CN105732709A - Photo-initiator 2,4,6-trimethylbenzoyldicyclohexyloxyphosphine and preparation method and application thereof - Google Patents
Photo-initiator 2,4,6-trimethylbenzoyldicyclohexyloxyphosphine and preparation method and application thereof Download PDFInfo
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- CN105732709A CN105732709A CN201610149744.9A CN201610149744A CN105732709A CN 105732709 A CN105732709 A CN 105732709A CN 201610149744 A CN201610149744 A CN 201610149744A CN 105732709 A CN105732709 A CN 105732709A
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- Prior art keywords
- trimethylbenzoyl
- preparation
- phosphine oxide
- temperature
- dicyclohexyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003999 initiator Substances 0.000 title abstract description 4
- PLGGZKBJDZQPMU-UHFFFAOYSA-N dicyclohexyloxyphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=C(C(=O)P(OC2CCCCC2)OC2CCCCC2)C(=CC(=C1)C)C PLGGZKBJDZQPMU-UHFFFAOYSA-N 0.000 title abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 38
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 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 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 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 9
- 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
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- HJPHBJYOODQSLK-UHFFFAOYSA-N dicyclohexyl(oxo)phosphanium Chemical compound C1CCCCC1[P+](=O)C1CCCCC1 HJPHBJYOODQSLK-UHFFFAOYSA-N 0.000 claims abstract description 4
- JYFUHKJVYIRMBT-UHFFFAOYSA-N dicyclohexylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C1CCCCC1)C1CCCCC1 JYFUHKJVYIRMBT-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000243 solution 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- WDOKISJWRVNYNS-UHFFFAOYSA-N dicyclohexylphosphanium;chloride Chemical compound Cl.C1CCCCC1PC1CCCCC1 WDOKISJWRVNYNS-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 230000006837 decompression Effects 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- LMZHXYGJIFEDSC-UHFFFAOYSA-N cyclohexylphosphonoylcyclohexane Chemical class C1CCCCC1P(=O)C1CCCCC1 LMZHXYGJIFEDSC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 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 claims 1
- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- 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 1
- 238000000034 method Methods 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000002904 solvent 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
- -1 2,4,6-trimethylbenzoyl dicyclohexyl oxygen phosphorus Chemical compound 0.000 description 8
- 238000000576 coating method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 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
- 239000000178 monomer Substances 0.000 description 2
- 239000008096 xylene Substances 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- LEVJVKGPFAQPOI-UHFFFAOYSA-N phenylmethanone Chemical compound O=[C]C1=CC=CC=C1 LEVJVKGPFAQPOI-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 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
- 239000000376 reactant Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000004383 yellowing Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (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 2,4,6-trimethylbenzoyldicyclohexyloxyphosphine.Under the protection of argon, dicyclohexyl phosphine oxide, metallic sodium and tertiary butanol are reacted in methylbenzene 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 30-35 DEG C to obtain 2,4,6-trimethylbenzoyldicyclohexyloxyphosphine, and liquid phase purity is up to 99.21%.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 2,4,6-trimethylbenzoyl dicyclohexyl oxygen phosphorus
Preparation method.
Technical background
Acylphosphine oxide photoinitiator and D-1173, the alpha-alcohol ketone photoinitiator such as I-184, D-2959 is compared to be had
Following advantage: (1) their maximum absorption wavelength is at 350-380nm, and its spectral absorption extends to visible region；(2)
Acylphosphine oxide can penetrate deeper coating, and this photoinitiator can prepare higher concentration, is applied to consolidating of thick coating
Change；(3) lifetime of excited state of acylphosphine oxide is the shortest, is therefore difficult to be inactivated by other material cancellation, can apply with
Styrene is in the unsaturated polyester Recipe of diluting monomer；(4) acylphosphine oxide decomposition rate is fast, the free base unit weight of generation
Sub-efficiency is high, and laser curing velocity is fast, there is not residue initiator, do not have micromolecular compound to remain in firming body after illumination
In system, so not separating out, there is not Yellowing, desirably preventing the degraded of high polymer in ageing process simultaneously；(5)
Acylphosphine oxide volatility is low.Acylphosphine oxide compounds has above-mentioned many advantages and is widely used in light and draws just
Send out coating (such as powdery paints, optical fiber coatings), imaging printing plates, photo-induced etching agent, UV solidify binding agent, embossment
The aspects such as printed panel, therefore research and develop novel acylphosphine oxide photoinitiator the most necessary.
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 industrialization
The 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide preparation method produced.For solving above-mentioned technical problem, it is an object of the invention to this
Sample realizes: a kind of light trigger 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide, and this compound has a following chemical structural formula:
The present invention is by the following technical solutions:
A: under argon shield, to equipped with adding organic solvent in the reactor of organic solvent, opens stirring, adds metal
Sodium, is warming up to 80-110 DEG C and is incubated half an hour, then be slowly added dropwise dicyclohexyl phosphonium chloride in reactor, control reactant liquor
Temperature 80-110 DEG C, is incubated 3-4h, controls temperature 80-110 DEG C in reactor, then drips the tert-butyl alcohol, drips tertiary fourth
After alcohol, continue reaction 1.0-1.5h at 80-110 DEG C, containing intermediate I, toluene solution, it is not necessary to separate, be directly used in
The preparation of intermediate II；
In this step, dicyclohexyl phosphonium chloride, the tert-butyl alcohol, the ratio of amount of material of metallic sodium are 1:1-4:1-5.Described has
Machine solvent is any one in benzene, toluene or dimethylbenzene, preferably toluene, and the weight of organic solvent is metallic sodium weight 10-20
Times；Described preferable reaction temperature is 100-105 DEG C.
B: the organic solvent containing intermediate I is cooled to 20-30 DEG C, is slowly added dropwise 2,4,6-trimethylbenzenes in reactor
Formyl chloride, after dripping, controls reacting liquid temperature 10-40 DEG C (preferable reaction temperature is 20-30 DEG C), reacts about 2.0-3.0h,
Obtain the organic solution containing intermediate II, it is not necessary to separate, be directly used in 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxides
Preparation；
C: the organic solution temperature containing intermediate II is down to room temperature, then drips the hydrogen peroxide that mass fraction is 30%, drips
After adding, in controlling reactor, temperature is 20-50 DEG C of reaction 1.0-2.0h (preferable reaction temperature is 30-35 DEG C), and reaction completes
After, adding mass fraction in reactor is the sodium bicarbonate aqueous solution of 10%, insulated and stirred 30min at 20-50 DEG C,
Standing, layering, organic facies purified water is washed three times, and control temperature is at 70-80 DEG C, and decompression steams toluene, uses petroleum ether
Pure crystallizing to obtain xenyl four (2,4,6-trimethylbenzoyl) phosphine oxide, reaction equation is as follows:
Beneficial effects of the present invention is as follows:
1, the complete preparation method of 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide is provided.
The benzoyl radical of the 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide photodissociation generation 2, prepared and phosphono free radical
Can trigger monomer polymerization, full entry photopolymerization reaction, this initiator is can apply to pigmented system and deep cure new
Type acylphosphine oxide light trigger.
3,2,4, the 6-trimethylbenzoyl dicyclohexyl phosphine oxides prepared by this preparation method, liquid phase purity is high, up to 99.21%.
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 2,4, the preparation method of 6-trimethylbenzoyl dicyclohexyl phosphine oxide, the method comprises the steps of:
The preparation of intermediate I
Under argon shield, in the reactor, add toluene 100mL, open stirring, add metallic sodium 2.3g (0.1mol) successively,
It is warming up to 100-105 DEG C and is incubated half an hour, in reactor, be slowly added dropwise dicyclohexyl phosphonium chloride 23.3g (0.10mol),
About 2h drips off, and controls reacting liquid temperature 100-105 DEG C, is incubated 3-4h.Control temperature 100-105 DEG C in reactor, slow
Slow dropping tert-butyl alcohol 7.4g (0.1mol), about 0.5-1h drips off, and after dripping the tert-butyl alcohol, continues reaction at 100-105 DEG C
1.0-1.5h, containing intermediate I, toluene solution, it is not necessary to separates, is directly used in the preparation of intermediate II.
The preparation of intermediate II
Xylene solution containing intermediate I is cooled to 20-30 DEG C, in reactor, is slowly added dropwise 2,4,6-trimethylbenzenes
Formyl chloride 18.3g (0.1mol), about 0.5-1h drip off, and control reacting liquid temperature 30-35 DEG C, after being added dropwise to complete, continue anti-
Should about 2.0-3.0h, obtain the xylene solution containing intermediate II, it is not necessary to separate, be directly used in 2,4,6-trimethylbenzene first
The preparation of acyl dicyclohexyl phosphine oxide.
The preparation of 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide
Toluene solution temperature containing intermediate II being down to room temperature, is slowly added dropwise the hydrogen peroxide 34.0g of 30%, about 0.5h drips off,
In controlling reactor, temperature reacts 1.0-2.0h at 30-35 DEG C, after having reacted, adds the bicarbonate of 60g 10% in reactor
Sodium water solution, insulated and stirred 30min at 30-35 DEG C, stand, layering, organic facies purified water is washed three times, controls
Temperature is at 70-80 DEG C, and decompression steams toluene, crystallizes to obtain sterling 2,4,6-trimethylbenzoyl dicyclohexyl oxygen with petroleum ether is pure
Phosphine, yield 79.5%.1HNMR(CDCl3,400MHz)δ:4.21(s,3H,Ar-H),2.46(s,6H,2CH3),2.27(s,
3H,CH3),1.72-1.51(m,10H,CH2),1.45-1.38(m,12H,CH2).
Embodiment 2:
The amount of the tert-butyl alcohol increases to 14.8g (0.2mol), the amount of sodium increases to 4.6g (0.2mol), other same example
One, 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide yields 83.2%.
Embodiment 3:
The amount of the tert-butyl alcohol increases to 15.2g (0.3mol), the amount of sodium increases to 6.9g (0.3mol), other same example
One, 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide yields 88.7%.
Embodiment 4:
The amount of the tert-butyl alcohol increases to 29.6g (0.4mol), the amount of sodium increases to 9.2g (0.4mol), other same example
One, 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide yields 84.3%.
Embodiment 5:
The amount of sodium increases to 11.5g (0.5mol), and other is received with example one, 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxides
Rate 82.4%.
Embodiment 6:
By the light trigger 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide obtained by embodiment, commercially available TPO (2,4,6-
Trimethyl benzoyl diphenyl base phosphine oxide) add acrylic acid epoxy resin sample system with 4% (mass ratio) ratio respectively
(formula is: bisphenol A epoxy acrylate 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 over cleaning, dry copper clad plate, uses 1kw high voltage mercury lamp irradiation so that liquid film polymerizing curable, survey
Determine result as shown in table 1 below.
The table 1 light trigger of the present invention flame retardant effect to acrylic acid epoxy resin
Claims (7)
1. light trigger 2,4, a 6-trimethylbenzoyl dicyclohexyl phosphine oxide, it is characterised in that its chemical structural formula is as follows:
2. light trigger 2,4, a 6-trimethylbenzoyl dicyclohexyl phosphine oxide preparation method, it is characterised in that this preparation method includes
Following steps:
A: under argon shield, to equipped with adding organic solvent in the reactor of organic solvent, opens stirring, adds metallic sodium,
It is warming up to 100-105 DEG C and is incubated half an hour, then in reactor, be slowly added dropwise dicyclohexyl phosphonium chloride, control reacting liquid temperature
100-105 DEG C, it is incubated 3-4h, controls temperature 100-105 DEG C in reactor, then drip the tert-butyl alcohol, after dripping the tert-butyl alcohol,
Reaction 1.0-1.5h is continued, containing intermediate I, toluene solution, it is not necessary to separate, be directly used in intermediate II at 100-105 DEG C
Preparation；
B: the organic solvent containing intermediate I is cooled to 20-30 DEG C, is slowly added dropwise 2,4,6-trimethylbenzene first in reactor
Acyl chlorides, after dripping, controls reacting liquid temperature 10-40 DEG C, reacts about 2.0-3.0h, obtain the organic solution containing intermediate II,
Without separating, it is directly used in 2, the preparation of 4,6-trimethylbenzoyl dicyclohexyl phosphine oxides；
C: the organic solution temperature containing intermediate II is down to room temperature, then drips the hydrogen peroxide that mass fraction is 30%, dropping
After complete, in controlling reactor, temperature reacts 1.0-2.0h at 20-50 DEG C, and after having reacted, adding mass fraction in reactor is 10%
Sodium bicarbonate aqueous solution, insulated and stirred 30min at 20-50 DEG C, stand, layering, organic facies with purified water wash three times,
Control temperature is at 70-80 DEG C, and decompression steams toluene, crystallizes to obtain xenyl four (2,4,6-trimethylbenzoyl) with petroleum ether is pure
Phosphine oxide, reaction equation is as follows:
Light trigger 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide preparation method the most according to claim 2, its feature
Being: in step A, dicyclohexyl phosphonium chloride, the tert-butyl alcohol, the ratio of amount of material of metallic sodium are 1:1-4:1-5.
Light trigger 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide preparation method the most according to claim 1, its feature
Being: in step A, described organic solvent is any one in benzene, toluene or dimethylbenzene, preferably toluene, organic solvent
Weight is metallic sodium weight 10-20 times；Described preferable reaction temperature is 100-105 DEG C.
Light trigger 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide preparation method the most according to claim 1, its feature
Being: in step B, described preferable reaction temperature is 20-30 DEG C.
Light trigger 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide preparation method the most according to claim 1, its feature
Being: in step C, described preferable reaction temperature is 30-35 DEG C.
7. the light trigger 2,4,6-trimethylbenzoyl dicyclohexyl phosphine oxide described in any one stated according to claim 1-6 exists
Application in acrylic acid epoxy resin.
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| CN106083928A (en) * | 2016-08-04 | 2016-11-09 | 长沙优阳机电设备有限公司 | A kind of organic phosphorus compound |
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| 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 |
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| 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 |
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| T. MAJIMA ,ET AL.: ""The photolysis of acylphosphine oxides IV. Investigations with di-n-butyl-2,6-dichlorobenzoyl phosphine oxide and dicyclohexyl-2,4,6-trimethylbenzoyl phosphine oxide"", 《J. PHOTOCHEM. PHOTOBIOL. A: CHEM.》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106083928A (en) * | 2016-08-04 | 2016-11-09 | 长沙优阳机电设备有限公司 | A kind of organic phosphorus compound |
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