CN102532182A - Silicon-containing vinyl ether cationic polymerization monomer having side chain with aryl, and synthesis method for monomer - Google Patents
Silicon-containing vinyl ether cationic polymerization monomer having side chain with aryl, and synthesis method for monomer Download PDFInfo
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- CN102532182A CN102532182A CN2010105980296A CN201010598029A CN102532182A CN 102532182 A CN102532182 A CN 102532182A CN 2010105980296 A CN2010105980296 A CN 2010105980296A CN 201010598029 A CN201010598029 A CN 201010598029A CN 102532182 A CN102532182 A CN 102532182A
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- aryl
- vinyl ether
- side chain
- monomer
- cationoid polymerisation
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- PFQGIPIBSWYYMH-UHFFFAOYSA-N C[Si](c1ccccc1)(c1ccccc1)OCCOC=C Chemical compound C[Si](c1ccccc1)(c1ccccc1)OCCOC=C PFQGIPIBSWYYMH-UHFFFAOYSA-N 0.000 description 1
- DWZOEUMUWPZZQB-UHFFFAOYSA-N Cc(cc1)ccc1[Si+](C)(c1ccc(C)cc1)O[Si+](C)(C)OCCCCCCOC=C Chemical compound Cc(cc1)ccc1[Si+](C)(c1ccc(C)cc1)O[Si+](C)(C)OCCCCCCOC=C DWZOEUMUWPZZQB-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses synthesis of a radiation cured monomer in the technical field of optically functional materials in imaging information recording materials, in particular synthesis of a silicon-containing vinyl ether cationic polymerization monomer having a side chain with aryl. Arylchlorosilane or arylchlorosiloxane and hydroxyalkyl vinyl ether which are taken as raw materials are prepared into the silicon-containing vinyl ether cationic polymerization monomer having the side chain with aryl; and the reaction is simple in steps, mild in conditions, contributes to purification, and ensures that the yield is about 80 percent. The invention solves the problems that the conventional process for preparing silicon-containing vinyl ether is complicated, the yield is low, a metal catalyst is high in cost, environment is polluted and the like. The cationic polymerization monomer prepared by the method can be used for radiation cured materials and optical imaging information recording materials.
Description
Technical field
The invention belongs to optical function material technical field in the image-forming information recording materials, particularly a kind of side chain has the monomeric compound method of siliceous vinyl ether cationoid polymerisation of aryl.
Background technology
Cationic polymerization mainly be by photoinitiator under the effect of UV-light, the process of cationic crosslinked and polyreaction takes place in initiating activity resin and reactive thinner.The monomer of cationic photopolymerization mainly contains epoxy resin, vinyl ethers, lactone, acetal, cyclic ethers etc.It is active that vinyl ethers compound has very high photo-induced cationic polymerization, and its reaction mechanism is that under action of ultraviolet light, initiator produces acid and causes vinyl ether functional group and forms the activated carbon positive ion, further trigger monomer polymerization then.Shown in the following compound structure of polymerization mechanism.The cationoid polymerisation of vinyl ethers compound has that velocity of initiation is fast, polymerization velocity soon, does not receive characteristics such as oxygen interference.
Vinyl ethers compound is compared advantages such as having nonpoisonous and tasteless, low contraction, HS, high adherence with other kind; The polymkeric substance of its formation has good mechanical intensity and curing performance, is widely used in fields such as coating, printing ink, tackiness agent, imaging, microelectronics and biomaterial.And siliceous vinyl ether sensitization monomer has also had except that possessing above advantage characteristics such as anti-dry etching property is strong, low-viscosity, so received extensive concern in recent years.
The synthetic of siliceous vinyl ether normally makes (Hiroshi Ito, Frances A Houle, Mark W.Hart et.al. with the vinyl ether reaction by silicon methyl alcohol under the catalysis of mercuric acetate; Vnilyl ether resist system for UV-cured nanoimprint lithography [J] .Proc.SPIE; 2006, vol.6153:1A-1-1A-11), this reaction divided for three steps accomplished; Make catalyzer with mercuric acetate, yield is low and aftertreatment catalyzer is big for environment pollution.
Summary of the invention
The objective of the invention is to solve existing siliceous vinyl ether prepared in reaction complex process, productive rate lower, use problems such as metal catalyst cost height, contaminate environment.
A kind of side chain has the siliceous vinyl ether cationoid polymerisation monomer of aryl, its structure such as A-1, and A-3, shown in the A-16:
Concrete preparation process of the present invention is:
1) raw material is arylchlorosilane or aryl chloride siloxanes, under the anaerobic anhydrous condition, raw material is used solvent cut, adds catalyzer, stirs;
2) under the ice-water bath, dropwise add the hydroxyalkyl vinyl ether behind the solvent cut, the ratio of the amount of substance of raw material is 1 in hydroxyalkyl vinyl ether and the step 1): 1-2: 1;
3) remove ice-water bath after dropwising, returned to stirring at room 1-3 hour;
4) reaction finishes after-filtration, and concentrated filtrate obtains thick product;
5) thick product is used organic solvent extraction, and with insoluble contaminant filter, filtrating concentrates down at 50-100 ℃, and lower boiling impurity is removed in underpressure distillation then, promptly obtains the siliceous vinyl ether cationoid polymerisation monomer that side chain has aryl.
The general formula of arylchlorosilane described in the step 1) or aryl chloride siloxanes is following:
R in the formula
1, R
2Be Cl, CH
3Or aryl, said aryl is phenyl, Bian Ji or 1-naphthyl; R
3, R
4Be H or CH
3R
5Be Cl; N is the integer of 0-3.
Step 2) described hydroxyalkyl vinyl ether general formula is following:
M is the integer of 2-6 in the formula.
Solvent described in the step 1) is common organic solvents such as acetone, butanone, ETHYLE ACETATE, toluene, THF, and consumption is 8-25 a times of raw materials quality.
Step 2) solvent described in is acetone, butanone, ETHYLE ACETATE, toluene or THF, and consumption is 8-12 a times of hydroxyalkyl vinyl ether quality.
Catalyzer described in the step 1) is an organic bases, is specially pyridine, methylamine, ethamine, diethylamine, triethylamine, diisopropylethylamine, aniline or hydroxide tetramine, and consumption is 2-2.5 a times of raw materials quality.
The organic solvent that extraction described in the step 5) is used is ethylene glycol ether acetate, glycol methyl ether acetate, normal hexane, hexanaphthene or tetracol phenixin, and consumption is 5-10 a times of thick small product size.
The monomeric structure of siliceous vinyl ether cationoid polymerisation that described product side chain has aryl is shown below:
R in the formula
1Be H or CH
3R
2, R
3Be H, CH
3Or aryl (aryl is phenyl, Bian Ji or 1-naphthyl), and have at least one to be aryl; R
4, R
5Be H or CH
3R
6Be the vinyl ether alkoxyl group; N is the integer of 0-3.
Described vinyl ether alkoxyl group is the structure shown in the following formula:
M is the integer of 2-6 in the formula.
The monomeric concrete structure of siliceous vinyl ether cationoid polymerisation that described product side chain has an aryl like monomer A-1 to A-25, monomers B-1 to shown in B-25, monomer C-1 to C-25, the monomer D-1 to D-25:
Monomer A-1 is to A-25:
Monomers B-1 is to B-25:
Monomer C-1 to C-25:
Monomer D-1 to D-25:
The substitution reaction of hydroxyl and halogen ten minutes is rapid in the building-up process of the present invention, and the siliceous vinyl ether cationoid polymerisation monomer yield that the side chain that obtains has aryl is about 80%.The a series of side chains of synthetic of the present invention have the siliceous vinyl ether cationoid polymerisation monomer of aryl under UV-irradiation, and cationoid polymerisation can take place carbon-carbon double bond, and it is fast to have a velocity of initiation, and the characteristics that polymerization velocity is fast can be accomplished in 30s; And the aryl on the side chain has improved the anti-dry etching property of cross-linked polymer, and the silicon chain has reduced the surface tension of this compound, makes viscosity lower, and film forming homogeneity improves.This monomeric maximum absorption wavelength is at 200nm, and is stable to visible light, makes storage and transportation comparatively convenient.This monomer can be used as photo-resist and optical information recording material.
Below in conjunction with embodiment, the present invention is done further description, rather than limit scope of the present invention.
Embodiment
Embodiment 1:
Monomer A-3
is the compound method of 1-phenyl-1-vinyloxy group butoxy dimethylsilane:
1, get there-necked flask, the 1-phenyl dimethylchlorosilane with 0.0522mol under nitrogen environment adds in the 200mL THF triethylamine 16mL (0.1148mol), magnetic agitation;
2, ice-water bath is dissolved in 4-hydroxybutyl vinyl ether 13.5mL (0.1096mol) in the 80mL THF again, dropwise slowly adds;
3, remove ice-water bath after dropwising, returned to stirring at room 2 hours;
4, filter, revolve and steam solvent, obtain thick product;
5, thick product is used the 50mL n-hexane extraction, refilters, and filtrating concentrates down at 70 ℃, removes lower boiling impurity with the oil pump underpressure distillation then, obtains colourless transparent liquid, is the siliceous vinyl ether cationoid polymerisation monomer that side chain has aryl, and yield is 79%.
Embodiment 2:
Monomers B-23
promptly 1, the compound method of 1-two Bian Ji-3-vinyloxy group butoxy trimethylammonium sily oxide:
With 1, the 1-phenyl dimethylchlorosilane in 1-two Bian Ji-3-chlorine trimethylammonium sily oxide alternate embodiment 1, all the other are identical with embodiment 1, and yield is 83%.
Embodiment 3:
Monomer C-13
is the synthetic of 1-naphthyl-1-vinyloxy group butoxy hexam ethylcyclotrisiloxane: replace the 1-phenyl dimethylchlorosilane among the embodiment 1 with 1-naphthyl-5-chlorine hexamethyl siloxanes, all the other are identical with embodiment 1.
Embodiment 4:
Monomer D-16
promptly 1; Synthesizing of 1-phenylbenzene-7-vinyloxy group oxyethyl group seven methyl tetrasiloxanes: with 1; 1-phenylbenzene-7-chlorine seven methyl tetrasiloxanes replace the 1-phenyl dimethylchlorosilane among the embodiment 1; Replace 13.5mL (0.1096mol) the 4-hydroxybutyl vinyl ether among the embodiment 1 with 10mL (0.1096mol) glycol monomethyl vinyl ether, all the other are identical with embodiment 1.
Claims (10)
1. a side chain has the siliceous vinyl ether cationoid polymerisation monomer of aryl; It is characterized in that; Its structure such as A-1; A-3 is shown in the A-16: A-1
A-3
A-16
2. a side chain has the monomeric compound method of siliceous vinyl ether cationoid polymerisation of aryl, it is characterized in that its concrete preparation process is:
1) raw material is arylchlorosilane or aryl chloride siloxanes, under the anaerobic anhydrous condition, raw material is used solvent cut, adds catalyzer, stirs;
2) under the ice-water bath, dropwise add the hydroxyalkyl vinyl ether behind the solvent cut, the ratio of the amount of substance of raw material is 1 in hydroxyalkyl vinyl ether and the step 1): 1-2: 1;
3) remove ice-water bath after dropwising, returned to stirring at room 1-3 hour;
4) reaction finishes after-filtration, and concentrated filtrate obtains thick product;
5) thick product is used organic solvent extraction, and with insoluble contaminant filter, filtrating concentrates down at 50-100 ℃, and lower boiling impurity is removed in underpressure distillation then, promptly obtains the siliceous vinyl ether cationoid polymerisation monomer that side chain has aryl.
3. a kind of side chain according to claim 2 has the monomeric compound method of siliceous vinyl ether cationoid polymerisation of aryl, it is characterized in that the general formula of arylchlorosilane described in the step 1) or aryl chloride siloxanes is following:
R in the formula
1, R
2Be Cl, CH
3Or aryl, said aryl is phenyl, Bian Ji or 1-naphthyl; R
3, R
4Be H or CH
3R
5Be Cl; N is the integer of 0-3.
4. a kind of side chain according to claim 3 has the monomeric compound method of siliceous vinyl ether cationoid polymerisation of aryl, it is characterized in that step 2) described hydroxyalkyl vinyl ether general formula is following:
M is the integer of 2-6 in the formula.
5. a kind of side chain according to claim 4 has the monomeric compound method of siliceous vinyl ether cationoid polymerisation of aryl; It is characterized in that; Solvent described in the step 1) is common organic solvents such as acetone, butanone, ETHYLE ACETATE, toluene, THF, and consumption is 8-25 a times of raw materials quality.
6. a kind of side chain according to claim 5 has the monomeric compound method of siliceous vinyl ether cationoid polymerisation of aryl; It is characterized in that; Step 2) solvent described in is acetone, butanone, ETHYLE ACETATE, toluene or THF, and consumption is 8-12 a times of hydroxyalkyl vinyl ether quality.
7. a kind of side chain according to claim 6 has the monomeric compound method of siliceous vinyl ether cationoid polymerisation of aryl; It is characterized in that; Catalyzer described in the step 1) is an organic bases; Be specially pyridine, methylamine, ethamine, diethylamine, triethylamine, diisopropylethylamine, aniline or hydroxide tetramine, consumption is 2-2.5 a times of raw materials quality; The organic solvent that extraction described in the step 5) is used is ethylene glycol ether acetate, glycol methyl ether acetate, normal hexane, hexanaphthene or tetracol phenixin, and consumption is 5-10 a times of thick small product size.
8. a kind of side chain according to claim 7 has the monomeric compound method of siliceous vinyl ether cationoid polymerisation of aryl, it is characterized in that, the monomeric structure of siliceous vinyl ether cationoid polymerisation that described side chain has aryl is shown below:
R in the formula
1Be H or CH
3R
2, R
3Be H, CH
3Or aryl (aryl is phenyl, Bian Ji or 1-naphthyl), and have at least one to be aryl; R
4, R
5Be H or CH
3R
6Be the vinyl ether alkoxyl group; N is the integer of 0-3.
9. a kind of side chain according to claim 8 has the monomeric compound method of siliceous vinyl ether cationoid polymerisation of aryl, it is characterized in that described vinyl ether alkoxyl group is the structure shown in the following formula:
M is the integer of 2-6 in the formula.
10. a kind of side chain according to claim 7 has the monomeric compound method of siliceous vinyl ether cationoid polymerisation of aryl; It is characterized in that, the monomeric structure of siliceous vinyl ether cationoid polymerisation that described side chain has an aryl like monomer A-1 to A-25, monomers B-1 to shown in B-25, monomer C-1 to C-25, the monomer D-1 to D-25:
Monomer A-1 is to A-25:
Monomers B-1 is to B-25:
Monomer C-1 to C-25:
Monomer D-1 to D-25:
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|---|---|---|---|
| CN201010598029.6A CN102532182B (en) | 2010-12-21 | 2010-12-21 | Silicon-containing vinyl ether cationic polymerization monomer having side chain with aryl, and synthesis method for monomer |
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| CN201010598029.6A CN102532182B (en) | 2010-12-21 | 2010-12-21 | Silicon-containing vinyl ether cationic polymerization monomer having side chain with aryl, and synthesis method for monomer |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0624827A1 (en) * | 1993-05-12 | 1994-11-17 | Ciba-Geigy Ag | Method of making micropatterns |
| CN1269825C (en) * | 2003-02-27 | 2006-08-16 | 国家淀粉及化学投资控股公司 | Compound comprising vinyl silane and functionality of electron donor or acceptor |
-
2010
- 2010-12-21 CN CN201010598029.6A patent/CN102532182B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0624827A1 (en) * | 1993-05-12 | 1994-11-17 | Ciba-Geigy Ag | Method of making micropatterns |
| CN1269825C (en) * | 2003-02-27 | 2006-08-16 | 国家淀粉及化学投资控股公司 | Compound comprising vinyl silane and functionality of electron donor or acceptor |
Non-Patent Citations (4)
| Title |
|---|
| HIDEYUKI ITOH: "Synthesis of Silicon-Containing Vinyl Ether Monomers and Their Photoinitiated Polymerization", 《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》 * |
| KIM ET AL: "Vinyl ether formulations for step and flash imprint lithography", 《JOURNAL OF VACUUM SCIENCE & TECHNOLOGY. B. MICROELECTRONICS AND NANOMETER STRUCTURES. PROCESSING, MEASUREMENT AND PHENOMENA》 * |
| M. URBALA ET AL.: "The synthesis of allyl ether functionalized siloxane monomers under ultrasonic irradiation at ambient conditions", 《ULTRASONICS SONOCHEMISTRY》 * |
| 霍永恩等: "纳米压印抗蚀剂研究进展", 《影像科学与光化学》 * |
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