CN101029136A - Production and use for high-oxygen light-transmittance connected network - Google Patents
Production and use for high-oxygen light-transmittance connected network Download PDFInfo
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- CN101029136A CN101029136A CNA2007100368850A CN200710036885A CN101029136A CN 101029136 A CN101029136 A CN 101029136A CN A2007100368850 A CNA2007100368850 A CN A2007100368850A CN 200710036885 A CN200710036885 A CN 200710036885A CN 101029136 A CN101029136 A CN 101029136A
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Abstract
Production of high-oxygen transmissivity continuous network and its use are disclosed. The process is carried out by preparing modified poly-glycol and its other copolymer, synthesizing modified cross-linking agent/filler-di(dimethyl-siloxy)oxyethyl-phenyl-silane, taking poly-glycol, its copolymer and organic silicone as raw materials to prepare amphoteric random block copolymer, chemical cross-linking reacting to obtain the final product. It has excellent anti-oxidant degradability and can be used for contact lens, artificial organotherapy and medicinal controllable release carrier.
Description
Technical field
The invention belongs to network intelligence material field, particularly a kind of preparation method of high-oxygen light-transmittance connected network and application.
Background technology
It is that one of raw material prepares both sexes contiguous network altogether that present bibliographical information adopts with the polyoxyethylene more, because oxidative degradation can take place in polyoxyethylene under field conditions (factors), thereby cause network performance in use to worsen, thereby need to adopt other raw materials to prepare new type amphoteric contiguous network altogether with resistance of oxidation.
Document:
1.Wang，Shanfeng；Lu，Lichun；Yaszemski，Michael?J.“Hydrophilic/hydrophobicpolymer?networks?containing?caprolactone?fumarate?and?ethylene?glycolfumarate?units”，PCT?Int.Appl.(2006)，WO?2006118987?A1?20061109，
2.J.P.Kennedy; G.Erdodi, " Amphiphilic co-networks; films made fromamphiphilic co-networks and uses for such co-networks and films ", WO2006073499 A2 20060713. used wetting ability raw materials are modified PE G.
3.D.Myung, J.Noolandi, A.J.Smith, C.W.Frank, C.Ta, Y.Hu, W.Koh, M.R.Carrasco, Artificial comeal implant comprising biocompatible polymers, WO2006042272 A2 20060420, adopting end group is that acrylic acid modified PE G or polyacrylic acid are that raw material prepares.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method and application of high-oxygen light-transmittance connected network, with polyglycol, organosiloxane polymer is raw material, preparation both sexes statistic copolymer, pass through chemical crosslink reaction, obtain both sexes contiguous network altogether, this network has good antioxygen degradation property.Be applied to bio-medical material such as contact lenses, artificial organ, controlled delivery of pharmaceutical agents release vehicle.
The preparation method of a kind of high-oxygen light-transmittance connected network of the present invention comprises the following steps:
(1) preparation of modification polyglycol and multipolymer thereof:
Polyglycol and multipolymer thereof are dissolved in the solvent, and proportioning is 1: 4～7: 3, and making concentration is 20-70% solution, under agitation drops into 10-50% alkali, and with (20～500%) allyl halide, proportioning (5: 1～1: 5) is 35-75 ℃ of reaction down;
(2) synthesizing of modified crosslinking agent/weighting agent---two (dimethylmethane siloxy) phenetole base silane:
Three (dimethylmethane siloxy) phenyl silanes and dehydrated alcohol (proportioning: 1: 3～10: 1) are under 1-1000ppm Karstedt (Gelest Corp. company provides) catalyst action, room temperature reaction 1-6 hour, rectification under vacuum obtains 95% above high purity linking agent/weighting agent;
(3) the both sexes statistic copolymer is synthetic:
(5-65%) modification polyglycol and multipolymer thereof and (35-95%) organosiloxane polymer, (1: 19～2: 1) are dissolved in the solvent according to a certain ratio, making concentration is 2-20% solution, under the effect of modified crosslinking agent/weighting agent and 30-500ppmKarstedt (Gelest Corp. company provides) catalyzer, hydrosilation reaction, reaction times 6-48 hour take place down at 25-105 ℃.Purified, obtain containing the both sexes statistic copolymer of oxyethyl group;
(4) preparation of contiguous network altogether:
The both sexes statistic copolymer is dissolved in the solvent, proportioning is 1: 49～3: 7, making concentration is 2-30% solution, with the alkylbenzene sulfonate is catalyzer, consumption is 0.1%～10%, and 35-75 ℃ issues that unboiled water is separated, condensation reaction, and the time is 3-48 hour, obtain common contiguous network, wherein polysiloxane level is at 40-80%.
Described step 1 polyglycol and multipolymer thereof are polyethylene oxide-polypropylene oxide-three sections multipolymers of polyethylene oxide;
Described step 1 solvent is tetrahydrofuran (THF), methylene dichloride or toluene;
Described step 1 alkali is sodium hydroxide or potassium hydroxide;
The organosiloxane polymer of described step 3 is that end group is the polydimethylsiloxane of vinyl;
The solvent of described step 3 is tetrahydrofuran (THF), methylene dichloride or toluene;
Modified crosslinking agent/the weighting agent of described step 3 and the mol ratio of performed polymer are at 1.05-2.5;
The solvent of described step 4 is tetrahydrofuran (THF), methylene dichloride or toluene;
Resulting the colloidal sol rate of contiguous network in tetrahydrofuran (THF) is at 1-10% altogether, and the swelling ratio in water is 20-80%.The transmitance of oxygen is 150-600barrers.Has certain transmitance for Regular Insulin and glucose.Mass loss rate through 7 days under 70 ℃ is 0-8%.
The application of a kind of high-oxygen light-transmittance connected network of the present invention comprises bio-medical material, as contact lenses, artificial organ, controlled delivery of pharmaceutical agents release vehicle.
The advantage of invention
The preparation-obtained both sexes of the present invention contiguous network altogether have certain mechanical property and pore size distribution, all have certain swelling ratio in wetting ability and lipophilicity solvent.For in the certain size, low molecule (as glucose, Regular Insulin etc.) has certain transmission rates, has good oxygen permeability simultaneously, has good antioxygen degradation property.At aspects such as bio-medical materials potential use is arranged, comprise contact lenses, artificial organ, controlled delivery of pharmaceutical agents release vehicle etc.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) 10 parts of polyethylene oxide-polypropylene oxide-three sections multipolymers of polyethylene oxide is dissolved in 40 parts of solvents, drop into 2 parts of sodium hydroxide, issue biochemical reaction with 5 parts of chlorallylenes at 45 ℃, obtaining end group is allylic modified poly ethylene oxide compound-polypropylene oxide-three sections multipolymers of polyethylene oxide.
Synthesizing of (2) two (dimethylmethane siloxy) phenetole base silane: 10 part of three (dimethylmethane siloxy) phenyl silane and 1 part of dehydrated alcohol mix, add the 700ppmKarstedt catalyzer, at room temperature reacted 1 hour, product is through rectification under vacuum, obtains purity and be two (dimethylmethane siloxy) phenetole base silane of 98%.
(3) the both sexes statistic copolymer is synthetic: 1 part of modified poly ethylene oxide compound-polypropylene oxide-three sections multipolymer of polyethylene oxide and 4 parts of polysiloxane are dissolved in 40 parts of solvents, add under the effect of two (dimethylmethane siloxy) phenetole base silane (mol ratio of itself and performed polymer is 1.3) and 100ppmKarstedt catalyzer, reacted 24 hours down at 40 ℃, purified, obtain 3 parts of both sexes statistic copolymers.
(4) preparation of contiguous network altogether: 1 part of both sexes statistic copolymer is dissolved in 15 parts of solvents, under 1% alkyl benzene sulphonate (ABS) salt action, reacts 15 hours down at 40 ℃, obtains common contiguous network.
The resulting colloidal sol rate of contiguous network in tetrahydrofuran (THF) altogether is 5%, and the swelling ratio in water is 16%.The transmitance of oxygen is 550barrers.Has certain transmitance for Regular Insulin and glucose.Mass loss rate through 7 days under 70 ℃ is 3%.
Embodiment 2:
(1) 10 parts of polyethylene oxide-polypropylene oxide-three sections multipolymers of polyethylene oxide is dissolved in 20 parts of solvents, drop into 3 parts of sodium hydroxide, issue biochemical reaction with 4 parts of chlorallylenes at 55 ℃, obtaining end group is allylic modified poly ethylene oxide compound-polypropylene oxide-three sections multipolymers of polyethylene oxide.
Synthesizing of (2) two (dimethylmethane siloxy) phenetole base silane: 10 part of three (dimethylmethane siloxy) phenyl silane and 1 part of dehydrated alcohol mix, add the 700ppmKarstedt catalyzer, at room temperature reacted 7 hours, product is through rectification under vacuum, obtains purity and be two (dimethylmethane siloxy) phenetole base silane of 98%.
(3) the both sexes statistic copolymer is synthetic: 1 part of modified poly ethylene oxide compound-polypropylene oxide-three sections multipolymer of polyethylene oxide and 2 parts of polysiloxane are dissolved in 40 parts of solvents, add under the effect of two (dimethylmethane siloxy) phenetole base silane (mol ratio of itself and performed polymer is 1.3) and 100ppmKarstedt catalyzer, reacted 24 hours down at 40 ℃, purified, obtain 2 parts of both sexes statistic copolymers.
(4) preparation of contiguous network altogether: 1 part of both sexes statistic copolymer is dissolved in 15 parts of solvents, under 1% alkyl benzene sulphonate (ABS) salt action, reacts 15 hours down at 40 ℃, obtains common contiguous network.
The resulting colloidal sol rate of contiguous network in tetrahydrofuran (THF) altogether is 5%, and the swelling ratio in water is 32%.The transmitance of oxygen is 480barrers.Has certain transmitance for Regular Insulin and glucose.Mass loss rate through 7 days under 70 ℃ is 3%.
Embodiment 3:
(1) 10 parts of polyethylene oxide-polypropylene oxide-three sections multipolymers of polyethylene oxide is dissolved in 10 parts of solvents, drop into 4 parts of sodium hydroxide, issue biochemical reaction with 5 parts of vinyl benzene methyl chlorides at 50 ℃, obtaining end group is modified poly ethylene oxide compound-polypropylene oxide-three sections multipolymers of polyethylene oxide of styryl.
Synthesizing of (2) two (dimethylmethane siloxy) phenetole base silane: 10 part of three (dimethylmethane siloxy) phenyl silane and 1 part of dehydrated alcohol mix, add the 1000ppmKarstedt catalyzer, at room temperature reacted 5 hours, product is through rectification under vacuum, obtains purity and be two (dimethylmethane siloxy) phenetole base silane of 98%.
(3) the both sexes statistic copolymer is synthetic: 2 parts of modified poly ethylene oxide compound-polypropylene oxide-three sections multipolymers of polyethylene oxide and 3 parts of polysiloxane are dissolved in 50 parts of solvents, under the effect of two (dimethylmethane siloxy) phenetole base silane (mol ratio of itself and performed polymer is 1.8) and 350ppmKarstedt catalyzer, reacted 48 hours down at 40 ℃, purified, obtain the both sexes statistic copolymer.
(3) preparation of contiguous network altogether: 1 part of both sexes statistic copolymer is dissolved in 19 parts of solvents, under 1% alkyl benzene sulphonate (ABS) effect, reacts 15 hours down at 45 ℃, obtains common contiguous network.
The resulting colloidal sol rate of contiguous network in tetrahydrofuran (THF) altogether is 5%, and the swelling ratio in water is 43%.The transmitance of oxygen is 350barrers.Has certain transmitance for Regular Insulin and glucose.Mass loss rate through 7 days under 70 ℃ is 2%.
Embodiment 4:
(1) 10 parts of polyethylene oxide-polypropylene oxide-three sections multipolymers of polyethylene oxide is dissolved in 5 parts of solvents, drop into 3 parts of sodium hydroxide, issue biochemical reaction with 5 parts of vinyl benzene methyl chlorides at 65 ℃, obtaining end group is modified poly ethylene oxide compound-polypropylene oxide-three sections multipolymers of polyethylene oxide of styryl.
Synthesizing of (2) two (dimethylmethane siloxy) phenetole base silane: 13 part of three (dimethylmethane siloxy) phenyl silane and 1 part of dehydrated alcohol mix, add the 700ppmKarstedt catalyzer, at room temperature reacted 2 hours, product is through rectification under vacuum, obtains purity and be two (dimethylmethane siloxy) phenetole base silane of 98%.
(3) the both sexes statistic copolymer is synthetic: 1 part of modified poly ethylene oxide compound-polypropylene oxide-three sections multipolymer of polyethylene oxide and 1 part of polysiloxane are dissolved in 25 parts of solvents, under the effect of two (dimethylmethane siloxy) phenetole base silane (mol ratio of itself and performed polymer is 1.5) and 200ppmKarstedt catalyzer, reacted 48 hours down at 40 ℃, purified, obtain the both sexes statistic copolymer.
(4) preparation of contiguous network altogether: 1 part of both sexes statistic copolymer is dissolved in 19 parts of solvents, under 3% alkyl benzene sulphonate (ABS) effect, reacts 15 hours down at 45 ℃, obtains common contiguous network.
The resulting colloidal sol rate of contiguous network in tetrahydrofuran (THF) altogether is 9%, and the swelling ratio in water is 70%.The transmitance of oxygen is 190b8rrers.Has certain transmitance for Regular Insulin and glucose.Mass loss rate through 7 days under 70 ℃ is 0%.
Claims (7)
1. the preparation method of a high-oxygen light-transmittance connected network comprises the following steps:
(1) preparation of modification polyglycol and multipolymer thereof:
Polyglycol and multipolymer thereof are dissolved in the solvent, and proportioning is 1: 4～7: 3, and making concentration is 20-70% solution, under agitation drops into 10-50% alkali, and with 20～500% allyl halides, proportioning 5: 1～1: 5 is 35-75 ℃ of reaction down;
(2) synthesizing of modified crosslinking agent/weighting agent---two (dimethylmethane siloxy) phenetole base silane:
Three (dimethylmethane siloxy) phenyl silane and dehydrated alcohol, proportioning: room temperature reaction 1-6 hour, rectification under vacuum obtained 95% above high purity linking agent/weighting agent under 1-1000ppm Karstedt catalyst action in 1: 3～10: 1;
(3) the both sexes statistic copolymer is synthetic:
5-65% modification polyglycol and multipolymer thereof and 35-95% organosiloxane polymer, be dissolved in the solvent in 1: 19～2: 1 by proportioning, making concentration is 2-20% solution, under the effect of modified crosslinking agent/weighting agent and 30-500ppmKarstedt catalyzer, hydrosilation reaction, reaction times 6-48 hour take place down at 25-105 ℃.Purified, obtain containing the both sexes statistic copolymer of oxyethyl group;
(4) preparation of contiguous network altogether:
The both sexes statistic copolymer is dissolved in the solvent, proportioning is 1: 49～3: 7, making concentration is 2-30% solution, with the alkylbenzene sulfonate is catalyzer, consumption is 0.1%～1%, and 35-75 ℃ issues that unboiled water is separated, condensation reaction, and the time is 3-48 hour, obtain common contiguous network, wherein polysiloxane level is at 40-80%.
2. the preparation method of a kind of high-oxygen light-transmittance connected network according to claim 1, it is characterized in that: described step 1 is that polyglycol and multipolymer thereof are polyethylene oxide-polypropylene oxide-three sections multipolymers of polyethylene oxide.
3. the preparation method of a kind of high-oxygen light-transmittance connected network according to claim 1, it is characterized in that: described step 1,3,4 solvents are tetrahydrofuran (THF), methylene dichloride or toluene.
4. the preparation method of a kind of high-oxygen light-transmittance connected network according to claim 1, it is characterized in that: described step 1 alkali is sodium hydroxide or potassium hydroxide.
5. the preparation method of a kind of high-oxygen light-transmittance connected network according to claim 1, it is characterized in that: the organosiloxane polymer of described step 3 is that end group is the polydimethylsiloxane of vinyl.
6. the preparation method of a kind of high-oxygen light-transmittance connected network according to claim 1, it is characterized in that: the modified crosslinking agent/weighting agent of described step 3 and the mol ratio of performed polymer are at 1.05-2.5.
7. the application of a kind of high-oxygen light-transmittance connected network according to claim 1 comprises bio-medical material, as contact lenses, artificial organ, controlled delivery of pharmaceutical agents release vehicle.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710036885A CN101029136B (en) | 2007-01-26 | 2007-01-26 | Production and use for high-oxygen light-transmittance connected network |
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| CN200710036885A CN101029136B (en) | 2007-01-26 | 2007-01-26 | Production and use for high-oxygen light-transmittance connected network |
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| CN101029136A true CN101029136A (en) | 2007-09-05 |
| CN101029136B CN101029136B (en) | 2010-05-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012817A (en) * | 2012-12-28 | 2013-04-03 | 东华大学 | Controllable preparation method of high-oxygen transmission rate co-continuous network |
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| DE4407189A1 (en) * | 1994-03-04 | 1995-09-07 | Goldschmidt Ag Th | Polysiloxane-polyoxyalkylene block copolymers and their use as additives for hair cosmetics |
| US6346553B1 (en) * | 2000-04-13 | 2002-02-12 | Archimica (Florida), Inc. | Alkylmethylsiloxane-dimethylsilicone polyalkylene oxide copolymers |
| DE50302270D1 (en) * | 2003-10-04 | 2006-04-13 | Goldschmidt Gmbh | Process for the preparation of organic silicon compounds |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103012817A (en) * | 2012-12-28 | 2013-04-03 | 东华大学 | Controllable preparation method of high-oxygen transmission rate co-continuous network |
| CN103012817B (en) * | 2012-12-28 | 2014-12-10 | 东华大学 | Controllable preparation method of high-oxygen transmission rate co-continuous network |
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Inventor after: He Chunju Inventor after: Cao Xiaohui Inventor after: Sun Zhipeng Inventor after: Sun Junfen Inventor after: Wang Qingrui Inventor after: Li Xiaolei Inventor after: Li Songtao Inventor after: Xu Jianfeng Inventor after: Liu Chunyi Inventor after: Du De Inventor after: Liu Yang Inventor before: He Chunju Inventor before: Sun Junfen Inventor before: Wang Qingrui |
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Free format text: CORRECT: INVENTOR; FROM: HE CHUNJU SUN JUNFEN WANG QINGRUI TO: HE CHUNJU SUN JUNFEN WANG QINGRUI LI XIAOLEI LI SONGTAO XU JIANFENG LIU CHUNYI DU DE LIU YANG CAO XIAOHUI SUN ZHIPENG |
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Granted publication date: 20100519 Termination date: 20160126 |
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