CN103865067B - A kind of preparation method of amphipathic copolymerization network - Google Patents
A kind of preparation method of amphipathic copolymerization network Download PDFInfo
- Publication number
- CN103865067B CN103865067B CN201410107880.2A CN201410107880A CN103865067B CN 103865067 B CN103865067 B CN 103865067B CN 201410107880 A CN201410107880 A CN 201410107880A CN 103865067 B CN103865067 B CN 103865067B
- Authority
- CN
- China
- Prior art keywords
- parts
- amphipathic
- block polymers
- solvent
- double bond
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a kind of preparation method of amphipathic copolymerization network, it is characterized in that, concrete steps comprise: will mix containing PDMS base macromolecular chain transfering reagent, hydrophilic monomer, solvent and initiator, and be obtained by reacting amphipathic triblock polymer; By amphipathic triblock polymer, initiator, containing two double bond small molecule monomer and solvent, be obtained by reacting amphipathic five block polymers of end containing pendency double bond; Amphipathic five block polymers and the alkyl primary amine reaction that the end of gained are contained pendency double bond obtain terminal-modified amphipathic five block polymers; By terminal-modified amphipathic five block polymers, containing hydrogen silicone oil or silane containing hydrogen, solvent and catalyst mix, be obtained by reacting amphipathic copolymerization network.Amphipathic altogether contiguous network prepared by the present invention in biomedical materials field, as all there is application controlled drug release vehicle, artificial pancreas structure, contact lens material aspect.
Description
Technical field
The present invention does not relate to a kind of preparation method of amphipathic copolymerization network.
Background technology
The majority that current document is reported is to synthesize amphiphilic polymer network with radical polymerization, group transfer polymerization polymerization (GTP) method, as " AnomalousSwellingBehaviorofPoly (N-vinylimidazole)-l-Poly (tetrahydrofuran) AmphiphilicConetworkinWaterStudiedbySolid-StateNMRandPos itronAnnihilationLifetimeSpectroscopy " (Domjan, Attila; Fodor, Csaba; Kovacs, Szabolcs.Macromolecules2012,45,18) what adopt is the cross-linked network that N-vinyl imidazole and tetrahydrofuran (THF) have been prepared in radical polymerization." ThermallyResponsiveAmphiphilicConetworksandGelsBasedonPo ly (N-isopropylacrylamide) andPolyisobutylene " (Kali, Gergely; Vavra, Szilvia; Laszlo, KrisztinaMacromolecules2013,46,5337-5344), employing be that the cross-linked network of PNiPAAm-I-PIB has been prepared in radical polymerization." Thermoplasticamphiphilicconetworks " (JungmeeKang; Erdodi, G.; Kennedy, J.P.JournalofPolymerScience, PartA:PolymerChemistry, 47,682-91), employing be that radical polymerization has been prepared containing PDMS-PDMAAm polymer network, thermoplastic processing can be carried out with polyurethane PU is blended.The product relative molecular weight distribution obtained with this kind of polymerization process is wide, molecular weight poor controllability, causes that prepared polymer segment size is uncontrollable, network mechanical property is poor.RAFT (RAFT) activity/controllable polymerization method is the polymer synthesis techniques grown up gradually in recent years.Accurately control the advantages such as polymericular weight, narrower molecular weight distribution, good functional group's tolerance by means of it, in block polymer synthesis, have obvious advantage, be widely used in designing various complicated macromole.Containing hydrogen silicone oil or hydrogen-containing siloxane have the advantages such as good reactive behavior, biocompatibility is good, bio-toxicity is low, are widely used in preparing various biomaterial or biological devices.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of amphipathic copolymerization network, amphipathic copolymerization network prepared by this invention has certain mechanical property and pore size distribution, certain swelling ratio is all shown in wetting ability and liphophilic solvents, there is good antioxygen degradation property simultaneously, at 65 DEG C, 15 days rate of loss <0.5%.Its transmittance is 50% ~ 93%.In bio-medical material, there is potential use, comprise contact lens, artificial organ, drug controlled release carrier etc.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of amphipathic copolymerization network, it is characterized in that, concrete steps comprise:
The first step: n-dodecyl mercaptan, alkali lye, acetone and catalyzer are mixed under-15 DEG C of-15 DEG C of conditions, adds CS
2and alkyl polyhalides, under protection of inert gas, reaction 1-48h, obtains RAFT reagent; Wherein, n-dodecyl mercaptan, alkali lye, acetone, catalyzer, CS
2, alkyl polyhalides mass ratio be 100:30-300:100-1000:0.1-1:30-300:30-300;
Second step: by the RAFT reagent of gained, functional poly dimethyl siloxane (containing PDMS yl), carboxylic acid activating agent, dewatering agent and solvent, under 0-100 DEG C of condition, reaction 1-48h, obtains containing PDMS base macromolecular chain transfering reagent; The weight ratio of RAFT reagent, functional poly dimethyl siloxane, carboxylic acid activating agent, dewatering agent, solvent is 100:10-500:50-200:5-20:500-5000;
3rd step: will mix containing PDMS base macromolecular chain transfering reagent, hydrophilic monomer, solvent and initiator, under protection of inert gas, under 60-100 DEG C of condition, reaction 0.5-24h, obtains amphipathic triblock polymer; Wherein hydrophilic monomer, be 100:0.1-10:0.01-0.1:200-5000 containing the mass ratio of PDMS macromolecular chain transfering reagent, initiator, solvent;
4th step: by above-mentioned amphipathic triblock polymer, initiator, containing two double bond small molecule monomer and solvent, under an inert atmosphere, react 0.5-24h at 60-100 DEG C, obtains amphipathic five block polymers of end containing pendency double bond; Wherein contain two double bond small molecule monomers, amphipathic five block polymers, initiator and solvent quality than being 100:100-500:10-100:500-1000;
5th step: by the end of gained containing pendency amphipathic five block polymers of double bond and alkyl primary amine under an inert atmosphere, at 0-100 DEG C of conditioned response 1-48h, obtain terminal-modified amphipathic five block polymers; Wherein end is 100:50-500 containing pendency amphipathic five block polymers of double bond and the weight ratio of alkyl primary amine;
6th step: by terminal-modified amphipathic five block polymers of gained, containing hydrogen silicone oil or silane containing hydrogen, solvent and catalyst mix, at 30 DEG C-130 DEG C isothermal reaction 0.1-48h, obtain amphipathic copolymerization network; Wherein terminal-modified amphipathic five block polymers, containing hydrogen silicone oil or silane containing hydrogen, the mass ratio of catalysts and solvents are 100:50-500:0.1-10:500-2000.
Preferably, NaOH solution or the KOH solution of to be mass percent concentration the be 40%-80% of the alkali lye in the described the first step; Catalyzer is methyl three capryloyl ammonium chloride or trimethyl butyl ammonium sulfate; Alkyl polyhalides is in methylene dichloride, trichloromethane, methylene bromide or methenyl bromide.
Preferably, the RAFT reagent in the described the first step is S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate.
Preferably, the functional poly dimethyl siloxane in described second step is end hydroxypropyl polydimethylsiloxane or end aminopropyl polydimethylsiloxane.
Preferably, the carboxylic acid activating agent in described second step is DMAP DMAP; Dewatering agent is dicyclohexylcarbodiimide (DCC) or 1-ethyl-(3-bis-alkyl primary amine groups propyl group) carbodiimide hydrochloride (EDCI); Solvent is one or more the mixture in methylene dichloride, normal hexane, Isosorbide-5-Nitrae-dioxane and pimelinketone.
Preferably, hydrophilic monomer in described 3rd step is Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, hy-droxybutyl, methacrylate, N, the acid of N-DMAA, N, N-dimethylmethacryl amide, acrylic or methacrylic; Initiator is Diisopropyl azodicarboxylate (AIBN), benzoyl peroxide (BPO) or azo (4-cyanopentanoic acid) (ACVA); Solvent is one or more the mixture in tetrahydrofuran (THF) (THF), Virahol (IPA) and toluene (toluene); Rare gas element is ultrapure argon (Ar) or nitrogen (N
2).
Preferably, in described 4th step is allyl methacrylate(AMA), ethylacrylic acid allyl ester or methacrylic acid alkene butyl ester containing two double bond small molecule monomers; Initiator is Diisopropyl azodicarboxylate (AIBN), benzoyl peroxide (BPO) or azo (4-cyanopentanoic acid) (ACVA), and solvent is one or more the mixture in tetrahydrofuran (THF) (THF), Virahol (IPA) and toluene (toluene).
Preferably, the alkyl primary amine in described 5th step is one or more the mixture in n-Butyl Amine 99, normal hexyl Amine and dodecyl amine.
Preferably, the silane containing hydrogen in described 6th step is D
3h, D
4h and D
5one or more mixture in H, containing hydrogen silicone oil is one in Methyl Hydrogen Polysiloxane Fluid (Mn=200 ~ 20000) and methyl and phenyl hydrogen-containing silicon oil (Mn=200 ~ 20000) or its mixture, and catalyzer is Karstedt catalyst made from platonic; Solvent is one or more the mixture in toluene, Virahol and tetrahydrofuran (THF).
Amphipathic copolymerization network of the present invention is preparing the application in bio-medical material.
Compared with prior art, the invention has the beneficial effects as follows:
Amphipathic contiguous network altogether prepared by the present invention has certain mechanical property and pore size distribution, and in wetting ability and liphophilic solvents, all show certain swelling ratio, in tetrahydrofuran (THF), swelling capacity is 10% ~ 600%.Swelling capacity in water is 5% ~ 500%.Biological micromolecule (as synanthrin, Regular Insulin etc.) for certain size has certain transmission rates, and having good oxygen permeability, is 800 ~ 1700Barres, has good antioxygen degradation property simultaneously, at 65 DEG C, 15 days rate of loss <0.5%.Its transmittance is 50% ~ 93%.In bio-medical material, there is potential use, comprise contact lens, artificial organ, drug controlled release carrier etc.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.Each number in embodiment, if no special instructions, is weight part.
Embodiment 1
(1) be 40%NaOH alkali lye, 500 parts of acetone and 0.5 part of methyl three capryloyl ammonium chloride by the n-dodecyl mercaptan of 100 parts, the massfraction of 150 parts; mix under 5 DEG C of conditions, then add dithiocarbonic anhydride, 150 parts of trichloromethanes of 150 parts successively.Under nitrogen protection, in 10 DEG C of reaction 10h, S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent) is obtained.
(2) 100 parts of ends hydroxypropyl polydimethylsiloxane (Mn=4000), 10 parts of RAFT reagent, 50 parts of EDCI and 50 part of DMAP are mixed, and be dissolved in 500 parts of methylene dichloride, under 15 DEG C of conditions, reaction 2h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of hydroxyethyl methylacrylates are dissolved in 200 parts of Virahols; make the hydroxyethyl methylacrylate solution that concentration is 50%; drop into 1 part containing PDMS base macromolecular chain transfering reagent and 0.01 part of AIBN; under nitrogen protection; at 60 DEG C, react 0.5h, obtain amphipathic triblock polymer.
(4) by 100 parts containing amphipathic triblock polymer, 150 parts be dissolved in 700 parts of Virahols containing allyl methacrylate, 50 parts of ACVA; under nitrogen protection; at 60 DEG C, react 0.5h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 150 parts of n-Butyl Amine 99s, under nitrogen protection, in 0 DEG C of reaction 48h, obtain amphipathic five block polymers of terminal groups modification.
(6) amphipathic five block polymers of 100 parts of terminal groups modifications, 150 parts of Methyl Hydrogen Polysiloxane Fluids (Mn=200), 5 parts of Karstedt catalyst made from platonic are dissolved in 1000 parts of Virahols, at 130 DEG C, isothermal reaction 48h, obtains amphipathic copolymerization network.
The common contiguous network transparence obtained is 93%, tensile strength 3Mpa, breaking tenacity 130%, and the swelling ratio in tetrahydrofuran (THF) is 65%, and the swelling ratio in water is 180%.The transmitance of oxygen is 700barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.1%.
Embodiment 2
(1) be 50%NaOH alkali lye, 100 parts of acetone and 0.1 part of methyl three capryloyl ammonium chloride by the n-dodecyl mercaptan of 100 parts, the massfraction of 30 parts, mix under-5 DEG C of conditions, then add dithiocarbonic anhydride, 150 parts of methylene dichloride of 30 parts successively.Under argon shield, in 0 DEG C of reaction 1h, obtain S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent).
(2) 100 parts of ends aminopropyl polydimethylsiloxane (Mn=4000), 200 parts of RAFT reagent, 100 parts of EDCI and 10 part of DMAP are mixed, and be dissolved in 1000 parts of normal hexanes, under 15 DEG C of conditions, reaction 15h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of Hydroxyethyl acrylates are dissolved in 900 parts of tetrahydrofuran (THF)s; make the Hydroxyethyl acrylate solution that concentration is 10%; drop into 5 parts containing PDMS base macromolecular chain transfering reagent and 0.05 part of initiator; under argon shield; at 60 DEG C, react 2h, obtain amphipathic triblock polymer.
(4) 100 parts are dissolved in 500 parts of tetrahydrofuran (THF)s containing amphipathic triblock polymer, 100 parts of allyl methacrylate, 10 parts of AIBN, under argon shield, at 60 DEG C, react 2h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphiphilic five block polymer of pendency double bond, 50 parts of n-Butyl Amine 99s, under argon shield, in 8 DEG C of reaction 45h, obtain amphipathic five block polymers of terminal groups modification.
(6) amphipathic five block polymers of 100 parts of terminal groups modifications, 50 parts of Methyl Hydrogen Polysiloxane Fluids (Mn=300), 50 parts of methyl and phenyl hydrogen-containing silicon oils (Mn=20000), 0.1 part of Karstedt catalyst made from platonic are dissolved in 500 parts of tetrahydrofuran (THF)s, at 130 DEG C, isothermal reaction reaction 44h, obtains amphipathic copolymerization network.
The common contiguous network transparence obtained is 93%, tensile strength 3Mpa, breaking tenacity 100%, and the swelling ratio in tetrahydrofuran (THF) is 70%, and the swelling ratio in water is 50%.The transmitance of oxygen is 800barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.3%.
Embodiment 3
(1) be 60%KOH alkali lye by the n-dodecyl mercaptan of 100 parts, the massfraction of 300 parts, 1000 parts of acetone and 1 part of methyl three capryloyl ammonium chloride mixes, then add dithiocarbonic anhydride, 300 parts of methylene dichloride of 300 parts successively under 10 DEG C of conditions.Under nitrogen gas shielded, in 15 DEG C of reaction 20h, obtain S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent).
(2) 100 parts of ends hydroxypropyl polydimethylsiloxane (Mn=4000), 500 parts of RAFT reagent, 200 parts of DCC and 20 part of DMAP are mixed, and be dissolved in 5000 parts of Isosorbide-5-Nitrae dioxane, under 30 DEG C of conditions, reaction 24h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of Propylene glycol monoacrylates are dissolved in 5000 parts of tetrahydrofuran (THF)/Virahols (v/v=1:1); make the Propylene glycol monoacrylate solution that concentration is 10%; drop into 10 parts containing PDMS base macromolecular chain transfering reagent and 0.1 part of ACVA; under argon shield; at 60 DEG C, react 3.5h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 500 parts of allyl methacrylate, 100 parts of BPO are dissolved in 1000 parts of tetrahydrofuran (THF)/Virahols (v/v=1:1); under argon shield; at 60 DEG C, react 3.5h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphiphilic five block polymer of pendency double bond, 500 parts of n-Butyl Amine 99s, under nitrogen protection, in 16 DEG C of reaction 42h, obtain amphipathic five block polymers of terminal groups modification.
(6) by amphipathic five block polymers of 100 parts of terminal groups modifications, 500 parts of D
5h, 10 parts of Karstedt catalyst made from platonic are dissolved in 2000 parts of tetrahydrofuran (THF)/Virahols (v/v=1:1), and at 120 DEG C, isothermal reaction 40h, obtains amphipathic copolymerization network.
The common contiguous network transparence obtained is 93%, tensile strength 5Mpa, breaking tenacity 160%, swelling ratio in tetrahydrofuran (THF) is 600%, swelling ratio in water is 500%, the transmitance of oxygen is 1700barrers, has certain transmitance for Regular Insulin and glucose, at 65 DEG C through the mass loss rate of 7 days be 0.5%.
Embodiment 4
(1) be 80%KOH alkali lye, 50 parts of acetone and 0.2 part of trimethyl butyl ammonium sulfate by the n-dodecyl mercaptan of 100 parts, the massfraction of 50 parts, mix under 0 DEG C of condition, then add dithiocarbonic anhydride, 300 parts of methylene bromides of 50 parts successively.Under argon shield, in 5 DEG C of reaction 3h, obtain S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent).
(2) 100 parts of ends aminopropyl polydimethylsiloxane (Mn=4000), 30 parts of RAFT reagent, 70 parts of EDCI and 5 part of DMAP are mixed, and be dissolved in 700 parts of pimelinketone, under 15 DEG C of conditions, reaction 4h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of Rocryl 410s are dissolved in 400 parts of tetrahydrofuran (THF)/Virahols (v/v=1:1); make the Rocryl 410 solution that concentration is 25%; drop into 0.3 part containing PDMS base macromolecular chain transfering reagent and 0.03 part of AIBN; under argon shield; at 70 DEG C, react 4.5h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 150 parts of ethylacrylic acid allyl esters, 20 parts of ACVA are dissolved in 700 parts of tetrahydrofuran (THF)/Virahols (v/v=1:1); under argon shield; at 70 DEG C, react 5h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 100 parts of n-Butyl Amine 99s, under argon shield, in 24 DEG C of reaction 39h, obtain amphipathic five block polymers of terminal groups modification.
(6) amphipathic five block polymers of 100 parts of terminal groups modifications, 100 parts of Methyl Hydrogen Polysiloxane Fluids (Mn=500), 10 parts of methyl and phenyl hydrogen-containing silicon oils (Mn=15000), 1 part of Karstedt catalyst made from platonic are dissolved in 700 parts of tetrahydrofuran (THF)/Virahols (v/v=1:1), at 110 DEG C, isothermal reaction 2h, obtains amphipathic copolymeric network.
The common contiguous network transparence obtained is 93%, tensile strength 5Mpa, breaking tenacity 160%, swelling ratio in tetrahydrofuran (THF) is 50%, swelling ratio in water is 50%, the transmitance of oxygen is 1500barrers, has certain transmitance for Regular Insulin and glucose, at 65 DEG C through the mass loss rate of 7 days be 0.4%.
Embodiment 5
(1) be 40%KOH alkali lye, 150 parts of acetone and 0.4 part of methyl three capryloyl ammonium chloride by the n-dodecyl mercaptan of 100 parts, the massfraction of 150 parts; mix under-4 DEG C of conditions, then add dithiocarbonic anhydride, 150 parts of methenyl bromides of 150 parts successively.Under nitrogen protection, in 10 DEG C of reaction 5h, S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent) is obtained.
(2) 100 parts of ends hydroxypropyl polydimethylsiloxane (Mn=4000), 50 parts of RAFT reagent, 90 parts of DCC and 7 part of DMAP are mixed, and be dissolved in 900 parts of normal hexane/methylene dichloride (v/v=1:1) mixed solvents, under 20 DEG C of conditions, reaction 6h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) by 100 parts of N; N-DMAA is dissolved in 500 parts of toluene; make the N that concentration is 20%; N-DMAA solution; drop into 0.5 part containing PDMS base macromolecular chain transfering reagent and 0.05 part of BPO; under nitrogen protection, at 75 DEG C, react 6h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 200 parts of ethylacrylic acid allyl esters, 25 parts of AIBN are dissolved in 900 parts of toluene, under nitrogen protection, at 75 DEG C, react 6.5h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 100 parts of n-Butyl Amine 99s, under nitrogen protection, in 32 DEG C of reaction 35h, obtain amphipathic five block polymers of terminal groups modification.
(6) amphipathic five block polymers of 100 parts of terminal groups modifications, 100 parts of methyl and phenyl hydrogen-containing silicon oils (Mn=200), 2 parts of Karstedt catalyst made from platonic are dissolved in 900 parts of toluene, at 100 DEG C, isothermal reaction reaction 32h, obtains amphipathic copolymeric network.
The common contiguous network transparence obtained is 90%, tensile strength 3Mpa, and the swelling ratio of breaking tenacity 110% in tetrahydrofuran (THF) is 100%, and the swelling ratio in water is 100%.The transmitance of oxygen is 1300barrers, has certain transmitance for Regular Insulin and glucose.At 65 DEG C through the mass loss rate of 7 days be 0.3%.
Embodiment 6
(1) be 60%NaOH alkali lye by the n-dodecyl mercaptan of 100 parts, the massfraction of 200 parts, 200 parts of acetone and 0.6 part of methyl three capryloyl ammonium chloride mixes, then add dithiocarbonic anhydride, 200 parts of methylene dichloride of 200 parts successively under-6 DEG C of conditions.Under argon shield, in 0 DEG C of reaction 7h, obtain S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent).
(2) 100 parts of ends aminopropyl polydimethylsiloxane (Mn=4000), 100 parts of RAFT reagent, 110 parts of EDCI and 9 part of DMAP are mixed, and be dissolved in 1100 parts of methylene dichloride/pimelinketone (v/v=1:1) mixed solvents, under 22 DEG C of conditions, reaction 8h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) by 100 parts of N; N-dimethylmethacryl amide is dissolved in 700 parts of toluene/tetrahydrofuran (THF)s (v/v=1:1); make the N that concentration is 14.28%; N-dimethylmethacryl amide solution; drop into 0.7 part containing PDMS base macromolecular chain transfering reagent and 0.07 part of ACVA; under argon shield, at 80 DEG C, react 7.5h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 300 parts of ethylacrylic acid allyl esters, 30 parts of BPO are dissolved in 1100 parts of toluene/tetrahydrofuran (THF)s (v/v=1:1); under argon shield; at 80 DEG C, react 8h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 150 parts of normal hexyl Amines, under argon shield, in 40 DEG C of reaction 31h, obtain amphipathic five block polymers of terminal groups modification.
(6) amphipathic five block polymers of 100 parts of terminal groups modifications, 100 parts of Methyl Hydrogen Polysiloxane Fluids (Mn=10000), 100 parts of methyl and phenyl hydrogen-containing silicon oils (Mn=1000), 3 parts of Karstedt catalyst made from platonic are dissolved in 1100 parts of toluene/tetrahydrofuran (THF)s (v/v=1:1), at 90 DEG C, isothermal reaction 28h, obtains amphipathic copolymeric network.
The common contiguous network transparence obtained is 91%, tensile strength 3.5Mpa, and the swelling ratio of breaking tenacity 125% in tetrahydrofuran (THF) is 110%, and the swelling ratio in water is 110%.The transmitance of oxygen is 1100barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.2%.
Embodiment 7
(1) be 70%KOH alkali lye by the n-dodecyl mercaptan of 100 parts, the massfraction of 250 parts, 250 parts of acetone and 0.8 part of trimethyloctyl ammonium sulfate mixes, then add dithiocarbonic anhydride, 250 parts of trichloromethanes of 250 parts successively under-8 DEG C of conditions.Under nitrogen protection, in-5 DEG C of reaction 9h, S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent) is obtained.
(2) 100 parts of ends hydroxypropyl polydimethylsiloxane (Mn=4000), 100 parts of RAFT reagent, 130 parts of DCC and 11 part of DMAP are mixed, and be dissolved in 1300 parts of normal hexane/pimelinketone (v/v=1:1) mixed solvents, under 23 DEG C of conditions, reaction 10h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of methacrylic acids are dissolved in 900 parts of toluene/tetrahydrofuran (THF)s (v/v=1:1); make the methacrylate solution that concentration is 18.52%; drop into 0.9 part containing PDMS base macromolecular chain transfering reagent and 0.09 part of AIBN; under nitrogen protection; at 85 DEG C, react 9h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 350 parts of methacrylic acid alkene butyl esters, 40 parts of ACVA are dissolved in 1500 parts of toluene/tetrahydrofuran (THF)s (v/v=1:1); under nitrogen protection; at 85 DEG C, react 10h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 200 parts of normal hexyl Amines, under nitrogen protection, in 48 DEG C of reaction 28h, obtain amphipathic five block polymers of terminal groups modification.
(6) amphipathic five block polymers of 100 parts of terminal groups modifications, 150 parts of methyl and phenyl hydrogen-containing silicon oils (Mn=5000), 3 parts of Karstedt catalyst made from platonic are dissolved in 1500 parts of toluene/tetrahydrofuran (THF)s (v/v=1:1), at 80 DEG C, isothermal reaction 24h, obtains amphipathic copolymeric network.
The common contiguous network transparence obtained is 92%, tensile strength 4.0Mpa, and the swelling ratio of breaking tenacity 135% in tetrahydrofuran (THF) is 90%, and the swelling ratio in water is 130%.The transmitance of oxygen is 900barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.3%.
Embodiment 8
(1) be 70%NaOH alkali lye by the n-dodecyl mercaptan of 100 parts, the massfraction of 300 parts, 300 parts of acetone and 1 part of methyl three capryloyl ammonium chloride mixes, then add dithiocarbonic anhydride, 300 parts of methylene bromides of 300 parts successively under 10 DEG C of conditions.Under argon shield, in-10 DEG C of reaction 11h, obtain S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent).
(2) 100 parts of ends aminopropyl polydimethylsiloxane (Mn=4000), 200 parts of RAFT reagent, 150 parts of EDCI and 12 part of DMAP are mixed, and be dissolved in 1500 part 1, in 4-dioxane/methylene dichloride/pimelinketone (v/v/v=1:1:1) mixed solvent, under 24 DEG C of conditions, reaction 11h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of hy-droxybutyl are dissolved in 1100 parts of toluene/tetrahydrofuran (THF)s (v/v=1:1); make the hy-droxybutyl solution that concentration is 9.09%; drop into 1 part containing PDMS base macromolecular chain transfering reagent and 0.1 part of BPO; under argon shield; at 90 DEG C, react 10h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 400 parts of methacrylic acid alkene butyl esters, 60 parts of AIBN are dissolved in 1700 parts of toluene/tetrahydrofuran (THF)s (v/v=1:1); under argon shield; at 90 DEG C, react 12h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 300 parts of normal hexyl Amines, under argon shield, in 56 DEG C of reaction 24h, obtain amphipathic five block polymers of terminal groups modification.
(6) amphipathic five block polymers of 100 parts of terminal groups modifications, 250 parts of methyl and phenyl hydrogen-containing silicon oils (Mn=15000), 5 parts of Karstedt catalyst made from platonic are dissolved in 1700 parts of toluene/tetrahydrofuran (THF)s (v/v=1:1), at 80 DEG C, isothermal reaction 20h, obtains amphipathic copolymeric network.
The common contiguous network transparence obtained is 91%, tensile strength 4.3Mpa, and the swelling ratio of breaking tenacity 135% in tetrahydrofuran (THF) is 120%, and the swelling ratio in water is 150%.The transmitance of oxygen is 800barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.2%.
Embodiment 9
(1) be 50%KOH by the n-dodecyl mercaptan of 100 parts, the massfraction of 300 parts, 300 parts of acetone and 1 part of trimethyloctyl ammonium sulfate mixes, then add dithiocarbonic anhydride, 300 parts of methylene dichloride of 300 parts successively under 10 DEG C of conditions.Under nitrogen protection, in-15 DEG C of reaction 15h, S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent) is obtained.
(2) 100 parts of ends hydroxypropyl polydimethylsiloxane (Mn=4000), 200 parts of RAFT reagent, 150 parts of DCC and 12 part of DMAP are mixed, and be dissolved in 2500 parts of methylene dichloride/1, in 4 dioxane/normal hexane (v/v/v=1:1:1) mixed solvent, under 26 DEG C of conditions, reaction 15h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of Propylene glycol monoacrylates are dissolved in 2000 parts of Virahol/tetrahydrofuran (THF)s (v/v=1:1); make the Propylene glycol monoacrylate solution that concentration is 5%; drop into 2 parts containing PDMS base macromolecular chain transfering reagent and 0.2 part of ACVA; under nitrogen protection; at 90 DEG C, react 10.5h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 400 parts of methacrylic acid alkene butyl esters, 60 parts of BPO are dissolved in 1000 parts of Virahol/tetrahydrofuran (THF)s: in toluene (v/v/v=1:1:1); under nitrogen protection; at 90 DEG C, react 14h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 400 parts of normal hexyl Amine/dodecyl amine, under nitrogen protection, in 64 DEG C of reaction 20h, obtain amphipathic five block polymers of terminal groups modification.
(6) by amphipathic five block polymers of 100 parts of terminal groups modifications, 50 parts of D
5h, 350 parts of D
4h, 7 parts of Karstedt catalyst made from platonic are dissolved in 1900 parts of Virahol/tetrahydrofuran (THF)s (v/v=1:1), and at 70 DEG C, isothermal reaction 16h, obtains amphipathic copolymeric network.
The common contiguous network transparence obtained is 92%, tensile strength 4.8Mpa, and the swelling ratio of breaking tenacity 175% in tetrahydrofuran (THF) is 400%, and the swelling ratio in water is 300%.The transmitance of oxygen is 700barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.2%.
Embodiment 10
(1) be 80%NaOH alkali lye by the n-dodecyl mercaptan of 100 parts, the massfraction of 300 parts, 300 parts of acetone and 1 part of methyl three capryloyl ammonium chloride mixes, then add dithiocarbonic anhydride, 300 parts of methenyl bromides of 300 parts successively under 5 DEG C of conditions.Under argon shield, in 10 DEG C of reaction 15h, obtain S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent).
(2) 100 parts of ends aminopropyl polydimethylsiloxane (Mn=4000), 300 parts of RAFT reagent, 200 parts of EDCI and 16 part of DMAP are mixed, and be dissolved in 3000 parts of methylene dichloride/1, in 4 dioxane (v/v=1:1) mixed solvent, under 28 DEG C of conditions, reaction 18h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of NVPs are dissolved in 3000 parts of toluene/isopropanol (v/v=1:1); make the NVP solution that concentration is 3.3%; drop into 5 parts containing PDMS base macromolecular chain transfering reagent and 0.5 part of AIBN; under argon shield; at 95 DEG C, react 12h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 450 parts of methacrylic acid alkene butyl esters, 80 parts of ACVA are dissolved in 1000 parts of toluene/isopropanol (v/v=1:1); under argon shield; at 95 DEG C, react 16h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 450 parts of normal hexyl Amine/n-Butyl Amine 99/dodecyl amine (v:v:v=1:1:1); under argon shield; in 72 DEG C of reaction 16h, obtain amphipathic five block polymers of terminal groups modification.
(6) by amphipathic five block polymers of 100 parts of terminal groups modifications, 400 parts of D
4h, 9 parts of Karstedt catalyst made from platonic are dissolved in 1900 parts of toluene/isopropanol (v/v=1:1), and at 60 DEG C, isothermal reaction 12h, obtains amphipathic copolymeric network.
The common contiguous network transparence obtained is 90%, tensile strength 3.8Mpa, and the swelling ratio of breaking tenacity 135% in tetrahydrofuran (THF) is 450%, and the swelling ratio in water is 450%.The transmitance of oxygen is 900barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.3%.
Embodiment 11
(1) be 80%KOH by the n-dodecyl mercaptan of 100 parts, the massfraction of 300 parts, 300 parts of acetone and 1 part of methyl three capryloyl ammonium chloride mixes, then add dithiocarbonic anhydride, 300 parts of methylene bromides of 300 parts successively under 0 DEG C of condition.Under nitrogen protection, in 5 DEG C of reaction 17h, S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent) is obtained.
(2) 100 parts of ends hydroxypropyl polydimethylsiloxane (Mn=4000), 400 parts of RAFT reagent, 200 parts of DCC and 18 part of DMAP are mixed, and be dissolved in 3500 part 1, in 4 dioxane/pimelinketone (v/v=1:1) mixed solvent, under 30 DEG C of conditions, reaction 20h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of vinylformic acid are dissolved in 3500 parts of tetrahydrofuran (THF)s; make the acrylic acid solution that concentration is 2.86%, drop into 6 parts containing PDMS base macromolecular chain transfering reagent and 0.6 part of BPO, under nitrogen protection; at 100 DEG C, react 14h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 500 parts of methacrylic acid alkene butyl esters, 100 parts of BPO are dissolved in 1000 parts of tetrahydrofuran (THF)s; under nitrogen protection; at 100 DEG C, react 18h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 500 parts of dodecyl amine, under nitrogen protection, in 80 DEG C of reaction 8h, obtain amphipathic five block polymers of terminal groups modification.
(6) by amphipathic five block polymers of 100 parts of terminal groups modifications, 400 parts of D
3h, 10 parts of Karstedt catalyst made from platonic are dissolved in 2000 parts of tetrahydrofuran (THF)s, and at 50 DEG C, isothermal reaction 18h, obtains amphipathic copolymeric network.
The common contiguous network transparence obtained is 95%, tensile strength 4.8Mpa, and the swelling ratio of breaking tenacity 175% in tetrahydrofuran (THF) is 550%, and the swelling ratio in water is 500%.The transmitance of oxygen is 1100barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.2%.
Embodiment 12
(1) be 70%NaOH alkali lye by the n-dodecyl mercaptan of 100 parts, the massfraction of 300 parts, 300 parts of acetone and 1 part of trimethyloctyl ammonium sulfate mixes, then add dithiocarbonic anhydride, 300 parts of methylene dichloride of 300 parts successively under-5 DEG C of conditions.Under argon shield, in 15 DEG C of reaction 19h, obtain S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent).
(2) 100 parts of ends aminopropyl polydimethylsiloxane (Mn=4000), 400 parts of RAFT reagent, 200 parts of EDCI and 19 part of DMAP are mixed, and be dissolved in 4000 parts of normal hexane/pimelinketone: methylene dichloride: 1, in 4 dioxane (v/v/v/v=1:1:1:1) mixed solvent, under 30 DEG C of conditions, reaction 22h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of methacrylic acids are dissolved in 4000 parts of toluene/isopropanol (v/v=1:1); make the methacrylic acid solution that concentration is 2.5%; drop into 8 parts containing PDMS base macromolecular chain transfering reagent and 0.8 part of AIBN; under argon shield; at 100 DEG C, react 17h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 500 parts of allyl methacrylate, 100 parts of ACVA are dissolved in 1000 parts of toluene/isopropanol (v/v=1:1); under argon shield; at 100 DEG C, react 20h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 500 parts of dodecyl amine, under argon shield, in 88 DEG C of reaction 8h, obtain amphipathic five block polymers of terminal groups modification.
(6) amphipathic five block polymers of 100 parts of terminal groups modifications, 400 parts of Methyl Hydrogen Polysiloxane Fluids (Mn=5000), 100 parts of methyl and phenyl hydrogen-containing silicon oils (Mn=15000), 10 parts of Karstedt catalyst made from platonic are dissolved in 2000 parts of toluene/isopropanol (v/v=1:1), at 40 DEG C, isothermal reaction 5h, obtains amphipathic copolymeric network
The common contiguous network transparence obtained is 92%, tensile strength 3.8Mpa, breaking tenacity 195%, and the swelling ratio in tetrahydrofuran (THF) is 250%, and the swelling ratio in water is 450%.The transmitance of oxygen is 900barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.1%.
Embodiment 13
(1) be 40%KOH by the n-dodecyl mercaptan of 100 parts, the massfraction of 270 parts, 900 parts of acetone and 0.9 part of methyl three capryloyl ammonium chloride mixes, then add dithiocarbonic anhydride, 300 parts of methenyl bromides of 250 parts successively under-10 DEG C of conditions.Under nitrogen protection, in 10 DEG C of reaction 15h, S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent) is obtained.
(2) 100 parts of ends hydroxypropyl polydimethylsiloxane (Mn=4000), 450 parts of RAFT reagent, 150 parts of DCC and 18 part of DMAP are mixed, and be dissolved in 4500 parts of normal hexane/1, in 4 dioxane/toluene (v/v/v=1:1:1) mixed solvent, under 28 DEG C of conditions, reaction 20h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of Rocryl 410s are dissolved in 4500 parts of tetrahydrofuran (THF)/Virahols (v/v=1:1); make the Rocryl 410 solution that concentration is 2.2%; drop into 9 parts containing PDMS base macromolecular chain transfering reagent and 0.9 part of BPO; under nitrogen protection; at 60 DEG C, react 20h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 450 parts of allyl methacrylate, 90 parts of ACVA are dissolved in 900 parts of tetrahydrofuran (THF)s/Virahol/tetrahydrofuran (THF) (v/v/v=1:1:1); under nitrogen protection; at 80 DEG C, react 22h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 450 parts of dodecyl amine/n-Butyl Amine 99s (v/v=1:1); under nitrogen protection; in 96 DEG C of reaction 12h, obtain amphipathic five block polymers of terminal groups modification.
(6) by amphipathic five block polymers of 100 parts of terminal groups modifications, 450 parts of D
4h, 50 parts of D
3h, 10 parts of Karstedt catalyst made from platonic are dissolved in 1500 parts of tetrahydrofuran (THF)s/Virahol/tetrahydrofuran (THF) (v/v/v=1:1:1), and at 30 DEG C, isothermal reaction 3h, obtains amphipathic copolymeric network.
The common contiguous network transparence obtained is 92%, tensile strength 4.9Mpa, breaking tenacity 170%, and the swelling ratio in tetrahydrofuran (THF) is 530%, and the swelling ratio in water is 400%, and the transmitance of oxygen is 1600barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.5%.
Embodiment 14
(1) be 60%NaOH alkali lye by the n-dodecyl mercaptan of 100 parts, the massfraction of 60 parts, 200 parts of acetone and 0.2 part of trimethyloctyl ammonium sulfate mixes, then add dithiocarbonic anhydride, 300 parts of methylene bromides of 60 parts successively under-13 DEG C of conditions.Under argon shield, in 13 DEG C of reaction 3h, obtain S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent).
(2) 100 parts of ends aminopropyl polydimethylsiloxane (Mn=4000), 400 parts of RAFT reagent, 200 parts of EDCI and 20 part of DMAP are mixed, and be dissolved in 1500 parts of methylene dichloride, under 10 DEG C of conditions, reaction 2h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of methacrylate are dissolved in 1800 parts of tetrahydrofuran (THF)/Virahols (v/v=1:1); make the methacrylate solution that concentration is 5.55%; drop into 10 parts containing PDMS base macromolecular chain transfering reagent and 0.10 part of AIBN; under argon shield; at 65 DEG C, react 22h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 200 parts of allyl methacrylate, 20 parts of AIBN are dissolved in 1000 parts of tetrahydrofuran (THF)/Virahols (v/v=1:1); under argon shield; at 65 DEG C, react 23h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 100 parts of dodecyl amine, under argon shield, in 98 DEG C of reaction 4h, obtain amphipathic five block polymers of terminal groups modification.
(6) by amphipathic five block polymers of 100 parts of terminal groups modifications, 10 parts of D
5h, 10 parts of Methyl Hydrogen Polysiloxane Fluids (Mn=20000), 100 parts of methyl and phenyl hydrogen-containing silicon oils (Mn=200), 0.2 part of Karstedt catalyst made from platonic are dissolved in 1000 parts of tetrahydrofuran (THF)/Virahols (v/v=1:1), at 50 DEG C, isothermal reaction 1h, obtains amphipathic copolymeric network.
The common contiguous network transparence obtained is 70%, tensile strength 3Mpa, breaking tenacity 140%, and the swelling ratio in tetrahydrofuran (THF) is 90%, and the swelling ratio in water is 80%.The transmitance of oxygen is 900barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.2%.
Embodiment 15
(1) be 50%KOH by the n-dodecyl mercaptan of 100 parts, the massfraction of 90 parts, 250 parts of acetone and 0.4 part of methyl three capryloyl ammonium chloride mixes, then add dithiocarbonic anhydride, 1200 parts of methylene dichloride of 120 parts successively under-15 DEG C of conditions.Under nitrogen gas shielded, in 15 DEG C of reaction 6h, obtain S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate (RAFT reagent).
(2) 100 parts of ends hydroxypropyl polydimethylsiloxane (Mn=4000), 300 parts of RAFT reagent, 300 parts of DCC and 10 part of DMAP are mixed, and be dissolved in 1200 parts of pimelinketone, under 16 DEG C of conditions, reaction 6h, obtains containing PDMS base macromolecular chain transfering reagent.
(3) 100 parts of methacrylate are dissolved in 2000 parts of toluene/isopropanol/tetrahydrofuran (THF)s (v/v/v=1:1:1); make the methacrylate solution that concentration is 5%; drop into 6 parts containing PDMS base macromolecular chain transfering reagent and 0.6 part of BPO; under nitrogen protection; at 75 DEG C, react 24h, obtain amphipathic triblock polymer.
(4) 100 parts of amphipathic triblock polymers, 350 parts of allyl methacrylate, 40 parts of ACVA are dissolved in 1500 parts of toluene/isopropanol/tetrahydrofuran (THF)s (v/v/v=1:1:1); under nitrogen protection; at 75 DEG C, react 24h, obtain amphipathic five block polymers of end group containing pendency double bond.
(5) 100 parts of end groups are mixed containing amphipathic five block polymers of pendency double bond, 150 parts of dodecyl amine/just own ammonia (v:v=1:1); under nitrogen protection; in 100 DEG C of reaction 0.1h, obtain amphipathic five block polymers of terminal groups modification.
(6) amphipathic five block polymers of 100 parts of terminal groups modifications, 100 parts of Methyl Hydrogen Polysiloxane Fluids (Mn=20000), 0.6 part of Karstedt catalyst made from platonic are dissolved in 1600 parts of toluene/isopropanol/tetrahydrofuran (THF)s (v/v/v=1:1:1), at 50 DEG C, isothermal reaction 0.1h, obtains amphipathic copolymeric network.
The common contiguous network transparence obtained is 90%, tensile strength 6Mpa, breaking tenacity 120%, and the swelling ratio in tetrahydrofuran (THF) is 180%, and the swelling ratio in water is 280%.The transmitance of oxygen is 700barrers.For Regular Insulin and glucose, there is certain transmitance.At 65 DEG C through the mass loss rate of 7 days be 0.4%.
Claims (9)
1. a preparation method for amphipathic copolymerization network, is characterized in that, concrete steps comprise:
The first step: n-dodecyl mercaptan, alkali lye, acetone and catalyzer are mixed under-15 DEG C of-15 DEG C of conditions, adds CS
2and alkyl polyhalides, under protection of inert gas, reaction 1-48h, obtains RAFT reagent; Wherein, n-dodecyl mercaptan, alkali lye, acetone, catalyzer, CS
2, alkyl polyhalides mass ratio be 100:30-300:100-1000:0.1-1:30-300:30-300;
Second step: by the RAFT reagent of gained, functional poly dimethyl siloxane, carboxylic acid activating agent, dewatering agent and solvent, under 0-100 DEG C of condition, reaction 1-48h, obtains containing PDMS base macromolecular chain transfering reagent; The weight ratio of RAFT reagent, functional poly dimethyl siloxane, carboxylic acid activating agent, dewatering agent, solvent is 100:10-500:50-200:5-20:500-5000;
3rd step: will mix containing PDMS base macromolecular chain transfering reagent, hydrophilic monomer, solvent and initiator, under protection of inert gas, under 60-100 DEG C of condition, reaction 0.5-24h, obtains amphipathic triblock polymer; Wherein hydrophilic monomer, be 100:0.1-10:0.01-0.1:200-5000 containing the mass ratio of PDMS macromolecular chain transfering reagent, initiator, solvent; Described hydrophilic monomer is Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, hy-droxybutyl, methacrylate, N, the acid of N-DMAA, N, N-dimethylmethacryl amide, acrylic or methacrylic;
4th step: by above-mentioned amphipathic triblock polymer, initiator, containing two double bond small molecule monomer and solvent, under an inert atmosphere, react 0.5-24h at 60-100 DEG C, obtains amphipathic five block polymers of end containing pendency double bond; Wherein contain two double bond small molecule monomers, amphipathic triblock polymer, initiator and solvent quality than being 100:100-500:10-100:500-1000; Described is allyl methacrylate(AMA), ethylacrylic acid allyl ester or methacrylic acid alkene butyl ester containing two double bond small molecule monomers;
5th step: by the end of gained containing pendency amphipathic five block polymers of double bond and alkyl primary amine under an inert atmosphere, at 0-100 DEG C of conditioned response 1-48h, obtain terminal-modified amphipathic five block polymers; Wherein end is 100:50-500 containing pendency amphipathic five block polymers of double bond and the weight ratio of alkyl primary amine;
6th step: by terminal-modified amphipathic five block polymers of gained, containing hydrogen silicone oil or silane containing hydrogen, solvent and catalyst mix, at 30 DEG C-130 DEG C isothermal reaction 0.1-48h, obtain amphipathic copolymerization network; Wherein terminal-modified amphipathic five block polymers, containing hydrogen silicone oil or silane containing hydrogen, the mass ratio of catalysts and solvents are 100:50-500:0.1-10:500-2000; Described silane containing hydrogen is D
3h, D
4h and D
5one or more mixture in H, containing hydrogen silicone oil is one in Methyl Hydrogen Polysiloxane Fluid and methyl and phenyl hydrogen-containing silicon oil or its mixture.
2. the preparation method of amphipathic copolymerization network as claimed in claim 1, is characterized in that, NaOH solution or the KOH solution of to be mass percent concentration the be 40%-80% of the alkali lye in the described the first step; Catalyzer is methyl three capryloyl ammonium chloride or trimethyl butyl ammonium sulfate; Alkyl polyhalides is in methylene dichloride, trichloromethane, methylene bromide or methenyl bromide.
3. the preparation method of amphipathic copolymerization network as claimed in claim 1, is characterized in that, the RAFT reagent in the described the first step is S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate.
4. the preparation method of amphipathic copolymerization network as claimed in claim 1, is characterized in that, the functional poly dimethyl siloxane in described second step is end hydroxypropyl polydimethylsiloxane or end aminopropyl polydimethylsiloxane.
5. the preparation method of amphipathic copolymerization network as claimed in claim 1, is characterized in that, the carboxylic acid activating agent in described second step is DMAP; Dewatering agent is dicyclohexylcarbodiimide or 1-ethyl-(3-bis-alkyl primary amine groups propyl group) carbodiimide hydrochloride; Solvent is one or more the mixture in methylene dichloride, normal hexane, Isosorbide-5-Nitrae-dioxane and pimelinketone.
6. the preparation method of amphipathic copolymerization network as claimed in claim 1, is characterized in that, described initiator is Diisopropyl azodicarboxylate, benzoyl peroxide or azo (4-cyanopentanoic acid); Solvent is one or more the mixture in tetrahydrofuran (THF), Virahol and toluene; Rare gas element is ultrapure argon or nitrogen.
7. the preparation method of amphipathic copolymerization network as claimed in claim 1; it is characterized in that; described initiator is Diisopropyl azodicarboxylate, benzoyl peroxide or azo (4-cyanopentanoic acid), and solvent is one or more the mixture in tetrahydrofuran (THF), Virahol and toluene.
8. the preparation method of amphipathic copolymerization network as claimed in claim 1, is characterized in that, the alkyl primary amine in the 5th described step is one or more the mixture in n-Butyl Amine 99, normal hexyl Amine and dodecyl amine.
9. the preparation method of amphipathic copolymerization network as claimed in claim 1, is characterized in that, described catalyzer is Karstedt catalyst made from platonic; Solvent is one or more the mixture in toluene, Virahol and tetrahydrofuran (THF).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410107880.2A CN103865067B (en) | 2014-03-21 | 2014-03-21 | A kind of preparation method of amphipathic copolymerization network |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410107880.2A CN103865067B (en) | 2014-03-21 | 2014-03-21 | A kind of preparation method of amphipathic copolymerization network |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103865067A CN103865067A (en) | 2014-06-18 |
| CN103865067B true CN103865067B (en) | 2016-01-06 |
Family
ID=50904114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410107880.2A Active CN103865067B (en) | 2014-03-21 | 2014-03-21 | A kind of preparation method of amphipathic copolymerization network |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103865067B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10676575B2 (en) * | 2016-10-06 | 2020-06-09 | Johnson & Johnson Vision Care, Inc. | Tri-block prepolymers and their use in silicone hydrogels |
| CN108546308B (en) * | 2018-04-17 | 2020-02-18 | 华南理工大学 | Multi-responsiveness ionic gel based on super-amphiphilic molecules and preparation method thereof |
| US11891526B2 (en) | 2019-09-12 | 2024-02-06 | Johnson & Johnson Vision Care, Inc. | Ink composition for cosmetic contact lenses |
| WO2021224855A1 (en) | 2020-05-07 | 2021-11-11 | Alcon Inc. | Method for producing silicone hydrogel contact lenses |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293963A (en) * | 2007-07-06 | 2008-10-29 | 东华大学 | Amphiprotic co-continuous polymer network, preparation method and application thereof |
| CN101597361A (en) * | 2009-07-24 | 2009-12-09 | 厦门大学 | A kind of preparation method of segmented copolymer of polydimethylsiloxane--b-polystyrene |
| CN101983976A (en) * | 2010-12-10 | 2011-03-09 | 华东理工大学 | Preparation method of fluorine-silicon segmented copolymer |
| CN102775567A (en) * | 2012-07-20 | 2012-11-14 | 天津大学 | POSS (polyhedral oligomeric silsesquioxane) contained polyacrylate-polysiloxane block copolymer and preparation method thereof |
| CN103012817A (en) * | 2012-12-28 | 2013-04-03 | 东华大学 | Controllable preparation method of high-oxygen transmission rate co-continuous network |
| CN103214680A (en) * | 2013-04-02 | 2013-07-24 | 东华大学 | Preparation method and application method of novel amphipathic copolymerization network |
| CN103380153A (en) * | 2010-07-30 | 2013-10-30 | 诺瓦提斯公司 | Amphiphilic polysiloxane prepolymers and uses thereof |
| WO2013177523A2 (en) * | 2012-05-25 | 2013-11-28 | Johnson & Johnson Vision Care, Inc. | Polymers and nanogel materials and methods for making and using the same |
-
2014
- 2014-03-21 CN CN201410107880.2A patent/CN103865067B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293963A (en) * | 2007-07-06 | 2008-10-29 | 东华大学 | Amphiprotic co-continuous polymer network, preparation method and application thereof |
| CN101597361A (en) * | 2009-07-24 | 2009-12-09 | 厦门大学 | A kind of preparation method of segmented copolymer of polydimethylsiloxane--b-polystyrene |
| CN103380153A (en) * | 2010-07-30 | 2013-10-30 | 诺瓦提斯公司 | Amphiphilic polysiloxane prepolymers and uses thereof |
| CN101983976A (en) * | 2010-12-10 | 2011-03-09 | 华东理工大学 | Preparation method of fluorine-silicon segmented copolymer |
| WO2013177523A2 (en) * | 2012-05-25 | 2013-11-28 | Johnson & Johnson Vision Care, Inc. | Polymers and nanogel materials and methods for making and using the same |
| CN102775567A (en) * | 2012-07-20 | 2012-11-14 | 天津大学 | POSS (polyhedral oligomeric silsesquioxane) contained polyacrylate-polysiloxane block copolymer and preparation method thereof |
| CN103012817A (en) * | 2012-12-28 | 2013-04-03 | 东华大学 | Controllable preparation method of high-oxygen transmission rate co-continuous network |
| CN103214680A (en) * | 2013-04-02 | 2013-07-24 | 东华大学 | Preparation method and application method of novel amphipathic copolymerization network |
Non-Patent Citations (2)
| Title |
|---|
| Poly(dimethylsiloxane-b-styrene) Diblock Copolymers Prepared by Reversible Addition-Fragmentation Chain Transfer Polymerization: Kinetic Model;Cheng-Mei Guan, et al.;《Journal of Applied Polymer Science》;20110809;第132卷;全文 * |
| RAFT聚合制备氟硅嵌段共聚物及结构性能;赵镇 等;《功能高分子学报》;20110615;第24卷(第2期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103865067A (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103865067B (en) | A kind of preparation method of amphipathic copolymerization network | |
| US4085168A (en) | Chemically joined, phase separated self-cured hydrophilic thermoplastic graft copolymers and their preparation | |
| CN100432180C (en) | Densifier for aqueous breakdown fluid and its production method | |
| CN108912384B (en) | Ultrahigh-temperature expandable thermoplastic microspheres and preparation method and application thereof | |
| CN109071730A (en) | High molecular material and its manufacturing method and polymerizable monomer composition | |
| CN104610484B (en) | A kind of preparation method of the reactive polymer of the double bond containing pendency | |
| CN105199050A (en) | Polyurethane grafted copolymer and preparation method of polyurethane grafted copolymer | |
| CN104829780A (en) | Preparation method for high-strength hydrogel with rapid response to both pH value and temperature | |
| CN103408777A (en) | Preparation method of organogel | |
| CN1318463C (en) | Environment responding aquogel copolymer and its prepn | |
| CN103865014B (en) | The preparation method of amphipathic copolymerization network | |
| CN104744650A (en) | Preparation and application of hybrid copolymer containing POSS (polyhedral oligomeric silsesquioxane) base | |
| CN107973881A (en) | A kind of preparation of high stretch hydroxyethyl cellulose/polyacrylamide hydrogel | |
| CN104592532B (en) | Amphiphilic copolymer network and preparation method thereof | |
| CN104761673A (en) | Carbomer and preparation method thereof | |
| US20210253770A1 (en) | High melt index thermoplastic elastomer and preparation method therefor | |
| CN103214625A (en) | Thermo-sensitive grafted hydrogel with function of resisting protein adsorption and preparation method thereof | |
| CN103724573B (en) | A kind of preparation method of amphipathic copolymerization network | |
| CN115141310B (en) | Degradable micro-crosslinking drag reducer for slickwater fracturing fluid and preparation method thereof | |
| CN114015000B (en) | Preparation method of block copolymer latex | |
| CN115873185A (en) | Sulfur-containing polymer and preparation method thereof | |
| JP3688235B2 (en) | Emulsion polymerization using polymer emulsifier | |
| CN105622836A (en) | Multi-molecular-weight formed polyacrylonitrile spinning stock solution and preparation method and application thereof | |
| CN100572402C (en) | Preparation method of linear polyolefin porous materials | |
| KR100597418B1 (en) | Solvent for polymerization and method for preparing polymer using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |