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WO2018169236A1 - Polymère de polydiméthylsiloxane utilisant une aziridine et son procédé de préparation - Google Patents

Polymère de polydiméthylsiloxane utilisant une aziridine et son procédé de préparation Download PDF

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WO2018169236A1
WO2018169236A1 PCT/KR2018/002620 KR2018002620W WO2018169236A1 WO 2018169236 A1 WO2018169236 A1 WO 2018169236A1 KR 2018002620 W KR2018002620 W KR 2018002620W WO 2018169236 A1 WO2018169236 A1 WO 2018169236A1
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formula
aziridine
azipdms
integer
pdms
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Korean (ko)
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윤효재
문현경
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Korea University Research and Business Foundation
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Korea University Research and Business Foundation
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen

Definitions

  • the present invention relates to a polydimethylsiloxane polymer using aziridine, a three-membered cyclic compound, and a preparation method thereof.
  • epoxides have received particular attention in developing functional polymeric materials.
  • the delicate ring structure of epoxides can be easily opened in the presence of nucleophiles. These features are actively used in many categories of polymer material development, including adhesives, surface coatings, self-healing materials and matrices for making nanometer-sized materials.
  • epoxide has a problem that the ring opening reaction occurs by being promoted by water.
  • the ring-opening reaction of epoxides usually depends on amine-based nucleophiles.
  • Aziridine is a ternary N-heterocyclic compound that is structurally similar to epoxide, but differs greatly in chemical properties.
  • the chemical and regioselectivity of aziridine for the ring-opening reaction is programmable by regulating the electronic structure and steric hindrance of substituents on the nitrogen of two sp3 carbons and aziridine.
  • aziridine can be structurally robust designed even at ambient conditions, including harsh conditions such as high temperature and acidic / basic conditions. Despite the long history of using aziridine in organic synthesis, the use of aziridine in materials science has rarely been achieved.
  • the inventors of the present invention have focused on polydimethylsiloxane as a polymer support.
  • PDMS is widely used in technology requiring organic polymers because it is optically transparent, flexible, inexpensive, commercially available, and non-toxic. This unique feature allows PDMS to be applied to flexible displays and electronics or lab-on-a-chips.
  • the general strategy is for post-modification of PDMS surfaces using oxygen / ultraviolet treatment, chemical click reactions and methods of mixing nanometer-sized particles into PDMS.
  • PDMS analogs formed through this strategy often suffer from the loss of original optical and / or elastomeric properties.
  • Another strategy is to prepare PDMS derivatives with the desired functions based on the synthesis of new siloxane monomers having functional groups and their polymers.
  • This strategy allows the design of PDMS structures at the molecular level and allows for relatively uniform compositions and structures across the sample.
  • Several clickable moieties such as azide and thiols have been incorporated into PDMS by polymerizing siloxane monomers containing these moieties, but it has been difficult to represent a wide range of substrates as well as clickable PDMS based on simple, efficient and direct click reactions.
  • Patent Document 1 Republic of Korea Patent Publication No. 10-2006-0003749
  • Patent Document 2 Republic of Korea Patent No. 10-16314781
  • the present invention is to provide a polydimethylsiloxane polymer using aziridine, a three-membered cyclic compound, and a preparation method thereof.
  • the present invention provides a polymer represented by the following [Formula 1] to solve the above problems.
  • a is an integer of 1 to 20
  • b is an integer of 0 to 20
  • c is an integer of 1 to 20
  • l is an integer of 1 to 20
  • m is an integer of 1 to 20. to be.
  • the present invention by reacting the compound represented by the following [Formula 2], the compound represented by the following [Formula 3] and the compound represented by the following [Formula 4] under a karstedt 'catalyst It provides a method for producing a polydimethylsiloxane-based polymer having an aziridine group comprising the step of preparing a polymer represented by 1].
  • a is an integer of 1 to 20
  • b is an integer of 0 to 20
  • c is an integer of 1 to 20
  • l is an integer of 1 to 20
  • m is It is an integer of 1-20
  • a + b + c n.
  • the manufacturing method according to the invention can be used for the production of customized PDMS.
  • the method for producing clickable PDMS (aziPDMS) according to the present invention can be prepared using a simple, general PDMS curing process without damaging the ring structure of aziridine.
  • the orthogonal ring-opening reaction of aziridine according to the present invention is efficient for the post-modification of the polymer support (PDMS) having a wide substrate range.
  • Post-modification of PDMS through the ring opening reaction of aziridine according to the present invention is not limited to the surface, but also possible in internal pores, and may be performed in a region-specific manner.
  • the programmable reactivity and chemical selectivity of aziridine allow the design of advanced materials that respond to the desired reaction conditions.
  • PDMS comprising aziridine covalently linked may be post-modified by orthogonal ring-opening reaction of aziridine with carboxylic acid, alcohol, amine or thiol.
  • This post-modification characterizes the ring-opened aziPDMS by using photoluminescent and fluorinated molecules on the macroscopic and molecular scale, respectively, through ultraviolet irradiation and XPS specificity.
  • the amount inside the PDMS scaffold is directly adjustable.
  • the customized PDMS and its manufacturing method according to the present invention are unprecedentedly attractive and efficient, requiring molecularly controlled functions such as flexible displays, nano ink pens, biomedical sensor chips, optical materials and contact charging surfaces. It can be usefully applied to construct functional materials and devices.
  • Figure 1a is a structure of a compound used to prepare a polydimethylsiloxane-based polymer comprising aziridine according to the present invention.
  • Figure 1b is a schematic of the post-modification through the production and ring-opening reaction of the polydimethylsiloxane-based polymer (aziPDMS) containing aziridine.
  • 1C is a static contact angle image (right) of Comparative Example 1 (PDMS) and Example 1.6 (aziPDMS) film photo (left) and water droplets according to the present invention (right).
  • 1D shows the results of irradiation scans of PDMS (gray, control) and aziPDMS (black line) obtained by X-ray photoelectron spectroscopy (XPS).
  • 1E is an XPS depth profile result obtained through in situ etching of aziPDMS.
  • FIG. 2A shows the Comparative Example 1 (PDMS) and Example 1.6 (aziPDMS) films incubated in 2.5 mM 5 (6) carboxyfluorescein solution, followed by visible light (above) and 254 nm UV light (below). ). aziPDMS emits a significant amount of fluorescence, while PDMS emits little fluorescence.
  • FIG. 2B is a strength-elongation curve of PDMS and aziPDMS fibers before and after ring opening with a carboxylic acid compound (5 (6) -carboxyfluorescein).
  • Figure 2c is a result showing the image of the ring-opening aziPDMS fibers of the present invention according to different elongation.
  • Figure 2d shows the result of post-modification using 5 (5) -carboxyfluorine after preparing the PDMS / aziPDMS laminated structure. Selective post-modification was observed in the aziPDMS region.
  • 3B is the UV absorption spectrum of aziPDMS film. As the aziridine content increased, the absorption strength increased.
  • Figure 3c is a photograph of the aziPDMS film taken after the ring-opening reaction incubated in 2.5 mM 5 (6) -carboxyfluorescein.
  • 3D is the photoluminescence emission spectrum result of the ring-opened aziPDMS film.
  • Figure 3e is a measure of the substrate range of aziPDMS through XPS measurement, a result of incorporating various fluorinated carboxylic acid, alcohol, amine and thiol derivatives into aziPDMS through aziridine ring opening reaction.
  • Inset graph shows high resolution spectral results of the F1s region for PDMS (control) and ring-opened aziPDMS.
  • Figure 4b is a result of confirming the post-modified surface depth of aziPDMS according to the polarity of the solution. As the amount of methanol decreased, the surface depth increased after the first modification (yellow region).
  • 4C is a plot of% surface depth as a function of volume ratio of methanol in solution (defined as the ratio of surface depth after first modification to half width of the entire film).
  • FIG. 5 shows a schematic of the Pt (0) -catalyzed hydrosilylation between aziridine 1 and PDMS prepolymer having a vinyl group at the end.
  • FIG. 6 shows the results of 1 H NMR spectroscopy of Pt (0) -catalyzed hydrosilylation and ring-opening reaction of aziridine and benzoic acid between silyl hydride (curing agent B) and aziridine (1) having a vinyl group at the end.
  • Curing agent B which is a commercial reagent, may be added with a small amount of an additive, and thus a peak may be detected.
  • FIG. 7 shows photoluminescence spectra of aziPDMS incubated in 5 (6) -carboxyfluorescein (red) and 2.5 mM 5 (6) -carboxyfluorescein (black) solutions in methanol.
  • FIG. 8 is a result of applying a thresholding technique for the cut aziPDMS film in FIG. 4B.
  • the inventors of the present invention have completed the present invention by developing a method of introducing aziridine onto a molecular substrate and using a ring-opening reaction of aziridine in order to devise a customized polymer support at the molecular level.
  • the present invention provides a custom-made PDMS (hereinafter referred to as aziPDMS) functionalized by aziridine prepared by curing a conventional PDMS prepolymer (Sylgard 184 Silicone elastomer kit) in the presence of aziridine with vinyl at the end and a method for preparing the same. .
  • the present invention provides a polymer represented by the following [Formula 1].
  • a is an integer of 1 to 20
  • b is an integer of 0 to 20
  • c is an integer of 1 to 20
  • l is an integer of 1 to 20
  • m is an integer of 1 to 20. to be.
  • the polymer of [Formula 1] may be ring-opened by reacting with a compound containing a carboxylic acid, alcohol, amine group or thiol group, the carboxylic acid, alcohol, amine group to the ring-opened aziridine moiety Or a compound containing a thiol group may be attached.
  • the polymer of [Formula 1] is characterized by retaining elasticity, it can be easily stretched up to 250%.
  • the polymer of [Formula 1] is improved in light weight and mechanical elasticity without loss of optical and mechanical properties compared to the conventional PDMS.
  • aziridine-functionalized PDMS according to the present invention can be easily synthesized from readily available prepolymers.
  • the present invention reacts the compound represented by the following [Formula 2], the compound represented by the following [Formula 3] and the compound represented by the following [Formula 4] under a karstedt 'catalyst (Formula 1) It provides a method for producing a polydimethylsiloxane-based polymer having an aziridine group, including the step of preparing a polymer represented by.
  • a is an integer of 1 to 20
  • b is an integer of 0 to 20
  • c is an integer of 1 to 20
  • l is an integer of 1 to 20
  • m is It is an integer of 1-20
  • a + b + c n.
  • the reaction may be a thermosetting reaction carried out at 50 to 100 °C for 0.5 to 3 hours.
  • the compound of [Formula 4] may be prepared by reacting (1-benzylaziridin-2-yl) methanol with chlorodimethyl (vinyl) silane at 40 to 80 ° C., preferably a base It may be reacted in the organic solvent in the presence.
  • the base may be triethylamine, but is not limited thereto.
  • the organic solvent may be an organic solvent selected from methylene chloride, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, toluene, ethanol, methanol, ethyl acetate and ether, but is not limited thereto. Toluene.
  • the (1-benzylaziridin-2-yl) methanol is reacted with ethyl 2,3-dibromopropanoate in the presence of a base such as benzylamine in a nitrogen stream and triethylamine.
  • a base such as benzylamine in a nitrogen stream and triethylamine.
  • the present invention with respect to 10 parts by weight of the compound represented by [Formula 2], 0.5 to 2 parts by weight of the compound represented by [Formula 3] and 0.02 to 0.2 parts by weight of the compound represented by [Formula 4] It may be to.
  • the content of the compound represented by the above [Formula 4] is less than the above range, the clickable portion is too small, so that post-modification is not easy, and it is difficult to exhibit elasticity.
  • the above range is exceeded, a serious interference phenomenon occurs in the crosslinking between the base and the curing agent, and the transparency is lost, and powder or oily opaque polymer is produced, which is not preferable.
  • the compound represented by the above [Formula 1] according to the present invention is reacted with a compound containing a carboxylic acid, alcohol, amine group or thiol group to ring-open the aziridine group of [Formula 1];
  • the compound containing the carboxylic acid, alcohol, amine group or thiol group may be attached to the moiety of the ring-opened aziridine.
  • the present invention has three features as follows.
  • the post-modification of PDMS is not limited to the surface, but also inside the pores through the ring opening reaction of aziridine.
  • the molecular substrate may be polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • PDMS containing aziridine can be prepared by thermosetting the prepolymer in the presence of aziridine which is terminally vinyl.
  • the prepolymer may include a base (part A) and a curing agent (part B) in a weight ratio of 8: 1 to 20: 1, and preferably in a 10: 1 weight ratio. Can be.
  • the thermosetting may be performed at 80 ° C. for 2 hours, thereby obtaining a composite (aziPDMS) converted to PDMS having a covalently bonded aziridine pendant.
  • the aziPDMS thus obtained may maintain optical transparency and mechanical elasticity of the existing PDMS.
  • Post-modification of aziPDMS can be achieved through the orthogonal ring-opening reaction of aziridine pendants (FIG. 1B).
  • alcohols, amines, thiols and carboxylic acids can be used for the post-modification of aziPDMS.
  • the production process and structural modification reactions according to the invention are simple and effective and can be carried out using commercial reagents. Together with these advantages, the various and robust ring opening reactions of aziridine are useful for preparing custom polymeric materials.
  • the thickness of the sample inevitably causes errors at the microscopic level, but does not affect the overall tendency of ⁇ max as a function of the mass ratio of aziridine.
  • Photoluminescence spectra were measured using a Hitachi F-7000 Fluorescence spectrophotometer.
  • Tensile strength of PDMS and aziPDMS was measured using a Universal Testing Machine (UTM; WL 2100).
  • Sylgard 184 (Dow Corning) silicone elastomer kit with base and curing agent was used.
  • a conventional synthesis method for preparing PDMS is to add a platinum catalyst to vinyl and Si-H. Specifically, the base and the curing agent are mixed at a weight ratio of 10: 1, and the mixture is left under reduced pressure for 2 hours to form internal bubbles. After the removal, it was prepared by curing at 80 °C for 2 hours.
  • aziPDMS was prepared using a known PDMS manufacturing method. As shown in FIG. 1A, aziPDMS was prepared by mixing the base (A), the curing agent (B), and the aziridine (1) having a vinyl group at the end thereof, and Sylgard 184 was used as a model elastomer. Specifically, 1-benzyl-2-(((dimethyl (vinyl) silyl) oxy) methyl) aziridine is poured into a polytetrafluoroethylene (PTFE) mold to remove the contained bubbles. The degassed was put into a vacuum desiccator for 20 minutes. The mixture was thermoset at 80 ° C. for 2 hours to prepare aziPDMS film.
  • PTFE polytetrafluoroethylene
  • base curing agent: 1-benzyl-2-(((dimethyl (vinyl) silyl) oxy) methyl) aziridine was mixed in a 10: 1: X weight ratio, and X was contained in a range of 0.025 to 0.2 weight ratio.
  • X is larger than 0.2, crosslinking between the base and the curing agent is severely caused by aziridine having a vinyl group at a large amount of terminal, which is not preferable because a powder or oily opaque PDMS is produced.
  • Test Example 1 Silyl using 1H NMR Hydride With polymer (B in FIG. 1A; curing agent) At the end Vinyl Determination of reaction of aziridine having and ring opening reaction by benzoic acid
  • the thermal curing process of the PDMS prepolymer is the basis for hydrosilylation crosslinking by Pt (0) catalyst between silylhydride and vinyl derivative.
  • the Pt catalyst Karlstedt's catalyst, 1 mg, in a clean environment at room temperature
  • a Pt catalyst B 600 mg
  • Compound 1 120 mg, 0.48 mmol
  • the black 1 H NMR spectrum at the bottom is the result of the starting mixture
  • the red 1 H NMR spectrum at the top is the result after 1.5 hours of reaction.
  • the hydrosilylation reaction between Compounds 1 and B was confirmed through 1 H NMR spectra.
  • the chemical shifts of 5.75, 6.01 and 6.10 ppm corresponding to the vinyl protons of Compound 1 disappeared completely within 1.5 hours, confirming that the desired coupling reaction was very efficient.
  • the aziridine ring structure was maintained after the reaction, and the chemical shifts corresponding to the aziridine residues (1.45, 1.69 and 1.77 ppm) were confirmed by being kept unchanged.
  • Test Example 2 X-ray photoelectron spectroscopy; XPS ) analysis
  • the apparent optical transparency of the aziPDMS of Example 1 and the PDMS of Comparative Example 1 was not distinguished.
  • aziPDMS was immersed for 6 hours in hexane and dichloromethane without impurities, and then rinsed.
  • a scan of aziPDMS showed Si2p ( ⁇ 102 eV) and O1s ( ⁇ 532 eV) signals corresponding to the PDMS backbone, and C1s ( ⁇ 284 eV) and N1s corresponding to aziridine pendants. ( ⁇ 398 eV) signal appeared.
  • Table 1 the atomic concentration (atomic%) of the calculated value and the experimental value was consistent in both PDMS and aziPDMS.
  • the depth profile XPD scan was performed by etching the aziPDMS surface (etching rate: ⁇ 5 nm / min).
  • the depth profile of aziPDMS showed the highest atomic percent of Si and O and the lowest atomic percent of c during etching.
  • the atomic% of N1s in aziPDMS was constant during the measurement, which means that aziridine is present at the same surface and interior.
  • Atomic% is calculated using (SiOC 2 ) as a repeating unit
  • all image pixels can be classified as foreground (regions of the aziridine of the present invention ring-opened by 5 (6) -carboxyfluorescein) or background pixels.
  • the percentage of surface depth after the first post-modification was determined by determining the ratio of the width of the white pixels (corresponding to the surface post-modification) to half the width of the film in the line, and estimated by averaging from each of at least 10 samples.
  • Aziridine having an electron-donating substituent (benzyl N-substituent of the present invention) under a nitrogen atmosphere at a slightly higher temperature, such as 50 ° C., was subjected to ring opening by treatment with carboxylic acid without catalyst and additives.
  • the acidic protons of the carboxylic acids react with the lone pair of nitrogen atoms of the aziridine. This reaction produces an activated aziridinium structure followed by subsequent addition of carboxylate.
  • the ring opening reaction of aziridine shows good chemical and regioselectivity and high yield (> 90%).
  • mapping analysis was performed by reacting aziridine in aziPDMS with 5 (6) -carboxyfluorine, a photoluminescent carboxylic acid derivative.
  • the photoluminescence spectrum of aziPDMS showed ⁇ max at ⁇ 531 nm.
  • the red shift of ⁇ max is an indicator that identifies 5 (6) -carboxyfluorescein covalently bound to the backbone of aziPDMS, and the interaction between 5 (6) -carboxyfluorescein molecules linked to PDMS is ⁇ max . Because it induces a change.
  • FIG. 2B is a strength-elongation curve of PDMS and aziPDMS fibers before and after ring opening with a carboxylic acid compound (5 (6) -carboxyfluorescein).
  • Tensile strength for untreated and ring-opened aziPDMS showed no significant change ( ⁇ ⁇ 1.3) of 0.66 MPa and 0.51 MPa, respectively.
  • Figure 2c shows the image of the ring-opening aziPDMS fiber of the present invention according to different elongation, it was confirmed that it is sufficiently extended to 200%.
  • the PDMS and the aziPDMS were repeatedly thermally cured as shown in FIG. 2D to prepare a laminated structure.
  • the laminated films prepared in order to perform mapping analysis on the entire structure were incubated in 5 (5) -carboxyfluorescein solution.
  • photoluminescence was selectively observed in the aziPDMS region rather than the PDMS region, and it was confirmed that the aziPDMS region was selectively modified.
  • Figure 3a is aziPDMS film according to Examples 1.1 to 1.5 showed a slight change in the optical transparency apparent.
  • the intensity of the absorption band at 259 nm increased linearly with the amount of aziridine.
  • the aziPDMS film according to Examples 1.1 to 1.5 was incubated in a 2.5 mM 5 (6) -carboxyfluorescein solution for 18 hours at room temperature, and then washed with chloroform and methanol. And dried under hot oven and vacuum.
  • 3C is an image of the films taken under visible and UV irradiation.
  • the photoluminescence intensity of ring-opened aziPDMS increased with increasing content of aziridine, which is vinyl at the end. As shown in Figure 3d through the above results, it was confirmed that the photoluminescence emission characteristic has a linear correlation with the content of aziridine.
  • the substrate of the aziPDMS ring opening compounds having various functional groups such as carboxylic acids, thiols, alcohols and amine derivatives can be used.
  • the fluorine atom gives a strong signal in the XPS measurement, it is easy to confirm whether or not the ring opening reaction of aziPDMS is by XPS.
  • the fluorine-containing compound was used for the experiment.
  • AziPDMS of Examples 1.1 to 1.5 and PDMS of Comparative Example 1 were treated with THF solution of 0.25 mM fluorine-containing compound at room temperature for 3 or 6 hours, then washed with pure THF, CH 2 Cl 2 and methanol, Dry in oven and in vacuo. As shown in FIG. 3E, the F1s peak appeared in the XPS spectrum of the ring-opening aziPDMS, but was not detected in the PDMS. These results indicate a broad substrate range of ring opening reaction of aziridine after modification.
  • Test Example 8 Evaluation using surface wettability
  • High dielectric constant liquids such as water and methanol show very low wettability, while low dielectric constant liquids such as n-hexane and chloroform diffuse into the majority of the area on the surface and expand PDMS.
  • the surface wettability of these PDMS was used to further demonstrate the site specificity (surface to volume) post-modification of aziPDMS.
  • the customized PDMS and its manufacturing method according to the present invention are unprecedentedly attractive and efficient, requiring molecularly controlled functions such as flexible displays, nano ink pens, biomedical sensor chips, optical materials and contact charging surfaces. It can be usefully applied to construct functional materials and devices.

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Abstract

La présente invention concerne un polymère de polydiméthylsiloxane et un procédé de préparation associé.
PCT/KR2018/002620 2017-03-14 2018-03-06 Polymère de polydiméthylsiloxane utilisant une aziridine et son procédé de préparation Ceased WO2018169236A1 (fr)

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Publication number Priority date Publication date Assignee Title
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WO2012016097A2 (fr) * 2010-07-30 2012-02-02 Novartis Ag Prépolymères de polysiloxane amphiphiles et utilisations de ceux-ci
KR101348107B1 (ko) * 2011-06-23 2014-01-07 명지대학교 산학협력단 Ｐｄｍｓ에 ａｈｐｏｓｓ를 혼합한 유무기 복합막 및 복합막의 제조방법
KR101631481B1 (ko) * 2015-04-07 2016-06-17 고려대학교 산학협력단 아지리딘을 이용한 고분자 및 이의 제조방법
JP2017502095A (ja) * 2013-11-07 2017-01-19 スリーエム イノベイティブ プロパティズ カンパニー アジリジン化合物を含むフルオロポリマーコーティング

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6867246B2 (en) * 2000-05-31 2005-03-15 3M Espe Ag N-alkyl aziridine block copolymers and the uses thereof
WO2012016097A2 (fr) * 2010-07-30 2012-02-02 Novartis Ag Prépolymères de polysiloxane amphiphiles et utilisations de ceux-ci
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