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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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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US5777169A (en) * | 1997-07-01 | 1998-07-07 | Albemarle Corporation | Production of high purity alkali metal diarylphosphide and cycloalkyldiarylphosphines |
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CH691970A5 (en) * | 1996-03-04 | 2001-12-14 | Ciba Sc Holding Ag | Photoinitiator mixture for photopolymerising compounds having ethylenically unsaturated double bonds |
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CZ302512B6 (en) * | 1998-11-30 | 2011-06-29 | Ciba Specialty Chemicals Holding Inc. | Process for preparing acylphosphines, acylphosphine oxides and acylphosphine sulfides |
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EP1106627B1 (en) * | 1999-12-08 | 2003-10-29 | Ciba SC Holding AG | Novel phosphine oxide photoinitiator systems and curable compositions with low color |
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