CN102863559B - Photoinitiator for UV (ultraviolet)-LED curing - Google Patents
Photoinitiator for UV (ultraviolet)-LED curing Download PDFInfo
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- 0 *[n]1c(C=CCC2)c2c2c1cccc2 Chemical compound *[n]1c(C=CCC2)c2c2c1cccc2 0.000 description 2
- ZECQLHQEHJJSAN-UHFFFAOYSA-N C(C1)C=Cc2c1[nH]c1c2cccc1 Chemical compound C(C1)C=Cc2c1[nH]c1c2cccc1 ZECQLHQEHJJSAN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a structure of a photoinitiator applicable to UV (ultraviolet)-LED curing and a method for preparing the photoinitiator. The carbazolyl acyl phosphine oxide type photoinitiator is fine in electron delocalizability, has high intramolecular electron transfer performance and excellent photoelectric performance, has high absorbability in a long-wave region (365nm-395nm), is adaptable to high-power UV-LED ultraviolet curing, overcomes the shortcomings of high curing energy consumption and heavy pollution of traditional mercury lamps, and gets rid of the defects of proneness to yellow and high mobility of micromolecular photoinitiator due to the macromolecular structure.
Description
Technical field
The present invention relates to a kind of light trigger and preparation method thereof, particularly a kind of for curing light trigger of UV-LED and preparation method thereof.
Background technology
Photocuring refers to monomer, oligomer or the polymer matrix solidification process under photoinduction, and light trigger is a kind of energy absorbed radiation energy, through exciting generation chemical transformation, produces the material of the active intermediate (free radical or positively charged ion) with initiated polymerization ability.Light trigger is the key ingredient of photocuring product, and it plays a decisive role to the photo-curing rate of photocuring product.
At present, photocuring technology is mainly ultraviolet light polymerization, light source is mainly high voltage mercury lamp, 365nm, 313nm in its emmission spectrum, 302nm, 254nm spectral line are very useful, many light triggers all have larger absorption at above-mentioned wavelength, although UV mercury lamp can provide effective ultraviolet source, in its radiative process, also there are some obvious defects:
1, the usage quantity of UV mercury lamp is large, uv equipment use UV mercury lamp at least 1-2 prop up, 6-8 props up at most.
2, the power of UV mercury lamp is very large, and not etc., current consumption is not huge for 3KW-20KW.
3, traditional UV mercury lamp thermal value is very large, selects limitation very large to curing substrate.
4, traditional UV mercury lamp starts slowly, and warm up time is long, is only suitable for non-stop run, and normal production is caused to waste, and handiness is very poor.
5, a large amount of use mercury lamps will certainly cause mercury pollution.
LED light source relies on its energy-saving and environmental protection, durable and remarkable luminescent properties to be widely used in domestic lighting field,
The application of UV-LED light source in radiation curing industry also obtained exploitation gradually, relate to the various fields in industrial and agricultural production, as optics processing, laser and optical communication product are manufactured, LCD and touch-screen encapsulation, medical product bonding, PCB exposure, vision-based detection etc., more traditional UV mercury lamp solidifies, and UV-LED solidifies tool and has the following advantages:
1, UV optical purity is high;
2, current consumption is low, and long service life is energy-conservation 70% compared with mercury lamp, has reduced maintenance cost;
3, cold light source irradiates and is applicable to multiple base material, especially plastics film equitemperature sensitive material;
4, be applicable to opening i.e. pass, simple to operate, be applicable to the system integration;
5, concentration of energy: more than 98% light is exported all at ultraviolet band;
6, stable output power, adjustable continuously;
Just because of the relatively traditional UV mercury lamp of UV-LED has embodied huge superiority; it must be the development trend of following photocuring technology that UV-LED solidifies; but; because the luminescent spectrum of UV-LED light source own is very narrow; concentration of energy, just can reach good initiation effect in conjunction with LED light trigger, in existing light trigger; only have acylphosphine oxide, this two photoinitiator of thioxanthone to have certain absorption in long wave (365nm-395nm) region, can support the use with LED light source reluctantly.Thioxanthone is in exposure easily jaundice afterwards; form thus the limited degraded product of stability; while preservation, there is original Huang and move in result; this has limited its range of application to a certain extent; acylphosphine oxide has certain photobleaching; effectively overcome Yellowing, but the absorption in its 365nm-395nm region is still limited, enough initiating activities can not be provided.Therefore, being badly in need of exploitation one has absorption more by force in 365nm-395nm region, can not produce the red shift light trigger of xanthochromia in elicitation procedure.
Click is trembled and is had the performance of two-photon absorption. and have good rigidity conjugate planes, electron delocalization is good, and having transfer transport performance in strong molecule and good photoelectric property provides favourable condition as good light trigger for its derivative.The carbazole derivative initiator of design synthesizing new becomes one of focus of photocuring area research in recent years.
The research and development of the light trigger based on carbazole concentrate on carbazole oxime ester mostly, as U.S. Pat 2004/0170924A1, US2006/0241259A1, US2008/0096115A1, US2010/0136491A1, US2010/0086881A1 have announced multiple single or multi-functional carbazyl oxime ester lightlike initiating agent, although carbazyl oxime ester lightlike initiating agent initiating activity is high, but its synthesis step is many, and product stability is not good enough.
Chinese patent CN102250115A has reported a kind of carbazole ring derivative type aromatic ketone compound, constructed two or multi-functional-group photoinitiator by introduce different active groups on carbazole aromatic ring, but these compounds still inevitably can produce the phenomenon such as smell, xanthochromia after very limited and certain structures photodissociation in the absorption of Long wavelength region.
Therefore, still need to develop and in the time that LED exposes, there is high curing rate and synthesis technique simple optical initiator.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, provides a kind of for curing light trigger of UV-LED and preparation method thereof.Particularly; polynary carbazyl acylphosphine oxide complex body light trigger that provides the carbazyl acylphosphine oxide complex body of a class novelty or connect with carbazole nitrogen-atoms and preparation method thereof; this light trigger has stronger absorption in 365nm-395nm region, is a kind of light trigger that is applicable to high-power UV-LED ultraviolet light polymerization.
In order to achieve the above object, technical scheme provided by the invention is:
For the curing light trigger of UV-LED, its chemical structure is suc as formula shown in (I) or formula (II):
Wherein, R1 is C1-C12 alkyl, C1-C12 cycloalkyl, C1-C12 alkoxyl group, C2-C12 alkenyl, phenyl, replacement or unsubstituted alkaryl, heteroaryl, wherein, phenyl can be replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, by the C2-C18 alkyl of one or more O atomic separation;
R2 is unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
R3 is C1-C12 alkoxyl group, by the C2-C18 alkyl of one or more O atomic separation, unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
Q is the n valency N-alkyl spacer group of C2-C24 straight or branched; Preferably, in Q, contain the nitrogen, sulphur or the Sauerstoffatom that are no more than 6, n≤4, Q is derived by polynary halohydrocarbon.
Preferably, light trigger shown in formula (I) comprises that formula (III) is to the compound shown in formula (XII), and wherein, formula (III) is to the compound shown in formula (XII) successively corresponding product numbering PI6301 to PI6310, the preferred compound of formula (I) light trigger is preferably as follows, but is not limited to this:
Preferably, light trigger shown in formula (II) comprises that formula (XIII) is to the compound shown in formula (XX), wherein, formula (XIII) is to the compound shown in formula (XX) successively corresponding product numbering PI6401 to PI6408, the preferred compound of formula (II) light trigger is preferably as follows, but is not limited to this:
The present invention also provides the method for a kind of preparation formula (I) compound, comprises the steps:
(1) prepare the carbazole of N-hydrocarbylation;
(2) prepare carboxylated N-hydrocarbylation carbazole by the carbazole of above-mentioned N-hydrocarbylation;
(3) prepared the N-hydrocarbylation carbazole of carboxyl carboxylic acid halides by above-mentioned carboxylated N-hydrocarbylation carbazole;
(4) prepare suc as formula the compound shown in (XXI):
(5) the N hydrocarbylation carbazole of carboxyl carboxylic acid halides is carried out to Arbuzov with compound shown in formula (XXI) and react, prepare carbazyl acylphosphine oxide;
Concrete synthetic method is as follows:
Wherein, R1 is C1-C12 alkyl, C1-C12 cycloalkyl, C1-C12 alkoxyl group, C2-C12 alkenyl, phenyl, replacement or unsubstituted alkaryl, heteroaryl, wherein, phenyl can be replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, by the C2-C18 alkyl of one or more O atomic separation;
R2 is unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
R3 is C1-C12 alkoxyl group, by the C2-C18 alkyl of one or more O atomic separation, unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
R is the alkyl of C1-C12, is preferably the alkyl of C1-C4.
X is Cl or Br.
The present invention also provides the method for a kind of preparation formula (II) compound, comprises the steps:
(1) N-that preparation is connected by spacer group Q joins polynary carbazole;
(2) joining polynary carbazole by above-mentioned N-prepares carboxylated N-and joins polynary carbazole;
(3) joining polynary carbazole by above-mentioned carboxylated N-prepares the N-of carboxyl carboxylic acid halides and joins polynary carbazole;
(4) prepare suc as formula the compound shown in (XXI):
(5) N-of carboxyl carboxylic acid halides is joined to polynary carbazole and carry out Arbuzov with compound shown in formula (XXI) and react, prepare polynary carbazyl acylphosphine oxide;
Concrete synthetic method is as follows:
Wherein, R2 is unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
R3 is C1-C12 alkoxyl group, by the C2-C18 alkyl of one or more O atomic separation, unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
R is the alkyl of C1-C12, is preferably the alkyl of C1-C4;
X is Cl or Br.
Q is the n valency N-alkyl spacer group of C2-C24 straight or branched.
Preferably, Q is that following polynary halohydrocarbon is removed halogen residue afterwards:
The outstanding advantages of light trigger of the present invention is:
(1) the carbazyl acylphosphine oxide light trigger electron delocalization shown in logical formula I, (II) is good, has transfer transport performance and good photoelectric property in strong molecule, at Long wavelength region
(365nm-395nm) there is stronger absorption, be applicable to high-power UV-LED ultraviolet light polymerization, overcome traditional mercury lamp and solidified the shortcoming that power consumption is high, pollution is heavy.
(2) the carbazyl acylphosphine oxide photoinitiator molecules structure shown in logical formula I, (II) is larger; cause the small molecules photodissociation fragment that is difficult for producing high volatility in solidification process, the active function groups of acylphosphine oxide has also effectively suppressed the problem of xanthochromia in solidification process.
Accompanying drawing explanation
Fig. 1 is the IR spectrogram of embodiment 1 compound PI6301;
Fig. 2 is the IR spectrogram of embodiment 3 compound PI6401.
Embodiment:
The following example describes the present invention in detail, but following example is not limited only to again the present invention.
Embodiment 1: the preparation of formula (III) compound PI6301
The first step: carbazole N-ethylizes
In 250ml there-necked flask, add respectively sodium hydroxide solution, the 1g Tetrabutyl amonium bromide of 20g carbazole, 30ml benzene, 60ml30%, after 50 ℃ of reaction 3h of temperature control, slowly drip 14.3g monobromethane, back flow reaction 5h.TLC follows the tracks of reaction process, adds after completion of the reaction 70ml benzene, 50ml water, stirs stratification, and organic phase is used respectively 50ml water washing twice, after desolvation, obtains N-ethyl carbazole 20.5g, yield 87.9% by re-crystallizing in ethyl acetate.
Second step: carboxylated
(a) reference literature Inorganic Chemistry Communications 9 (2006) 351 – 354, AlCl
3(40g, 0.3mol) and Acetyl Chloride 98Min. (35ml, 0.5mol) are dissolved in 25ml methylene dichloride; under normal temperature; to the dichloromethane solution that drips 9-ethyl carbazole (21g, 0.107mol) in above-mentioned solution, 1-2h drips off; drip off rear continuation temperature control reaction 2h; after completion of the reaction gained solution is poured in frozen water, filtered, obtain a kind of powder of deep yellow; this powder is 3,6-diacetyl-9-ethyl carbazole.Yield:93.36%;Anal.Calcd.for?C
19H
19NO
2:C,77.79;H,6.53;N,4.77%.Found:C,77.76;H,6.54;N,4.76%。
(b) 2.0g(0.0071mol) 3; 6-diacetyl-9-ethyl carbazole and a small amount of Tetrabutyl amonium bromide are dissolved in 25ml chloroform; the chlorine bleach liquor of 30ml 10% is added dropwise in above-mentioned solution; 65 ℃ of back flow reaction 12h; after completion of the reaction; be cooled to room temperature; saturated sodium sulfite solution reduction for excessive clorox; water regulates PH≤4 with dilute sulphuric acid; separate out white solid, filter, obtain 1.8g (0.0063mol) 3 with ethyl alcohol recrystallization; 6-dicarboxyl-9-ethyl carbazole product, Yield:89.58%; Anal.Calcd.forC
16h
13nO
4: C, 67.84; H, 4.63; N, 4.94%.Found:C, 67.82; H, 4.64; N, 4.93%.
The 3rd step: chloride
Get 14.2g (0.05mol) 3,6-dicarboxyl-9-ethyl carbazole is in 250ml there-necked flask, slowly add thionyl chloride 14.5ml, after temperature rising reflux reaction 4-6h, steam except excessive thionyl chloride, obtain the chloro-9-ethyl carbazole of 3,6-diacetyl 15.5g(0.048mol), yield 97.2%.
The 4th step: the preparation of phenylbenzene butoxy phosphine
By 14g(0.19mol) propyl carbinol, 14.82g(0.19mol) pyridine and 50ml ether mix, and with ice-cooled, stirs lower dropping 41.8g diphenyl phosphine chloride, stirring at room temperature 30min.Elimination pyridinium salt, by 30ml ether washed twice, merges ether solution, boils off underpressure distillation after solvent, obtains product 27g, yield 52.7%.
The 5th step: Arbuzov reaction
Under nitrogen protection, upper step reaction gained acyl chlorides 15.5g, solvent benzol are added in reactor, open and stir, control temperature of reaction, drip slowly phenylbenzene butoxy phosphine 27g, after dropping finishes, be warming up to back flow reaction 2～4h.The washed twice that adds water after having reacted, after point anhydrating mutually, organic phase is transferred to crystallization kettle distilling off solvent, residual material sherwood oil recrystallization in still, then through centrifuging, be dried, obtain light yellow crystallization 24.3g, be product P I6301, yield 78.4%.
Embodiment 2: the preparation of formula (IV) compound PI6302
With reference to the chloro-9-ethyl carbazole of embodiment 1 first, second and third step preparation 3,6-diacetyl;
The 4th step: the preparation of phenyl diethyl phosphite
Under stirring, 179g (1.0mol) phenylphosphonic dichloride is slowly added drop-wise to ice bath and remains on the 266.6g(2.2mol of 20-30) in the mixture of DMA and 276g (0.6mol) ethanol, add rear stirring at room temperature 3h.Elimination solid salt, washs several times with ether, merging filtrate and washings, and normal pressure boils off after solvent, and underpressure distillation is collected b.p.109 ℃/1.59kpa cut 158.5g, yield 80%.
The 5th step: Arbuzov reaction
By obtain 3, the chloro-9-ethyl carbazole of 6-diacetyl 31g is placed in the there-necked flask of 250ml, control and under certain temperature and vacuum tightness, slowly drip phenyl diethyl phosphite 38g, control time for adding 1-2h, dropwise rear continuation and stir 30min, be cooled to after completion of the reaction room temperature and obtain faint yellow solid crude product, after recrystallization, obtain light yellow crystal 51.4g and be product P I6302, yield 91.2%.
Other logical formula I compound can, take different N-hydrocarbylation carbazoles as starting raw material, obtain with reference to the preparation method of example 1,2.
Embodiment 3: the preparation of formula (XIII) compound PI6401
The preparation of the two carbazole hexanes of the first step: 1,6-
In 250ml there-necked flask, add respectively sodium hydroxide solution, the 1g Tetrabutyl amonium bromide of 20g carbazole, 30ml benzene, 60ml30%, after 50 ℃ of reaction 3h of temperature control, slowly drip 16.5g1,6-dibromo-hexane, back flow reaction 5h.TLC follows the tracks of reaction process, adds after completion of the reaction 70ml benzene, 50ml water, stirs stratification, and organic phase is used respectively 50ml water washing twice, after desolvation, obtains the two carbazole hexane 18g of 1,6-, yield 71% by re-crystallizing in ethyl acetate.
The two carbazole hexanes of second step: 1,6-are carboxylated
(a) reference literature Inorganic Chemistry Communications 9 (2006) 351 – 354, AlCl
3(40g, 0.3mol) and Acetyl Chloride 98Min. (33.6ml, 0.48mol) are dissolved in 80ml methylene dichloride, under normal temperature, in above-mentioned solution, drip the two carbazole hexane (41.6g of 1,6-, dichloromethane solution 0.1mol), 1-2h drips off, and drips off rear continuation temperature control reaction 2h, after completion of the reaction gained solution is poured in frozen water, filter, obtain a kind of powder of deep yellow, this powder is the two carbazole hexane tetraketones of 1,6-.Yield:91.3%;Anal.Calcd.for?C
38H
36N
2O
4:C,78.04;H,6.23;N,4.77;O,10.97%.Found:C,78.06;H,6.21;N,4.79;O,10.95%。
(b) 5.84g(0.01mol) 1; 6-bis-carbazyl hexane tetraketones and a small amount of Tetrabutyl amonium bromide are dissolved in 25ml chloroform; the chlorine bleach liquor of 42ml 10% is added dropwise in above-mentioned solution; 65 ℃ of back flow reaction 12h; after completion of the reaction; be cooled to room temperature; saturated sodium sulfite solution reduction for excessive clorox; water regulates PH≤4 with dilute sulphuric acid; separate out white solid, filter, obtain 5.2g (0.088mol) 1 with ethyl alcohol recrystallization; 6-bis-carbazyl hexane tetracid products, Yield:88.01%; Anal.Calcd.For C
34h
28n
2o
8: C, 68.88; H, 4.78; N, 4.71; O, 21.8%.Found:C, 68.91; H, 4.76; N, 4.73; O, 21.6%.
The 3rd step: chloride
Get 29.6g (0.05mol) 1,6-bis-carbazyl hexane tetracids are in 250ml there-necked flask, slowly add thionyl chloride 15.6ml, after temperature rising reflux reaction 4-6h, steam except excessive thionyl chloride, obtain 31.8g 1,6-bis-carbazyl hexane tetrem acyl chlorides products (0.047mol), yield 95.5%.
The 4th step: the preparation of phenylbenzene butoxy phosphine
By 28g(0.38mol) propyl carbinol, 29.64g(0.38mol) pyridine and 80ml ether mix, and with ice-cooled, stirs lower dropping 83.6g diphenyl phosphine chloride, stirring at room temperature 30min.Elimination pyridinium salt, by 50ml ether washed twice, merges ether solution, boils off underpressure distillation after solvent, obtains product 48g, yield 52.7%.
The 5th step: Arbuzov reaction
Under nitrogen protection, upper step reaction gained acyl chlorides 29.7g, solvent benzol are added in reactor, open and stir, control temperature of reaction, drip slowly phenylbenzene butoxy phosphine 48g, after dropping finishes, be warming up to back flow reaction 2～4h.The washed twice that adds water after having reacted, after point anhydrating mutually, organic phase is transferred to crystallization kettle distilling off solvent, residual material sherwood oil recrystallization in still, then through centrifuging, be dried, obtain yellow crystal 43.4g, be product P I6401, yield 74.2%.
Embodiment 4: the preparation of formula (XIII) compound PI6402
With reference to embodiment 1 first, second and third step preparation 1,6-bis-carbazyl hexane tetrem acyl chlorides;
The 4th step: the preparation of phenyl diethyl phosphite
Under stirring, 179g (1.0mol) phenylphosphonic dichloride is slowly added drop-wise to ice bath and remains on the 266.6g(2.2mol of 20-30) in the mixture of DMA and 276g (0.6mol) ethanol, add rear stirring at room temperature 3h.Elimination solid salt, washs several times with ether, merging filtrate and washings, and normal pressure boils off after solvent, and underpressure distillation is collected b.p.109 ℃/1.59kpa cut 158.5g, yield 80%.
The 5th step: Arbuzov reaction
Under nitrogen protection, upper step is reacted to gained acyl chlorides 1; 6-bis-carbazyl hexane tetrem acyl chlorides 33.8g, solvent benzol add in reactor, open and stir, and control temperature of reaction; drip slowly phenyl diethyl phosphite 39.6g, after dropping finishes, be warming up to back flow reaction 2～4h.The washed twice that adds water after having reacted, after point anhydrating mutually, organic phase is transferred to crystallization kettle distilling off solvent, residual material sherwood oil recrystallization in still, then through centrifuging, be dried, obtain yellow crystal 46.5g, be product P I 6402, yield 77.5%.
Other logical formula II compound can, take different polynary carbazole alkane as starting raw material, obtain with reference to the preparation method of example 3,4.
Claims (9)
1. for the curing light trigger of UV-LED, it is characterized in that, the chemical structure of this light trigger is suc as formula shown in (I) or formula (II):
Wherein, R1 is C1-C12 alkyl, C1-C12 cycloalkyl, C1-C12 alkoxyl group, C2-C12 alkenyl, replacement or unsubstituted phenyl, replacement or unsubstituted alkaryl, heteroaryl, wherein, the phenyl of replacement can be replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, by the C2-C18 alkyl of one or more O atomic separation;
R2 is unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
R3 is C1-C12 alkoxyl group, by the C2-C18 alkyl of one or more O atomic separation, unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
Q is the n valency N-alkyl spacer group of C2-C24 straight or branched.
2. light trigger as claimed in claim 1, is characterized in that, Q is derived by polynary halohydrocarbon.
3. light trigger as claimed in claim 1, is characterized in that, light trigger shown in formula (I) specifically comprises that formula (III) is to the compound shown in formula (XII):
4. light trigger as claimed in claim 1, is characterized in that, light trigger shown in formula (II) specifically comprises the compound shown in formula (XIII) or formula (XIV):
5. a method of preparing formula described in claim 1 (I) compound, is characterized in that, comprises the steps:
(1) prepare the carbazole of N-hydrocarbylation;
(2) prepare carboxylated N-hydrocarbylation carbazole by the carbazole of above-mentioned N-hydrocarbylation;
(3) prepared the N-hydrocarbylation carbazole of carboxyl carboxylic acid halides by above-mentioned carboxylated N-hydrocarbylation carbazole;
(4) prepare suc as formula the compound shown in (XXI):
(5) the N-hydrocarbylation carbazole of carboxyl carboxylic acid halides is carried out to Arbuzov with compound shown in formula (XXI) and react, prepare carbazyl acylphosphine oxide;
Concrete synthetic method is as follows:
Wherein, R1 is C1-C12 alkyl, C1-C12 cycloalkyl, C2-C12 alkenyl, replacement or unsubstituted phenyl, replacement or unsubstituted alkaryl, and wherein, the phenyl of replacement can be replaced by following groups: the alkyl of C1-C20, phenyl, alkenyl;
R2 is unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
R3 is C1-C12 alkoxyl group, by the C2-C18 alkyl of one or more O atomic separation, unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
R is the alkyl of C1-C12;
X is Cl or Br.
6. preparation method as claimed in claim 5, is characterized in that, the alkyl that R is C1-C4.
7. a method of preparing formula described in claim 1 (II) compound, is characterized in that, comprises the steps:
(1) N-that preparation is connected by spacer group Q joins polynary carbazole;
(2) joining polynary carbazole by above-mentioned N-prepares carboxylated N-and joins polynary carbazole;
(3) joining many carbazoles by above-mentioned carboxylated N-prepares the N-of carboxyl carboxylic acid halides and joins polynary carbazole;
(4) prepare suc as formula the compound shown in (XXI):
(5) N-of carboxyl carboxylic acid halides is joined to polynary carbazole and carry out Arbuzov with compound shown in formula (XXI) and react, prepare polynary carbazyl acylphosphine oxide;
Concrete synthetic method is as follows:
Wherein, R2 is unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
R3 is C1-C12 alkoxyl group, by the C2-C18 alkyl of one or more O atomic separation, unsubstituted phenyl or the phenyl that replaced by following groups: the alkyl of C1-C20, C1-C12 alkoxyl group, phenyl, alkenyl, halogen, cyclopentyl, cyclohexyl;
R is the alkyl of C1-C12;
X is Cl or Br;
Q is the n valency N-alkyl spacer group of C2-C24 straight or branched.
8. preparation method as claimed in claim 7, is characterized in that, the alkyl that R is C1-C4.
9. preparation method according to claim 7, is characterized in that, Q is that following polynary halohydrocarbon is removed the residue after halogen:
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| ATE253082T1 (en) * | 1999-12-08 | 2003-11-15 | Ciba Sc Holding Ag | NEW PHOTOINITIATOR SYSTEM MADE OF PHOSPHINE OXIDE COMPOUNDS AND LOW-COLORED CURABLE COMPOSITIONS |
| WO2006018405A1 (en) * | 2004-08-18 | 2006-02-23 | Ciba Specialty Chemicals Holding Inc. | Oxime ester photoinitiators |
| CN102250115A (en) * | 2011-05-13 | 2011-11-23 | 深圳市有为化学技术有限公司 | Carbazole cyclic derived type aromatic ketone compound as well as preparation method and photo initiator thereof |
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