CN102924256B - The economy that dihydroxyphenyl propane derives two aromatic ketone compound manufactures novel process and the UV radical UV curing system containing this compound - Google Patents
The economy that dihydroxyphenyl propane derives two aromatic ketone compound manufactures novel process and the UV radical UV curing system containing this compound Download PDFInfo
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- CN102924256B CN102924256B CN201110227640.2A CN201110227640A CN102924256B CN 102924256 B CN102924256 B CN 102924256B CN 201110227640 A CN201110227640 A CN 201110227640A CN 102924256 B CN102924256 B CN 102924256B
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- dihydroxyphenyl propane
- lewis acid
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- -1 aromatic ketone compound Chemical class 0.000 title claims abstract description 19
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000003848 UV Light-Curing Methods 0.000 title description 3
- 239000011968 lewis acid catalyst Substances 0.000 claims description 9
- 230000029936 alkylation Effects 0.000 claims description 7
- 238000005804 alkylation reaction Methods 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- OPTDDWCXQQYKGU-UHFFFAOYSA-N diphenyldichloromethane Chemical compound C=1C=CC=CC=1C(Cl)(Cl)C1=CC=CC=C1 OPTDDWCXQQYKGU-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Chemical group 0.000 claims description 2
- 150000002602 lanthanoids Chemical group 0.000 claims description 2
- 239000011777 magnesium Chemical group 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 7
- 239000005977 Ethylene Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000012965 benzophenone Substances 0.000 description 12
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004577 thatch Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical group CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
- C07C45/43—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis of >CX2 groups, X being halogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to UV optical radiation radical polymerization solidification and polymer-electronics chemical new material technology field, the economy deriving two aromatic ketone compound in particular to dihydroxyphenyl propane shown in general formula I manufactures novel process, and containing this compound containing ethylene linkage unsaturated component UV radical photopolymerization curing system and application thereof.
Description
[technical field]
The present invention relates to UV optical radiation radical polymerization solidification and polymer-electronics chemical new material technology field, the economy deriving two aromatic ketone compound in particular to a class dihydroxyphenyl propane manufactures novel process, and containing this compound containing ethylene linkage unsaturated component UV radical photopolymerization curing system and application thereof.
[background technology]
The aromatic ketone compound being parent nucleus with benzophenone (BP) is the Functional Chemicals with essential industry using value, such as they can be used as hydrogen-abstraction or the cracking type photoinitiator of UV radical UV curing system, or can be used as the key molecule building block of polyketone macromolecular material.BP industrial output is every year up to tens thousand of ton, but BP compound easily distils and pollutes, on the other hand, the such as UV photocuring system in a lot of application scenario, BP photodestruciton product easily produces Yellowing and high volatility and cause unpleasant remaining smell, and this is not by be liked or flagrant in application.Because BP industry supply has the nominal price of competitive power, find and the BP surrogate of above-mentioned undesirable property effectively can be avoided in practical application, to meet with cost bottleneck and become abnormal difficult.
Patent application CN101941952A discloses two aromatic ketone compound that the bisphenol A skeleton shown in the following general formula I of a class derives, wherein R
1, R
2, R
3, or R
4the straight or branched of to be carbonatoms be independently of one another 1-24, containing or alkyl not containing ring system structure, this alkyl can for the N being no more than 4, S, or O atom discontinuity is interrupted; Or R
1, R
2, R
3, or R
4independent of one another is substituted or unsubstituted phenyl.In view of in dihydroxyphenyl propane molecular structure containing 2 reactive phenyl ring and the cheap price of dihydroxyphenyl propane self, this compounds is very potential BP surrogate.But bisphenol A skeleton is (such as anhydrous AlCl under strong lewis acid condition
3) easy cracked decomposition, therefore traditional application Fu Rui get very widely-Kerafyrm thatch (Friedel-Crafts) acylation reaction cannot carry out or low yield on this substrate, and the report about this type of reaction in document is very limited.Therefore, the lead industrial manufacturing process with economic competitiveness of this class formation of exploration discovery has great using value.
[summary of the invention]
This application has now unexpectedly been found that, although bisphenol A skeleton does not carry out the economic possibility of efficient Fu Rui get-Kerafyrm thatch acylations process, (this type of reaction usually must use super superstoichiometric strong lewis acid such as anhydrous AlCl
3and cause skeletal disintegration), but bisphenol A skeleton can replace fragrant compound (ArCCl with trichloromethyl under the acid of catalytic amount Louis promotes
3) carry out efficient Fu Rui get-Crafts alkylation and prepare compound shown in general formula I.This manufacturing process raw material is cheap and easy to get, mild condition, and lewis acid catalyst consumption is few, and product yield is high, therefore has the Financial cost competitive power of advantage.
Shown in following reaction expression, to facilitate the R be easy to get
1dihydroxyphenyl propane precursor A and CCl of group end capping
3the fragrant compound B that group replaces carries out Fu Rui get-Crafts alkylation and obtains duplex dichloro diphenyl methane type key intermediate C under Lewis acid catalyst.C in-situ hydrolysis under acid type or alkaline condition can obtain target product I.Or, similar, from the initial elder generation of A and CCl
4next carry out Fu Rui get-Crafts alkylation to obtain dihydroxyphenyl propane and derive trichloromethyl and replace fragrant compound D, D and again carry out Fu Rui get-Crafts alkylation with aromatic ring E and obtain same advanced intermediate C, and then be hydrolyzed and obtain target product.Suitable lewis acid catalyst is form is MCl
nmetal halide or M (OTf)
nmetal trifluoroacetate sulfonate compound; Preferred M is aluminium, zinc, iron, magnesium, or lanthanide series rare-earth elements.More preferably AlCl
3.Lewis acid catalyst addition is selected between 1-60% equivalent molar ratio, preferred 5-30%.
This application discloses the UV photocuring system and application purpose thereof that contain compound of Formula I simultaneously.It is polymerisable containing the unsaturated component of ethylene linkage that suitable this kind of UV photocuring system comprises at least one, and to comprise at least one compound of Formula I be one of light trigger or light trigger component.To contain the every 100 parts of Weight computation of ethylene linkage unsaturated component total amount in system, the suitable amounts of compound of Formula I is 0.05-15 weight part, preferred 0.5-10 weight part.
This application disclose suitable UV photocuring system comprise polymerisable containing the unsaturated component of ethylene linkage be the compound or mixture that can be crosslinked by the Raolical polymerizable of this double bond, this can be monomer containing the unsaturated component of ethylene linkage, oligopolymer or prepolymer, or their mixture or multipolymer.The monomer of suitable radical polymerization is such as containing ethylene linkage polymerisable monomer, includes but not limited to (methyl) acrylate, propenal, alkene, conjugated diolefin, vinylbenzene, maleic anhydride, fumaric acid anhydride, vinyl-acetic ester, vinyl pyrrolidone, vinyl imidazole, (methyl) vinylformic acid, (methyl) acrylic acid derivative is (methyl) acrylamide such as, vinyl halide, vinylidene halide etc.Suitable prepolymer and oligopolymer include but not limited to (methyl) acrylic copolymer of (methyl) acryloyl functional group, urethane manthanoate (methyl) acrylate, polyester (methyl) acrylate, unsaturated polyester, polyethers (methyl) acrylate, siloxanes (methyl) acrylate, epoxy resin (methyl) acrylate etc.Its suitable number-average molecular weight can such as change between 500 to 10000, preferred 500-5000 span.
[embodiment]
Below in conjunction with specific embodiment further illustrate this application described in manufacture method and application system.
Embodiment one:
At room temperature by 22 grams of PhCCl
3be mixed in 300 milliliters of dry methylene dichloride with 1.4 grams of aluminum trichloride (anhydrous)s, add 10 grams of dihydroxyphenyl propane dme under fully stirring in batches, observe reaction system colour-change immediately, finish and continue reaction 2 hours.Reaction solution is poured in 500 ml waters, static layering after the medicine half an hour of shaking, and organic phase washed with water and saturated aqueous common salt respectively wash once, dried over mgso, filters, after filtrate is concentrated resistates in ethanol recrystallization obtain faint yellow target product 17 grams, yield 94%.
Nuclear magnetic resonance data:
1h-NMR (CDCl
3, 300MHz): 7.79-7.76 (m, 4H), 7.49-7.25 (m, 10H), 6.88 (d, 2H, J=8.7Hz), 3.68 (s, 6H), 1.67ppm (s, 3H).C/H ultimate analysis: theoretical value: C, 80.15%; H, 6.08%; Measured value: C, 80.22%; H, 6.13%.
Embodiment two:
The first step: 1, 3, the synthesis of 5-trimethylammonium-2-trichloromethyl-benzene: mix 1.82 liters of tetracol phenixin and 2.5 kilograms of aluminum trichloride (anhydrous)s under room temperature in a reaction flask, in one hour, 1.5 kilograms of sym-trimethylbenzene (namely 1 are dripped under effective mechanical stirring, 3, 5-Three methyl Benzene), reaction system presents scarlet immediately and discharges HCl gas (noting absorbing acid gas), finish and continue stirring 2 hours at 45 degrees Celsius, reaction solution pours in the acid of equal-volume 1N cryosel slowly, be separated organic phase, with equal-volume dichloromethane extraction 2 times, merge organic phase, anhydrous sodium sulfate drying, filter, concentrated, the underpressure distillation of oily raffinate obtains colourless 1, 3, 5-trimethylammonium-2-trichloromethyl-benzene liquid, yield about 95%.
Nuclear magnetic resonance data:
1h-NMR (CDCl
3, 500MHz): 6.88 (s, 2H), 2.74 (s, 6H), 2.25ppm (s, 3H);
13c-NMR (CDCl
3, 125MHz): 139.1,138.1,136.7,132.5,98.3,25.6,20.5ppm.
Second step: reference and the similar operation steps of embodiment one; react in stirring at room temperature back flow reaction 2 hours again after 1 hour; from 10 grams of dihydroxyphenyl propane dme and 27.8 gram 1; 3; 5-trimethylammonium-2-trichloromethyl-benzene obtains 16.5 grams of target products (77% yield) under 2.2 grams of Catalyzed by Anhydrous Aluminium Chloride, obtains 2.8 grams of monoacylated product simultaneously.
C/H ultimate analysis: theoretical value: C, 80.99%; H, 7.35%; Measured value: C, 81.11%; H, 7.51%.
Embodiment three:
With reference to the operation of embodiment two the first step, in tetracol phenixin, obtain 11.8 grams (83% yield) two trichloromethyl dihydroxyphenyl propane dibutyl ether from 8.4 grams of dihydroxyphenyl propane dibutyl ethers and 1.1 grams of aluminum trichloride (anhydrous)s.This compound has then obtained 10.7 grams of target products, yield 86% with the methyl-phenoxide of the operation of embodiment one and 11.1 grams under 0.8 gram of Catalyzed by Anhydrous Aluminium Chloride.
C/H ultimate analysis: theoretical value: C, 76.95%; H, 7.29%; Measured value: C, 77.07%; H, 7.41%.
Same legal system is operated for obtaining following pair of aromatic ketone compound according to embodiment one:
Embodiment four embodiment five embodiment six embodiment seven
96% yield 94% yield 81% yield 87% yield
UV photocuring system containing above-claimed cpd is tested: paper polish ink
Each component (sum 100 parts) is measured in the preparation of UV light-curable ink system by weight percentage:
14 parts: epoxy acrylate;
14 parts: urethane acrylate;
49.5 parts: Viscoat 295;
10 parts: hexanediyl ester;
7 parts: embodiment light trigger;
4 parts: methyldiethanolamine aided initiating;
0.5 part: wetting agent;
1.0 parts: wax.
Take BP as reference example compound under equal conditions, the remaining Odor Evaluations of cured film is divided into 1 (odorlessness) to 3 (smell is strong) Three Estate; The xanthochromia evaluation of cured film is also divided into 1 (without xanthochromia) to 3 (xanthochromia is obvious) Three Estate.Light trigger is active in increase continuously the speed of sample by this device under certain irradiator condition till solidification occurs not exclusively, demarcates active with its top speed.
Test result is as shown in the table:
| Light trigger | Remaining oder levels | Xanthochromia grade | Curing speed (meter per second) |
| Reference example BP | 3 | 3 | 40 |
| Embodiment one | 2 | 1 | 40 |
| Embodiment two | 1 | 1 | 60 |
| Embodiment three | 1 | 1 | 70 |
| Embodiment four | 2 | 1 | 40 |
| Embodiment five | 1 | 1 | 40 |
| Embodiment six | 1 | 1 | 60 |
| Embodiment seven | 1 | 1 | 50 |
These results show, two aromatic ketone compound that the bisphenol A skeleton shown in general formula I derives are effective photoinitiator compound.UV radiation polymerization of radicals curing system containing this compounds presents good low remaining smell, yellowing resistance with under equal conditions compared with the system of conventional benzophenone BP, and higher or suitable space charge force.Such compound synthesis technology is easy, with low cost, and over-all properties is superior, is desirable BP surrogate.
Claims (3)
1. the economy manufacture method of two aromatic ketone compound that the bisphenol A skeleton shown in formula I derives,
It is characterized in that, this technique is to facilitate the R be easy to get
1dihydroxyphenyl propane precursor A and CCl of group end capping
3the fragrant compound B that group replaces carries out not Rui get – Crafts alkylation and obtains duplex dichloro diphenyl methane type key intermediate C under Lewis acid catalyst, and C under acid or alkaline conditions in-situ hydrolysis can obtain target product I; Or, from the initial elder generation of A and CCl
4next carry out not Rui get – Crafts alkylation to obtain dihydroxyphenyl propane and derive trichloromethyl and replace fragrant compound D, D and again carry out not Rui get – Crafts alkylation with aromatic ring E and obtain same advanced intermediate C, and then be hydrolyzed and obtain target product; Suitable lewis acid catalyst is form is MCl
nmetal halide or M (OTf)
nmetal trifluoroacetate sulfonate compound; M is aluminium, zinc, iron, magnesium, or lanthanide series rare-earth elements; Lewis acid catalyst addition is selected between 1-60% equivalent molar ratio; Wherein R
1, R
2, R
3or R
4the straight or branched of to be carbonatoms be independently of one another 1-24, containing or alkyl not containing ring system structure, or this alkyl is that N, S or O atom discontinuity being no more than 4 is interrupted; Or R
1, R
2, R
3or R
4independent of one another is substituted or unsubstituted phenyl;
2. manufacture method according to claim 1, is characterized in that, described lewis acid catalyst is AlCl
3.
3. manufacture method according to claim 1, is characterized in that, described lewis acid catalyst addition is selected between 5-30% equivalent molar ratio.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110227640.2A CN102924256B (en) | 2011-08-09 | 2011-08-09 | The economy that dihydroxyphenyl propane derives two aromatic ketone compound manufactures novel process and the UV radical UV curing system containing this compound |
| PCT/CN2012/079419 WO2013020467A1 (en) | 2011-08-09 | 2012-07-31 | Method for preparing bis-aromatic ketone derived from bisphenol a derivative, and uv free radical light curing system having the compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110227640.2A CN102924256B (en) | 2011-08-09 | 2011-08-09 | The economy that dihydroxyphenyl propane derives two aromatic ketone compound manufactures novel process and the UV radical UV curing system containing this compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102924256A CN102924256A (en) | 2013-02-13 |
| CN102924256B true CN102924256B (en) | 2016-04-27 |
Family
ID=47639219
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| 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 |
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| Synthesis and properties of self-protecting polyarylates;V.V.Korshak et al;《Journal of polymer science: part A-1》;19691231;第7卷;157-172 * |
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