CN1594370A - Thioxanthone photoinitiator containing aid initiator amino group and preparation method therefor - Google Patents
Thioxanthone photoinitiator containing aid initiator amino group and preparation method therefor Download PDFInfo
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- CN1594370A CN1594370A CN 200410025685 CN200410025685A CN1594370A CN 1594370 A CN1594370 A CN 1594370A CN 200410025685 CN200410025685 CN 200410025685 CN 200410025685 A CN200410025685 A CN 200410025685A CN 1594370 A CN1594370 A CN 1594370A
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Abstract
The invention discloses thioxanthone photoinitiator containing aid initiator amino group and preparation method which consists of, using 2-mercaptobenzoic acid, dioxybenzene and epichlorohydrin as raw material, dissolving 2-mercaptobenzoic acid into concentrated sulfuric acid, charging diphenol for reaction, preparing thioxanthene ketone containing double hydroxyl, then reacting bishydroxy thioxanthene ketone with epichlorohydrin 24 hours at 120-140 deg. C at the presence of potasium carbonate, so as to synthesize thioxanthene ketone having double epoxy radicals, then reacting thioxanthene ketone with double epoxy radicals with secondary amine or primary amine to obtain thioxanthene ketone photo-initiation agent containing amido initiator.
Description
Technical field: the invention belongs to a kind of light trigger and preparation method thereof, particularly contain thioxanthone photo initiator of aided initiating amino and preparation method thereof.
Background technology: 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 (isopropyl thioxanthone, US Patent 6025408) as the efficiency light initiator is not only poor with the photocuring system consistency, and must could use at aided initiating amine.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, this can reduce the photopolymerization efficiency of initiation on the one hand, the aided initiating aminated compounds can cause product smell and toxicity to occur owing to volatile on the other hand.So research and development is efficient, become the focus that people pay close attention to system consistency light trigger good, that toxicity is little.
Summary of the invention: the present invention is incorporated into the aided initiating amino group in the thioxanthone molecule, not only improved the solubility property of thioxanthone, improved the consistency of initiator and initiator system, use separately under the condition that can also not need aided initiating amine to exist, so not only improved the light-initiated efficient of thioxanthone, and widened the range of application of thioxanthone as light trigger.
The present invention contains the thioxanthone photo initiator of aided initiating amino, and its structural formula is as follows:
R wherein
1, R
2Independently be selected from hydrogen, halogen, C1-C22 alkyl or alkoxyl group respectively, R
3And R
4Independently be selected from hydrogen respectively, C1-C22 alkyl, alkoxyl group, amino or hydroxyl.
The method of preparation of thioxanthone photo initiator that the present invention contains aided initiating amino is as follows, and following umber is in weight unit:
(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 of diepoxy group; Then the thioxanthone of 1 part diepoxy group and the aminocompound of 1-10 part are dissolved in the organic solvent of 5-50 part, 40-120 ℃ of reaction is after 1-20 hour, reaction soln is poured in the dilute hydrochloric acid, toluene wash for several times, regulate aqueous pH values to 10, chloroform extraction is drained the thioxanthone photo initiator that residue recrystallization behind the chloroform obtains containing aided initiating amino.
The entire reaction equation that the present invention's preparation contains the thioxanthone photo initiator of aided initiating amino can be expressed as:
Organic solvent used in the present invention comprises: methyl alcohol, ethanol, propyl alcohol, acetone, butanone, pimelinketone, chloroform, benzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, toluene or dimethylbenzene.Alcohols, ketone, chloroform, benzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, toluene or dimethylbenzene.
Di-secondary amine monomers chemical structure used in the present invention is shown below:
Wherein, R
3And R
4Independently be selected from hydrogen respectively, C1-C22 alkyl, alkoxyl group, amino or hydroxyl.
The chemical structure of diphenol used in the present invention is shown below:
R wherein
1, R
2Independently be selected from hydrogen, halogen, C1-C22 alkyl or alkoxyl group respectively.
The present invention contains the thioxanthone photo initiator of aided initiating amino, owing to contain aided initiating amine and light trigger thioxanthone simultaneously, makes light-initiated performance improve; And contain coinitiator amine in the molecular structure, must not add coinitiator again in the use, so it will have wide practical use in the photocuring field.
Description of drawings:
Fig. 1 is the infrared spectra that embodiment 1 contains the thioxanthone photo initiator of aided initiating amino.
Fig. 2 is the nucleus magnetic hydrogen spectrum that embodiment 1 contains the thioxanthone photo initiator of aided initiating amino.
Concrete embodiment:Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1
(a): the thiosalicylic acid of 16g (0.1mol) is dissolved in the vitriol oil of 150ml, and stirring at room 10 minutes slowly adds the Resorcinol of 44gl (0.4mo), 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 3.56g (0.01mol), 4-dihydroxyl thioxanthone, the Anhydrous potassium carbonate of 6.9g (0.05mol), the epoxy chloropropane of 20g join in the pimelinketone of 40g, 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%; Then the thioxanthone of the diepoxy group of 3.56g (0.01mol) and the hexahydropyridine of 4.2g (0.05mol) are dissolved in the ethanol of 30g, 80 ℃ of reactions are after 4 hours, reaction soln is poured in the dilute hydrochloric acid, toluene wash for several times, regulate aqueous pH values to 10, chloroform extraction is drained the thioxanthone photo initiator that residue recrystallization behind the chloroform obtains containing aided initiating amino.
1H NMR ([d
6] DMSO, 400MHz): δ=8.26-7.11 (6H, phenyl ring), 4.82 (2H ,-OH), 4.10-3.93 (6H ,-OCH
2,-OCH), 2.50-2.34 (6H ,-NCH
2), 1.47-1.34 (12H ,-CH
2) see Fig. 2.FT-IR (KBr): 3400 (O-H), 2931 (C-H), 1632cm
-1(C=O), see Fig. 1.
Embodiment 2
(a): the thiosalicylic acid of 16g (0.1mol) is dissolved in the vitriol oil of 150ml, and stirring at room 10 minutes slowly adds the Resorcinol of 44g l (0.4mo), 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 3.56g (0.01mol), 4-dihydroxyl thioxanthone, the Anhydrous potassium carbonate of 6.9g (0.05mol), the epoxy chloropropane of 20g join in the pimelinketone of 40g, 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%; Then the thioxanthone of the diepoxy group of 3.56g (0.01mol) and the diethylamine of 4.2g (0.05mol) are dissolved in the ethanol of 30g, 80 ℃ of reactions are after 4 hours, reaction soln is poured in the dilute hydrochloric acid, toluene wash for several times, regulate aqueous pH values to 10, chloroform extraction is drained the thioxanthone photo initiator that residue recrystallization behind the chloroform obtains containing aided initiating amino.
1H NMR ([d
6] DMSO, 400MHz): δ=8.26-7.11 (6H, phenyl ring), 4.82 (2H ,-OH), 4.10-3.93 (6H ,-OCH
2,-OCH), 2.48-2.34 (12H ,-NCH
2), 1.01-0.94 (12H ,-CH
2) FT-IR (KBr): 3400 (O-H), 2931 (C-H), 1632cm
-1(C=O).
(a): the thiosalicylic acid of 16g (0.1mol) is dissolved in the vitriol oil of 150ml, and stirring at room 10 minutes slowly adds the methyl hydroquinone of 48g (0.4mol), 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 1500g, boiled again after dripping 10 minutes, cooled and filtered, filter cake is in water and 1, and recrystallization in the 4-dioxane obtains the 11.2 2-methyl isophthalic acids that restrain, 4-dihydroxyl thioxanthone, productive rate 50%.
(b): with the 2-methyl isophthalic acid of 3.56g (0.01mol), 4-dihydroxyl thioxanthone, the Anhydrous potassium carbonate of 6.9g (0.05mol), the epoxy chloropropane of 20g join in the pimelinketone of 40g, 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 the 2-methyl isophthalic acid, 4-two (glycidoxy) thioxanthone 2.8 grams, and productive rate is 78.6%; Then the thioxanthone of the diepoxy group of 3.56g (0.01mol) and the hexahydropyridine aminocompound of 4.2g (0.05mol) are dissolved in the ethanol of 30g, 80 ℃ of reactions are after 4 hours, reaction soln is poured in the dilute hydrochloric acid, toluene wash for several times, regulate aqueous pH values to 10, chloroform extraction is drained the thioxanthone photo initiator that residue recrystallization behind the chloroform obtains containing aided initiating amino.
1H NMR ([d
6] DMSO, 400MHz): δ=8.26-7.11 (5H, phenyl ring), 4.82 (2H ,-OH), 4.10-3.93 (6H ,-OCH
2,-OCH), 2.50-2.34 (6H ,-NCH
2), 1.47-1.34 (12H ,-CH
2).FT-IR(KBr)：3400(O-H)，2931(C-H)，1632cm
-1(C＝O)。
Claims (5)
1. the thioxanthone photo initiator that contains aided initiating amino 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 or alkoxyl group respectively; R
3And R
4Solely be selected from hydrogen respectively, C1-C22 alkyl, alkoxyl group, amino or hydroxyl.
2. the preparation method who contains the thioxanthone photo initiator of aided initiating amino is characterized in that the preparation method is as follows, and following umber is in weight unit:
(a) 1 part of thiosalicylic acid at room temperature is dissolved in the vitriol oil of 10-40 part, the diphenol that adds 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 is added drop-wise to reaction soln 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 of diepoxy group; Then the thioxanthone of 1 part diepoxy group and the aminocompound of 1-10 part are dissolved in the organic solvent of 5-50 part, 40-120 ℃ of reaction is after 1-20 hour, reaction soln is poured in the dilute hydrochloric acid, toluene wash for several times, regulate aqueous pH values to 10, chloroform extraction is drained the thioxanthone photo initiator that residue recrystallization behind the chloroform obtains containing aided initiating amino.
3. the preparation method who contains the thioxanthone photo initiator of aided initiating amino 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 or alkoxyl group respectively.
4. the preparation method who contains the thioxanthone photo initiator of aided initiating amino according to claim 2 is characterized in that employed aminocompound chemical structural formula is as follows:
Wherein, R
3And R
4Independently be selected from hydrogen respectively, C1-C22 alkyl, alkoxyl group, amino or hydroxyl.
5. the preparation method who contains the thioxanthone photo initiator of diepoxy group according to claim 2 is characterized in that organic solvent comprises methyl alcohol, ethanol, propyl alcohol, acetone, butanone, pimelinketone, chloroform, benzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, toluene or dimethylbenzene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410025685 CN1594370A (en) | 2004-07-01 | 2004-07-01 | Thioxanthone photoinitiator containing aid initiator amino group and preparation method therefor |
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|---|---|---|---|
| CN 200410025685 CN1594370A (en) | 2004-07-01 | 2004-07-01 | Thioxanthone photoinitiator containing aid initiator amino group and preparation method therefor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120783A (en) * | 2011-04-26 | 2011-07-13 | 盐城工学院 | Aliphatic tertiary amine-containing thioxanthone photoinitiator and preparation method thereof |
| CN102212150A (en) * | 2011-04-26 | 2011-10-12 | 盐城工学院 | Polymerizable thioxanthone photoinitiator containing auxiliary initiator amine and preparation method thereof |
| CN102250059A (en) * | 2011-04-26 | 2011-11-23 | 盐城工学院 | Tertiary aromatic amino- and dyhydroxyl-containing thioxanthone photoinitiators and preparation method thereof |
| US20120046377A1 (en) * | 2009-04-30 | 2012-02-23 | Siegwerk Benelux Sa | Photoinitiators |
| CN108586639A (en) * | 2018-05-11 | 2018-09-28 | 合肥工业大学 | A kind of thioxanthone photo initiator and preparation method of the amine containing aided initiating of photopolymerization |
| CN113698382A (en) * | 2021-08-10 | 2021-11-26 | 武汉大学 | Novel thioxanthone visible light initiator and preparation method and application thereof |
-
2004
- 2004-07-01 CN CN 200410025685 patent/CN1594370A/en active Pending
Cited By (11)
| 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 |
| CN102120783A (en) * | 2011-04-26 | 2011-07-13 | 盐城工学院 | Aliphatic tertiary amine-containing thioxanthone photoinitiator and preparation method thereof |
| CN102212150A (en) * | 2011-04-26 | 2011-10-12 | 盐城工学院 | Polymerizable thioxanthone photoinitiator containing auxiliary initiator amine and preparation method thereof |
| CN102250059A (en) * | 2011-04-26 | 2011-11-23 | 盐城工学院 | Tertiary aromatic amino- and dyhydroxyl-containing thioxanthone photoinitiators and preparation method thereof |
| CN102120783B (en) * | 2011-04-26 | 2012-11-28 | 盐城工学院 | Aliphatic tertiary amine-containing thioxanthone photoinitiator and preparation method thereof |
| CN102212150B (en) * | 2011-04-26 | 2012-11-28 | 盐城工学院 | Polymerizable thioxanthone photoinitiator containing auxiliary initiator amine and preparation method thereof |
| CN108586639A (en) * | 2018-05-11 | 2018-09-28 | 合肥工业大学 | A kind of thioxanthone photo initiator and preparation method of the amine containing aided initiating of photopolymerization |
| CN108586639B (en) * | 2018-05-11 | 2020-02-14 | 合肥工业大学 | Photopolymerisable thioxanthone photoinitiator containing coinitiator amine 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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