.52 2H, phenyl ring), 7.22-7.20 (2H, phenyl ring), and 6.49-6.47 (1H, CH=), 6.31-6.29 (1H ,=CH).
(c) 4.38 gram 4-chloro-, 4 '-[(4-maleinamide acidic group) thiophenyl] benzophenone, 0.82 gram anhydrous sodium acetate and 30mL diacetyl oxide are joined in the there-necked flask; slowly be warmed up to 95～100 ℃ under the nitrogen protection; reacted 0.5 hour; pour in the cold water of 100mL after reducing to room temperature, pour out most of water layer after leaving standstill.The mixture of ice and water that adds 150mL then, vigorous stirring 0.5 hour, suction filtration, washing, petroleum ether gets 4.14 gram dark yellow products after the vacuum-drying.Get 2.49 gram glassy yellows behind the ethyl alcohol recrystallization to bolarious 4-chloro-4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone, productive rate: 59.1%.Fusing point: 67～68 ℃.FT-IR(KBr)：1716(C＝O?of
)，1652(
)，1588(CH＝CH)，1082(C-O)，755(Cl)。
1H NMR (CDCl
3, 400MHz): δ=7.73-7.67 (4H, phenyl ring), 7.58-7.55 (2H, phenyl ring), 7.48-7.41 (4H, phenyl ring), 7.32-7.30 (2H, phenyl ring), 6.88-6.87 (2H, CH=CH).C
23H
14ClNO
3S (419.5gmol
-1): ultimate analysis, theoretical value: C65.79, H3.36, N3.34, S7.64; Actual value: C65.54, H3.49, N3.23, S7.58.
(d) 2.098 gram 4-chloro-, 4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone, the dimethylaminoethyl methacrylate of 1.572 grams and 36.70 milligrams Diisopropyl azodicarboxylate are placed long-neck single port flask, the N that adds 15mL, the dinethylformamide dissolving; Be placed in the liquid nitrogen and cool off, vacuumize after 20 minutes and led to nitrogen 5 minutes, circulate and with gaslight glass single port flask is sealed under three final vacuum states, place 90 ℃ of oil bath reactions after 72 hours then, product is inserted obtain the bolarious high molecular benzophenone photoinitiator of 1.90 grams in the 150mL methyl alcohol after precipitation, suction filtration, the drying.FT-IR (KBr, cm
-1): 3466 (OH, hydrogen bonds), 1715 (C=O of
With
), 1652 (
), 1588 (Ar), 1081 (C-S).
1H NMR (CDCl
3, 400MHz): δ=7.75-7.26 (12H, phenyl ring), 4.37-3.82 (3H, CH, CH
2Of-CH-CH
2-), 2.75-2.42 (2H ,-OCH
2-), 2.41-1.54 (8H ,-CH
2-N-(CH
3)
2), 1.49-0.42 (CH
3Of-C-CH
3).Ultraviolet maximum absorption corresponding in chloroform is λ
Max: 263nm and 321nm.With N, dinethylformamide is an eluent, and its number-average molecular weight Mn is 4393, molecular weight distribution width: M
w/ M
n=2.022.Ultimate analysis: S6.40,4-chloro-4 '-[(4-dimaleoyl imino) thiophenyl] benzophenone and dimethylaminoethyl methacrylate mol ratio in polymkeric substance are 1: 0.5170.
Embodiment 3:
(a) in the there-necked flask that water trap, prolong and nitrogen protection device are housed; add 1-Methyl-2-Pyrrolidone, 1.68 gram potassium hydroxide, 6.48 4-chlorobenzophenone and the 30mL toluene that restrain of 3.27 gram p-aminophenol, 50mL under the nitrogen protection successively, stirring makes system evenly mixed.Under oil bath, slowly be warmed up to 130～135 ℃, reacted 3 hours, during moisture in the system go out with methylbenzene azeotropic.Slowly be warmed up to 170～175 ℃ once more, reacted 3 hours.Slowly reduce to suction filtration after the room temperature, remove insolubles.In 1 hour, slowly join in the 60mL concentrated hydrochloric acid and 140mL mixture of ice and water of vigorous stirring considering liquid.Suction filtration, washing, petroleum ether is inserted the vacuum drying oven drying with filter cake, gets 8.04 gram products.The mixing solutions of water and Virahol is heavily tied product, gets 7.01 gram 4-[(4-amino) phenoxy group] the benzophenone hydrochloride.Productive rate: 72.8%.Fusing point: 143～145 ℃.M/z:289 (removing HCl), FT-IR (KBr): 3420 (NH
2), 1648 (C=O), 1258,1167,1147 (C-O).
1H NMR ([D6] DMSO, 400MHz): δ=9.21 (2H, NH2), 7.78-7.52 (7H, phenyl ring), 7.22-7.05 (6H, phenyl ring).C
19H
16ClNO
2(325.5gmol
-1): ultimate analysis, theoretical value: C70.05, H5.02, N3.91; Actual value: C71.96, H4.92, N4.30.
(b) with the 4-[(4-amino of 1.20 grams) phenoxy group] the benzophenone hydrochloride is dissolved in the saturated aqueous sodium acetate solution of 50mL, stirred 2 hours, suction filtration, petroleum ether is inserted filter cake in the there-necked flask, adding 10mL acetone solution.Get 0.40 gram maleic anhydride, be dissolved in the 10ml acetone, it is inserted in the constant pressure funnel, drip slowly in 10 minutes and contain the acetone soln of maleic anhydride to there-necked flask, stirring at room 1.5 hours is poured in the mixture of ice and water of 50mL vigorous stirring, and suction filtration gets yellow mercury oxide.Vacuum-drying gets 1.07 gram 4-[(4-maleinamide acidic groups) phenoxy group] benzophenone.Productive rate: 75.5%.Fusing point: 183～185 ℃.FT-IR(KBr)：3447(NH)，3286(COOH)，1706(C＝O?of
)，1656(
)，1595(CH＝CH)，1258，1166，1150(C-O)。
1H NMR ([D6] DMSO, 400MHz): δ=13.07 (1H, COOH), 10.47 (1H, NH), 7.77-7.51 (9H, phenyl ring), 7.15-7.05 (4H, phenyl ring), 6.49-6.46 (1H ,-CH=), 6.31-6.28 (1H ,-CH=).
(c) with 1.07 gram 4-[(4-maleinamide acidic groups) phenoxy group] benzophenone, 0.20 restrains anhydrous sodium acetate and the 10mL diacetyl oxide joins in the there-necked flask, slowly is warmed up to 95～100 ℃ under the nitrogen protection, react to naturally cool to room temperature after 0.5 hour.Reaction solution is poured in the mixture of ice and water of 40mL vigorous stirring, washing, petroleum ether, with 40mL dissolve with ethanol product, heat filtering is removed insolubles after the vacuum-drying.Separate out yellow crystals behind the naturally cooling, suction filtration, washing with alcohol.Vacuum-drying gets 0.47 gram xanchromatic 4-[(4-dimaleoyl imino) phenoxy group] benzophenone, productive rate: 46.1%, fusing point: 142～144 ℃.Mass spectrum, m/z:369.FT-IR(KBr)：1714(C＝O?of
)，1651(
)，1593(CH＝CH)，1262，1166，1154(C-O)。
1H NMR (CDCl3,400MHz): δ=7.85-7.78 (4H, phenyl ring), 7.57-7.60 (1H, phenyl ring), (7.50-7.47 2H, phenyl ring), 7.39-7.36 (2H, phenyl ring), 7.19-7.16 (2H, phenyl ring), 7.10-7.07 (2H, phenyl ring), 6.49-6.46 (2H, CH=CH).C
23H
15NO
4(369gmol
-1): ultimate analysis, theoretical value: C74.80, H4.07, N3.79; Actual value: C74.78, H4.01, N3.63.
(d) with 2.214 gram 4-[(4-dimaleoyl iminos) phenoxy group] benzophenone, the dimethylaminoethyl methacrylates of 1.887 grams and 41.01 milligrams Diisopropyl azodicarboxylate place long-neck single port flask, adds the N of 18mL, the dinethylformamide dissolving; Be placed in the liquid nitrogen and cool off, vacuumize after 20 minutes and led to nitrogen 5 minutes, circulate and with gaslight glass single port flask is sealed under three final vacuum states, place 90 ℃ of oil bath reactions after 72 hours then, product is inserted obtain the bolarious high molecular benzophenone photoinitiator of 1.50 grams in the 160mL methyl alcohol after precipitation, suction filtration, the drying.FT-IR (KBr, cm
-1): 3468 (OH, hydrogen bonds), 1713 (C=O of
With
), 1654 (
), 1592 (Ar), 1245,1167,1149 (C-O).
1H NMR (CDCl
3, 400MHz): δ=7.87-7.02 (13H, phenyl ring), 4.36-3.73 (3H, CH, CH
2Of-CH-CH
2-), 2.67-2.38 (2H ,-OCH
2-), 2.36-1.48 (8H ,-CH
2-N-(CH
3)
2), 1.40-0.41 (CH
3Of-C-CH
3).Ultraviolet maximum absorption corresponding in chloroform is λ
Max: 284nm.With N, dinethylformamide is an eluent, its number-average molecular weight M
nBe 3978, molecular weight distribution width: M
w/ M
n=1.246.Ultimate analysis: C72.65,4-[(4-dimaleoyl imino) phenoxy group] benzophenone and dimethylaminoethyl methacrylate mol ratio in polymkeric substance be 1: 0.4357.
Claims (7)
1. high molecular benzophenone photoinitiator is characterized in that its chemical structural formula is as follows:
In the formula: R
1Be selected from hydrogen, fluorine, chlorine, methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, nitro, dimethylin or diethylin; R
2Be selected from hydrogen, methyl, ethyl or propyl group;
R
3Be selected from
X is selected from oxygen or sulphur; 1＜a＜10000,1＜b＜10000.
2. the preparation method of a kind of high molecular benzophenone photoinitiator as claimed in claim 1 is characterized in that the preparation method is as follows, below all represents with mass parts:
(a) 1 part of halogenated benzophenone and 0.3～3 part of p-aminophenol or p-aminophenyl thiophenol at room temperature are dissolved in 40～150 parts the organic solvent, reacting 1～5 hour in the presence of potassium hydroxide, salt of wormwood, sodium hydroxide or the yellow soda ash, between 100～140 ℃, be warming up to then between 140～185 ℃, reacted 1～10 hour, reaction finishes postcooling to room temperature, then reaction solution is poured into to 10～100 parts 5～30% aqueous hydrochloric acid and precipitated, obtain containing the benzophenone hydrochloride of aniline structure, the mixed solution of using Virahol and water is to its recrystallization; The benzophenone hydrochloride structural formula that wherein contains the aniline structure is as follows:
(b) 1 part of benzophenone hydrochloride that contains the aniline structure is slowly joined to stir in 20 parts of saturated aqueous sodium acetate solutions sloughed hydrochloride in two hours, to consider cake behind the suction filtration at room temperature is dissolved in 40～150 parts the organic solvent, other gets 0.5～5 part maleic anhydride, be dissolved in 10～100 parts the organic solvent, under vigorous stirring, slowly drip and contain the solution of maleic anhydride in the benzophenone solution that contains the aniline structure, reacted 0.5～5 hour down at 0～30 ℃ then, again reaction soln is poured in 20～200 parts the mixture of ice and water or in the ice-cold ether, filters the benzophenone that precipitation obtains containing the maleinamic acid structure; The benzophenone structural formula that wherein contains the maleinamic acid structure is as follows:
(c) 1 part of benzophenone that contains the maleinamic acid structure is dissolved in 5～50 parts the diacetyl oxide; the anhydrous sodium acetate that adds 0.1～2 part; nitrogen protection slowly heats up down; reacted 0.5～5 hour down at 60～120 ℃; reaction naturally cools to room temperature with reaction solution after finishing; then it is slowly poured in the mixture of ice and water of 20～100 parts of vigorous stirring; stirred 0.5～2 hour; ice bath cooling back suction filtration; again at hexanaphthene; chloroform; ethanol; methyl alcohol; recrystallization in ethyl acetate or its mixture; obtain containing the benzophenone of maleimide base group, the benzophenone structural formula that wherein contains maleimide base group is as follows:
(d) contain the benzophenone of maleimide base group, 0.1～10 part unsaturated tertiary amine and 0.005～0.22 part Diisopropyl azodicarboxylate with 1 part and place long-neck single port flask, add 5～40 parts organic solvent dissolution; Be placed in the liquid nitrogen and cool off, vacuumize after 20 minutes and led to nitrogen 5 minutes, circulate and with gaslight glass single port flask is sealed under three final vacuum states, place 50～100 ℃ to react down after 1～96 hour then, product is inserted in 50～400 parts of methyl alcohol obtain high molecular benzophenone photoinitiator after precipitation, suction filtration, the drying.
3. the preparation method of a kind of high molecular benzophenone photoinitiator according to claim 2 is characterized in that the halogenated benzophenone structural formula is as follows:
In the formula: R
1Be selected from hydrogen, fluorine, chlorine, methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, nitro, dimethylin or diethylin; R
4Be selected from fluorine, chlorine or bromine.
4. the preparation method of a kind of high molecular benzophenone photoinitiator according to claim 2, it is characterized in that halogenated benzophenone be 4-chlorobenzophenone, 4-methyl-4 '-chlorobenzophenone, 4-fluorine benzophenone, 4-bromine benzophenone, 4-methyl-4 '-fluorine benzophenone, 4-methyl-4 '-bromine benzophenone, 4-fluoro-4 '-methoxy benzophenone, 4-chloro-4 '-nitro benzophenone, 4-ethyl-4 '-bromine benzophenone, 4,4 '-difluoro benzophenone, 4,4 '-dichloro benzophenone or 4-chloro-4 '-nitro benzophenone.
5. the preparation method of a kind of high molecular benzophenone photoinitiator according to claim 2 is characterized in that the organic solvent in (a) is selected from pimelinketone, butanone, N, dinethylformamide, N,N-dimethylacetamide or N-methyl-2-pyridine alkane ketone; (b) organic solvent in is selected from acetone, chloroform, butanone, N, dinethylformamide, N,N-dimethylacetamide or N-methyl-2-pyridine alkane ketone; (d) organic solvent in is selected from tetrahydrofuran (THF), butanone, 1,4-dioxane, N, dinethylformamide, N,N-dimethylacetamide or N-methyl-2-pyridine alkane ketone.
6. the preparation method of a kind of high molecular benzophenone photoinitiator according to claim 2 is characterized in that the structural formula of unsaturated tertiary amine is as follows:
R
2Be selected from hydrogen, methyl, ethyl or propyl group;
R
3Be selected from
7. the preparation method of a kind of high molecular benzophenone photoinitiator according to claim 2 is characterized in that unsaturated tertiary amine is dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate methyl amine propyl ester, dimethylamino propyl acrylamide, dimethylamino-propyl Methacrylamide, diallyl methylamine or diene butyl methylamine.
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| CN101941952B (en) * | 2010-07-21 | 2015-04-08 | 深圳市有为化学技术有限公司 | Resin monomer skeleton-derivative ketone compound photoinitiator |
| JP6951765B2 (en) * | 2016-07-06 | 2021-10-20 | 株式会社サクラクレパス | Plasma treatment detection composition and plasma treatment detection indicator |
| CN110054731B (en) * | 2019-05-10 | 2021-01-05 | 济南大学 | Preparation method of reversible acid-base discoloration maleimide copolymer |
| CN114656592B (en) * | 2020-12-23 | 2023-06-13 | 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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| CN1562481A (en) * | 2004-04-22 | 2005-01-12 | 上海交通大学 | Photoinitiator of benzophenone in macromolecule type and preparation method |
| CN1727335A (en) * | 2005-06-16 | 2006-02-01 | 上海交通大学 | Photoinitiator of benzophenone containing N-phenyl maleimide base group, and preparation method |
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| CN1020627C (en) * | 1986-12-10 | 1993-05-12 | 国际壳牌研究有限公司 | Process for manufacture of kerosene and/or gas oils |
| WO2001068769A1 (en) * | 2000-03-16 | 2001-09-20 | Kraton Polymers Research B.V. | Polymeric composition |
| CN1562481A (en) * | 2004-04-22 | 2005-01-12 | 上海交通大学 | Photoinitiator of benzophenone in macromolecule type and preparation method |
| CN1727335A (en) * | 2005-06-16 | 2006-02-01 | 上海交通大学 | Photoinitiator of benzophenone containing N-phenyl maleimide base group, and preparation method |
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