CN104592298B - A kind of acylphosphanes efficiency light initiator and preparation method thereof - Google Patents
A kind of acylphosphanes efficiency light initiator and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003999 initiator Substances 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 15
- -1 phosphine compound Chemical class 0.000 claims abstract description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 125000001624 naphthyl group Chemical group 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 12
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 9
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 9
- 229910000497 Amalgam Inorganic materials 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000004414 alkyl thio group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 4
- NEMFQSKAPLGFIP-UHFFFAOYSA-N magnesiosodium Chemical compound [Na].[Mg] NEMFQSKAPLGFIP-UHFFFAOYSA-N 0.000 claims description 4
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 claims description 4
- 229910001023 sodium amalgam Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- UCTTYTFENYGAPP-UHFFFAOYSA-N 1,2,3,4-tetraphenylnaphthalene Chemical compound C1=CC=CC=C1C(C(=C1C=CC=CC1=C1C=2C=CC=CC=2)C=2C=CC=CC=2)=C1C1=CC=CC=C1 UCTTYTFENYGAPP-UHFFFAOYSA-N 0.000 claims description 2
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 claims description 2
- 229940105324 1,2-naphthoquinone Drugs 0.000 claims description 2
- 229910000567 Amalgam (chemistry) Inorganic materials 0.000 claims description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical group C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229910000861 Mg alloy Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical group CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NYRAVIYBIHCEGB-UHFFFAOYSA-N [K].[Ca] Chemical compound [K].[Ca] NYRAVIYBIHCEGB-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Abstract
The invention discloses a kind of acylphosphanes efficiency light initiator and preparation method thereof.The method first in a solvent in the presence of a catalyst, the alloy reaction with organophosphor halogenide for raw material Yu active metal；Then generation hydrogenation phosphine compound is reacted with the aliphatic alcohol compounds containing active hydrogen；Then react with carboxylic acid halides, obtain acylphosphine compounds；After question response completes, when not being easily separated, continue in reaction vessel, add oxidant and prepare acylphosphine oxide.The preparation method of the acylphosphanes efficiency light initiator of present invention design, it is not necessary to separation of intermediates, improves productivity and the production efficiency of product, it is possible to meet the demand of industrialized production.
Description
Technical field:
The invention belongs to light trigger preparing technical field, particularly to a kind of acylphosphanes efficiency light initiator and preparation method thereof.
Background technology:
Be known in the art acylphosphine compounds especially with TPO, 819 be representative compound be the efficiency light initiator that is widely used in photo polymerization is reacted.The synthetic technology difficulty of this series products is big.EP2004/008497 described a kind of technique preparing monoacyl phosphine and bisacyl phospine; with single halophosphines or P; P-dihalo phosphine is raw material; making this organophosphor halogenide react in the presence of a catalyst to produce metallized phosphine with alkali metal lithium, sodium, potassium or its mixture, it reacts generation acylphosphanes subsequently with carboxylic acid halides.
Summary of the invention:
Above-mentioned existing technique has been improved by the present invention, it is provided that a kind of acylphosphanes efficiency light initiator and preparation method thereof.
The structural formula of acylphosphanes efficiency light initiator of the present invention is as shown in (I):
Wherein, n is 1 or 2；
R1It is C1-C18 alkyl, by the C2-C18 alkyl at one or more discontinuous O atom interval；C1-C4 alkyl that phenyl replaces, C2-C8 alkenyl, phenyl, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing 5 yuan or 6 yuan of heterocycles of O, S or N, phenyl therein, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing O, S or N 5 yuan or 6 yuan of heterocycles are unsubstituted or by the replacement of 1-5 halogen, C1-C8 alkyl, C1-C8 alkylthio group and/or C1-C8 alkoxyl；
R2It is C1-C18 alkyl, C3-C12 cycloalkyl, C2-C18 alkenyl, phenyl, naphthyl, xenyl or is unsubstituted or by 1-4 C1-C8 alkyl, C1-C8 alkoxyl, alkylthio group and/or halogen substiuted containing 5 yuan of O, S or N or 6 yuan of heterocycles；
R3It is C1-C18 alkyl, by the C2-C18 alkyl at one or more discontinuous O atom interval；C1-C4 alkyl that phenyl replaces, C2-C8 alkenyl, phenyl, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing 5 yuan or 6 yuan of heterocycles of O, S or N, phenyl therein, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing O, S or N 5 yuan or 6 yuan of heterocycles are unsubstituted or by the replacement of 1-5 halogen, C1-C8 alkyl, C1-C8 alkylthio group and/or C1-C8 alkoxyl.
The preparation method of acylphosphanes efficiency light initiator of the present invention:
(1) in a solvent in the presence of a catalyst, the alloy reaction being raw material Yu active metal with organophosphor halogenide (II), production (IIa) compound, as following formula reacts:
(2) generation hydrogenation phosphine formula (IIb) compound is then reacted with the aliphatic alcohol compounds containing active hydrogen；
(3) then react with the carboxylic acid halides of formula (III), obtain acylphosphine compounds formula (Ia)；
(4) after question response (3) completes, when not being easily separated, continue in reaction vessel, add oxidant and prepare acylphosphine oxide (I)；
In each structural formula above-mentioned: n is 1 or 2；
R1It is C1-C18 alkyl, by the C2-C18 alkyl at one or more discontinuous O atom interval；C1-C4 alkyl that phenyl replaces, C2-C8 alkenyl, phenyl, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing 5 yuan or 6 yuan of heterocycles of O, S or N, phenyl therein, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing O, S or N 5 yuan or 6 yuan of heterocycles are unsubstituted or by the replacement of 1-5 halogen, C1-C8 alkyl, C1-C8 alkylthio group and/or C1-C8 alkoxyl；
R2It is C1-C18 alkyl, C3-C12 cycloalkyl, C2-C18 alkenyl, phenyl, naphthyl, xenyl or is unsubstituted or by 1-4 C1-C8 alkyl, C1-C8 alkoxyl, alkylthio group and/or halogen substiuted containing 5 yuan of O, S or N or 6 yuan of heterocycles；
R3It is C1-C18 alkyl, by the C2-C18 alkyl at one or more discontinuous O atom interval；C1-C4 alkyl that phenyl replaces, C2-C8 alkenyl, phenyl, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing 5 yuan or 6 yuan of heterocycles of O, S or N, phenyl therein, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing O, S or N 5 yuan or 6 yuan of heterocycles are unsubstituted or by the replacement of 1-5 halogen, C1-C8 alkyl, C1-C8 alkylthio group and/or C1-C8 alkoxyl；
X is Br or Cl；
M is the alloy of active metal.
The alloy of described active metal is selected from the amalgam of alkali metal with the alloy of alkaline-earth metal, alkali metal and/or alkaline-earth metal.
The alloy of described alkali metal and alkaline-earth metal is selected from sodium magnesium alloy, sodium calcium alloy, potassium magnesium alloy, potassium calcium alloy；Described alkali metal and/or the amalgam of alkaline-earth metal are selected from sodium amalgam, potassium amalgam, magnesium amalgam, sodium magnesium amalgam.
The described aliphatic alcohol compounds containing active hydrogen is the aliphatic tertiary alcohol containing 4-15 carbon atom, it is preferable that the tert-butyl alcohol, tert-pentyl alcohol, tertiary hexanol.
The solvent of step (1) and (2) is aliphatic or aromatic solvent；Wherein aliphatic solvent includes pentane, hexane, hexamethylene；Aromatic solvent includes benzene, toluene, ethylbenzene.
Step (1) reaction temperature is 50-200 DEG C.
The reaction temperature of step (2) is 30-150 DEG C.
The reaction temperature of step (3) is-10 DEG C-200 DEG C, it is preferable that 30 DEG C-120 DEG C.
The reaction temperature of step (4) is-10 DEG C-100 DEG C, it is preferable that 10 DEG C-50 DEG C.
Oxidant described in step (4) is hydrogen peroxide.
Described catalyst is naphthalene or naphthalene derivatives；Described naphthalene derivatives includes naphthane, 1,2,3,4-tetraphenyl naphthalene, acenaphthene, acenaphthylene, 1,4-naphthoquinone, 1,2-naphthoquinone.The addition of catalyst is the 0.01-20% of the mole of the alloy of active metal, it is preferable that 1-10%, more preferably 2-6%.
The reaction of step (1), first adds in solvent by the alloy of active metal, then heating blends under high velocity agitation, makes the alloy of active metal be scattered in solvent with small particulate form.Disperse the temperature during alloy of active metal for usually >=90 DEG C of sodium magnesium alloy in a solvent, for instance 90-200 DEG C；For usually >=50 DEG C of potassium magnesium alloy, for instance 50-200 DEG C；>=30 DEG C are usually for amalgam, for instance sodium amalgam 30-200 DEG C.The alloy of active metal is disperseed after in a solvent, do not cool down, transfer, directly in reaction vessel, add organic phosphorus halide and react, produce metallized phosphine (IIa).
The preparation method of the acylphosphanes efficiency light initiator of present invention design, it is not necessary to separation of intermediates, improves productivity and the production efficiency of product, it is possible to meet the demand of industrialized production.
Detailed description of the invention
Embodiment 1
The synthesis of double; two acylphosphine compounds: under an inert atmosphere to equipped with Dropping funnel, agitator, put into toluene 650ml, sodium amalgam (1:1) 124g in the four-hole boiling flask (1000ml) of thermometer successively；Temperature rises to 40 DEG C and starts stirring, is continuously heating to backflow dropping phenyl dichloro phosphorus 44g.It is heated to reflux 1h.In reaction bulb, drip tert-butyl alcohol 42g, be heated to reflux 1h.React complete, nitrogen protection, it is cooled to less than 30 DEG C, drips 2,4,6-tri-methyl chloride 93g, drip off rear temperature and control 40 ± 5 DEG C, react 1h.Drip 5% sodium carbonate again, regulate PH=7, separate water layer, then through washing, concentration, crystallization, filtration, dry to obtain target product 114g, yield 91%, content >=99%, fusing point 127-131 DEG C.
Embodiment 2
The synthesis of double; two acylphosphine compounds: under an inert atmosphere to equipped with Dropping funnel, agitator, put into toluene 650ml, magnesium metal sodium alloy (1:1) 24g in the four-hole boiling flask (1000ml) of thermometer successively；Temperature rises to 90 DEG C and starts stirring, is continuously heating to backflow dropping phenyl dichloro phosphorus 44g.It is heated to reflux 1h.In reaction bulb, drip tert-butyl alcohol 42g, be heated to reflux 1h.React complete, nitrogen protection, it is cooled to less than 30 DEG C, drips 2,4,6-tri-methyl chloride 93g, drip off rear temperature and control 40 ± 5 DEG C, react 1h.Drip 5% sodium carbonate again, regulate PH=7, separate water layer, then through washing, concentration, crystallization, filtration, dry to obtain target product 112g, yield 90%, content >=99%, fusing point 127-133 DEG C.
Embodiment 3
The synthesis of double; two acylphosphine compounds: under an inert atmosphere to equipped with Dropping funnel; agitator; the four-hole boiling flask (1000ml) of thermometer puts into toluene 650ml successively; metallic potassium magnesium (1:1) 30g; temperature rises to 50 DEG C; start stirring, be continuously heating to backflow dropping phenyl dichloro phosphorus 44g, be heated to reflux 1h.In reaction bulb, drip tert-butyl alcohol 42g, be heated to reflux 1h.React complete, nitrogen protection, it is cooled to less than 30 DEG C, drips 2,4,6-tri-methyl chloride 93g, drip off rear temperature and control 40 ± 5 DEG C, react 1h.Drip 5% sodium carbonate again, regulate PH=7, separate water layer, then through washing, concentration, crystallization, filtration, dry to obtain target product 114g, yield 91%, content >=99%, fusing point 127-131 DEG C.
Claims (7)
1. the preparation method of an acylphosphanes efficiency light initiator, it is characterised in that its concrete preparation process is:
(1) in a solvent in the presence of a catalyst, the alloy reaction being raw material Yu active metal with organophosphor halogenide (II), production (IIa) compound, as following formula reacts:
(2) generation hydrogenation phosphine formula (IIb) compound is then reacted with the aliphatic alcohol compounds containing active hydrogen；
(3) then react with the carboxylic acid halides of formula (III), obtain acylphosphine compounds formula (Ia)；
(4) after question response (3) completes, when not being easily separated, continue in reaction vessel, add oxidant and prepare acylphosphine oxide (I)；
In each structural formula above-mentioned: n is 1 or 2；
R1It is C1-C18 alkyl, by the C2-C18 alkyl at one or more discontinuous O atom interval；C1-C4 alkyl that phenyl replaces, C2-C8 alkenyl, phenyl, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing 5 yuan or 6 yuan of heterocycles of O, S or N, phenyl therein, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing O, S or N 5 yuan or 6 yuan of heterocycles are unsubstituted or by the replacement of 1-5 halogen, C1-C8 alkyl, C1-C8 alkylthio group and/or C1-C8 alkoxyl；
R2It is C1-C18 alkyl, C3-C12 cycloalkyl, C2-C18 alkenyl, phenyl, naphthyl, xenyl or is unsubstituted or by 1-4 C1-C8 alkyl, C1-C8 alkoxyl, alkylthio group and/or halogen substiuted containing 5 yuan of O, S or N or 6 yuan of heterocycles；
R3It is C1-C18 alkyl, by the C2-C18 alkyl at one or more discontinuous O atom interval；C1-C4 alkyl that phenyl replaces, C2-C8 alkenyl, phenyl, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing 5 yuan or 6 yuan of heterocycles of O, S or N, phenyl therein, xenyl, naphthyl, acenaphthenyl, C5-C12 cycloalkyl or containing O, S or N 5 yuan or 6 yuan of heterocycles are unsubstituted or by the replacement of 1-5 halogen, C1-C8 alkyl, C1-C8 alkylthio group and/or C1-C8 alkoxyl；
X is Br or Cl；
M is the alloy of active metal；
The alloy of described active metal is the amalgam of alkali metal and/or alkaline-earth metal；
Described catalyst is naphthane, 1,2,3,4-tetraphenyl naphthalene, acenaphthene, acenaphthylene, 1,4-naphthoquinone, 1,2-naphthoquinone.
2. preparation method according to claim 1, it is characterised in that described alkali metal and/or the amalgam of alkaline-earth metal are selected from sodium amalgam, potassium amalgam, magnesium amalgam, sodium magnesium amalgam.
3. preparation method according to claim 1, it is characterised in that the described aliphatic alcohol compounds containing active hydrogen is the aliphatic tertiary alcohol containing 4-15 carbon atom.
4. preparation method according to claim 1, it is characterised in that the solvent of step (1) and (2) is aliphatic or aromatic solvent；Wherein aliphatic solvent is pentane, hexane, hexamethylene；Aromatic solvent is benzene, toluene, ethylbenzene.
5. preparation method according to claim 1, it is characterised in that step (1) reaction temperature is 50-200 DEG C；The reaction temperature of step (2) is 30-150 DEG C；The reaction temperature of step (3) is-10 DEG C-200 DEG C；The reaction temperature of step (4) is-10 DEG C-100 DEG C.
6. preparation method according to claim 1, it is characterised in that the oxidant described in step (4) is hydrogen peroxide.
7. preparation method according to claim 1, it is characterised in that the addition of catalyst is the 1-10% of the mole of the alloy of active metal.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5777169A (en) * | 1997-07-01 | 1998-07-07 | Albemarle Corporation | Production of high purity alkali metal diarylphosphide and cycloalkyldiarylphosphines |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SE520727C2 (en) * | 1996-03-04 | 2003-08-19 | Ciba Sc Holding Ag | Alkylphenyl bisacylphosphine oxide and photoinitiator mixtures |
| SG53043A1 (en) * | 1996-08-28 | 1998-09-28 | Ciba Geigy Ag | Molecular complex compounds as photoinitiators |
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