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CN101029136A - Production and use for high-oxygen light-transmittance connected network - Google Patents

Production and use for high-oxygen light-transmittance connected network Download PDF

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Publication number
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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continuous network
preparation
high oxygen
oxygen permeability
copolymer
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CN101029136B (en
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何春菊
孙俊芬
王庆瑞
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Donghua University
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Donghua University
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  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)

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

A kind of preparation method of high-oxygen light-transmittance connected network and application
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)

1.一种高氧透过率共连续网络的制备方法，包括下列步骤：1. A method for preparing a high oxygen permeability co-continuous network, comprising the following steps: (1)改性聚二醇及其共聚物的制备：(1) Preparation of modified polyglycol and copolymer thereof: 聚二醇及其共聚物溶解在溶剂中，配比为1∶4～7∶3，制成浓度为20-70％溶液，在搅拌下投入10-50％碱，与20～500％烯丙基卤化物，配比5∶1～1∶5，在35-75℃下反应；Polyglycol and its copolymers are dissolved in the solvent, and the ratio is 1:4 to 7:3 to make a solution with a concentration of 20-70%, and 10-50% alkali is added under stirring, and 20-500% allyl Halides, proportioning 5:1～1:5, react at 35-75°C; (2)改性交联剂/填充剂——二(二甲基甲烷硅氧基)乙氧基苯基硅烷的合成：(2) Synthesis of modified crosslinking agent/filler - bis(dimethylsilyloxy)ethoxyphenylsilane: 三(二甲基甲烷硅氧基)苯基硅烷与无水乙醇，配比：1∶3～10∶1在1-1000ppm Karstedt催化剂作用下，室温反应1-6小时，真空精馏，得到95％以上高纯度交联剂/填充剂；Tris(dimethylsilyloxy)phenylsilane and absolute ethanol, proportioning: 1:3～10:1 under the action of 1-1000ppm Karstedt catalyst, react at room temperature for 1-6 hours, and vacuum rectify to obtain 95 % above high-purity cross-linking agent/filler; (3)两性无规嵌段共聚物的合成：(3) Synthesis of amphoteric random block copolymers: 5-65％改性聚二醇及其共聚物和35-95％有机硅氧烷聚合物，按配比1∶19～2∶1溶解在溶剂中，制成浓度为2-20％溶液，在改性交联剂/填充剂和30-500ppmKarstedt催化剂的作用下，在25-105℃下发生硅氢化反应，反应时间6-48小时。经纯化，得到含有乙氧基的两性无规嵌段共聚物；5-65% modified polyglycol and its copolymer and 35-95% organosiloxane polymer are dissolved in the solvent according to the ratio of 1:19 to 2:1 to make a solution with a concentration of 2-20%. Under the action of modified cross-linking agent/filler and 30-500ppm Karstedt catalyst, hydrosilation reaction occurs at 25-105°C, and the reaction time is 6-48 hours. After purification, an amphoteric random block copolymer containing ethoxy groups is obtained; (4)共连续网络的制备：(4) Preparation of co-continuous network: 两性无规嵌段共聚物溶解在溶剂中，配比为1∶49～3∶7，制成浓度为2-30％溶液，以烷基苯磺酸盐为催化剂，用量为0.1％～1％，35-75℃下发生水解、缩合反应，时间为3-48小时，得到共连续网络，其中聚硅氧烷含量在40-80％。The amphoteric random block copolymer is dissolved in a solvent with a ratio of 1:49 to 3:7 to make a solution with a concentration of 2-30%, using alkylbenzene sulfonate as a catalyst, and the dosage is 0.1% to 1%. , Hydrolysis and condensation reactions occur at 35-75°C for 3-48 hours to obtain a co-continuous network in which the polysiloxane content is 40-80%. 2.根据权利要求1所述的一种高氧透过率共连续网络的制备方法，其特征在于：所述步骤1是聚二醇及其共聚物为聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物。2. The preparation method of a high oxygen permeability co-continuous network according to claim 1, characterized in that: said step 1 is that polyglycol and its copolymers are polyethylene oxide-polypropylene oxide- Polyethylene oxide three-block copolymer. 3.根据权利要求1所述的一种高氧透过率共连续网络的制备方法，其特征在于：所述步骤1、3、4溶剂是四氢呋喃、二氯甲烷或甲苯。3. The preparation method of a high oxygen permeability co-continuous network according to claim 1, characterized in that: the solvent in the steps 1, 3 and 4 is tetrahydrofuran, dichloromethane or toluene. 4.根据权利要求1所述的一种高氧透过率共连续网络的制备方法，其特征在于：所述步骤1碱是氢氧化钠或氢氧化钾。4. The preparation method of a high oxygen permeability co-continuous network according to claim 1, characterized in that: the alkali in step 1 is sodium hydroxide or potassium hydroxide. 5.根据权利要求1所述的一种高氧透过率共连续网络的制备方法，其特征在于：所述步骤3的有机硅氧烷聚合物为端基为乙烯基的聚二甲基硅氧烷。5. The preparation method of a co-continuous network with high oxygen transmission rate according to claim 1, characterized in that: the organosiloxane polymer in step 3 is polydimethylsiloxane whose terminal group is a vinyl group oxane. 6.根据权利要求1所述的一种高氧透过率共连续网络的制备方法，其特征在于：所述步骤3的改性交联剂/填充剂与预聚体的摩尔比在1.05-2.5。6. The preparation method of a high oxygen permeability co-continuous network according to claim 1, characterized in that: the molar ratio of the modified crosslinking agent/filler to the prepolymer in step 3 is 1.05-2.5 . 7.根据权利要求1所述的一种高氧透过率共连续网络的应用，包括生物医用材料，如隐型眼镜、人工脏器、药物的控制释放载体。7. The application of a high oxygen permeability co-continuous network according to claim 1, including biomedical materials, such as contact lenses, artificial organs, and controlled release carriers of drugs.
CN200710036885A 2007-01-26 2007-01-26 Preparation method and application of a co-continuous network with high oxygen transmission rate Expired - Fee Related CN101029136B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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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* Cited by examiner, † Cited by third party
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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
DE50302270D1 (en) * 2003-10-04 2006-04-13 Goldschmidt Gmbh Process for the preparation of organic silicon compounds

Cited By (2)

* Cited by examiner, † Cited by third party
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
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

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