CN1256364C - Macromolecule thioxanthone photo-initiator and its preparation method - Google Patents
Macromolecule thioxanthone photo-initiator and its preparation method Download PDFInfo
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- CN1256364C CN1256364C CN 200310109362 CN200310109362A CN1256364C CN 1256364 C CN1256364 C CN 1256364C CN 200310109362 CN200310109362 CN 200310109362 CN 200310109362 A CN200310109362 A CN 200310109362A CN 1256364 C CN1256364 C CN 1256364C
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Abstract
本发明公开了下式所示的一类新型高分子型硫杂蒽酮光引发剂及其制备方法。先以硫代水杨酸、二酚、环氧氯丙烷为原料合成含双环氧基团的硫杂蒽酮，再将硫杂蒽酮和二仲胺单体溶于溶剂中，升温聚合几小时，得到高分子型硫杂蒽酮光引发剂。该光引发剂主链上同时含有光引发剂硫杂蒽酮和助引发剂胺，具有较高的光引发性能，在涂料、微电子及光学等领域有着广泛应用前景。
The invention discloses a novel polymer thioxanthone photoinitiator represented by the following formula and a preparation method thereof. First use thiosalicylic acid, diphenol, and epichlorohydrin as raw materials to synthesize thioxanthone containing diepoxy groups, then dissolve thioxanthone and di-secondary amine monomers in a solvent, heat up and polymerize Hours, to obtain polymer type thioxanthone photoinitiator. The main chain of the photoinitiator contains photoinitiator thioxanthone and co-initiator amine at the same time, has high photoinitiation performance, and has wide application prospects in the fields of coatings, microelectronics, optics and the like.
Description
Technical field: the invention belongs to-kind of light trigger and preparation method thereof, particularly polymer thioxanthone photo initiator 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 (2-chlorothiaxanthenone and 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, owing to volatilize easily with photocuring system consistency difference and move, this can reduce the photopolymerization efficiency of initiation on the one hand, can cause product smell and toxicity to occur on the other hand as the light trigger of small molecules type.Therefore research and development polymer light trigger efficient, low toxicity becomes the focus that people pay close attention to.
Summary of the invention: the present invention prepares a kind of novel polymer thioxanthone photo initiator by with small molecules light trigger thioxanthone and aided initiating two secondary amine addition polymerizations.Not only allow thioxanthone use under the condition of aided initiating need not, improved the light-initiated efficient of thioxanthone, and widened the range of application of thioxanthone as light trigger.
Polymer thioxanthone photo initiator of the present invention, its repeated structural unit is as follows:
Wherein, polymerization degree n=1-100, R
1Independently be selected from the alkyl of C2-C18 respectively, R
2Independently be selected from the alkyl of C1-C18 respectively, R
3And R
4Independently be selected from hydrogen respectively, halogen, the alkyl of C1-C18, alkoxyl group.
The method of the preparation of polymer thioxanthone photo initiator of the present invention is as follows:
(a) 1 part thiosalicylic acid at room temperature is dissolved in the vitriol oil of 5-50 part, adds the diphenol of 0.5-5 part then gradually, at stirring at normal temperature 1-10 hour, be warmed up to 60-100 ℃ of reaction 2-10 hour then, quiet the causing of lowering the temperature spent the 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.Two hydroxyl thioxanthones of 1 part are dissolved in the organic solvent of 5-50 part, add Anhydrous potassium carbonate of 1-10 part and the epoxy chloropropane of 0.5-10 part, reaction is 2-24 hour under 60-100C, 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.
(b) 1 part the thioxanthone that contains two epoxide groups is dissolved in the organic solvent of 5-50 part, adds the di-secondary amine monomers, 40 ℃-100 ℃ reactions 1-20 hour down, the molar ratio range of thioxanthone and two secondary amine is 2: 1-2: 4.After reaction finishes, solution poured in the water precipitate, filter, filter cake is washed for several times with deionized water, 40 ℃ of vacuum-dryings 48 hours target product polymer thioxanthone photo initiator.
The entire reaction equation that the present invention prepares the polymer thioxanthone photo initiator can be expressed as:
Organic solvent used in the present invention comprises: dimethyl sulfoxide (DMSO), alcohols, N-methyl-pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide, butanone.
Di-secondary amine monomers chemical structure used in the present invention is shown below:
R wherein
1Independently be selected from the alkyl of C2-C18 respectively, R
2Independently be selected from the alkyl of C1-C18 respectively.
The chemical structure of diphenol used in the present invention is shown below:
R wherein
3And R
4Independently be selected from hydrogen respectively, halogen, the alkyl of C1-C18, alkoxyl group.
Polymer thioxanthone photo initiator of the present invention because main chain contains aided initiating amine and light trigger thioxanthone simultaneously, makes light-initiated performance improve; Simultaneously, it is again a kind of polymer, is difficult for moving to the surface in light-cured resin preservation process, has reduced the toxicity of light trigger; 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 of embodiment 1 polymer thioxanthone photo initiator.
Fig. 2 is the nucleus magnetic hydrogen spectrum of embodiment 1 polymer thioxanthone photo initiator.
The GPC spectrogram of Fig. 3 formula embodiment 1 polymer thioxanthone photo initiator.
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 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%.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%.
(b): with 5mmol 1,4-(glycidoxy) thioxanthone is dissolved in the dimethyl sulfoxide (DMSO) of 30ml, adds the piperazine of 5mmol, after the dissolving, is warming up to 80 ℃ of reactions 12 hours fully.React in the aqueous solution of after finishing solution being poured into the 500ml dilute sodium hydroxide and precipitate, filter, filter cake is given a baby a bath on the third day after its birth time with deionized water, and filter cake was dry 48 hours of 40 ℃ vacuum drying oven, get target product polymer thioxanthone photo initiator 2.02g, getting productive rate with respect to thioxanthone is 90%.Mn=8.6 * 10
3(record by GPC, N, dinethylformamide is an eluent, sees Fig. 3).
1H NMR ([d
6] DMSO, 400MHz): δ=8.24-7.08 (6H, phenyl ring), 4.86 (2H ,-OH), 4.10-3.93 (6H ,-OCH
2,-OCH), 2.48-2.41 (12H ,-NCH
2), see Fig. 2.FT-IR (KBr): 3401 (O-H), 2923,2813 (C-H), 1628cm
-1(C=O), see Fig. 1.
Embodiment 2
(a): the thiosalicylic acid of 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%.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%.
(b): with 5mmol 1,4-(glycidoxy) thioxanthone is dissolved in the dimethyl sulfoxide (DMSO) of 30ml, adds the N of 5mmol, and N '-dimethyl-quadrol after the dissolving, is warming up to 80 ℃ of reactions 12 hours fully.React in the aqueous solution of after finishing solution being poured into the 500ml dilute sodium hydroxide and precipitate, filter, filter cake is given a baby a bath on the third day after its birth time with deionized water, and filter cake was dry 48 hours of 40 ℃ vacuum drying oven, get target product polymer thioxanthone photo initiator 1.98g, getting productive rate with respect to thioxanthone is 90%.Mn=9 * 10
3(recorded by GPC, N, dinethylformamide are eluent).
1H NMR ([d
6] DMSO, 400MHz): δ=8.24-7.08 (6H, phenyl ring), 4.86 (2H ,-OH), 4.10-3.93 (6H ,-OCH
2,-OCH), 2.48-2.41 (14H ,-NCH
2,-NC
3) .FT-IR (KBr): 3401 (O-H), 2923,2813 (C-H), 1628cm
-1(C=O).
Embodiment 3
(a): the thiosalicylic acid of 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%.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%.
(b): with 5mmol 1,4-two (glycidoxy) thioxanthone is dissolved in the dimethyl sulfoxide (DMSO) of 30ml, adds the N of 5mmol, and N '-phenylbenzene-quadrol after the dissolving, is warming up to 80 ℃ of reactions 12 hours fully.React in the aqueous solution of after finishing solution being poured into the 500ml dilute sodium hydroxide and precipitate, filter, filter cake is given a baby a bath on the third day after its birth time with deionized water, and filter cake was dry 48 hours of 40 ℃ vacuum drying oven, get target product polymer thioxanthone photo initiator 2.42g, getting productive rate with respect to thioxanthone is 90%.Mn=7.5 * 10
3(record by GPC, N, N-two basic methane amides are eluent).
1H NMR ([d
6] DMSO, 400MHz): δ=8.24-6.88 (16H, phenyl ring), 4.86 (2H ,-OH), 4.10-3.93 (6H ,-OCH
2,-OCH), 2.48-2.41 (8H ,-NCH
2) .FT-IR (KBr): 3401 (O-H), 2923,2813 (C-H), 1628cm
-1(C=O).
Claims (5)
1. polymer thioxanthone photo initiator is characterized in that the repeated structural unit of polymer thioxanthone photo initiator is shown below:
Wherein, polymerization degree n=1-100; R
1Independently be selected from the alkyl of C2-C18 respectively; R
2Independently be selected from the alkyl of C1-C18 respectively; R
3And R
4Independently be selected from hydrogen respectively, halogen, the alkyl of C1-C18 or alkoxyl group.
2. the preparation method of polymer thioxanthone photo initiator as claimed in claim 1 is characterized in that the preparation method is as follows:
(a) 1 part thiosalicylic acid at room temperature is dissolved in the vitriol oil of 5-50 part, the diphenol that adds 0.5-5 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 be in water and 1, recrystallization in the 4-dioxane, obtain the thioxanthone of two hydroxyls, two hydroxyl thioxanthones of 1 part are dissolved in the organic solvent of 5-50 part, add Anhydrous potassium carbonate of 1-10 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;
(b) 1 part the thioxanthone that contains diepoxy group is dissolved in the organic solvent of 5-50 part, add the di-secondary amine monomers, reacted 1-20 hour down at 40 ℃-100 ℃, the molar ratio range of thioxanthone and two secondary amine is 2: 1-2: 4, after reaction finishes, solution poured in the water precipitate, filter, filter cake is washed for several times with deionized water, and 40 ℃ of vacuum-dryings got target product polymer thioxanthone photo initiator in 48 hours.
3. the preparation method of polymer thioxanthone photo initiator according to claim 2 is characterized in that employed di-secondary amination structure is shown below:
R wherein
1Independently be selected from the alkyl of C2-C18 respectively; R
2Independently be selected from the alkyl of C1-C18 respectively.
4. the preparation method of polymer thioxanthone photo initiator according to claim 2 is characterized in that the chemical structural formula of employed diphenol is shown below:
R wherein
3And R
4Independently be selected from hydrogen respectively, halogen, the alkyl of C1-C18 or alkoxyl group.
5. the preparation method of polymer thioxanthone photo initiator according to claim 2, it is characterized in that employed organic solvent is selected from dimethyl sulfoxide (DMSO), alcohols, N-methyl-pyrrolidone, N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, butanone, pimelinketone, toluene or dimethylbenzene.
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| CN113698382B (en) * | 2021-08-10 | 2022-06-14 | 武汉大学 | Novel thioxanthone visible light initiator and preparation method and application thereof |
| CN119708499A (en) * | 2023-09-28 | 2025-03-28 | 上海交通大学 | Low surface energy macromolecular photoinitiator, UV LED (ultraviolet) photocureable coating and photocuring skin-feel coating |
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