CN1847275A - High molecular benzophenone photoinitiator and its prepn process - Google Patents
High molecular benzophenone photoinitiator and its prepn process Download PDFInfo
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Abstract
The present invention discloses one kind of high molecular benzophenone photoinitiator and its preparation process. The preparation process includes the first reaction of benzophenone halide and p-amino phenol or p-amino thiophenol to produce benzophenone with amino group; the subsequent reaction between the amino group and acryloyl chloride or methyl acryloyl chloride to produce polymerisable benzophenone photoinitiator; and final freed radical copolymerization with tertiary amine with unsaturated double bond to produce high molecular benzophenone photoinitiator. Owing to the phenoxy radical or thiophenyl radical, the high molecular benzophenone photoinitiator has great red shift of ultraviolet absorption relative to that of benzophenone. The introduction of tertiary amine as hydrogen donor makes it possible to initiate polymerization without introducing other hydrogen donor. The present invention has no toxicity and no migration and may be applied in ultraviolet curing and other fields.
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 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 high-molecular optical initiator; R.Stephen etc. (75 pages of nineteen ninety-five periodical Journal of Photochemistry and Photobiology 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 propylene or methacrylic group in the benzophenone structural simultaneously by molecular designing, it is further passed through radical copolymerization with unsaturated tertiary amine monomers, prepared high molecular benzophenone photoinitiator.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 the coinitiator tertiary 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; R
2Be selected from hydrogen, methyl, ethyl or propyl group;
R
3Be selected from
Or
R
4Be selected from hydrogen or methyl; X is selected from oxygen or sulphur; 1＜x＜10000,1＜y＜10000.
4-[(4-methacryloyl amido is wherein arranged) phenoxy group] multipolymer of benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-chloro-4 '-[(4-methacryloyl amido) phenoxy group] benzophenone and dimethylaminoethyl methacrylate, the 4-[(4-acrylamido) phenoxy group] multipolymer of benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-chloro-4 '-[(4-acrylamido) phenoxy group] benzophenone and dimethylaminoethyl methacrylate, 4-[(4-methacryloyl amido) thiophenyl] multipolymer of benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-chloro-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone and dimethylaminoethyl methacrylate, the 4-[(4-acrylamido) thiophenyl] multipolymer of benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-chloro-4 '-[(4-acrylamido) thiophenyl] benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-methyl-4 '-[(4-methacryloyl amido) phenoxy group] benzophenone and dimethylaminoethyl methacrylate, the multipolymer of 4-methyl-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone and dimethylaminoethyl acrylate methyl amine propyl ester, 4-[(4-methacryloyl amido) thiophenyl] multipolymer of benzophenone and dimethylaminoethyl acrylate methyl amine propyl ester, the multipolymer of 4-chloro-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone and dimethylaminoethyl acrylate methyl amine propyl ester, 4-[(4-methacryloyl amido) thiophenyl] multipolymer of benzophenone and dimethylamino propyl acrylamide, the multipolymer of 4-chloro-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone and dimethylamino propyl acrylamide, 4-[(4-methacryloyl amido) thiophenyl] multipolymer of benzophenone and dimethylamino-propyl Methacrylamide, the multipolymer of 4-chloro-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone and dimethylamino-propyl Methacrylamide, 4-[(4-methacryloyl amido) thiophenyl] multipolymer of benzophenone and diallyl methylamine, the multipolymer of 4-chloro-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone and diallyl methylamine, 4-[(4-methacryloyl amido) thiophenyl] benzophenone and the multipolymer of diene butyl methylamine or the multipolymer of 4-chloro-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone and diene butyl methylamine.
The preparation method of high molecular benzophenone photoinitiator is as follows among the present invention: followingly all represent 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) under magnetic agitation and ice bath, the benzophenone hydrochloride that contains the aniline structure of 1 part of porphyrize is slowly joined in 10～50 part of 10～40% ammonia soln or the aqueous sodium acetate solution, vigorous stirring 0.5～5 hour is sloughed hydrochloric acid, obtains containing the benzophenone of aniline structure;
(c) 1 part of benzophenone that contains the aniline structure is dissolved in 5～50 parts the organic solvent; other gets 0.3～2 part 0.3～2 part acrylate chloride or methacrylic chloride and is dissolved in the organic solvent; nitrogen protection and ice bath slowly drip the mixed solution of acrylate chloride or methacrylic chloride down; after stirring reaction 10～20 hours at room temperature; after reaction solution is poured in the frozen water; the suction filtration precipitation; aqueous sodium carbonate with 5wt% washs three times; obtain polymerisable benzophenone after washing three times, wherein the polymerisable benzophenone structural formula is as follows:
(d) 1 part of polymerisable benzophenone, 0.1～10 part unsaturated tertiary amine and 0.005～0.22 part Diisopropyl azodicarboxylate are placed 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; R
5Be 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; (c) organic solvent in is selected from acetone, tetrahydrofuran (THF), butanone, N, dinethylformamide, N,N-dimethylacetamide or N-methyl-2-pyridine alkane ketone; (d) organic solvent in is selected from butanone, 1,4-dioxane, N, dinethylformamide, 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
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 propylene or methacrylic group are incorporated in the benzophenone molecule simultaneously, it is further obtained high molecular benzophenone photoinitiator with unsaturated tertiary amine copolymerization, the introducing of benzene oxygen or thiophenyl group makes benzophenone produce big red shift.This type of polymer light trigger overcome the small molecules light trigger volatile, in photocuring system the easy shortcoming of migration, significantly reduced the toxicity of small molecules light trigger and to the destructiveness of cured product.Because it contains the coinitiator amine structure, need not to add again coinitiator amine and use, this will overcome the shortcoming that traditional small molecules light trigger need add tertiary amine in addition.Expanded the range of application of diphenyl ketone photo initiator greatly, so it will have a wide range of applications at the ultraviolet light polymerization industrial circle.
Description of drawings:
Fig. 1 is a 4-[(4-methacryloyl amido) thiophenyl] the high molecular benzophenone photoinitiator infrared spectrogram of benzophenone and dimethylaminoethyl methacrylate copolymerization.
Fig. 2 is a 4-[(4-methacryloyl amido) thiophenyl] the hydrogen nuclear magnetic resonance spectrogram of high molecular benzophenone photoinitiator of benzophenone and dimethylaminoethyl methacrylate copolymerization.
Fig. 3 is a 4-[(4-methacryloyl amido) 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.After slowly reducing to room temperature, suction filtration removes insolubles.Filtrate was slowly joined in 1 hour in the 100mL concentrated hydrochloric acid and 500mL mixture of ice and water of vigorous stirring.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).C
19H
16ClNOS (341.5gmol
-1): ultimate analysis, theoretical value: C 66.75, H 4.72, and N 4.10, and S 9.38; Actual value: C 65.29, H 4.93, and N 3.76, and S 9.02.
(b) under magnetic agitation and ice bath, with the 4-[(4-amino of 13.00 gram porphyrizes) thiophenyl] the benzophenone hydrochloride slowly is added in 10% the ammoniacal liquor of 400mL, stirs after 2 hours suction filtration; Filter cake inserted in 40 ℃ the vacuum drying oven dry 48 hours, 11.4 gram glassy yellow 4-[(4-amino) thiophenyl] benzophenone.FT-IR(KBr)：3476，3362(NH)，1641
1594(CH＝CH)，1076(C-S)。
1H NMR ([D6] CDCl
3, 400MHz): δ=7.76-7.73 (2H, phenyl ring), 7.66-7.64 (2H, phenyl ring), 7.58-7.54 (1H, phenyl ring), 7.47-7.43 (2H, phenyl ring), 7.37-7.35 (2H, phenyl ring), 7.11-7.09 (2H, phenyl ring), 6.74-6.72 (2H, phenyl ring), 4.01 (2H, NH
2).
(c) under the nitrogen protection in the there-necked flask, with 10.20 gram 4-[(4-amino) thiophenyl] benzophenone and 6mL triethylamine be dissolved in the 30mL dimethyl formamide; Other gets the 6mL methacrylic chloride and is dissolved in the 10mL dimethyl formamide and places constant pressure funnel, and ice bath slowly drips the mixed solution of methacrylic chloride to there-necked flask in following half an hour.Stir after 12 hours under the room temperature, reaction solution is poured in the 300mL icy water, the suction filtration precipitation, filter cake washs three times with 5% aqueous sodium carbonate, deionized water wash three times, 50 ℃ of vacuum-dryings 30 hours, get 11.20 gram xanchromatic 4-[(4-methacryloyl amidos) thiophenyl] benzophenone, with the mixing solutions recrystallization of 1: 3 first alcohol and water.Fusing point: 91～93 ℃, m/z:373.FT-IR(KBr)：3269(NH)，1648
1623
1587(CH＝CH)，1081(C-S)。
1H NMR (DMSO, 400MHz): δ=7.85-7.82 (2H, phenyl ring), 7.69-7.63 (5H, phenyl ring), 7.54-7.50 (4H, phenyl ring), 7.20-7.18 (2H, phenyl ring), 5.81 (1H, CH), 5.54 (1H, CH), 1.94 (3H, CH
3).Ultimate analysis, theoretical value: C 73.97, H 5.13, and N 3.75, and S 8.59; Measured value: C 73.37, H 5.39, and N 3.96, S7.36.
(d) with 1.492 gram 4-[(4-methacryloyl amidos) thiophenyl] benzophenone, the dimethylaminoethyl methacrylates of 1.258 grams and 28.40 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 after three times, under vacuum state, glass single port flask is sealed with gaslight, place 90 ℃ of oil bath reactions after 72 hours then, product is inserted obtain 1.48 gram Huangs in the 150mL methyl alcohol after precipitation, suction filtration, the drying to bolarious high molecular benzophenone photoinitiator.Fig. 1 is a 4-[(4-methacryloyl amido) thiophenyl] the high molecular benzophenone photoinitiator infrared spectrogram of benzophenone and dimethylaminoethyl methacrylate copolymerization, FT-IR (KBr, cm
-1): 3526,3353 (OH: hydrogen bond, NH), 1731
1682
Free), 1659
Hydrogen bonding), 1652
1588 (Ar), 1081 (C-S).Fig. 2 is a 4-[(4-methacryloyl amido) thiophenyl] the hydrogen nuclear magnetic resonance spectrogram of high molecular benzophenone photoinitiator of benzophenone and dimethylaminoethyl methacrylate copolymerization,
1HNMR (CDCl
3, 400MHz): δ=7.68-7.10 (13H, phenyl ring), 5.74
5.43 (CH of
3.98 (CH
2Of CH
2O), 2.48
2.20-2.15
And CH
3Of N-(CH
3)
2), 2.00
1.94-1.58
1.49-0.74
Fig. 3 is a 4-[(4-methacryloyl amido) thiophenyl] uv absorption spectra of high molecular benzophenone photoinitiator in chloroform of benzophenone and dimethylaminoethyl methacrylate copolymerization, its corresponding maximum absorption is λ
Max: 251nm and 317nm.With the tetrahydrofuran (THF) is eluent, 4-[(4-methacryloyl amido) thiophenyl] the number-average molecular weight M of polymeric diphenylmethane ketone of benzophenone and dimethylaminoethyl methacrylate copolymerization
nBe 24220, molecular weight distribution width: M
w/ M
n=1.455.Ultimate analysis: S 4.71,4-[(4-methacryloyl amido) thiophenyl] benzophenone and dimethylaminoethyl methacrylate mol ratio in polymkeric substance be 1: 1.953.
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, NH
2).C
19H
15C
L2NOS (376gmol
-1): ultimate analysis, theoretical value: C 60.64, H 4.02, and N 3.72, and S 8.52; Actual value: C 60.84, H 4.21, and N 3.43, and S 7.53.
(b) 4-chloro-4 '-[(4-amino) thiophenyl] the benzophenone hydrochlorides with 12.71 gram porphyrizes slowly are added in 10% the ammoniacal liquor of 400mL, stir after 2 hours suction filtration; Filter cake inserted in 40 ℃ the vacuum drying oven dry 48 hours, 10.61 gram yellow 4-chloro-4 '-[(4-amino) thiophenyl] benzophenone.Mass spectrum, m/z:339.FT-IR(KBr)：3465，3380(NH)，1645
1620，1588(C＝C)，1082(C-S)。
1H NMR (CDCl
3, 400MHz): δ=7.74-7.68 (2H, phenyl ring), 7.62-7.58 (2H, phenyl ring), 7.48-7.42 (2H, phenyl ring), 7.37-7.33 (2H, phenyl ring), 7.11-7.06 (2H, phenyl ring), 6.74-6.71 (2H, phenyl ring), 3.92 (NH
2).
(c) under the nitrogen protection; 12.40 gram 4-chloro-4 '-[(4-amino) thiophenyl] benzophenone and 6mL triethylamine are dissolved in the 30mL dimethyl formamide; other gets the 6mL methacrylic chloride and is dissolved in the 10mL dimethyl formamide and places constant pressure funnel; ice bath slowly is added drop-wise in the there-necked flask following half an hour; stirring at room is poured in the cold water of 300mL after 12 hours; suction filtration; 5% aqueous sodium carbonate washing three times; deionized water wash three times; 50 ℃ of following vacuum-dryings get 14.30 gram yellow 4-chloro-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone after 36 hours; with 1: 3 water and alcohol mixed solution recrystallization, get 12.10 gram pure products after the drying.Fusing point: 105～107 ℃.Mass spectrum, m/z:407.FT-IR(KBr)：3293(NH)，1647
1621
1587(CH＝CH)，1082(C-S)。
1H NMR (CDCl
3, 400MHz): δ=7.74-7.61 (6H, phenyl ring), 7.52-7.43 (4H, phenyl ring), 7.19-7.14 (2H, phenyl ring), 5.83 (1H, CH), 5.60 (1H, CH), 2.08-2.07 (3H, CH
3).
(d) 1.630 gram 4-chloro-, 4 '-[(4-methacryloyl amido) thiophenyl] benzophenone, the dimethylaminoethyl methacrylate of 1.258 grams and 29.00 milligrams Diisopropyl azodicarboxylate are placed long-neck single port flask, add 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 jonquilleous high molecular benzophenone photoinitiator of 2.51 grams in the 150mL methyl alcohol after precipitation, suction filtration, the drying.FT-IR (KBr, cm
-1): 3336 (OH: hydrogen bond, NH), 1731
1682
Free), 1659
Hydrogen bonding), 1652
1588 (Ar), 1081 (C-S).
1H NMR (CDCl
3, 400MHz): δ=7.68-7.10 (12H, phenyl ring), 5.75 (CH
5.44
3.98 (CH
2Of CH
2O), 2.96
2.49
2.21-2.16 (CH
3Of-N-(CH
3)
2), 2.01
1.95-1.59 (CH
3Of
1.48-0.72
Ultraviolet maximum absorption in chloroform is λ
Max: 256nm and 321nm.With the tetrahydrofuran (THF) is eluent, the number-average molecular weight M of polymeric diphenylmethane ketone
nBe 63430, molecular weight distribution width: M
w/ M
n=1.816.Ultimate analysis: S 5.13,4-chloro-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone and dimethylaminoethyl methacrylate mol ratio in polymkeric substance are 1: 1.379.
Embodiment 3:
(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 6.54 gram p-aminophenol, 70mL 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 150mL 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 17.04 gram products.The mixing solutions recrystallization of water, concentrated hydrochloric acid and Virahol gets 14.31 gram 4-[(4-amino) phenoxy group] the benzophenone hydrochloride.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, NH
2), 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: C 70.05, H 5.02, and N 3.91; Actual value: C 71.96, H 4.92, and N 4.30.
(b) with the 4-[(4-amino of 13.02 grams) phenoxy group] benzophenone hydrochloride and 12mL triethylamine be dissolved in the 30mL dimethyl formamide, stirred 10 minutes, slough hydrochloride and get 4-[(4-amino) phenoxy group] benzophenone, because corresponding aminobenzophenone instability is directly carried out next step reaction.
(c) getting the 7mL methacrylic chloride is dissolved in the 10mL dimethyl formamide and places constant pressure funnel, ice bath slowly is added drop-wise in the above-mentioned there-necked flask following half an hour, stirring at room is poured in the cold water of 400mL after 12 hours, suction filtration, 5% aqueous sodium carbonate washing three times, deionized water wash three times, 50 ℃ of following vacuum-dryings get the yellow 4-[(4-methacryloyl amido of 13.60 grams after 36 hours) phenoxy group] benzophenone, product gets 10.60 gram pure products after the recrystallization drying in water/ethanol of 1: 5.Fusing point: 129～131 ℃.Mass spectrum, m/z:357.FT-IR(KBr)：3263(NH)，1646
1624(C＝O
1598(CH＝CH)，1258，1167，1150(C-O)。
1H NMR ([D6] CDCl
3, 400MHz): δ=7.82-7.77 (4H, phenyl ring), 7.63-7.56 (3H, phenyl ring), 7.50-7.46 (2H, phenyl ring), 7.09-7.07 (2H, phenyl ring), 7.02-7.00 (2H, phenyl ring), 2.08-2.07 (3H, CH
3).C
23H
19NO
3(357gmol
-1): ultimate analysis, theoretical value: C 77.29, H 5.36, and N 3.92; Actual value: C 76.79, H 5.58, and N 4.18.
(d) with 1.787 gram 4--[(4-methacryloyl amidos) phenoxy group] benzophenone, the dimethylaminoethyl methacrylates of 1.572 grams and 33.60 milligrams Diisopropyl azodicarboxylate place long-neck single port flask, adds the N of 18mL, dissolve in the dinethylformamide; Be placed in the liquid nitrogen and cool off, vacuumize after 20 minutes and led to nitrogen 5 minutes, circulate after three times, under vacuum state, glass single port flask is sealed with gaslight, place 90 ℃ of oil bath reactions after 72 hours then, product is inserted obtain the khaki high molecular benzophenone photoinitiator of 2.03 grams in the 180mL methyl alcohol after precipitation, suction filtration, the drying.FT-IR (KBr, cm
-1): 3634,3410,3266 (OH: hydrogen bond, NH), 1728
1682 (C=O
Free), 1658
Hydrogen bonding), 1652
1597 (Ar), 1232,1167,1148 (C-O).
1H NMR (CDCl
3, 400MHz): δ=7.77-6.92 (13H, phenyl ring), 5.74
5.41
3.96 (CH
2Of CH
2O), 2.49
2.20-2.15 (CH of
And CH
3Of-N-(CH
3)
2), 2.00
1.98-1.60
1.52-0.73
Ultraviolet maximum absorption in chloroform is λ
Max: 256nm and 290nm.With the tetrahydrofuran (THF) is eluent, the number-average molecular weight M of polymeric diphenylmethane ketone
nBe 26170, molecular weight distribution width: M
w/ M
n=1.343.Ultimate analysis: C 70.18,4-[(4-methacryloyl amido) phenoxy group] benzophenone and dimethylaminoethyl methacrylate mol ratio in polymkeric substance be 1: 1.608.
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
Or
R
4Be selected from hydrogen or methyl; X is selected from oxygen or sulphur; 1＜x＜10000,1＜y＜10000.
2. a kind of high molecular benzophenone photoinitiator as claimed in claim 1 is characterized in that the preparation method is as follows: followingly all represent 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 mixing of using Virahol and water is to its recrystallization; The benzophenone hydrochloride structural formula that wherein contains the aniline structure is as follows:
(b) under magnetic agitation and ice bath, the benzophenone hydrochloride that contains the aniline structure of 1 part of porphyrize is slowly joined in 10～50 part of 10～40% ammonia soln or the aqueous sodium acetate solution, vigorous stirring 0.5～5 hour is sloughed hydrochloric acid, obtains containing the benzophenone of aniline structure;
(c) 1 part of benzophenone that contains the aniline structure is dissolved in 5～50 parts the organic solvent; other gets 0.3～2 part 0.3～2 part acrylate chloride or methacrylic chloride and is dissolved in the organic solvent; nitrogen protection and ice bath slowly drip the mixed solution of acrylate chloride or methacrylic chloride down; after stirring reaction 10～20 hours at room temperature; after reaction solution is poured in the frozen water; the suction filtration precipitation; aqueous sodium carbonate with 5wt% washs three times; obtain polymerisable benzophenone after washing three times, wherein the polymerisable benzophenone structural formula is as follows:
(d) 1 part of polymerisable benzophenone, 0.1～10 part unsaturated tertiary amine and 0.005～0.22 part Diisopropyl azodicarboxylate are placed 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
5Be 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. among the preparation method of a kind of high molecular benzophenone photoinitiator according to claim 2, it 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; (c) organic solvent in is selected from acetone, tetrahydrofuran (THF), butanone, N, dinethylformamide, N,N-dimethylacetamide or N-methyl-2-pyridine alkane ketone; (d) organic solvent in is selected from butanone, 1,4-dioxane, N, dinethylformamide, N,N-dimethylacetamide or N-methyl-2-pyridine alkane ketone.
6. among the preparation method of a kind of high molecular benzophenone photoinitiator according to claim 2, it 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. among the preparation method of a kind of high molecular benzophenone photoinitiator according to claim 2, it 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941952A (en) * | 2010-07-21 | 2011-01-12 | 深圳市有为化学技术有限公司 | Resin monomer skeleton-derivative ketone compound photoinitiator |
| CN102746480A (en) * | 2011-11-10 | 2012-10-24 | 北京化工大学常州先进材料研究院 | Polymerizable macromolecule photoinitiator and preparation method thereof |
| CN104844736A (en) * | 2015-04-30 | 2015-08-19 | 上海交通大学 | Fluorated hydrogen abstracting type macromolecular photoinitiator, and preparation method and application thereof |
| CN106633063A (en) * | 2016-10-21 | 2017-05-10 | 广西师范学院 | Click chemistry-based polyester type ultraviolet absorbent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB8629477D0 (en) * | 1986-12-10 | 1987-01-21 | Shell Int Research | Manufacture of kerosene/gas oils |
| AU2001250391A1 (en) * | 2000-03-16 | 2001-09-24 | Kraton Polymers Research B.V. | Polymeric composition |
| CN1290872C (en) * | 2004-04-22 | 2006-12-20 | 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941952A (en) * | 2010-07-21 | 2011-01-12 | 深圳市有为化学技术有限公司 | Resin monomer skeleton-derivative ketone compound photoinitiator |
| 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 |
| CN102746480A (en) * | 2011-11-10 | 2012-10-24 | 北京化工大学常州先进材料研究院 | Polymerizable macromolecule photoinitiator and preparation method thereof |
| CN102746480B (en) * | 2011-11-10 | 2013-10-23 | 北京化工大学常州先进材料研究院 | Polymerizable macromolecule photoinitiator and preparation method thereof |
| CN104844736A (en) * | 2015-04-30 | 2015-08-19 | 上海交通大学 | Fluorated hydrogen abstracting type macromolecular photoinitiator, and preparation method and application thereof |
| CN106633063A (en) * | 2016-10-21 | 2017-05-10 | 广西师范学院 | Click chemistry-based polyester type ultraviolet absorbent and preparation method thereof |
| CN106633063B (en) * | 2016-10-21 | 2018-08-24 | 广西师范学院 | Polyester-type ultra-violet absorber based on click chemistry and preparation method thereof |
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