CN105732710A - Preparation method and application of photo-initiator diphenyl tetra(2,4,6-trimethylbenzoyl)oxyphosphine - Google Patents
Preparation method and application of photo-initiator diphenyl tetra(2,4,6-trimethylbenzoyl)oxyphosphine Download PDFInfo
- Publication number
- CN105732710A CN105732710A CN201610149797.0A CN201610149797A CN105732710A CN 105732710 A CN105732710 A CN 105732710A CN 201610149797 A CN201610149797 A CN 201610149797A CN 105732710 A CN105732710 A CN 105732710A
- Authority
- CN
- China
- Prior art keywords
- trimethylbenzoyl
- xenyl
- preparation
- phosphine oxide
- light trigger
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004305 biphenyl Substances 0.000 title abstract description 5
- 235000010290 biphenyl Nutrition 0.000 title abstract description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000003999 initiator Substances 0.000 title abstract description 3
- 125000006267 biphenyl group Chemical group 0.000 title abstract 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 25
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XHIKSLHIZYVEQI-UHFFFAOYSA-N CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C Chemical compound CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C XHIKSLHIZYVEQI-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 12
- 239000008096 xylene Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- ZFJMTDFOGDGPTF-UHFFFAOYSA-N phosphanium;chloride;hydrochloride Chemical compound P.Cl.Cl ZFJMTDFOGDGPTF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 208000035126 Facies Diseases 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- UKRQMDIFLKHCRO-UHFFFAOYSA-N 2,4,6-trimethylbenzoyl chloride Chemical compound CC1=CC(C)=C(C(Cl)=O)C(C)=C1 UKRQMDIFLKHCRO-UHFFFAOYSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- -1 Phosphine compound Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 0 *=Pc(cc1)ccc1-c(cc1)ccc1P Chemical compound *=Pc(cc1)ccc1-c(cc1)ccc1P 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- ORYMFWDSDBCSDX-UHFFFAOYSA-N Cc1cc(C)c(C(P(C(c2c(C)cc(C)cc2C)=O)c(cc2)ccc2-c(cc2)ccc2P(C(c2c(C)cc(C)cc2C)=O)C(c2c(C)cc(C)cc2C)=O)=O)c(C)c1 Chemical compound Cc1cc(C)c(C(P(C(c2c(C)cc(C)cc2C)=O)c(cc2)ccc2-c(cc2)ccc2P(C(c2c(C)cc(C)cc2C)=O)C(c2c(C)cc(C)cc2C)=O)=O)c(C)c1 ORYMFWDSDBCSDX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LEVJVKGPFAQPOI-UHFFFAOYSA-N phenylmethanone Chemical compound O=[C]C1=CC=CC=C1 LEVJVKGPFAQPOI-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention relates to a preparation method of a photo-initiator diphenyl tetra(2,4,6-trimethylbenzoyl)oxyphosphine.Under the protection of argon, 4,4/-diphenyl bis(phosphide dichloride), metallic sodium and tertiary butanol are reacted in xylol solution to obtain intermediate I; the intermediate I is reacted with 2,4,6-trimethylbenzoyl chloride to obtain intermediate II; the intermediate II is reacted with hydrogen peroxide at 40-45 DEG C to obtain diphenyl tetra(2,4,6-trimethylbenzoyl)oxyphosphine, and liquid phase purity is up to 99.06%.The preparation method is simple to perform and advanced, a solvent is recyclable, and the method is easy for industrial production.
Description
Technical field
The invention belongs to light trigger field, be specifically related to a kind of light trigger xenyl four (2,4,6-trimethylbenzoyl)
The preparation method of phosphine oxide.
Technical background
Photocuring technology is acted on photosensitive light trigger by light ray so that it is a series of optical physics, light occur
Chemical reaction, generates active substance, thus causes liquid-state oligomers to realize instaneous polymerization, crosslinking, the most at last resin of liquid
It is converted into the macromolecular material of solid-state.Photocuring technology has the advantage that (1) is in room temperature compared with traditional heat cure
Under quick and complete solidification, solidify coating materialization excellent performance;(2) need not extra drying plant, produce continuously, greatly
Amplitude improves production efficiency;(3) ultraviolet light polymerization does not use organic solvent, greatly reduces what organic solvent volatilization caused
Environmental pollution.Along with the increasingly stringent of environmental regulation, UV-curing technology is the most increasingly subject to people's attention.Although should
Various in style for the light trigger of ultraviolet light polymerization, such as alpha-alcohol ketone photoinitiator D-1173, I-184, D-2959
Deng, but these light triggers are dfficult to apply in the coating containing pigment mostly, because pigment can absorb ultraviolet light, affect light and draw
The light sending out agent absorbs, and pigment also can scatter ultraviolet light, makes ultraviolet light be difficult to arrive the bottom of coating, makes the system containing pigment
Being difficult to solidify, especially bottom is more difficult to solidification, thus causes and solidify incomplete and relatively low curing rate.For a long time, have
Color pigment is always a difficult problem at the cure system of Uv and visible light.So in the past few years, people are devoted to exploitation
The novel photoinitiator of red-shifted absorption spectrum, such as alpha-aminoacetophenone and thioxanthone etc. can be produced there is high reaction activity
Light trigger start application, but there is the most serious yellowing, aging and be not suitable for being applied to the oil of white and light color in them
In paint.
Acylphosphine oxide photoinitiator is owing to having the absorbing wavelength of its uniqueness, and its absorption region may extend to
Visible region, can absorb enough light in the presence of Chinese white and provide and cause performance efficiently, and acyl group oxidation
Phosphine compound carries out aroyl-phosphono chromophore during Photoinitiated reactions and is destroyed, and makes incident illumination penetrate trigger area consumingly
Territory enters coating deep layer, makes thick-layer be solidified into possibility.Do not have Yellowing after solidification, thus be coated with at white furniture
There is preferably application in material and relatively thick coating field, so it is the most necessary to research and develop novel acylphosphine oxide photoinitiator.
Summary of the invention
The task of the present invention is to provide that a kind of technique is simple, yield is high, low cost, pollution are little, good product quality, be suitable for
Four (2,4,6-trimethylbenzoyl) phosphine oxide preparation method of industrialized production.For solving above-mentioned technical problem, the present invention adopts
Use following technical scheme:
A: under argon shield, to equipped with adding metallic sodium in the reactor of organic solvent, is incubated after being warming up to 100-120 DEG C
20-40min, then drip 4, the double dichloride phosphine of 4 '-xenyl, after dripping off, insulation reaction 4-5h at 100-120 DEG C, then
At 100-120 DEG C, drip the tert-butyl alcohol, react 1.5-2h after dripping off, obtain the xylene solution containing intermediate I, reaction
Equation is as follows:
In this step, 4, the double dichloride phosphine of 4 '-xenyl, the tert-butyl alcohol, the ratio of amount of material of metallic sodium are 1:4-6:7-10.
In this step, described organic solvent is any one (more preferably dimethylbenzene) in benzene, toluene or dimethylbenzene,
The weight of organic solvent is 12-20 times of metallic sodium weight;The reaction temperature of this step is 105-110 DEG C.
B: the xylene solution containing intermediate compound I is cooled to 35-40 DEG C, and drips 2,4,6-tri-methyl chlorides, drip
Controlling (described reaction temperature is preferably 35-40 DEG C) at reaction temperature is 50-60 DEG C after adding, insulation reaction 1.5-2 is little
Time, obtaining the xylene solution containing intermediate II, reaction equation is as follows:
C: the xylene solution containing intermediate II is cooled to room temperature, and drips hydrogen peroxide, in 30~60 DEG C of temperature after dripping
React 1-3 hour (described reaction temperature is preferably 40-50 DEG C) under the conditions of degree, reacted in backward reactor and added
Sodium bicarbonate aqueous solution, insulated and stirred 30min at 45~55 DEG C, stand, layering, organic facies purified water washs three
Secondary, control temperature is at 90-100 DEG C, and decompression steams dimethylbenzene, crystallizes to obtain sterling xenyl four (2,4,6-front threes with normal heptane is pure
Base benzoyl) phosphine oxide, reaction equation is as follows:
Beneficial effects of the present invention is as follows:
1, the complete preparation method of xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide is provided.
2, xenyl four (2,4,6-trimethylbenzoyl) the phosphine oxide decomposition rate of preparation is fast, the free radical quantum effect of generation
Rate is high, and laser curing velocity is fast.Benzoyl radical and phosphono free radical that photodissociation generates can be polymerized by trigger monomer, all join
Adding photopolymerization reaction, both without residue initiator after illumination, remaining in curing system with or without micromolecular compound, so not analysing
Go out, xanthochromia does not occur, also prevent high polymer in ageing process from degrading.
3, xenyl four (2,4, the 6-trimethylbenzoyl) phosphine oxide prepared by this preparation method, liquid phase purity is high, up to
99.06%.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the scope of protection of present invention is not limited to implement
The scope of example statement.
Embodiment 1:
A kind of preparation method of xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide, the method comprises the steps of:
The preparation of intermediate I
Under argon shield, in the reactor, add dimethylbenzene 300mL, control moisture≤0.03%, after moisture is qualified, open
Open stirring, add metallic sodium 16.1g (0.7mol) successively, be warming up to 105-110 DEG C and be incubated half an hour, in reactor slowly
Dropping 4,4/Double dichloride phosphine 35.4g (0.10mol) of-xenyl, about 4h drips off, and controls reacting liquid temperature 105-110 DEG C,
Insulation 4-5h.Control temperature 105-110 DEG C in reactor, be slowly added dropwise tert-butyl alcohol 29.6g (0.4mol), about 0.5-1h
Drip off, after dripping the tert-butyl alcohol, continue reaction 1.5-2h at 105-110 DEG C, containing the xylene solution of intermediate I, nothing
Need to separate, be directly used in the preparation of intermediate II.
The preparation of intermediate II
Xylene solution containing intermediate I is cooled to 35-40 DEG C, in reactor, is slowly added dropwise 2,4,6-trimethylbenzenes
Formyl chloride 73.1g (0.4mol), about 0.5-1h drip off, and control reacting liquid temperature 50-60 DEG C, after being added dropwise to complete, continue anti-
Should about 1.5-2h, obtain the xylene solution containing intermediate II, it is not necessary to separate, be directly used in xenyl four (2,4,6-front threes
Base benzoyl) preparation of phosphine oxide.
The preparation of xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide
Xylene solution temperature containing intermediate II is down to room temperature, is slowly added dropwise 30% hydrogen peroxide 113.3g, control anti-
In answering still, temperature reacts 2-3h at 45-50 DEG C, after having reacted, adds the sodium bicarbonate aqueous solution of 200g 10% in reactor,
Insulated and stirred 30min at 45~55 DEG C, stands, layering, and organic facies purified water is washed three times, controls temperature and exists
90-100 DEG C, decompression steams dimethylbenzene, crystallizes to obtain sterling xenyl four (2,4,6-trimethylbenzoyl) oxidation with normal heptane is pure
Phosphine, yield 80.2%.1H NMR(CDCl3,400MHz)δ:7.82-7.76(m,4H,Ar-H),7.45-7.40(m,4H,
Ar-H),6.91(s,8H,Ar-H),2.45(s,24H,2CH3),2.29(s,12H,2CH3).
Embodiment 2:
The amount of the tert-butyl alcohol increases to 37.0g (0.5mol), the amount of sodium increases to 18.4g (0.8mol), other same example
One, xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide yield 85.6%.
Embodiment 3:
The amount of the tert-butyl alcohol increases to 44.4g (0.6mol), the amount of sodium increases to 20.7g (0.9mol), other same example
One, xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide yield 86.3%.
Embodiment 4:
The amount of sodium increases to 23.0g (1.0mol), and other is with example one, xenyl four (2,4,6-trimethylbenzoyl)
Phosphine oxide yield 84.1%.
Embodiment 5:
By light trigger xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide obtained by embodiment 1, commercially available TPO
(2,4,6-trimethyl benzoyl diphenyl base phosphine oxide), commercially available light trigger phenyl are double (2,4,6-trimethylbenzoyl)
Phosphine oxide adds acrylic acid epoxy resin sample system with 4% (mass ratio) ratio respectively, and (formula is: bisphenol-A epoxy third
Olefin(e) acid ester 30%;Amino acrylates 8%;Propoxylated glycerol triacrylate 30%;Hexanediyl ester 24%;
Silicone acrylates 0.5%;Ethoxylated pentaerythritol tetraacrylate 3.5%), it is uniformly coated on through over cleaning, does
On dry copper clad plate, using 1kw high voltage mercury lamp irradiation so that liquid film polymerizing curable, measurement result is as shown in table 1 below.
The light trigger that table 1 embodiment of the present invention 1 the prepares flame retardant effect to acrylic acid epoxy resin
Claims (7)
1. the preparation method of light trigger xenyl four (2,4, a 6-trimethylbenzoyl) phosphine oxide, it is characterised in that this is prepared
Method comprises the following steps:
A: under argon shield, to equipped with adding metallic sodium in the reactor of organic solvent, is incubated after being warming up to 100-120 DEG C
20-40min, then drip 4, the double dichloride phosphine of 4 '-xenyl, after dripping off, insulation reaction 4-5h at 100-120 DEG C, then
Drip the tert-butyl alcohol at 100-120 DEG C, react 1.5-2h after dripping off, obtain the xylene solution containing intermediate I, reaction equation
As follows:
B: the xylene solution containing intermediate compound I is cooled to 35-40 DEG C, and drips 2,4,6-tri-methyl chlorides, drip
At rear control reaction temperature is 50-60 DEG C, insulation reaction 1.5-2 hour, obtain the xylene solution containing intermediate II, reaction side
Formula is as follows:
C: the xylene solution containing intermediate II is cooled to room temperature, and drips hydrogen peroxide, in 30~60 DEG C of temperature strip after dripping
React 1-3 hour under part, reacted addition sodium bicarbonate aqueous solution, insulated and stirred at 45~55 DEG C in backward reactor
30min, stands, layering, and organic facies purified water is washed three times, and control temperature is at 90-100 DEG C, and decompression steams dimethylbenzene, uses
Normal heptane is pure crystallizes to obtain sterling xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide, and reaction equation is as follows:
The preparation method of light trigger xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide the most according to claim 1,
It is characterized in that: in step A, 4, the double dichloride phosphine of 4 '-xenyl, the tert-butyl alcohol, the ratio of amount of material of metallic sodium are 1:4-6:7-10.
The preparation method of light trigger xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide the most according to claim 1,
It is characterized in that: in step A, described organic solvent is any one in benzene, toluene or dimethylbenzene, the weight of organic solvent
For metallic sodium weight 12-20 times;The reaction temperature of this step is 105-110 DEG C.
The preparation method of light trigger xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide the most according to claim 1,
It is characterized in that: in step A, described organic solvent is dimethylbenzene.
The preparation method of light trigger xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide the most according to claim 1,
It is characterized in that: in step B, described reaction temperature controls as 35-40 DEG C.
The preparation side of a kind of light trigger xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide the most according to claim 1
Method, it is characterised in that: in step C, described reaction temperature controls as 40-50 DEG C.
7. light trigger xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide described in any one described in claim 1-6
Application in acrylic acid epoxy resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610149797.0A CN105732710A (en) | 2016-03-16 | 2016-03-16 | Preparation method and application of photo-initiator diphenyl tetra(2,4,6-trimethylbenzoyl)oxyphosphine |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610149797.0A CN105732710A (en) | 2016-03-16 | 2016-03-16 | Preparation method and application of photo-initiator diphenyl tetra(2,4,6-trimethylbenzoyl)oxyphosphine |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105732710A true CN105732710A (en) | 2016-07-06 |
Family
ID=56251718
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610149797.0A Pending CN105732710A (en) | 2016-03-16 | 2016-03-16 | Preparation method and application of photo-initiator diphenyl tetra(2,4,6-trimethylbenzoyl)oxyphosphine |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105732710A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114700108A (en) * | 2022-04-07 | 2022-07-05 | 中建安装集团有限公司 | Method for removing carbon deposition in inactivated propylene epoxy titanium silicalite molecular sieve catalyst |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1328564A (en) * | 1998-11-30 | 2001-12-26 | 西巴特殊化学品控股有限公司 | Process for preparing acylphosphines and derivatives |
-
2016
- 2016-03-16 CN CN201610149797.0A patent/CN105732710A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1328564A (en) * | 1998-11-30 | 2001-12-26 | 西巴特殊化学品控股有限公司 | Process for preparing acylphosphines and derivatives |
Non-Patent Citations (2)
Title |
---|
刘娜: ""双(2,4,6-三甲基苯甲酰基)苯基氧化膦的合成及其光引发性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
杨果: ""紫外光固化有色体系光引发剂的合成——酰基氧化膦光引发剂的合成"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114700108A (en) * | 2022-04-07 | 2022-07-05 | 中建安装集团有限公司 | Method for removing carbon deposition in inactivated propylene epoxy titanium silicalite molecular sieve catalyst |
CN114700108B (en) * | 2022-04-07 | 2023-12-01 | 中建安装集团有限公司 | Method for removing carbon deposition in deactivated propylene titanium oxide silicon molecular sieve catalyst |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102141769B1 (en) | Hybrid photosensitive resin and its manufacturing method | |
WO2018049976A1 (en) | Fluorene photoinitiator, preparation method therefor, photocurable composition having same, and use of same in photocuring field | |
EP1724291A1 (en) | Curable composition and process for producing cured fluorochemical | |
JP7387267B2 (en) | Endoperoxide compound with polycyclic aromatic skeleton | |
Cramer et al. | Thiol‐ene and Thiol‐yne Chemistry in Ideal Network Synthesis | |
CN114133877B (en) | Photo-curing composition glue containing large conjugated aromatic ring acrylic acid compound monomer, and use method and application thereof | |
CN105153329B (en) | Acetophenone type photoinitiators using fluorene as conjugated structure as well as preparation method and application of acetophenone type photoinitiators | |
CN109232668A (en) | A kind of ferrocene derivatives and combinations thereof can be used as photoredox catalyst in photopolymerization | |
CN110950768B (en) | Photobleachable visible light initiator and preparation method and application thereof | |
CN105732710A (en) | Preparation method and application of photo-initiator diphenyl tetra(2,4,6-trimethylbenzoyl)oxyphosphine | |
KR20190085078A (en) | A light-emitting resin composition for wavelength conversion, a method of producing the same, | |
CN104892798B (en) | A kind of new thioxanthones photoinitiator and in the application of UV-LED photocuring | |
CN106117394A (en) | A kind of phosphonic acid ester light trigger containing fluorocarbon chain and preparation method thereof | |
CN102863559B (en) | Photoinitiator for UV (ultraviolet)-LED curing | |
KR20000071215A (en) | (Co)polymers by photopolymerization | |
CN104151358A (en) | Preparation method for photoinitiator bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide | |
CN106365974B (en) | New hydroxyl ketone-type photoinitiators and its preparation and application | |
WO2006082845A1 (en) | Curable composition and optical member obtained by curing same | |
CN102863403A (en) | Benzophenone photoinitiator containing amine serving as promoter and preparation method thereof | |
CN105541913A (en) | Preparation method of 2,4,6-trimethylbenzoyldiphenyl phosphine oxide | |
CN112939779B (en) | Terephthaloyl formate type photoinitiator suitable for UV-LED deep photopolymerization and preparation method thereof | |
Monecke et al. | Thermally and photochemically induced cationic polymerization using 2-methyl-1-(2-phenyl-2-propenyloxy)-pyridinium salts as initiators | |
CN105732709A (en) | Photo-initiator 2,4,6-trimethylbenzoyldicyclohexyloxyphosphine and preparation method and application thereof | |
CN110092851B (en) | LED sensitive hybrid photoinitiator and preparation method and application thereof | |
CN108503556B (en) | Carbonyl compound with biphenyl diphenylamine as conjugated main structure and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160706 |