WO2014208604A1 - Gel à haute résistance dépendant d'une interaction intramoléculaire - Google Patents

Gel à haute résistance dépendant d'une interaction intramoléculaire Download PDF

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WO2014208604A1
WO2014208604A1 PCT/JP2014/066856 JP2014066856W WO2014208604A1 WO 2014208604 A1 WO2014208604 A1 WO 2014208604A1 JP 2014066856 W JP2014066856 W JP 2014066856W WO 2014208604 A1 WO2014208604 A1 WO 2014208604A1
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poly
gel
vinylamide
general formula
represented
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PCT/JP2014/066856
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English (en)
Japanese (ja)
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明石　満
広治 網代
友紀恵 竹本
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国立大学法人大阪大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to a high-strength gel based on intramolecular interaction, particularly a poly (vinylamide) gel.
  • Non-Patent Document 1 Non-Patent Document 1
  • actuators Non-Patent Document 2
  • drug sustained-release materials Non-Patent Document 3, Non-Patent Document 4, Non-Patent Document 5
  • the mechanical strength of gel is generally very weak, and various studies have been conducted to improve it.
  • there are composite Non-Patent Document 6) and double network gel (DN gel) (Non-Patent Document 7) using an interpenetrating network structure.
  • studies have been made on gels (Non-patent Document 8) and gels having a single polymer structure (Non-patent Document 9), which can obtain a pulley effect by devising the structure of the polymer chain.
  • Non-Patent Document 10 a strength of about 1.9-14.4 MPa is required (Non-Patent Document 10), but more biocompatible. Development of highly functional gel materials is desired.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a high-strength gel having high biocompatibility, particularly a poly (vinylamide) gel.
  • the present invention is a poly (vinyl amide) gel, and as a liquid dispersion medium, polyethylene glycol represented by the following general formula (I): (Wherein R 3 to R 5 each independently represents a hydrogen atom, an OH group or a C1-C3 alkyl group, and a C3-C6 cycloalkyl ring together with the carbon atom to which R 4 and R 5 are bonded, N 1 represents an integer of 2 or more and 20 or less.
  • the poly (vinylamide) gel of the present invention is strong and excellent in biocompatibility.
  • the figure which shows the profile of compressive strength and a compressive strain Infrared absorption spectrum of poly (N-vinylacetamide) gel using PEG400 as a dispersion medium. The figure which shows the profile of compressive strength and a compressive strain. The figure which shows the profile of compressive strength and a compressive strain.
  • the poly (vinylamide) gel of the present invention is a polyethylene glycol represented by the following general formula (I) as a liquid dispersion medium: , And / or Polypropylene glycol represented by the following general formula (II):
  • the main feature is that it preferably contains polyethylene glycol represented by the general formula (I).
  • R 3 to R 5 each independently represents a hydrogen atom, an OH group, or a C1 to C3 alkyl group (methyl group, ethyl group, propyl group, or isopropyl group).
  • R 4 and R 5 may be a C3-C6 cycloalkyl ring, preferably a cycloalkyl 5-membered ring or a 6-membered ring, together with the carbon atom to which they are bonded.
  • the hydrogen atom of the OH group at one or both ends of the polyethylene glycol represented by the general formula (I) may be a lower alkyl group, preferably a methyl group, an ethyl group, more preferably a methyl group.
  • R 3 to R 5 function in the same manner as in the case of a hydrogen atom because they do not affect the terminal hydroxyl group directly involved in hydrogen bonding.
  • R 3 ⁇ R 5 is a hydrogen atom and the other R 3 ⁇ R 5 is a hydrogen atom or a C1 ⁇ C3 alkyl group, preferably a hydrogen atom, a methyl group, ethyl group or propyl group More preferably represents a hydrogen atom, a methyl group or an ethyl group, still more preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.
  • n 1 is appropriately selected from such a viewpoint, and is usually an integer of 2 or more and 20 or less, preferably an integer of 4 or more and 17 or less. Preferably, it represents an integer of 8 to 9.
  • the polyethylene glycol represented by the general formula (I) can generally be purchased from, for example, chemical reagent manufacturers (Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., NOF Corporation, etc.).
  • Polyethylene glycol represented by the general formula (I) can also be synthesized by polymerizing cyclohexane oxide with a metal catalyst (Vandenberg E. J. et al, J. Polym. Sci. Polym. Chem. Ed. 1969, 7 , 525-567; Kuran, W. et al, Macromol. Chem. Phys. 1994, 195, 401-411). Moreover, it is also possible to synthesize using an oxidative ring closure reaction of an unsaturated compound (Giuseppe Bifulco et al, Tetrahedron Lett. 2003, 44, 5499-5503). Thus, the polyethylene glycol represented by the general formula (I) can be appropriately produced by those skilled in the art.
  • polyethylene glycol represented by the general formula (I) examples include polyethylene glycol (molecular weight about 200), polyethylene glycol (molecular weight about 400), polyethylene glycol (molecular weight about 600), decaethylene glycol, dodecaethylene glycol, hexa Ethylene glycol, heptaethylene glycol, nonaethylene glycol, octaethylene glycol, pentaethylene glycol, tetraethylene glycol, triethylene glycol, decaethylene glycol monomethyl ether, dodecaethylene glycol monomethyl ether, triethylene glycol monoethyl ether, hexaethylene glycol monomethyl Ether, heptaethylene glycol monomethyl ether, nonaethylene glycol monomethyl ether, Motor ethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, etc. are available.
  • R 6 to R 8 each independently represents a hydrogen atom, an OH group, or a C1 to C3 alkyl group (methyl group, ethyl group, propyl group, or isopropyl group).
  • the hydrogen atom of the OH group at one or both ends of the polypropylene glycol represented by the general formula (II) may be a lower alkyl group, preferably a methyl group, an ethyl group, more preferably a methyl group.
  • the propylene glycol of the formula (II) is the same as the ethylene glycol of the formula (I) because it has no influence on the terminal hydroxyl group directly involved in hydrogen bonding. It is considered to function.
  • R 6 to R 8 are hydrogen atoms
  • the other R 6 to R 8 are hydrogen atoms or C1-C3 alkyl groups, preferably hydrogen atoms, methyl groups, ethyl groups or propyl groups, more preferably Represents a hydrogen atom, a methyl group or an ethyl group, even more preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.
  • n 2 is appropriately selected from such a viewpoint, and usually represents an integer of 2 or more and 20 or less, preferably an integer of 4 or more and 17 or less. .
  • the polyprolene glycol represented by the general formula (II) can be synthesized by ring-opening polymerization of an epoxy monomer such as propylene oxide using Potassium t-Butoxide as an initiator (Charles C. Price). et al. J. Am. Chem. Soc. 1966, 88, 4039-4044). ) Can be produced by those skilled in the art.
  • molecular weights of 4000, 1000, 2000, 3000, 400, and the like are available from Wako Pure Chemical Industries.
  • a part or all of the polyethylene glycol represented by the general formula (I) and / or the polypropylene glycol represented by the general formula (II) may be substituted with glycerin. This is because, for the reason that the number of hydroxyl groups increases, it is considered to function similarly to the polyethylene glycol represented by the general formula (I) and / or the polypropylene glycol represented by the general formula (II).
  • water may be contained up to about 75% by weight or about 50% by weight of the total amount of the dispersion medium.
  • Water greatly affects the degree of swelling of the entire gel.
  • it is desirable that the water is up to 25% by weight, more preferably about 1 to 0% by weight, but the maximum strength obtained by the present invention is limited.
  • the strength can be adjusted.
  • the poly (vinylamide) dispersoid which is the dispersoid constituting the poly (vinylamide) gel of the present invention, is a vinylamide monomer, for example, an N-vinylalkylamide monomer represented by the general formula (III) and / or a general one described later.
  • a preferred vinylamide monomer is an N-vinylalkylamide monomer represented by the general formula (III).
  • R 1 is a hydrogen atom or a C1-C4 alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, iso-butyl group, sec-butyl group or ter-butyl group). Represents. Such a group is considered to be capable of forming a hydrogen bond with the polyethylene glycol represented by the general formula (I) and the polypropylene glycol represented by the general formula (II).
  • R 1 is preferably a hydrogen atom or a C1-C3 alkyl group, more preferably a hydrogen atom or a C1-C2 alkyl group, still more preferably a C1-C2 alkyl group, most preferably a methyl group.
  • N-vinylalkylamide monomer represented by the general formula (III) can be synthesized by thermal decomposition of N- (1-alkoxyethyl) -alkylamide (for example, M. Akashi et al., J. Polym. Sci. Part A: Polym. Chem. (1990, 28, 3487-3497) and available from Showa Denko KK
  • divinyl crosslinking monomer examples include various divinyl monomers, for example, general-purpose crosslinking agents having a methacrylic acid skeleton, an acrylic acid skeleton, a methacrylamide skeleton, and an acrylamide skeleton, such as methylene bisacrylamide, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate.
  • a preferred divinyl crosslinking monomer is a bis-N-vinylalkylamide crosslinking monomer represented by the general formula (IV).
  • R 2 has the same meaning as R 1 described above.
  • R 1 may be the same or different.
  • the general formula (V) represents a structure of a crosslinking agent containing an oxygen atom and a crosslinking agent not containing an oxygen atom as one structural formula.
  • n is 0 and m 3 represents 1.
  • m 1 and m 2 are each independently an integer of 2 to 4, preferably 4, and m is 0 or 1, preferably 0.
  • m 3 and m are 0 and n is 4, 6 or 7, preferably 4.
  • examples of Y include the following.
  • N-vinylalkylamide monomer represented by the general formula (III) is represented by the following general formula (VI) from the viewpoint of the structural isomer of the vinyl monomer having an amide group.
  • Acrylamide compounds can be used.
  • R 9 has the same meaning as R 1 described above.
  • the crosslinking monomer of the present invention is obtained by anionizing a secondary amide of a compound represented by the general formula (III) with sodium hydride using anhydrous dimethylformamide as a solvent in a nitrogen atmosphere, and then formula (VII): XYX (VII) (Wherein Y is as defined above, X represents a halogen atom) It can obtain by making it react with the compound represented by these. This reaction is generally known as a nucleophilic substitution reaction and can be prepared by one skilled in the art.
  • the compound represented by the above formula (VII) can be produced by converting the corresponding hydroxyl group into an alkyl halide with a halogenating reagent, and commercially available products such as 1,4-dichlorobutane and 1,6-dichloro Hexane, 1,5-dichloroheptane, bis (4-chlorobutyl) ether, bis (2-chloroethyl) ether, 1,2-bis (2-chloroethoxy) ethane, diethylene glycol bis (2-chloroethyl) ether, etc. are available Is possible.
  • the crosslinking monomer is a general-purpose crosslinking agent such as methylene bisacrylamide, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, Ethylene glycol dimethacrylate and the like can be preferably used.
  • methylene bisacrylamide, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, Ethylene glycol dimethacrylate and the like can be preferably used.
  • these general-purpose crosslinking agents may be used by replacing with a bis-N-vinylalkylamide crosslinking monomer represented by the general formula (IV).
  • a vinylamide monomer (formula (III) and / or formula (VI)) is polymerized in a suitable solvent with a crosslinking monomer and a polymerization initiator in a suitable solvent (hereinafter referred to as “pregel”). Form).
  • radical generators such as 2,2′-azobis [2- (2-imidazolin-2-yl) propanedihydrochloride] 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis ⁇ 2 -[1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'- Azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide ⁇ , 2,2′-azobis Examples include thermal polymerization initiators such as 2-methyl-N- (2-hydroxyethyl) propionamide] and re
  • a solution in which the above vinylamide monomer (formula (III) and / or formula (VI)), a crosslinking monomer, and a polymerization initiator are dissolved in an appropriate solvent is heated under an inert gas atmosphere with heat and UV light. Do by calling.
  • the shape of the gel can be arbitrarily controlled by performing the solution in a container having a desired shape.
  • [M] is 1 to 4 mol / L
  • [M] 100 is a crosslinking monomer.
  • the solution [C] may be prepared at a ratio of 5 to 0.01 and the initiator concentration [I] is approximately 10 to 0.01.
  • the residue of unreacted monomer and crosslinking monomer is removed from the system.
  • the removal can be performed by, for example, immersing the obtained gel in the solvent used for the reaction and driving out those compounds from the gel into the solvent.
  • the operation is more effective when performed a plurality of times. The completion of such washing may be based on the case where the gel is in an equilibrium swelling state where the weight of the gel does not change.
  • the pregel or dry poly (vinylamide) gel obtained above is a solution dispersion medium of the formula (I) and / or formula (II), and in the case of a pregel, it is dried in the case of a dry poly (vinylamide) gel by solvent exchange.
  • the dispersion medium is diffused into the gel to obtain the gel of the present invention.
  • the poly (vinyl amide) gel of the present invention can have a very high strength.
  • the strength is expressed in terms of breaking stress, even when the pressure reaches 50 MPa as shown in FIG.
  • a poly (vinyl amide) gel it has exceeded the unprecedented at least 0.5 MPa, more than at least 0.6 MPa, even more than at least 1 MPa, and has an upper limit of fracture stress of at least 50 MPa. be able to.
  • Solvent dispersion medium
  • poly (vinylamide) for example, hydrogen bonding, particularly hydrogen bonding between the hydroxyl group at the terminal of the dispersion medium and the carbonyl group in poly (vinylamide)
  • poly It is considered that the aggregate form of vinylamide acts in total to form a pseudo-crosslinked structure, and the high strength of the present invention is achieved.
  • N-vinylalkylamide monomer (formula (III)) is bis-N— from the viewpoint of compatibility with a solvent.
  • the vinyl alkylamide crosslinking monomer (formula (IV)) is converted into an N-vinylalkylamide monomer (formula (III)) and a bis-N-vinylalkylamide crosslinking monomer (formula ( IV)) is selected from the viewpoint of an appropriate degree of swelling, and the polyethylene glycol represented by the formula (I) and the polypropylene glycol represented by the general formula (II) are used as a dispersion medium. For example, it may be selected from the viewpoint of forming a pseudo-crosslinked structure.
  • a poly (N-vinylacetamide) gel (hereinafter sometimes abbreviated as “PNVA gel”) is prepared according to the literature [H. Ajiro, Y. Takemoto, M. Akashi, Chem. Lett. 2009, 38, 368.]. Obtained.
  • N-vinylacetamide (0.34 g, 4 mmol) (Showa Denko), azo compound V-50 (wako) (11 mg, 0.04 mmol) as an initiator, and 5-oxanona as a crosslinking monomer
  • Methylene-bis (N-vinylacetamide) (5ON-bis-NVA) (12 mg, 0.04 mmol) dissolved in water (4 mL) was injected into a 2 mm gap using two glass plates. This was reacted at 55 ° C. for 4 hours under a nitrogen atmosphere to obtain a poly (N-vinylacetamide) hydrogel.
  • PNVA gel and physical property measurement (1) The obtained hydrogel was thoroughly washed and cut into a disk shape (diameter 8 mm, thickness 3 mm), and this was used as one gel. By immersing it in an organic solvent (water, ethanol, ethylene glycol, triethylene glycol, polyethylene glycol (PEG400 (molecular weight 400)) and exchanging the solvent Each gel was prepared, and Table 1 shows the results of analysis (size change, breaking strength, breaking strain, etc.) of the PNVA gel in various organic solvents (dispersion media).
  • organic solvent water, ethanol, ethylene glycol, triethylene glycol, polyethylene glycol (PEG400 (molecular weight 400)
  • Fracture stress and Fracture strain were measured with a compression tester (EZ test manufactured by Shimadzu Corp.).
  • the size of the gel was remarkably different. Moreover, when ethanol, ethylene glycol, and triethylene glycol were used, all showed compressive strength larger than hydrogel. These are considered to have the effect of high concentration and the viscosity of the solvent as the size of the gel is reduced.
  • Fig. 1 shows the profile of gel strength evaluation using PEG400.
  • PEG400 unlike other organic solvents, extremely high compressive strength was exhibited.
  • the deformation behavior was plastic deformation. This indicates the intermolecular hydrogen bond of the gel of PEG400 and PNVA which is a liquid dispersion medium.
  • the gel obtained using TEGDME and PEGDME as the dispersion medium was measured for compressive strength.
  • the gel obtained with PEG400 showed extremely high compressive strength.
  • the deformation behavior was plastic deformation.
  • Each of the gels was obtained by impregnating the poly (N-vinylacetamide) hydrogel obtained by cutting into a disk shape (diameter 8 mm, thickness 3 mm) as described above into a solvent of about 20 mL as it was or after drying. ) Each gel was prepared by immersing it in a mixed system of water and PEG 400 as a solvent, and the change in gel size (H / H 0 ), swelling degree, solvent loading, breaking strength, and breaking strain were measured. The results are shown in Table 3 below.
  • breaking strength was measured by observing a point where the stress was peaked by using a compression tester EZ-test manufactured by Shimadzu.
  • “Breaking strain” was measured by observing a point that was compressed using a compression tester EZ-test manufactured by Shimadzu and showed the peak top of the stress.
  • the breaking strength is 75/25.
  • the gel thickness also showed a large value compared with 0.56 and 0.46. This indicates that the water can contain up to 25% by weight of water, and a high-strength gel can be obtained with the water content up to that point.
  • the above results show that the strength can be adjusted by including water in a range of up to 50 weights with the maximum strength obtained by the present invention as a limit.
  • a gel was prepared using polyacrylamide instead of the PNVA gel.
  • the polyacrylamide used was a radical polymerization (by combining acrylamide and N, N-methylenebisacrylamide), and the resulting hydrogel was thoroughly washed to form a disk (diameter 8mm, 3mm thickness) Cut out.
  • a gel was prepared by immersing it in the organic solvent PEG400 and performing solvent exchange. A profile of strength evaluation measured by the same method as shown in FIG. 1 is shown in FIG.
  • the poly (vinyl amide) gel of the present invention may be applied as a biomaterial field, for example, as a biological member such as cartilage, gums, and bedsore prevention agents. Furthermore, there is a possibility that it can be applied and used as a cushioning material, a packing material, a base material for electrophoresis, and a medical material (drug removal material, patch material, etc.). Further, it may be applicable to actuators, sensors, gel electrolytes of lithium ion polymer batteries, and the like.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention porte sur un gel à haute résistance ayant une biocompatibilité élevée, en particulier sur un gel de polyvinylamide qui contient, en tant que milieu de dispersion liquide, un polyéthylèneglycol représenté par la formule générale (I) (dans laquelle R3 à R5 représentent chacun indépendamment un atome d'hydrogène, un groupe OH ou un groupe alkyle en C1-C3 et chacun de R4 et R5 peut former, conjointement avec un atome de carbone auquel chacun de R4 et R5 est lié, un noyau cycloalkyle en C3-C6 ; n1 représente un nombre entier de 2 à 20 inclus) et/ou un propylèneglycol représenté par la formule générale (II) (dans laquelle R6 à R8 représentent chacun indépendamment un atome d'hydrogène, un groupe OH ou un groupe alkyle en C1-C3 ; n2 représente un nombre entier de 2 à 20 inclus).
PCT/JP2014/066856 2013-06-27 2014-06-25 Gel à haute résistance dépendant d'une interaction intramoléculaire WO2014208604A1 (fr)

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