CN102382212A - Cyclic acetal coumarin-containing photoinitiator and preparation method thereof - Google Patents
Cyclic acetal coumarin-containing photoinitiator and preparation method thereof Download PDFInfo
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- CN102382212A CN102382212A CN2011101687192A CN201110168719A CN102382212A CN 102382212 A CN102382212 A CN 102382212A CN 2011101687192 A CN2011101687192 A CN 2011101687192A CN 201110168719 A CN201110168719 A CN 201110168719A CN 102382212 A CN102382212 A CN 102382212A
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Abstract
The invention discloses a coumarin-containing photoinitiator shown in a formula in the specification and a preparation method thereof. The method comprises the following step: reacting hydroxycoumarin, hydroxycoumarin derivatives and formaldehyde used as the raw materials in an acidic solution used as the solvent at 10-100 DEG C for 1-10 hours to obtain cyclic acetal-containing coumarin. The compound can be singly used as the photoinitiator to replace a benzophenone/amine initiation system, thus the yellowing and toxicity caused by the amine initiator aid can be reduced and the compound has wide application prospect in the light-curing industrial field. In the formula, R represents H, CH3, CH2CH3, CH2CH2CH3, CH2CH2CH2CH3, C(CH3)3, COOH, Cl, F or I.
Description
Technical field: the invention belongs to a kind of light trigger and preparation method thereof, particularly contain ring acetal tonka bean camphor light trigger and preparation method thereof.
Technical background: polyfunctional monomers such as two (methyl) propenoate carry out photopolymerization reaction and can form highly cross-linked derivatized polymers fast, and these characteristics are particularly important to the higher field of curing speed, cured film physical strength and stability requirement at industrial coating, tooth dental repair material etc.
Light trigger is the key components of photocuring system, and can it is related to formula system oligopolymer and thinner when rayed become solid-state by liquid transformation rapidly.Its basic role characteristics are: initiator molecule has certain extinction ability at ultraviolet region (250-400nm) or visible region (400-800nm); After directly or indirectly absorbing luminous energy; Initiator molecule is scurried and is jumped to excited triplet state through between system from the ground state transition to the excited singlet; After excited singlet or triplet experience unit molecule or bimolecular chemical action, generation can trigger monomer polymeric biologically active fragment, and these biologically active fragments can be radical, positively charged ion, negatively charged ion or ion radical etc.Light trigger is according to the mechanism of action of generation living radical, and mainly be divided into two big types: the light-initiated body agent of cracking type is also referred to as I type light initiation system; Hydrogen-capture-type light initiator is also referred to as II type light trigger.Wherein hydrogen-capture-type light initiator is main with the aromatic ketone structure generally; They have certain photo absorption performance; In excited state and the effect of aided initiating generation bimolecular, capture the hydrogen on the aided initiating (hydrogen is given body), produce living radical; The requirement of ideal light trigger has the following advantages: (1) cheapness is synthetic simple; (2) light trigger and photodestruciton product thereof should be nonpoisonous and tasteless; (3) good stability is convenient to long-time preservation; (4) absorption spectrum of light trigger must be complementary with the emission band of radiating light source, has higher optical extinction coefficient; (5) higher efficiency of initiation.
UVNUL MS-40 is a kind of widely used hydrogen-capture-type light initiator, because its surface cure is good, and favorable solubility; Cheap and obtain easily; But it must be used with the amine aided initiating, after tonka bean camphor absorbs luminous energy, forms the sharp mixture of base through excited triplet state and aided initiating effect; Through transfer transport and hydrogen abstraction reaction, produce amine alkyl diradical initiated polymerization with higher initiating activity.But aminated compounds has toxicity and carinogenicity, and is prone to take place xanthochromia by its cured film that causes gained.Restricted its application at aspects such as food and drug packages.
Tonka bean camphor is claimed bifuran and coumarin again, is an important spices, natural being present in black tonka-bean, Liatris odoratissima, wild vanilla, the orchid.The verivate of tonka bean camphor is present in nature a bit, and some then can make through compound method; The free existence that has, what have combines with glucose, wherein much has important economic worth, temparin for example, the past is separated out by sweet alfalfa plant corruption, and present available synthetic is as anti-coagulant.Therefore, preparation feedback is active high, does not use the coumarins light trigger of amine aided initiating to become one of the exigence in field for this reason.
Summary of the invention: the invention provides a kind of cyclic acetal base tonka bean camphor light trigger and preparation method thereof that contains; This compound can replace UVNUL MS-40 directly to use as light trigger; Do not need the amine aided initiating, to reduce xanthochromia and the toxicity that causes by the amine aided initiating.And its preparation cost is low, and is simple to operate.
The present invention preparation contain the tonka bean camphor light trigger that encircles acetal, the chemical structure of this compound is shown below:
R=H wherein, CH
3, CH
2CH
3, CH
2CH
2CH
3, CH
2CH
2CH
2CH
3, C (CH
3)
3, COOH, Cl, F, I.
The preparation method that the present invention contains the tonka bean camphor light trigger that encircles acetal is following:
Claim 1, the 2 described preparing methods that contain the tonka bean camphor light trigger that encircles acetal is characterized in that: with the Hydroxycoumarin and the verivate thereof of 1 molfraction; 37% formaldehyde solution that adds 5 times of molfractions; Add the certain volume tart aqueous solution slowly, its volume (mL) be 4 hydroxy coumarin and verivate thereof molfraction 50-100 doubly, 10-100 ℃ of reaction 1-10 hour down; Filter then; With the mixed solvent recrystallization of second alcohol and water, vacuum-drying obtains containing the light trigger of the coumarins that encircles acetal.
It is following that the present invention contains the reaction formula of the tonka bean camphor light trigger that encircles acetal:
R=H wherein, CH
3, CH
2CH
3, CH
2CH
2CH
3, CH
2CH
2CH
2CH
3, C (CH
3)
3, COOH, Cl, F, I.
Acidic solution of the present invention is a hydrochloric acid, acetic acid and tosic acid, concentrated nitric acid, perchloric acid, the mixture of phosphoric acid.
The present invention contains cyclic acetal base tonka bean camphor light trigger and preparation method thereof, and this compound can replace UVNUL MS-40 directly to use as light trigger, does not need the amine aided initiating, to reduce xanthochromia and the toxicity that is caused by the amine aided initiating.And its preparation cost is low, and is simple to operate.And tonka bean camphor and verivate thereof extensively be present in the natural product, and the light trigger of preparation can improve the biocompatibility of initiator thus, and it is used on the drug and food packing.
The practical implementation method:
Following embodiment specifies the present invention, but does not limit the scope of the invention.
Embodiment 1:
0.02mol (3.24g) umbelliferone is at room temperature added 37% formaldehyde solution of 28mL, slowly drip 150mL hydrochloric acid, the mixed acid solution of 30mL phosphoric acid, the time was above 2 hours; Dropwise the back and slowly heat up, stirred 10 hours at 10 ℃, cool to room temperature filters; The filter cake water is washed till neutrality, and drying is with the mixed solvent (10: 2v/v) recrystallization, vacuum-drying with the second alcohol and water; Obtain 1,3-dioxy benzo Ji oxane benzophenone 3.85g, productive rate 94.4%.
Embodiment 2:
0.02mol (3.24g) umbelliferone is at room temperature added 37% formaldehyde solution of 28mL, slowly drip 150mL hydrochloric acid, the mixed acid solution of 10mL perchloric acid, the time was above 2 hours; Dropwise the back and slowly heat up, stirred 1 hour at 100 ℃, cool to room temperature filters; The filter cake water is washed till neutrality, and drying is with the mixed solvent (10: 2v/v) recrystallization, vacuum-drying with the second alcohol and water; Obtain 1,3-dioxy benzo Ji oxane benzophenone 3.16g, productive rate 77.5%.
Embodiment 3:
0.02mol (3.52g) 4-methyl-umbelliferone is at room temperature added 37% formaldehyde solution of 28mL, slowly drip 100mL hydrochloric acid, 20g tosic acid mixed acid solution, the time was above 2 hours; Dropwise the back and slowly heat up, stirred 6 hours at 30 ℃, filter, the filter cake water is washed till neutrality; Drying is with the mixed solvent (10: 1v/v) recrystallization, vacuum-drying with the second alcohol and water; Obtain 1,3-dioxy benzo Ji oxane-6-Methylcoumarin 3.16g, productive rate 72.4%.
Embodiment 4:
0.02mol (3.8g) 4-ethyl-umbelliferone is at room temperature added 37% formaldehyde solution of 28mL, slowly drip 150mL hydrochloric acid, 30mL concentrated nitric acid mixed acid solution, the time was above 2 hours; Dropwise the back and slowly heat up, stirred 10 hours at 58 ℃, cool to room temperature filters; The filter cake water is washed till neutrality, and drying is with the mixed solvent (10: 4v/v) recrystallization, vacuum-drying with the second alcohol and water; Obtain 1,3-dioxy benzo Ji oxane-6-ethyl coumarin 3.25g, productive rate 70.1%.
Embodiment 5:
0.02mol (4.36g) 4-normal-butyl-umbelliferone is at room temperature added 37% formaldehyde solution of 28mL, slowly drip 80mL acetic acid, 20mL vitriol oil mixed acid solution, the time was above 2 hours; Dropwise the back and slowly heat up, stirred 2 hours at 35 ℃, cool to room temperature filters; The filter cake water is washed till neutrality, and drying is with the mixed solvent (10: 5v/v) recrystallization, vacuum-drying with the second alcohol and water; Obtain 1,3-dioxy benzo Ji oxane-6-normal-butyl tonka bean camphor 3.53g, productive rate 68%.
Embodiment 6:
0.02mol (4.36g) the 4-tertiary butyl-umbelliferone is at room temperature added 37% formaldehyde solution of 28mL, slowly drip 150mL acetic acid, the mixed acid solution of 15g perchloric acid, the time was above 2 hours; Dropwise the back and slowly heat up, stirred 3 hours at 70 ℃, cool to room temperature filters; The filter cake water is washed till neutrality, and drying is with the mixed solvent (10: 3v/v) recrystallization, vacuum-drying with the second alcohol and water; Obtain 1,3-dioxy benzo Ji oxane-6-tertiary butyl tonka bean camphor 3.82g, productive rate 73.5%.
Embodiment 7:
0.02mol (3.93g) 4-chloro-umbelliferone is at room temperature added 37% formaldehyde solution of 28mL, slowly drip 180mL acetic acid, 20ml phosphoric acid mixed acid solution, the time was above 2 hours; Dropwise the back and slowly heat up, stirred 12 hours at 80 ℃, cool to room temperature filters; The filter cake water is washed till neutrality, and drying is with the mixed solvent (10: 1v/v) recrystallization, vacuum-drying with the second alcohol and water; Obtain 1,3-dioxy benzo Ji oxane-6-tertiary butyl tonka bean camphor 3.54g, productive rate 74.2%.
The application implementation example
Application implementation example 1
Under the lucifuge condition; In the Glass Containers of stirring is housed, add the initiator of 6g embodiment 1 gained, 46g aliphatic polyester acrylate resin (6000) adds 16g HDDA again 45 ℃ of stirring and dissolving; The 16g talcum powder, 84g ground barium sulfate and 32g ground dolomite mix.Can obtain radical photoinitiator curing figure layer material.The solution for preparing is applied on the substrate, placed under the 200mW high voltage mercury lamp illumination 2 minutes, obtain cured film, the transformation efficiency 85% of two keys.
Application implementation example 2
Obtain cured film, the transformation efficiency of two keys is 83%.
Application implementation example 3
Obtain cured film, the transformation efficiency of two keys is 82.8%.
Application implementation example 4
Obtain cured film, the transformation efficiency of two keys is 81.4%.
Application implementation example 5
Obtain cured film, the transformation efficiency of two keys is 79.4%.
Application implementation example 6
Obtain cured film, the transformation efficiency of two keys is 89.4%.
Application implementation example 7
Obtain cured film, the transformation efficiency of two keys is 86.4%.
Claims (6)
1. contain the tonka bean camphor light trigger that encircles acetal, it is characterized in that the chemical structure of this compound is shown below:
2. R=H wherein, CH
3, CH
2CH
3, CH
2CH
2CH
3, CH
2CH
2CH
2CH
3, C (CH
3)
3, COOH, Cl, F, I.
3. claim 1, the 2 described preparing methods that contain the coumarins light trigger that encircles acetal is characterized in that: with the Hydroxycoumarin and the verivate thereof of 1 molfraction; 37% formaldehyde solution that adds 5 times of molfractions; Add the certain volume acidic solution slowly, its volume (mL) be 4 hydroxy coumarin and verivate thereof molfraction 50-100 doubly, 10-100 ℃ of reaction 1-10 hour down; Filter then; With the mixed solvent recrystallization of second alcohol and water, vacuum-drying obtains containing the light trigger of the coumarins that encircles acetal.
4. preparation method according to claim 3 is characterized in that 10-100 ℃ of reaction, and the reaction times is 1-10 hour.
5. preparation method according to claim 3 is characterized in that: described acidic solution is a hydrochloric acid, acetic acid and tosic acid, concentrated nitric acid, perchloric acid, the mixture of phosphoric acid.
6. preparation method according to claim 3 is characterized in that: so the solvent of recrystallization is the mixture of second alcohol and water, its volume ratio is: ethanol/water=10/1-10/5.
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| CN2011101687192A CN102382212A (en) | 2011-06-17 | 2011-06-17 | Cyclic acetal coumarin-containing photoinitiator and preparation method thereof |
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|---|---|---|---|
| CN2011101687192A CN102382212A (en) | 2011-06-17 | 2011-06-17 | Cyclic acetal coumarin-containing photoinitiator and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817653A (en) * | 2015-04-22 | 2015-08-05 | 江南大学 | Coumarin oxime ester photoinitiator and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661595A (en) * | 1984-07-12 | 1987-04-28 | Sandoz Ltd. | Method for producing xanthone and thioxanthone compounds useful as photoinitiators |
| WO2005100292A1 (en) * | 2004-04-19 | 2005-10-27 | Ciba Specialty Chemicals Holding Inc. | New photoinitiators |
| CN101812141A (en) * | 2010-01-08 | 2010-08-25 | 北京化工大学 | Diphenyl ketone photo initiator containing cyclic acctals and preparation method thereof |
| CN101864006A (en) * | 2010-07-16 | 2010-10-20 | 北京化工大学常州先进材料研究院 | Thioxanthone photoinitiator containing cyclic acetal and preparation method thereof |
-
2011
- 2011-06-17 CN CN2011101687192A patent/CN102382212A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661595A (en) * | 1984-07-12 | 1987-04-28 | Sandoz Ltd. | Method for producing xanthone and thioxanthone compounds useful as photoinitiators |
| WO2005100292A1 (en) * | 2004-04-19 | 2005-10-27 | Ciba Specialty Chemicals Holding Inc. | New photoinitiators |
| CN101812141A (en) * | 2010-01-08 | 2010-08-25 | 北京化工大学 | Diphenyl ketone photo initiator containing cyclic acctals and preparation method thereof |
| CN101864006A (en) * | 2010-07-16 | 2010-10-20 | 北京化工大学常州先进材料研究院 | Thioxanthone photoinitiator containing cyclic acetal and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817653A (en) * | 2015-04-22 | 2015-08-05 | 江南大学 | Coumarin oxime ester photoinitiator and preparation method thereof |
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Application publication date: 20120321 |