CN1546488A - Diepoxy group containing thioxanthone photoinitiator and preparation method therefor - Google Patents
Diepoxy group containing thioxanthone photoinitiator and preparation method therefor Download PDFInfo
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- CN1546488A CN1546488A CNA2003101093611A CN200310109361A CN1546488A CN 1546488 A CN1546488 A CN 1546488A CN A2003101093611 A CNA2003101093611 A CN A2003101093611A CN 200310109361 A CN200310109361 A CN 200310109361A CN 1546488 A CN1546488 A CN 1546488A
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- thioxanthone
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- photo initiator
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Abstract
The invention discloses a diepoxy group containing thioxanthone photoinitiator and preparation method therefore which comprises, using 2-mercaptobenzoic acid, dioxybenzene and epichlorohydrin as raw material, dissolving 2-mercaptobenzoic acid into concentrated sulfuric acid, charging diphenols to prepare thioxanthene ketones containing bishydroxy, subjecting bishydroxy thioxanthene ketone with epichlorohydrin at the presence of potasium carbonate for 24 hours at 120-140 deg. C.
Description
Technical field: the invention belongs to a kind of light trigger and preparation method thereof, particularly contain thioxanthone photo initiator of diepoxy group and preparation method thereof.
Technical background: the widespread use of UV-curing technology on industrial circles such as photo-cured coating, photoresist material, light-curable ink, electronic package material, tackiness agent, optical media replication, paper glazing shown bright development prospect.In the technical progress process of photocuring system, the research and development of photoinitiator system are all the time in occupation of crucial position.Commercial a large amount of thioxanthone (2-chlorothiaxanthenone and isopropyl thioxanthone as the efficiency light initiator, US Patent 6025408) poor with the photocuring system consistency, this has not only reduced the light-initiated efficient of thioxanthone, and the field of having limited its application.
Along with science and technology development, also more and more higher to various performances (velocity of initiation is with the consistency of photocuring system, toxicity, the stability of the storage) requirement of light trigger.For photocuring system, in long process of preservation, light trigger is owing to volatilizing easily with photocuring system consistency difference and moving, and this can reduce the photopolymerization efficiency of initiation on the one hand, can cause product smell and toxicity to occur on the other hand.Therefore research and development efficient, become the focus that people pay close attention to the good light trigger of system consistency.
Summary of the invention: the present invention is incorporated into diepoxy group in the thioxanthone molecule, not only improved the solubility property of thioxanthone, improved the consistency of initiator and initiator system, can also generate the high-molecular optical initiator as monomer and diamines polymerization, and in the positively charged ion ultraviolet light polymerization, can be used as the copoly type light trigger, so not only improved the light-initiated efficient of thioxanthone, and widened the range of application of thioxanthone as light trigger.
The present invention is from Molecular Structure Design, and preparation contains the thioxanthone photo initiator of diepoxy group, and its chemical structure is shown below:
R wherein
1, R
2Independently be selected from hydrogen, halogen, C1-C22 alkyl, alkoxyl group respectively.
The method of preparation that the present invention contains the diepoxy group thioxanthone photo initiator is as follows:
(a) 1 part of thiosalicylic acid at room temperature is dissolved in the vitriol oil of 10-40 part, adds the diphenol of 1-5 part then gradually, at stirring at normal temperature 1-10 hour, be warmed up to 60-100 ℃ of reaction 2-10 hour then, the cooling standing over night.Reaction soln is added drop-wise in ten times the boiling water, cooled and filtered, filter cake is in water and 1, and recrystallization in the 4-dioxane obtains the thioxanthone of two hydroxyls.
(b) 1 part of two hydroxyl thioxanthone is dissolved in the organic solvent of 5-50 part, add Anhydrous potassium carbonate of 2-10 part and the epoxy chloropropane of 0.5-10 part, reacted 2-24 hour down at 60-100 ℃, then at 120-150 ℃ of following backflow 2-24 hour, after reaction finishes, wash organic phase with water and use the Calcium Chloride Powder Anhydrous drying, drain the solvent of organic phase, the non-volatile matter recrystallization obtains containing the thioxanthone photo initiator of diepoxy group.
The entire reaction equation that the present invention's preparation contains the thioxanthone photo initiator of diepoxy group can be expressed as:
Shown in the diphenol chemical structure following formula used in the present invention:
R wherein
1, R
2Independently be selected from hydrogen, halogen, C1-C22 alkyl, alkoxyl group respectively.
Organic solvent used in the present invention comprises pimelinketone, butanone, toluene or dimethylbenzene.
The present invention contains the diepoxy group thioxanthone photo initiator, by diepoxy group being incorporated in the thioxanthone molecule, not only improved the solubility property of thioxanthone, improved the consistency of initiator and initiator system, can also generate the high-molecular optical initiator as monomer and diamines polymerization, and in the positively charged ion ultraviolet light polymerization, can be used as the copoly type light trigger, so not only improved the light-initiated efficient of thioxanthone, and widened the range of application of thioxanthone as light trigger.So it will have a wide range of applications at the ultraviolet light polymerization industrial circle.
Description of drawings:
Fig. 1 is 1, the infrared spectra of 4-two (glycidoxy) thioxanthone photo initiator.
Fig. 2 is 1, the nucleus magnetic hydrogen spectrum of 4-two (glycidoxy) thioxanthone photo initiator.
Concrete embodiment: following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1:
(a) thiosalicylic acid with 0.1mol (16g) is dissolved in the vitriol oil of 150ml, and stirring at room 10 minutes slowly adds the Resorcinol of 0.4mol (44g), and reaction is 60 minutes under the room temperature, is warmed up to 80 ℃ of reactions then after 120 minutes, standing over night.Reaction solution is added drop-wise in the boiling water of 1500ml, boiled again after dripping 10 minutes, cooled and filtered, filter cake is in water and 1, and recrystallization in the 4-dioxane obtains 1 of 11.2 grams, 4-dihydroxyl thioxanthone, productive rate 50%.
(b) with 1 of 0.01mol (3.56g), 4-dihydroxyl thioxanthone, the Anhydrous potassium carbonate of 0.05mol (6.9g), the epoxy chloropropane of 20ml join in the pimelinketone of 40ml, and 80 ℃ were reacted 12 hours, refluxed 12 hours down at 135 ℃ then.After reaction finishes, drain organic layer, residue dissolves in water and chloroform, and organic phase is dewatered with Calcium Chloride Powder Anhydrous, and after draining, residue is recrystallization in toluene and ethanol, obtains 1,4-two (glycidoxy) thioxanthone 2.8 grams, and productive rate is 78.6%.Fusing point m.p.:142 ℃ .C
19H
16O
5S (356g mol
-1): ultimate analysis, theoretical value: C 64.04, H 4.65, and S 8.99 actual values: C 62.68, and H 4.49, and S 8.86.
1H NMR ([D6] DMSO, and 400MHz: δ=8.27-7.07 (6H, aromatic), 4.54-3.96 (4H, Ar-CH
2-), 3.42-3.32 (2H ,-CH, epoxy), 2.92-2.76 (4H ,-CH
2, epoxy), see accompanying drawing 2.FT-IR (KBr): 1644 (C=O), 1296,1040 (Ar-O-C), 1268,909cm
-1(epoxy) sees accompanying drawing 1.
Embodiment 2:
(a) thiosalicylic acid with 0.1mol (16g) is dissolved in the vitriol oil of 150ml, and stirring at room 10 minutes slowly adds the 2-methyl hydroquinone of 0.4mol (4.88g), and reaction is 60 minutes under the room temperature, is warmed up to 80 ℃ of reactions then after 120 minutes, standing over night.Reaction solution is added drop-wise in the boiling water of 1500ml, boiled again after dripping 10 minutes, cooled and filtered, filter cake is in water and 1, and recrystallization in the 4-dioxane obtains 1 of 11.9 grams, 4-dihydroxyl-2-methyl thioxanthone, productive rate 46.5%.
(b) with 1 of 0.01mol (3.68g), 4-dihydroxyl-2-methyl thioxanthone, the Anhydrous potassium carbonate of 0.05mol (6.9g), the epoxy chloropropane of 20ml join in the pimelinketone of 40ml, and 80 ℃ were reacted 12 hours, refluxed 12 hours down at 135 ℃ then.After reaction finishes, drain organic layer, residue dissolves in water and chloroform, and organic phase is dewatered with Calcium Chloride Powder Anhydrous, and after draining, residue is recrystallization in toluene and ethanol, obtains 1,4-two (glycidoxy)-2-methyl thioxanthone 2.9 grams, and productive rate is 78.1%.
1H NMR ([D6] DMSO, and 400MHz: δ=8.27-7.07 (5H, aromatic), 4.54-3.96 (4H, Ar-CH
2-), 3.42-3.32 (2H ,-CH, epoxy), 2.92-2.76 (4H ,-CH
2, epoxy) and .FT-IR (KBr): 1644 (C=O), 1296,1040 (Ar-O-C), 1268,909cm
-1(epoxy).
Embodiment (3)
(a) thiosalicylic acid with 0.1mol (16g) is dissolved in the vitriol oil of 150ml, and stirring at room 10 minutes slowly adds 2 of 0.4mol (5.36g), 3-dimethyl Resorcinol, reaction is 60 minutes under the room temperature, is warmed up to 80 ℃ of reactions then after 120 minutes, standing over night.Reaction solution is added drop-wise in the boiling water of 1500ml, boiled again after dripping 10 minutes, cooled and filtered, filter cake is in water and 1, and recrystallization in the 4-dioxane obtains 1 of 12.1 grams, 4-dihydroxyl-2,3-dimethyl-thioxanthone, productive rate 45.1%.
(b) with 1 of 0.01mol (3.8g), 4-dihydroxyl-2,3-dimethyl-thioxanthone, the Anhydrous potassium carbonate of 0.05mol (6.9g), the epoxy chloropropane of 20ml join in the pimelinketone of 40ml, and 80 ℃ were reacted 12 hours, refluxed 12 hours down at 135 ℃ then.After reaction finishes, drain organic layer, residue dissolves in water and chloroform, and organic phase is dewatered with Calcium Chloride Powder Anhydrous, after draining, residue is recrystallization in toluene and ethanol, obtains 1,4-two (glycidoxy)-2,3-dimethyl thia anthrone 3.1 grams, productive rate is 79.1%.
1H NMR ([D6] DMSO, and 400MHz: δ=8.27-7.07 (4H, aromatic), 4.54-3.96 (4H, Ar-CH
2-), 3.42-3.32 (2H ,-CH, epoxy), 2.92-2.76 (4H ,-CH
2, epoxy) and .FT-IR (KBr): 1644 (C=O), 1296,1040 (Ar-O-C), 1268,909cm
-1(epoxy).
Claims (4)
1. the thioxanthone photo initiator that contains diepoxy group is characterized in that the chemical structure of this compound is shown below:
R wherein
1, R
2Independently be selected from hydrogen, halogen, C1-C22 alkyl, alkoxyl group respectively.
2. the preparation method who contains the thioxanthone photo initiator of diepoxy group is characterized in that the preparation method is as follows:
(a) 1 part of thiosalicylic acid at room temperature is dissolved in the vitriol oil of 10-40 part, adds the diphenol of 1-5 part then gradually, at stirring at normal temperature 1-10 hour, be warmed up to 60-100 ℃ of reaction 2-10 hour then, the cooling standing over night.Reaction soln is added drop-wise in the long-pending boiling water of decaploid, cooled and filtered, filter cake is in water and 1, and recrystallization in the 4-dioxane obtains the thioxanthone of two hydroxyls;
(b) 1 part of two hydroxyl thioxanthone is dissolved in the organic solvent of 5-50 part, add Anhydrous potassium carbonate of 2-10 part and the epoxy chloropropane of 0.5-10 part, reacted 2-24 hour down at 60-100 ℃, then at 120-150 ℃ of following backflow 2-24 hour, after reaction finishes, wash organic phase with water and use the Calcium Chloride Powder Anhydrous drying, drain organic phase, the residue recrystallization obtains containing the thioxanthone photo initiator of diepoxy group.
3. the preparation method who contains the thioxanthone photo initiator of diepoxy group according to claim 2 is characterized in that employed diphenol chemical structural formula is as follows:
R wherein
1, R
2Independently be selected from hydrogen, halogen, C1-C22 alkyl, alkoxyl group respectively.
4. the preparation method who contains the thioxanthone photo initiator of diepoxy group according to claim 2 is characterized in that organic solvent comprises pimelinketone, butanone, toluene or dimethylbenzene.
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| CN 200310109361 CN1271069C (en) | 2003-12-12 | 2003-12-12 | Diepoxy group containing thioxanthone photoinitiator and preparation method therefor |
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| CN 200310109361 CN1271069C (en) | 2003-12-12 | 2003-12-12 | Diepoxy group containing thioxanthone photoinitiator and preparation method therefor |
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| CN1546488A true CN1546488A (en) | 2004-11-17 |
| CN1271069C CN1271069C (en) | 2006-08-23 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120046377A1 (en) * | 2009-04-30 | 2012-02-23 | Siegwerk Benelux Sa | Photoinitiators |
| CN103739745A (en) * | 2013-11-25 | 2014-04-23 | 盐城工学院 | Imidazole group-containing thioxanthone photoinitiator and preparation method thereof |
| JPWO2012077720A1 (en) * | 2010-12-09 | 2014-05-22 | 協立化学産業株式会社 | Compound suitable for photopolymerization initiator, photopolymerization initiator, and photocurable resin composition |
| CN113698382A (en) * | 2021-08-10 | 2021-11-26 | 武汉大学 | Novel thioxanthone visible light initiator and preparation method and application thereof |
-
2003
- 2003-12-12 CN CN 200310109361 patent/CN1271069C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120046377A1 (en) * | 2009-04-30 | 2012-02-23 | Siegwerk Benelux Sa | Photoinitiators |
| US8598249B2 (en) * | 2009-04-30 | 2013-12-03 | Siegwerk Druckfarben Ag & Co. Kgaa | Photoinitiators |
| JPWO2012077720A1 (en) * | 2010-12-09 | 2014-05-22 | 協立化学産業株式会社 | Compound suitable for photopolymerization initiator, photopolymerization initiator, and photocurable resin composition |
| JP5886758B2 (en) * | 2010-12-09 | 2016-03-16 | 協立化学産業株式会社 | Compound suitable for photopolymerization initiator, photopolymerization initiator, and photocurable resin composition |
| CN103739745A (en) * | 2013-11-25 | 2014-04-23 | 盐城工学院 | Imidazole group-containing thioxanthone photoinitiator and preparation method thereof |
| CN113698382A (en) * | 2021-08-10 | 2021-11-26 | 武汉大学 | Novel thioxanthone visible light initiator and preparation method and application thereof |
| CN113698382B (en) * | 2021-08-10 | 2022-06-14 | 武汉大学 | Novel thioxanthone visible light initiator and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1271069C (en) | 2006-08-23 |
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