CN102286113A - Silicon-containing polymeric photoinitiator and preparation method thereof - Google Patents
Silicon-containing polymeric photoinitiator and preparation method thereof Download PDFInfo
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- CN102286113A CN102286113A CN 201110168727 CN201110168727A CN102286113A CN 102286113 A CN102286113 A CN 102286113A CN 201110168727 CN201110168727 CN 201110168727 CN 201110168727 A CN201110168727 A CN 201110168727A CN 102286113 A CN102286113 A CN 102286113A
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Abstract
The invention relates to a silicon-containing polymeric photoinitiator and a preparation method thereof. The preparation method comprises the following steps: dissolving maleic anhydride in an organic solvent, adding the mixture in a four-necked flask protected by nitrogen, then dissolving silicone-containing resins in an organic solvent, dropwise adding the solution in the four-necked flask, and stirring at the room temperature for 1-3 hours; adding a Lewis acid in the four-necked flask, heating to 20-60 DEG C, then dropwise adding hexamethyldisilazane (HMDS) which is dissolved in an organic solvent, in the mixed solution, keeping the temperature at 20-60 DEG C, and performing refluxing, condensing and stirring for 1-3hours; and cooling the solution to the room temperature, filtering, and using a rotary evaporator to remove the solvent and obtain the silicon-containing polymeric photoinitiator. The preparation method has simple reaction steps, fewer post-treatment steps and low cost, and is easy to control; and by adopting the method, industrialization is easy to realize.
Description
Technical field
The invention belongs to light sensitive molecule material field, be specifically related to a kind of preparation method who contains the macromolecular photoinitiator of silicon.
Background technology
Shine on photosensitive compound by light (UV-light or visible light), make it that a series of optical physics, photochemical reaction take place, generate biologically active fragment, biologically active fragment causes liquid-state oligomers (comprising monomer) polymerization again, and the process that is converted into solid-state macromolecular material is called photopolymerization (claiming photocuring again) liquid coating moment the most at last.At present, light polymerization technique is applied to fields such as coating, printing ink, tackiness agent, microelectronics, the reparation of tooth section and biomaterial in real life.
Light trigger plays a part very important in photopolymerization reaction, and can it be related to formula system oligopolymer and thinner when rayed and be transformed into solid-state rapidly by liquid state.According to reaction mechanism, light trigger can be divided into radical photoinitiator and cationic photoinitiator.Radical photoinitiator is accepted luminous energy and is become excited state (PI from ground state under illumination
*), and then resolve into free radical.Free radical combines with the carbon-carbon double bond of monomer (M), and carries out chain-growth on this basis, makes carbon-carbon double bond generation polymerization.The radical photoinitiator curing system is a most widely used system in the photo-cured coating, and advantage is that curing speed is fast, and cost of material is cheap relatively.But problem, the especially latter such as this system existence is shunk greatly, oxygen inhibition usually are the problems that must overcome in the formulating of recipe.Cationic photoinitiator generally is to utilize the ring-opening polymerization of the protonic acid catalysis epoxy group(ing) that cation light initiator produces under illumination or the cationoid polymerisation of electron rich carbon-carbon double bond (as vinyl ether).This cationoid light trigger mainly contains sulfosalt, salt compounded of iodine.The cation photocuring system biggest advantage is the problem that does not have oxygen inhibition, and cure shrinkage is less and bonding strength is stronger in addition.Shortcoming is that curing speed is slower than free radical system, and cost of material is more expensive, and this is the major cause that applying of cationic system can not show a candle to free radical system.Therefore, be necessary radical photoinitiator is improved, solve its oxygen inhibition and shrink problems such as big.In the reality prescription, great majority are small molecules light triggers, the photodestruciton reaction can take place when polymerization produce the free small organic molecule, and this point restricts its application on biology, medicine and packaging material for food.So, study a kind of macromolecular photoinitiator and reduce photolytic product the influence of system is had bright development prospect.
People such as F.Sun have studied (Nucl.Instrum.Methods Phys.Rss., Sect B, 2009 (267): 3590-3593) a kind of dynamic performance of siliceous benzophenone derivates light trigger research.People such as Wang Ying have studied (information-recording material, 2008 (9): 8-11) a kind of synthetic and performance study of siliceous macromolecular photoinitiator.Chinese patent CN101220106A (open day: 2008.7.16) disclose a kind of siliceous macromolecular photoinitiator and preparation method and use thereof.Chinese patent CN101077897A (open day: 2007.11.28) disclose a kind of super-branching silicon-base macromolecule optical initiator and preparation method thereof.Chinese patent CN101481456A (open day: 2009.7.15) disclose a kind of preparation method who is used for the macromole evocating agent of polyreaction.
More than these methods have following shortcoming: 1, synthesis step is more, and cost is higher; 2, aftertreatment complexity, test more loaded down with trivial details, be difficult to control, yield is not high, is unfavorable for scale operation.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, the preparation method that a kind of synthesis step is few, aftertreatment simply contains the macromolecular photoinitiator of silicon is provided.This initiator general structure is as follows:
In the formula, R
1A kind of in hydrogen atom, methyl, methoxyl group, the halogen; R
2A kind of in hydrogen atom, methyl, methoxyl group, the halogen; R
3Be C
1-C
12The alkyl of different chain length, N, O, the C that heteroatomss such as S replace
1-C
12The alkyl of different chain length and the aryl that has different substituents.
1, a kind of preparation method of siliceous macromolecular photoinitiator is characterized in that may further comprise the steps:
(1) MALEIC ANHYDRIDE is dissolved in the organic solvent, joins in the four-hole boiling flask that has nitrogen protection, will contain silicone resin again and be dissolved in and being added drop-wise in the organic solvent in the four-hole boiling flask, dropwise back stirring at room 1～3h;
(2) Lewis acid is joined in the four-hole boiling flask, be warmed up to 20～60 ℃, the hmds (HMDS) that will be dissolved in organic solvent drips in the mixed solution, after dropwising, keeps 20～60 ℃, and reflux condensation mode stirs 1～3h;
(3) above-mentioned solution is cooled to room temperature, filters, remove with Rotary Evaporators then and desolvate, promptly get siliceous macromolecular photoinitiator.
2, method according to claim 1 is characterized in that, will contain silicone resin in the step (1) and join in the MALEIC ANHYDRIDE, and the mol ratio that wherein contains silicone resin and MALEIC ANHYDRIDE is 1: 1～3.
3, method according to claim 1 is characterized in that, containing silicone resin in the step (1) is the siliceous amine of macromole that contains methyl, methoxyl group, halogen.
4, method according to claim 1 is characterized in that, the organic solvent described in the step (1) is a kind of in tetrahydrofuran (THF), acetone, ethyl acetate, the methylene dichloride.
5, method according to claim 1 is characterized in that, Lewis acid and the hmds described in the step (2), and the mol ratio that wherein contains silicone resin and Lewis acid is 1: 1～3, the mol ratio that contains silicone resin and hmds is 1: 1～5.
6, method according to claim 1 is characterized in that, the Lewis acid described in the step (2) is a kind of in zinc bromide, aluminum chloride, iron(ic) chloride, the boron trifluoride.
7, method according to claim 1 is characterized in that, the solvent described in the step (2) is a kind of in tetrahydrofuran (THF), acetone, ethyl acetate, the methylene dichloride.
Compared with prior art, the present invention has the following advantages:
1, the preparation method of the siliceous light trigger of a kind of macromole provided by the invention has avoided too much reactions steps, and last handling process is simple, has reduced the cost in the actual mechanical process.
2, the siliceous light trigger of macromole of the present invention's preparation exists under the condition of aided initiating, can absorb UV-light, trigger monomer carries out polymerization, and because the surface tension of silicon is big, migrate to coatingsurface in the polymerization process, reduce the oxygen inhibition effect of radical photoinitiator effectively, had higher efficiency of initiation.
3, the siliceous light trigger of macromole of the present invention preparation itself can polymerization, has reduced the free small organic molecule that the photodestruciton reaction produces, and is applied to biomaterial, the potentiality in food, drug packing material field.
Embodiment
Embodiment 1
Synthesizing of the siliceous light trigger of methyl substituted macromole
0.4g MALEIC ANHYDRIDE and 10mL tetrahydrofuran (THF) are together added in the four-hole boiling flask that has mechanical stirring, nitrogen protection device; under the room temperature condition; take by weighing the methyl substituted silicone resin that contains of 4.4g; it is dissolved in the 15mL tetrahydrofuran (THF) again; in 1 hour, splash in the four-hole boiling flask; after dropwising, continue to stir 2 hours, obtain transparent liquid.Disposable adding 0.9gZnBr in transparent mixed solution
2, rising temperature of reaction to 50 ℃ takes by weighing 1.0g hmds (HMDS) and is dissolved in the 10mL tetrahydrofuran (THF), utilizes constant pressure funnel to splash in the four-hole boiling flask in 1.5 hours, after dropwising, continues reflux and stirs 1.5 hours.To obtain troubled liquor and filter, and remove with Rotary Evaporators and desolvate, and obtain oyster white and be with light yellow viscous liquid slightly, its structure is shown in structural formula 1.
1H NMR (250MHz) in CDCl
3: δ 0.08ppm (6H, CH
3), 1.74ppm (2H, C-CH
2-C), 3.48ppm (2H, C-CH
2-N), 3.79ppm (2H, O-CH
2), 6.94ppm (2H, two keys on the maleinamide ring).
Structural formula 1
Embodiment 2
Synthesizing of the siliceous light trigger of macromole that methoxyl group replaces
0.38g MALEIC ANHYDRIDE and 10mL tetrahydrofuran (THF) are together added in the four-hole boiling flask that has mechanical stirring, nitrogen protection device; under the room temperature condition; take by weighing the silicone resin that contains of 4.4g methoxyl group replacement; it is dissolved in the 15mL tetrahydrofuran (THF) again; in 1 hour, splash in the four-hole boiling flask; after dropwising, continue to stir 2 hours, obtain transparent liquid.Disposable adding 0.88gZnBr in transparent mixed solution
2, rising temperature of reaction to 50 ℃ takes by weighing 1.0g hmds (HMDS) and is dissolved in the 10mL tetrahydrofuran (THF), utilizes constant pressure funnel to splash in the four-hole boiling flask in 1.5 hours, after dropwising, continues reflux and stirs 1.5 hours.To obtain troubled liquor and filter, and remove with Rotary Evaporators and desolvate, and obtain oyster white and be with light yellow viscous liquid slightly, its structure is shown in structural formula 2.
1H NMR (250MHz) in CDCl
3: δ 1.74ppm (2H, C-CH
2-C), 3.48ppm (2H, C-CH
2-N), 3.79ppm (2H, O-CH
2), 3.55ppm (6H, OCH
3), 6.94ppm (2H, two keys on the maleinamide ring).
Structural formula 2
Embodiment 3
Synthesizing of the siliceous light trigger of macromole that chlorine replaces
0.38g MALEIC ANHYDRIDE and 10mL tetrahydrofuran (THF) are together added in the four-hole boiling flask that has mechanical stirring, nitrogen protection device; under the room temperature condition; take by weighing the silicone resin that contains of 4.4g chlorine replacement; it is dissolved in the 15mL tetrahydrofuran (THF) again; in 1 hour, splash in the four-hole boiling flask; after dropwising, continue to stir 2 hours, obtain transparent liquid.Disposable adding 0.88gZnBr in transparent mixed solution
2, rising temperature of reaction to 50 ℃ takes by weighing 1.0g hmds (HMDS) and is dissolved in the 10mL tetrahydrofuran (THF), utilizes constant pressure funnel to splash in the four-hole boiling flask in 1.5 hours, after dropwising, continues reflux and stirs 1.5 hours.To obtain troubled liquor and filter, and remove with Rotary Evaporators and desolvate, and obtain oyster white and be with light yellow viscous liquid slightly, its structure is shown in structural formula 3.
1H NMR (250MHz) in CDCl
3: δ 1.74ppm (2H, C-CH
2-C), 3.48ppm (2H, C-CH
2-N), 3.79ppm (2H, O-CH
2), 6.94ppm (2H, two keys on the maleinamide ring).
Structural formula 3
Embodiment 4
Synthesizing of the siliceous light trigger of methyl substituted macromole
0.4g MALEIC ANHYDRIDE and 10mL tetrahydrofuran (THF) are together added in the four-hole boiling flask that has mechanical stirring, nitrogen protection device; under the room temperature condition; take by weighing the methyl substituted silicone resin that contains of 4.4g; it is dissolved in the 15mL tetrahydrofuran (THF) again; in 1 hour, splash in the four-hole boiling flask; after dropwising, continue to stir 2 hours, obtain transparent liquid.Disposable adding 0.91gZnBr in transparent mixed solution
2, rising temperature of reaction to 50 ℃ takes by weighing 1.03g hmds (HMDS) and is dissolved in the 10mL tetrahydrofuran (THF), utilizes constant pressure funnel to splash in the four-hole boiling flask in 1.5 hours, after dropwising, continues reflux and stirs 1.5 hours.To obtain troubled liquor and filter, and remove with Rotary Evaporators and desolvate, and obtain oyster white and be with light yellow viscous liquid slightly, its structure is shown in structural formula 4.
1H NMR (250MHz) in CDCl
3: δ 0.08ppm (6H, CH
3), 3.67ppm (2H, C-CH
2-N), 4.05ppm (2H, O-CH
2), 6.94ppm (2H, two keys on the maleinamide ring).
Structural formula 4
Embodiment 5
Synthesizing of the siliceous light trigger of macromole that methoxyl group replaces
0.39g MALEIC ANHYDRIDE and 10mL tetrahydrofuran (THF) are together added in the four-hole boiling flask that has mechanical stirring, nitrogen protection device; under the room temperature condition; take by weighing the silicone resin that contains of 4.4g methoxyl group replacement; it is dissolved in the 15mL tetrahydrofuran (THF) again; in 1 hour, splash in the four-hole boiling flask; after dropwising, continue to stir 2 hours, obtain transparent liquid.Disposable adding 0.9gZnBr in transparent mixed solution
2, rising temperature of reaction to 50 ℃ takes by weighing 1.02g hmds (HMDS) and is dissolved in the 10mL tetrahydrofuran (THF), utilizes constant pressure funnel to splash in the four-hole boiling flask in 1.5 hours, after dropwising, continues reflux and stirs 1.5 hours.To obtain troubled liquor and filter, and remove with Rotary Evaporators and desolvate, and obtain oyster white and be with light yellow viscous liquid slightly, its structure is shown in structural formula 5.
1H NMR (250MHz) in CDCl
3: δ 3.55ppm (6H, OCH
3), 3.67ppm (2H, C-CH
2-N), 4.05ppm (2H, O-CH
2), 6.94ppm (2H, two keys on the maleinamide ring).
Structural formula 5
Embodiment 6
Synthesizing of the siliceous light trigger of macromole that chlorine replaces
0.39g MALEIC ANHYDRIDE and 10mL tetrahydrofuran (THF) are together added in the four-hole boiling flask that has mechanical stirring, nitrogen protection device; under the room temperature condition; take by weighing the silicone resin that contains of 4.4g chlorine replacement; it is dissolved in the 15mL tetrahydrofuran (THF) again; in 1 hour, splash in the four-hole boiling flask; after dropwising, continue to stir 2 hours, obtain transparent liquid.Disposable adding 0.89gZnBr in transparent mixed solution
2, rising temperature of reaction to 50 ℃ takes by weighing 1.01g hmds (HMDS) and is dissolved in the 10mL tetrahydrofuran (THF), utilizes constant pressure funnel to splash in the four-hole boiling flask in 1.5 hours, after dropwising, continues reflux and stirs 1.5 hours.To obtain troubled liquor and filter, and remove with Rotary Evaporators and desolvate, and obtain oyster white and be with light yellow viscous liquid slightly, its structure is shown in structural formula 6.
1H NMR (250MHz) in CDCl
3: δ 3.67ppm (2H, C-CH
2-N), 4.05ppm (2H, O-CH
2), 6.94ppm (2H, two keys on the maleinamide ring).
Structural formula 6
Embodiment 7
Synthesizing of the siliceous light trigger of macromole that methyl ethoxy replaces
0.39g MALEIC ANHYDRIDE and 10mL tetrahydrofuran (THF) are together added in the four-hole boiling flask that has mechanical stirring, nitrogen protection device; under the room temperature condition; take by weighing the silicone resin that contains of 4.4g methyl ethoxy replacement; it is dissolved in the 15mL tetrahydrofuran (THF) again; in 1 hour, splash in the four-hole boiling flask; after dropwising, continue to stir 2 hours, obtain transparent liquid.Disposable adding 0.9gZnBr in transparent mixed solution
2, rising temperature of reaction to 50 ℃ takes by weighing 1.02g hmds (HMDS) and is dissolved in the 10mL tetrahydrofuran (THF), utilizes constant pressure funnel to splash in the four-hole boiling flask in 1.5 hours, after dropwising, continues reflux and stirs 1.5 hours.To obtain troubled liquor and filter, and remove with Rotary Evaporators and desolvate, and obtain oyster white and be with light yellow viscous liquid slightly, its structure is shown in structural formula 7.
1H NMR (250MHz) in CDCl
3: δ 0.14ppm (6H, CH
3), 3.67ppm (2H, C-CH
2-N), 3.79ppm (2H, O-CH
2), 6.94ppm (2H, two keys on the maleinamide ring).
Structural formula 7
Claims (7)
- The invention provides a kind of siliceous macromolecular photoinitiator and preparation method thereof, general structure is as follows:In the formula, R1 is a kind of in hydrogen atom, methyl, methoxyl group, the halogen; R2 is a kind of in hydrogen atom, methyl, methoxyl group, the halogen; R3 is alkyl, the N of C1-C12 different chain length, O, the alkyl of the C1-C12 different chain length that heteroatomss such as S replace and the aryl that has different substituents.1. the preparation method of a siliceous macromolecular photoinitiator is characterized in that may further comprise the steps:(1) MALEIC ANHYDRIDE is dissolved in the organic solvent, joins in the four-hole boiling flask that has nitrogen protection, will contain silicone resin again and be dissolved in and being added drop-wise in the organic solvent in the four-hole boiling flask, dropwise back stirring at room 1～3h;(2) Lewis acid is joined in the four-hole boiling flask, be warmed up to 20～60 ℃, the hmds (HMDS) that will be dissolved in organic solvent drips in the mixed solution, after dropwising, keeps 20～60 ℃, and reflux condensation mode stirs 1～3h;(3) above-mentioned solution is cooled to room temperature, filters, remove with Rotary Evaporators then and desolvate, promptly get siliceous macromolecular photoinitiator.
- 2. method according to claim 1 is characterized in that, will contain silicone resin in the step (1) and join in the MALEIC ANHYDRIDE, and the mol ratio that wherein contains silicone resin and MALEIC ANHYDRIDE is 1: 1～3.
- 3. method according to claim 1 is characterized in that, containing silicone resin in the step (1) is the siliceous amine of macromole that contains methyl, methoxyl group, halogen.
- 4. method according to claim 1 is characterized in that, the organic solvent described in the step (1) is a kind of in tetrahydrofuran (THF), acetone, ethyl acetate, the methylene dichloride.
- 5. method according to claim 1 is characterized in that, Lewis acid and the hmds described in the step (2), and the mol ratio that wherein contains silicone resin and Lewis acid is 1: 1～3, the mol ratio that contains silicone resin and hmds is 1: 1～5.
- 6. method according to claim 1 is characterized in that, the Lewis acid described in the step (2) is a kind of in zinc bromide, aluminum chloride, iron(ic) chloride, the boron trifluoride.
- 7. method according to claim 1 is characterized in that, the solvent described in the step (2) is a kind of in tetrahydrofuran (THF), acetone, ethyl acetate, the methylene dichloride.
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|---|---|---|---|
| CN 201110168727 CN102286113A (en) | 2011-06-17 | 2011-06-17 | Silicon-containing polymeric photoinitiator and preparation method thereof |
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|---|---|---|---|
| CN 201110168727 CN102286113A (en) | 2011-06-17 | 2011-06-17 | Silicon-containing polymeric photoinitiator and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4075167A (en) * | 1974-12-28 | 1978-02-21 | Dai Nippon Printing Co., Ltd. | Maleimido group-containing organosilicon compounds |
| GB2109390A (en) * | 1981-10-01 | 1983-06-02 | Ciba Geigy Ag | Light-crosslinkable polysiloxanes |
| CN1434836A (en) * | 2000-06-16 | 2003-08-06 | 罗狄亚化学公司 | Novel organosilicon compounds comprising a multifunctional polyorganosiloxane bearing at least an activated imide-type double ethylene bond and method for preparing same |
-
2011
- 2011-06-17 CN CN 201110168727 patent/CN102286113A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4075167A (en) * | 1974-12-28 | 1978-02-21 | Dai Nippon Printing Co., Ltd. | Maleimido group-containing organosilicon compounds |
| GB2109390A (en) * | 1981-10-01 | 1983-06-02 | Ciba Geigy Ag | Light-crosslinkable polysiloxanes |
| CN1434836A (en) * | 2000-06-16 | 2003-08-06 | 罗狄亚化学公司 | Novel organosilicon compounds comprising a multifunctional polyorganosiloxane bearing at least an activated imide-type double ethylene bond and method for preparing same |
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Application publication date: 20111221 |