CN101029136B - Preparation method and application of a co-continuous network with high oxygen transmission rate - Google Patents
Preparation method and application of a co-continuous network with high oxygen transmission rate Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 230000005540 biological transmission Effects 0.000 title description 12
- -1 methylsilyloxy Chemical group 0.000 claims abstract description 32
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- YCPJMTBCGMBGLW-UHFFFAOYSA-N bis(dimethylsilyloxy)-ethoxy-phenylsilane Chemical compound CCO[Si](O[SiH](C)C)(O[SiH](C)C)C1=CC=CC=C1 YCPJMTBCGMBGLW-UHFFFAOYSA-N 0.000 description 3
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
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Abstract
本发明公开一种高氧透过率共连续网络的制备方法和应用，包括步骤(1)制备改性聚二醇共聚物；(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；(3)以聚二醇共聚物、有机硅氧烷聚合物为原料，制备两性无规嵌段共聚物；(4)通过化学交联反应，得到两性共连续网络，该网络具有良好的抗氧降解性。应用于生物医用材料如隐型眼镜、人工脏器、药物的控制释放载体。The invention discloses a preparation method and application of a high oxygen permeability co-continuous network, comprising the steps of (1) preparing a modified polyglycol copolymer; (2) modifying a crosslinking agent/filler—bis(dimethyl Synthesis of methylsilyloxy)ethoxyphenylsilane; (3) using polyglycol copolymer and organosiloxane polymer as raw materials to prepare amphoteric random block copolymers; (4) through chemical crosslinking reaction , resulting in an amphiphilic co-continuous network with good resistance to oxygen degradation. Applied to biomedical materials such as contact lenses, artificial organs, and controlled release carriers of drugs.
Description
技术领域technical field
本发明属网络智能材料领域，特别涉及一种高氧透过率共连续网络的制备方法和应用。The invention belongs to the field of network intelligent materials, in particular to a preparation method and application of a co-continuous network with high oxygen transmission rate.
背景技术Background technique
目前的文献报道多采用以聚氧化乙烯为原料之一来制备两性共连续网络，由于聚氧化乙烯在自然条件下会发生氧化降解，从而导致网络性能在使用过程中恶化，因而需采用具有抗氧化能力的其他原料来制备新型两性共连续网络。The current literature reports mostly use polyethylene oxide as one of the raw materials to prepare the amphoteric co-continuous network. Since polyethylene oxide will be oxidatively degraded under natural conditions, which will lead to the deterioration of network performance during use, it is necessary to use anti-oxidant Other raw materials with the ability to prepare novel amphiphilic cocontinuous networks.
文献：literature:
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 20061109，1.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.所用亲水性原料为改性PEG。2. J.P.Kennedy; G.Erdodi, "Amphiphilic co-networks, films made from amphiphilic co-networks and uses for such co-networks and films", WO2006073499 A2 20060713. The hydrophilic raw material used is modified PEG.
3.D.Myung，J.Noolandi，A.J.Smith，C.W.Frank，C.Ta，Y.Hu，W.Koh，M.R.Carrasco，Artificial corneal implant comprising biocompatible polymers，WO2006042272 A2 20060420，采用端基为丙烯酸的改性PEG或聚丙烯酸为原料来制备。3.D.Myung, J.Noolandi, A.J.Smith, C.W.Frank, C.Ta, Y.Hu, W.Koh, M.R.Carrasco, Artificial corneal implant comprising biocompatible polymers, WO2006042272 A2 20060420, modified by acrylic acid PEG or polyacrylic acid as raw material to prepare.
发明内容Contents of the invention
本发明所要解决的技术问题是提供一种高氧透过率共连续网络的制备方法和应用，以聚二醇、有机硅氧烷聚合物为原料，制备两性无规嵌段共聚物，通过化学交联反应，得到两性共连续网络，该网络具有良好的抗氧降解性。应用于生物医用材料如隐型眼镜、人工脏器、药物的控制释放载体。The technical problem to be solved by the present invention is to provide a preparation method and application of a high oxygen transmission rate co-continuous network, using polyglycol and organosiloxane polymers as raw materials to prepare amphoteric random block copolymers, through chemical The cross-linking reaction results in an amphoteric co-continuous network, which has good resistance to oxidative degradation. Applied to biomedical materials such as contact lenses, artificial organs, and controlled release carriers of drugs.
本发明的一种高氧透过率共连续网络的制备方法，包括下列步骤：A method for preparing a high oxygen permeability co-continuous network of the present invention comprises the following steps:
(1)改性聚二醇共聚物的制备：(1) Preparation of modified polyglycol copolymer:
聚二醇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；The polyglycol copolymer is dissolved in the solvent, and the ratio is 1:4 to 7:3, and the concentration is 20-70% solution, and 10-50% alkali is added under stirring, and (20-500%) allyl Halide, the ratio (5:1 ~ 1:5) reacts 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(Gelest Corp.公司提供)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 (ratio: 1:3～10:1) under the action of 1-1000ppm Karstedt (provided by Gelest Corp.) catalyst, room temperature reaction 1-6 Hours, vacuum distillation to obtain more than 95% high-purity crosslinking agent/filler;
(3)两性无规嵌段共聚物的合成：(3) Synthesis of amphoteric random block copolymers:
(5-65％)改性聚二醇共聚物和(35-95％)有机硅氧烷聚合物，按一定配比(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(Gelest Corp.公司提供)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 copolymer and (35-95%) organosiloxane polymer are dissolved in a solvent according to a certain ratio (1:19～2:1), and the concentration is 2 -20% solution, under the action of modified crosslinking agent/filler and 30-500ppm Karstedt (provided by Gelest Corp.) 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％～10％，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 10%. , 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%.
所述的步骤1聚二醇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；The step 1 polyglycol copolymer is polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer;
所述的步骤1溶剂是四氢呋喃、二氯甲烷或甲苯；The step 1 solvent is THF, methylene chloride or toluene;
所述的步骤1碱是氢氧化钠或氢氧化钾；The alkali in step 1 is sodium hydroxide or potassium hydroxide;
所述的步骤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；The organosiloxane polymer in step 3 is polydimethylsiloxane whose end group is vinyl;
所述的步骤3的溶剂是四氢呋喃、二氯甲烷或甲苯；The solvent of described step 3 is tetrahydrofuran, methylene dichloride or toluene;
所述的步骤3的改性交联剂/填充剂与预聚体的摩尔比在1.05-2.5；The molar ratio of the modified crosslinking agent/filler to the prepolymer in step 3 is 1.05-2.5;
所述的步骤4的溶剂是四氢呋喃、二氯甲烷或甲苯；The solvent of described step 4 is tetrahydrofuran, methylene dichloride or toluene;
所得到的共连续网络在四氢呋喃中的溶胶率在1-10％，在水中的溶胀率为20-80％。氧的透过率为150-600barrers。对于胰岛素和葡萄糖具有一定的透过率。70℃下经7天的质量损失率为0-8％。The obtained co-continuous network has a sol rate of 1-10% in tetrahydrofuran and a swelling rate of 20-80% in water. The oxygen transmission rate is 150-600barrers. It has a certain permeability for insulin and glucose. The mass loss rate is 0-8% after 7 days at 70°C.
本发明的一种高氧透过率共连续网络的应用，在于所述的高氧透过率共连续网络用于隐型眼镜、人工脏器、药物的控制释放载体。The application of the co-continuous network with high oxygen transmission rate of the present invention lies in that the co-continuous network with high oxygen transmission rate is used as a controlled release carrier for contact lenses, artificial organs and drugs.
发明的优点Advantages of the invention
本发明所制备得到的两性共连续网络具有一定的力学性能和孔径分布，在亲水性和亲油性溶剂中都具有一定的溶胀率。对于一定尺寸的中、低分子(如葡萄糖、胰岛素等)具有一定的透过速率，同时具有良好的氧透过率，具有良好的抗氧降解性。在生物医用材料等方面有潜在用途，包括隐型眼镜、人工脏器、药物的控制释放载体等。The amphoteric co-continuous network prepared by the invention has certain mechanical properties and pore size distribution, and has certain swelling rate in both hydrophilic and lipophilic solvents. It has a certain transmission rate for medium and low molecules of a certain size (such as glucose, insulin, etc.), and at the same time has a good oxygen transmission rate and good resistance to oxygen degradation. It has potential applications in biomedical materials, including contact lenses, artificial organs, controlled release carriers of drugs, etc.
具体实施方式Detailed ways
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
(1)将10份聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物溶解在40份溶剂中，投入2份氢氧化钠，与5份烯丙基氯在45℃下发生化学反应，得到端基为烯丙基的改性聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物。(1) Dissolve 10 parts of polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer in 40 parts of solvent, add 2 parts of sodium hydroxide, and react with 5 parts of allyl chloride at 45°C A chemical reaction is carried out to obtain a modified polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer whose terminal group is an allyl group.
(2)二(二甲基甲烷硅氧基)乙氧基苯基硅烷的合成：10份三(二甲基甲烷硅氧基)苯基硅烷与1份无水乙醇混合均匀，加入700ppmKarstedt催化剂，在室温下反应1小时，产物经真空精馏，得到纯度为98％的二(二甲基甲烷硅氧基)乙氧基苯基硅烷。(2) Synthesis of bis(dimethylsiloxy)ethoxyphenylsilane: 10 parts of tris(dimethylsiloxy)phenylsilane are mixed with 1 part of dehydrated alcohol, and 700ppm Karstedt catalyst is added, React at room temperature for 1 hour, and vacuum rectify the product to obtain bis(dimethylsilyloxy)ethoxyphenylsilane with a purity of 98%.
(3)两性无规嵌段共聚物的合成：1份改性聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物和4份聚硅氧烷溶解在40份溶剂中，加入二(二甲基甲烷硅氧基)乙氧基苯基硅烷(其与预聚体的摩尔比为1.3)和100ppmKarstedt催化剂的作用下，在40℃下反应24小时，经纯化，得到3份两性无规嵌段共聚物。(3) Synthesis of amphoteric random block copolymers: 1 part of modified polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer and 4 parts of polysiloxane are dissolved in 40 parts of solvent, add Under the action of bis(dimethylsiloxy)ethoxyphenylsilane (the molar ratio of it to the prepolymer is 1.3) and 100ppm Karstedt catalyst, it was reacted at 40°C for 24 hours, and after purification, 3 parts of amphoteric Random block copolymers.
(4)共连续网络的制备：1份两性无规嵌段共聚物溶解在15份溶剂中，在1％烷基苯磺酸盐作用下，在40℃下反应15小时，得到共连续网络。(4) Preparation of co-continuous network: 1 part of amphoteric random block copolymer was dissolved in 15 parts of solvent, and reacted at 40°C for 15 hours under the action of 1% alkylbenzene sulfonate to obtain a co-continuous network.
所得到的共连续网络在四氢呋喃中的溶胶率为5％，在水中的溶胀率为16％。氧的透过率为550barrers。对于胰岛素和葡萄糖具有一定的透过率。70℃下经7天的质量损失率为3％。The obtained co-continuous network had a sol ratio of 5% in THF and a swelling ratio of 16% in water. The oxygen transmission rate is 550 barrers. It has a certain permeability for insulin and glucose. The mass loss rate at 70° C. over 7 days was 3%.
实施例2：Example 2:
(1)将10份聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物溶解在20份溶剂中，投入3份氢氧化钠，与4份烯丙基氯在55℃下发生化学反应，得到端基为烯丙基的改性聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物。(1) Dissolve 10 parts of polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer in 20 parts of solvent, add 3 parts of sodium hydroxide, and react with 4 parts of allyl chloride at 55°C A chemical reaction is carried out to obtain a modified polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer whose end group is an allyl group.
(2)二(二甲基甲烷硅氧基)乙氧基苯基硅烷的合成：10份三(二甲基甲烷硅氧基)苯基硅烷与1份无水乙醇混合均匀，加入700ppmKarstedt催化剂，在室温下反应7小时，产物经真空精馏，得到纯度为98％的二(二甲基甲烷硅氧基)乙氧基苯基硅烷。(2) Synthesis of bis(dimethylsiloxy)ethoxyphenylsilane: 10 parts of tris(dimethylsiloxy)phenylsilane are mixed with 1 part of dehydrated alcohol, and 700ppm Karstedt catalyst is added, After reacting at room temperature for 7 hours, the product was subjected to vacuum distillation to obtain bis(dimethylsiloxy)ethoxyphenylsilane with a purity of 98%.
(3)两性无规嵌段共聚物的合成：1份改性聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物和2份聚硅氧烷溶解在40份溶剂中，加入二(二甲基甲烷硅氧基)乙氧基苯基硅烷(其与预聚体的摩尔比为1.3)和100ppmKafstedt催化剂的作用下，在40℃下反应24小时，经纯化，得到2份两性无规嵌段共聚物。(3) Synthesis of amphoteric random block copolymer: 1 part of modified polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer and 2 parts of polysiloxane are dissolved in 40 parts of solvent, and added Under the action of bis(dimethylsiloxy)ethoxyphenylsilane (the molar ratio of it to the prepolymer is 1.3) and 100ppm Kafstedt catalyst, react at 40°C for 24 hours, and after purification, 2 parts of amphoteric Random block copolymers.
(4)共连续网络的制备：1份两性无规嵌段共聚物溶解在15份溶剂中，在1％烷基苯磺酸盐作用下，在40℃下反应15小时，得到共连续网络。(4) Preparation of co-continuous network: 1 part of amphoteric random block copolymer was dissolved in 15 parts of solvent, and reacted at 40°C for 15 hours under the action of 1% alkylbenzene sulfonate to obtain a co-continuous network.
所得到的共连续网络在四氢呋喃中的溶胶率为5％，在水中的溶胀率为32％。氧的透过率为480barrers。对于胰岛素和葡萄糖具有一定的透过率。70℃下经7天的质量损失率为3％。The obtained co-continuous network had a sol ratio of 5% in THF and a swelling ratio of 32% in water. The oxygen transmission rate is 480 barrers. It has a certain permeability for insulin and glucose. The mass loss rate at 70° C. over 7 days was 3%.
实施例3：Example 3:
(1)将10份聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物溶解在10份溶剂中，投入4份氢氧化钠，与5份乙烯基苯甲基氯在50℃下发生化学反应，得到端基为苯乙烯基的改性聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物。(1) Dissolve 10 parts of polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer in 10 parts of solvent, add 4 parts of sodium hydroxide, and mix with 5 parts of vinylbenzyl chloride at 50 °C A chemical reaction occurs under the conditions to obtain a modified polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer whose terminal group is styrene group.
(2)二(二甲基甲烷硅氧基)乙氧基苯基硅烷的合成：10份三(二甲基甲烷硅氧基)苯基硅烷与1份无水乙醇混合均匀，加入1000ppmKarstedt催化剂，在室温下反应5小时，产物经真空精馏，得到纯度为98％的二(二甲基甲烷硅氧基)乙氧基苯基硅烷。(2) Synthesis of bis(dimethylsiloxy)ethoxyphenylsilane: 10 parts of tris(dimethylsiloxy)phenylsilane are mixed with 1 part of dehydrated alcohol, and 1000ppm Karstedt catalyst is added, After reacting at room temperature for 5 hours, the product was subjected to vacuum distillation to obtain bis(dimethylsilyloxy)ethoxyphenylsilane with a purity of 98%.
(3)两性无规嵌段共聚物的合成：2份改性聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物和3份聚硅氧烷溶解在50份溶剂中，在二(二甲基甲烷硅氧基)乙氧基苯基硅烷(其与预聚体的摩尔比为1.8)和350ppmKarstedt催化剂的作用下，在40℃下反应48小时，经纯化，得到两性无规嵌段共聚物。(3) Synthesis of amphoteric random block copolymer: 2 parts of modified polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer and 3 parts of polysiloxanes are dissolved in 50 parts of solvent, in Under the action of bis(dimethylsiloxy)ethoxyphenylsilane (the molar ratio of it to the prepolymer is 1.8) and 350ppm Karstedt catalyst, it was reacted at 40°C for 48 hours and purified to obtain amphoteric random block copolymers.
(3)共连续网络的制备：1份两性无规嵌段共聚物溶解在19份溶剂中，在1％烷基苯磺酸作用下，在45℃下反应15小时，得到共连续网络。(3) Preparation of co-continuous network: 1 part of amphoteric random block copolymer was dissolved in 19 parts of solvent, and reacted at 45°C for 15 hours under the action of 1% alkylbenzenesulfonic acid to obtain a co-continuous network.
所得到的共连续网络在四氢呋喃中的溶胶率为5％，在水中的溶胀率为43％。氧的透过率为350barrers。对于胰岛素和葡萄糖具有一定的透过率。70℃下经7天的质量损失率为2％。The obtained co-continuous network had a sol ratio of 5% in THF and a swelling ratio of 43% in water. The oxygen transmission rate is 350 barrers. It has a certain permeability for insulin and glucose. The mass loss rate over 7 days at 70°C was 2%.
实施例4：Example 4:
(1)将10份聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物溶解在5份溶剂中，投入3份氢氧化钠，与5份乙烯基苯甲基氯在65℃下发生化学反应，得到端基为苯乙烯基的改性聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物。(1) Dissolve 10 parts of polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer in 5 parts of solvent, add 3 parts of sodium hydroxide, and mix with 5 parts of vinylbenzyl chloride at 65 °C A chemical reaction occurs under the conditions to obtain a modified polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer whose terminal group is styrene group.
(2)二(二甲基甲烷硅氧基)乙氧基苯基硅烷的合成：13份三(二甲基甲烷硅氧基)苯基硅烷与1份无水乙醇混合均匀，加入700ppmKarstedt催化剂，在室温下反应2小时，产物经真空精馏，得到纯度为98％的二(二甲基甲烷硅氧基)乙氧基苯基硅烷。(2) Synthesis of bis(dimethylsilyloxy)ethoxyphenylsilane: 13 parts of tris(dimethylsiloxy)phenylsilane are mixed with 1 part of dehydrated alcohol, and 700ppm Karstedt catalyst is added, After reacting at room temperature for 2 hours, the product was subjected to vacuum distillation to obtain bis(dimethylsiloxy)ethoxyphenylsilane with a purity of 98%.
(3)两性无规嵌段共聚物的合成：1份改性聚乙烯氧化物-聚丙烯氧化物-聚乙烯氧化物三段共聚物和1份聚硅氧烷溶解在25份溶剂中，在二(二甲基甲烷硅氧基)乙氧基苯基硅烷(其与预聚体的摩尔比为1.5)和200ppmKarstedt催化剂的作用下，在40℃下反应48小时，经纯化，得到两性无规嵌段共聚物。(3) Synthesis of amphoteric random block copolymers: 1 part of modified polyethylene oxide-polypropylene oxide-polyethylene oxide three-stage copolymer and 1 part of polysiloxane are dissolved in 25 parts of solvent, in Under the action of bis(dimethylsiloxy)ethoxyphenylsilane (the molar ratio of it to the prepolymer is 1.5) and 200ppm Karstedt catalyst, it was reacted at 40°C for 48 hours and purified to obtain amphoteric random block copolymers.
(4)共连续网络的制备：1份两性无规嵌段共聚物溶解在19份溶剂中，在3％烷基苯磺酸作用下，在45℃下反应15小时，得到共连续网络。(4) Preparation of co-continuous network: 1 part of amphoteric random block copolymer was dissolved in 19 parts of solvent, and reacted at 45°C for 15 hours under the action of 3% alkylbenzenesulfonic acid to obtain a co-continuous network.
所得到的共连续网络在四氢呋喃中的溶胶率为9％，在水中的溶胀率为70％。氧的透过率为190barrers。对于胰岛素和葡萄糖具有一定的透过率。70℃下经7天的质量损失率为0％。The obtained co-continuous network has a sol ratio of 9% in THF and a swelling ratio of 70% in water. The oxygen transmission rate is 190 barrers. It has a certain permeability for insulin and glucose. The mass loss rate at 70° C. over 7 days was 0%.
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