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WO2006001313A1 - Gel, procédé servant à produire celui-ci, résine absorbant l'eau, matière lubrifiante et substrat pour la culture de cellules - Google Patents

Gel, procédé servant à produire celui-ci, résine absorbant l'eau, matière lubrifiante et substrat pour la culture de cellules Download PDF

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Publication number
WO2006001313A1
WO2006001313A1 PCT/JP2005/011469 JP2005011469W WO2006001313A1 WO 2006001313 A1 WO2006001313 A1 WO 2006001313A1 JP 2005011469 W JP2005011469 W JP 2005011469W WO 2006001313 A1 WO2006001313 A1 WO 2006001313A1
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Prior art keywords
gel
crosslinked polymer
network structure
polymer
semi
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PCT/JP2005/011469
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English (en)
Japanese (ja)
Inventor
Jian Ping Gong
Yoshihito Osada
Hiroyuki Tsukeshiba
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National University Corporation Hokkaido University
Medical & Biological Laboratories Co., Ltd
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Application filed by National University Corporation Hokkaido University, Medical & Biological Laboratories Co., Ltd filed Critical National University Corporation Hokkaido University
Priority to JP2006528567A priority Critical patent/JP5059407B2/ja
Publication of WO2006001313A1 publication Critical patent/WO2006001313A1/fr

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    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide

Definitions

  • Patent Document 1 discloses a low-friction material obtained by mixing a linear polymer with a gel or graft polymerization.
  • Patent Documents 2 to 7 disclose various techniques for increasing the mechanical strength of the gel (for example, Patent Documents 2 to 7 and Non-Patent Documents 1 to 4).
  • Patent Document 2 discloses that a second polymer is formed by polymerizing and crosslinking a monomer in a network structure having the strength of the first crosslinked polymer, thereby forming the first crosslinked polymer and the second polymer.
  • interpenetrating network structure refers to a network structure in which other network structures are entangled with the base network structure
  • sub-interpenetrating network structure refers to the base network structure.
  • a linear polymer is entangled to indicate a network structure.
  • Patent Document 1 JP 2002-212452
  • Patent Document 2 Pamphlet of International Publication No. 03Z093337
  • Patent Document 3 Japanese Patent Laid-Open No. 2004-91724
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2002-053762
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2002-053629
  • Patent Document 6 Japanese Unexamined Patent Publication No. 57-130543
  • Patent Document 7 JP-A-58-36630
  • Non-patent document 4 Long Zhao, Hiroshi Mitomo, Naotsugu Nagasawa, Fumio Yoshn, Tami kazu Kume, "Radiation synthesis and characteristic of the hydrogels based on carbo xymethylated chitin derivatives, Carbohydrate Polymers, 51, 169-175 (2003) Disclosure
  • Patent Documents 2-7 and Knowledge different from the development concept of the technology disclosed in Patent Documents 1 to 4 was obtained. That is, for example, in the technique disclosed in Patent Document 2 or Non-Patent Document 1, the most important factors for improving the strength of the gel are the molar ratio of the second monomer to the first crosslinked polymer and the degree of crosslinking of the second polymer. In particular, in the technique disclosed in Patent Document 2, the second polymer has a very slight cross-linked structure. Specifically, the degree of cross-linking of the second polymer is 0.001 mol% or more. Although there is an optimum condition for increasing the strength of the gel, there is a limit.
  • An object of the present invention is to provide a technique capable of dramatically improving the strength of a gel without impairing excellent properties such as high flexibility and high water retention property of the gel, and further to the gel To provide various uses.
  • the gel according to the present invention has a semi-interpenetrating network structure in which a non-crosslinked polymer invades a network structure composed of a crosslinked polymer and is physically entangled.
  • the degree of swelling is 5 or more
  • the weight content of the good solvent is 80% or more
  • the fracture energy is 700 jZm 2 or more and 2000 jZm 2 or less.
  • the second polymer that is not a crosslinked polymer is linear and has a high molecular weight without having any crosslinked structure. It was found that the strength of the gel is specifically improved only when the second polymer adopts a non-crosslinked polymer rather than a crosslinked structure. The invention's effect
  • a non-crosslinked polymer having high flexibility satisfying a predetermined condition enters and is physically entangled in a rigid network made of a crosslinked polymer and in which cavities are scattered. It is possible to provide a gel with mechanical strength and durability comparable to or better than tissue.
  • FIG. 1 is a diagram schematically showing a semi-interpenetrating network structure of a gel according to the present invention.
  • FIG. 2 A diagram schematically showing a cavity of a network structure made of a crosslinked polymer in a semi-interpenetrating network structure
  • FIG. 3 The state of deformation of the semi-interpenetrating network structure at the crack tip of the gel according to the present invention and the transient network due to physical entanglement regardless of chemical crosslinking in the velocity region where the non-crosslinked polymer exists.
  • FIG. 4 Schematic diagram showing the external force velocity region where a transient network is formed in a non-crosslinked polymer in a concentrated solution state.
  • the essence of the present invention is that a gel having a semi-interpenetrating network structure in which a non-crosslinked polymer in the form of a random coil having a size satisfying the cavity is entangled with a network structure in which cavities having a crosslinked polymer force are scattered. Is to form.
  • the size of the random coil depends on the molecular weight of the unbridged polymer.
  • “compressive strength” is used as an index indicating the mechanical strength
  • “breaking energy” is used as an index indicating the fracture mechanical strength.
  • “Compressive strength” is the value obtained by dividing the stress required to break the gel by the initial area
  • “Fracture energy” is the work used for steady progress of the gel divided by the fracture area. The value, i.e., the energy required to form a fracture surface. Therefore, as an index indicating the superiority or inferiority of the gel, it is more appropriate to use the fracture energy rather than the compressive strength, taking into account the characteristics of the gel that the deformation rate until fracture is extremely large (Y. Tanaka, K. rukao, Y. Miyamoto, Fracture energy of gels, ie European Physical Journal, 3, 395-401 (2000)).
  • FIG. 1 schematically shows a semi-interpenetrating network structure of the gel according to the present invention.
  • the cross-linked polymer that forms the basic skeleton of the gel forms a rigid network structure in which cavities, which are extremely sparse parts of the network, are scattered, while the non-cross-linked polymer is concentrated in these cavities, While maintaining flexibility, it is physically entangled with the network structure of the crosslinked polymer at its end.
  • a network structure in which cavities having a cross-linked polymer force are scattered is formed, for example, by radical copolymerization of a bull monomer and a dibul monomer. Bull monomers and dibules Since monomers are different in reactivity in radical polymerization, when they are copolymerized, a microgel is formed in the early stage of the reaction, and when it grows, the microgel crosslinks to form a non-uniform network structure.
  • the degree of cross-linking is the same, then the equilibrium swelling degree and the non-uniformity of the network are significantly greater in the former than in the latter, so the network structure composed of the crosslinked polymer of the electrolyte has a network structure. Considered very sparse portion or cavity is scattered reliably.
  • the measurement data by the dynamic light scattering method supports this idea.
  • non-crosslinked polymer refers to a polymer having a degree of crosslinking of less than 0.001 mol%, preferably a polymer that is not crosslinked at all, and the degree of crosslinking is a polymerization of a non-crosslinked polymer.
  • the quantity power of the crosslinking agent added at the time is also calculated.
  • a polymer having a low degree of cross-linking is soluble in a solvent in a sol state that does not form a gel, and tends to form a highly flexible random coil.
  • FIG. 2 schematically shows a cavity of a network structure that also has a cross-linked polymer force in a semi-interpenetrating network structure.
  • Non-crosslinked polymer is considered to be a random coil because it can move and deform freely in this cavity, and its diameter d 7? Is statistically the intrinsic viscosity [7?] And weight of the polymer solution.
  • Average molecular weight M and force Calculated by the following formula (M.-M.
  • the diameter of the random coil that has the calculated non-crosslinked polymer force is about 10 times or more the average interval of the network that also has the crosslinked polymer force, the mechanical strength and the fracture energy of the gel having a semi-interpenetrating network structure are reduced. Begin to improve specifically.
  • the molecular weight of the non-crosslinked polymer in this case is 10 6 or more in terms of weight average molecular weight, and the polymer is present at a concentration at which sufficient physical entanglement can occur.
  • the mechanism by which this phenomenon occurs is that random coils with non-crosslinked polymer force increase as the degree of polymerization increases.
  • V when it becomes larger and fills the cavity scattered in the network structure with the cross-linked polymer force, in other words, when the diameter of the random coil with the non-cross-linked polymer force becomes larger than the diameter of the cavity, the cross-linked polymer and It is presumed that the non-crosslinked polymers become physically entangled and these polymers behave like a continuous network by forming pseudo-crosslinking points due to the entanglement.
  • the diameter of the random coil made of the non-crosslinked polymer is smaller than the diameter of the cavity, a pseudo cross-linking point is not formed between the crosslinked polymer and the non-crosslinked polymer. In this case, the cross-linked polymer swells in the solvent whose viscosity has been increased due to the presence of the non-cross-linked polymer, so that the mechanical strength and fracture energy of the gel are remarkably improved. Absent.
  • the semi-interpenetrating network structure is a higher order structure having spatially hard, part (dense part of the crosslinked polymer) and soft part (very sparse part of the bridge polymer, ie, non-crosslinked polymer in the cavity).
  • FIG. 3 shows the deformation of the semi-interpenetrating network structure at the crack tip of the gel according to the present invention and the resistance to crack progression by forming a transient network in the velocity region where the non-crosslinked polymer is present.
  • the gel according to the present invention shows a speed dependency on the external force, and the optimum external force speed for increasing the strength of the gel is the non-crosslinked polymer in the cavity portion scattered in the network structure of the crosslinked polymer in the semi-interpenetrating network structure. This is considered to correspond to a velocity region in which a transitional network due to entanglement can be formed.
  • FIG. 4 schematically shows a velocity region of external force in which a transient network is formed in the non-crosslinked polymer in a concentrated solution state.
  • (B) cutting of the non-crosslinked polymer occurs preferentially from the stretched state. Therefore, it is considered that the mechanical strength and fracture energy of the gel are reduced.
  • the crack progress rate at the crack tip is slower than the movement speed of the non-crosslinked polymer, slipping of the (A) non-crosslinked polymer occurs preferentially from the stretched state as shown in the lower part of Fig. 3.
  • the non-crosslinked polymer in a concentrated solution state forms a transient network due to entanglement in the velocity region during which the non-crosslinked polymer behaves in a fluid state or enters a glassy state. It seems that it will show physical properties similar to rubber Therefore, the stress generated at the crack tip can be diffused.
  • the transient network formed by the non-crosslinked polymer in the concentrated solution state does not have a chemical cross-linking point and can slide when excessive stress is applied (stress concentration occurs). By friction, stress is converted to heat and diffused. Therefore, it is preferable that the non-crosslinked polymer moves slowly while maintaining fluidity in a state close to a high concentration solution.
  • the elastic modulus of this transitional network must be sufficiently smaller than the elastic modulus of rigid networks composed of cross-linked polymers.
  • the voids which are the network structure force of the crosslinked polymer, and the physical entanglement of the non-crosslinked polymer can avoid stress concentration that acts on cracks and disperse the energy that resists rupture. It becomes "crack prevention”.
  • the mechanical strength and fracture energy of the gel having a semi-interpenetrating network structure vary depending on the relationship between the speed of movement of the non-crosslinked polymer and the speed of the applied external force, and the movement speed of the non-crosslinked polymer Maximum for external force applied at close speed. Therefore, if the kinetic speed of the uncrosslinked polymer is changed by adjusting the gel temperature or the viscosity or compatibility of the solvent that swells the gel, the external force that maximizes the mechanical strength and fracture energy of the gel is obtained. The speed region can be changed.
  • Fig. 5 shows the relationship between the fracture energy and the weight average molecular weight M of the non-crosslinked polymer for a gel having a semi-interpenetrating network structure in which a non-crosslinked polymer is entangled with a network structure in which cavities made of a crosslinked polymer are scattered. The correlation is schematically shown.
  • Figure 5 shows the acrylic
  • the breaking energy of the gel increases remarkably near the weight average molecular weight M 1 X 10 6 of the non-crosslinked polymer, and reaches a peak at around 4 X 10 6 . This is non-w
  • the size (degree of polymerization) of the non-crosslinked polymer is considered to have an optimum range depending on the size of the cavities scattered in the semi-interpenetrating network structure.
  • the non-crosslinked polymer is also a linear polymer having almost no branching
  • the degree of polymerization that is, the length of the polymer is approximately linearly proportional to the molecular weight. Therefore, the fact that there is an optimal molecular weight for physical entanglement indicates that there is a length that is well-suited for physically entangled non-crosslinked polymers relative to crosslinked polymers with a network structure. . As can be inferred with reference to Fig. 1, it is expected that the cross-linking polymer will not slip through if the length of the non-crosslinked polymer is not long enough.
  • the non-crosslinked polymer itself cannot constitute a sufficiently wound random coil and cannot form a semi-interpenetrating network structure without being caught by the crosslinked polymer.
  • a pseudo cross-linking point is not formed. Therefore, the semi-penetrating network structure is a structure that occurs only when the random coil diameter of the non-crosslinked polymer is much larger than the average interval of the network of the crosslinked polymer.
  • the gel has a semi-interpenetrating network structure in which a non-crosslinked polymer having a size satisfying the cavity is physically entangled with a rigid network structure having a cross-linked polymer force and a space in which the cavity is scattered, Even when the swelling degree is 5 or more and the weight content of the good solvent is 80% or more at the time of equilibrium swelling with a good solvent, a non-crosslinked polymer is reliably formed when an external force is applied. Therefore, the fracture energy of 700jZm 2 or more and 2 OOOjZm 2 or less can achieve high durability that can not be achieved in the past.
  • this gel has a feature that when a nuclear magnetic resonance measurement is performed at the time of equilibrium swelling with a good solvent, a chemical shift appearing due to the presence of interaction between molecules is not observed. This observation means that there is no intermolecular interaction stronger than hydrogen bonds between non-crosslinked polymers. Thus, if there is no intermolecular interaction stronger than hydrogen bonding between the non-crosslinked polymers, the fluidity and mobility of the non-crosslinked polymer are impaired in the cavities scattered in the network structure of the crosslinked polymer. Therefore, the fracture energy of the gel is effectively improved. [0032] As if to support this, double-network gels exhibiting such high fracture energy cannot be explained by theories proposed for other mechanisms, such as Lake-Thomas theory. First, if estimated by Lake-Thomas theory, the breaking energy is only around lOjZm 2 , which is two orders of magnitude lower than the experimental value.
  • the ratio (bZa) of the transient elastic modulus (b) of the non-crosslinked polymer to the elastic modulus (a) of the crosslinked polymer is preferably from ⁇ to 1Z5.
  • the non-crosslinked polymer is stronger than hydrogen bonds and no intermolecular interaction exists, or the non-crosslinked polymer has a transient effect on the elastic modulus of the crosslinked polymer.
  • the gel has a semi-interpenetrating network structure with an elastic modulus ratio of 1Z100 or more and 1Z5 or less-and even if a crack occurs, the stress is generated at the tip of the crack, and the stress is caused by a transient network of non-crosslinked polymer. Since it is converted into heat by the formation and diffused effectively, the destruction energy is surely 700 jZm 2 or more and 2000 jZm 2 or less.
  • the gel has an equilibrium swelling degree of the crosslinked polymer with a good solvent of 5 to: LOOO, and the weight content of the non-crosslinked polymer is higher than the weight content of the crosslinked polymer.
  • the weight content of the non-crosslinked polymer is preferably 10 to 40% with respect to the total weight of the crosslinked polymer and the good solvent in the gel.
  • the cross-linked polymer constituting the gel must be highly rigid with a polymer chain having a high equilibrium swelling degree and a large extension, and specifically, the equilibrium swelling degree with a good solvent is 5%. It is preferably crosslinked so as to be ⁇ 1000 (solvent content 80 ⁇ 99.9 w%). The mechanical strength of the crosslinked polymer itself does not have to be so high.
  • the initial elastic modulus of the gel is almost determined by the initial elastic modulus of the network structure composed of the crosslinked polymer, and the influence of the non-crosslinked polymer on the initial elastic modulus of the gel is extremely small. Therefore, cross-linked polymers The initial elastic modulus of the gel can be adjusted by adjusting the degree of crosslinking.
  • the crosslinked polymer is preferably a strong electrolyte. We have electrolytes
  • this non-crosslinked polymer has characteristics such as non-electrolyte and high flexibility, no interaction such as electrostatic interaction and hydrophobic bond with the crosslinked polymer, or extremely weak if any. It is preferable to have.
  • the non-crosslinked polymer is in the form of a concentrated solution or sol within the network structure composed of the crosslinked polymer, and itself has fluidity like egg white and cannot maintain its outer shape.
  • the weight content of the non-crosslinked polymer in the gel according to the present invention needs to be higher than the concentration at which the high molecular weight non-crosslinked polymer can generate sufficient physical entanglement, Is preferably in the range of 5 to: LOO mole times.
  • concentration of the non-crosslinked polymer is too low or too high, the mechanical strength of the gel will not improve, so 0.5 to 5 molZL (3.5 ⁇ 35%).
  • the non-crosslinked polymer when the non-crosslinked polymer does not contain any cross-linked structure, the non-crosslinked polymer has a concentration of 0.5 to 5 molZL (3.5 to 35%) with respect to the solvent and has a molecular weight of Is preferably not less than the lower critical molecular weight described below.
  • the lower critical molecular weight of the non-crosslinked polymer a concentrated solution the molecular weight dependence of the viscosity, than the molecular weight giving the critical point that changes from ⁇ M by entanglement between port Rimmer 7?
  • ⁇ 3 ⁇ 4 10 ⁇ LOO times larger and its degree of polymerization (number of polymer units) It refers to molecular weight higher than that. If the average molecular weight of the non-crosslinked polymer is equal to or higher than the lower critical molecular weight, the mechanical strength and fracture energy of the gel having a semi-interpenetrating network structure increase with the molecular weight, and if the average molecular weight exceeds the upper critical molecular weight.
  • the mechanical strength and fracture energy of the gel show constant values. Therefore, in the example shown in FIG. 5, the lower critical molecular weight of the non-crosslinked polymer is around the weight average molecular weight M 1 X 10 6 where the fracture energy of the gel begins to increase specifically, and the upper critical critical mass of the non-crosslinked polymer.
  • the molecular weight is around the weight average molecular weight M 4 X 10 6 where the breaking energy of the gel peaks.
  • the lower and upper critical molecular weights of the non-crosslinked polymer vary depending on the size of the cavities scattered in the network structure composed of the crosslinked polymer.
  • the volume occupied by the non-crosslinked polymer is preferably equal to or greater than the volume of the vacancies scattered in the network structure composed of the crosslinked polymer, that is, the non-crosslinked polymer is sufficiently entangled in the network structure also having the crosslinked polymer force. It is preferable.
  • the non-crosslinked polymer present in the part behaves like a crosslinking point when the diffusion rate is significantly slow.
  • the non-crosslinked polymer has at least two cross-linking points at both ends across the cavity scattered in the network structure having the cross-linked polymer force, and further has a volume that completely fills the cavity. It is.
  • the molecular weight of the non-crosslinked polymer is indicated by a statistical average value, and therefore, the non-crosslinked polymer is formed when the both ends of all non-crosslinked polymers straddle the cavities scattered in the network structure of the crosslinked polymer.
  • the average molecular weight of the polymer is the upper critical molecular weight.
  • Raw material monomers constituting such a crosslinked polymer and a non-crosslinked polymer include 2-acrylamide-2-methylpropanesulfonic acid (AMPS), acrylamide (AAm), acrylic acid (AA), methacrylic acid, N-isopropylacrylamide, butylpyridine, hydroxyethyl acrylate, butyl acetate, dimethylsiloxane, styrene (St), methyl methacrylate (MMA), trifluoroethyl acrylate (TFE), styrene sulfonate (SS) Or dimethylacrylamide etc. are illustrated.
  • AMPS 2-acrylamide-2-methylpropanesulfonic acid
  • AAm acrylic acid
  • AA methacrylic acid
  • N-isopropylacrylamide butylpyridine
  • hydroxyethyl acrylate butyl acetate
  • dimethylsiloxane styrene
  • MMA methyl methacrylate
  • TFE
  • a fluorine-containing monomer specifically 2, 2, 2-trifluoroethylene Rumethyl Atarylate, 2, 2, 3, 3, 3 Pentafluoropropyl methacrylate, 3— (Perfluorobutyl) 2 Hydroxypropyl methacrylate, 1H, 1H, 9H Hexadecafluorono-methacrylate, 2, Examples thereof include 2,2-trifluoroethyl attareido, 2, 3, 4, 5, 6 pentafluorostyrene or vinylidene fluoride.
  • polysaccharides such as dielan, hyaluronic acid, carrageenan, chitin or alginic acid, or proteins such as gelatin and collagen can also be used.
  • the gel according to the present invention preferably has a water content of 10 to 99% in pure water, more preferably 50 to 95%, and even more preferably 85 to 95%. If the gel contains a large amount of pure water, the solvent absorption rate of the gel is increased and the permeability thereof is improved. At the same time, such a gel is a highly water-absorbent resin, soft contact lens, or liquid chromatography. It is useful for applications such as single-use separation frames, or applications that require sustained release.
  • this gel preferably has a volume retention rate of 20 to 95%, more preferably 60 to 95%, and particularly preferably 70 to 95% when transferred from pure water to physiological saline.
  • this gel has the feature that even if it is once dried, it can be re-swelled to restore its original physical properties, and the solvent at the time of re-swelling is not limited to water. Therefore, if this gel is used as a water-absorbing agent such as Omumu, it can absorb a large amount of a solution with high osmotic pressure such as urine. Can be provided.
  • another polymer may be entangled with a semi-interpenetrating network structure constituted by a crosslinked polymer and a non-crosslinked polymer. Since the surface layer of this semi-interpenetrating network structure is dominated by the last added polymer, if the other polymer is entangled with the semi-interpenetrating network structure, the other polymer properties are imparted to the gel. can do. Therefore, if the technique disclosed in Patent Document 1 is used to form a free end chain by mixing an electrolyte polymer or graft polymerization into this semi-interpenetrating network structure, the mechanical strength and fracture energy are extremely high. This is achieved by obtaining high and low friction materials.
  • the side chain of the non-crosslinked polymer constituting this semi-interpenetrating network structure is known means.
  • the kinetics of the non-crosslinked polymer can be changed to adjust the swelling property, fracture energy and viscoelastic properties of the gel.
  • the cross-linked polymer or non-cross-linked polymer constituting the semi-interpenetrating network structure and the above-described many functional groups are included.
  • a valence ion By reacting a valence ion, a chelate complex or a colloid containing a polyvalent ion is formed on the surface and inside of the semi-interpenetrating network structure, and the physical properties of the gel can be changed.
  • the content of metal ions in a gel increases, the water content decreases and the mechanical strength increases.
  • the non-crosslinked polymer needs to form a transient network.
  • the network structure which is also a crosslinked polymarker, and the polyvalent ions form a colloid, and It is preferable that the non-crosslinked polymer does not form a colloid with the multivalent ion.
  • the content of polyvalent ions in the gel is preferably 0.01 to Lmol / L at the time of equilibrium swelling with pure water, and more preferably 0.03 to 0.3 mol / L.
  • the polyvalent ion is not particularly limited as long as it is a metal ion capable of forming a complex, and examples thereof include zinc ion, iron ion, nickel ion, cobalt ion, and chromium ion.
  • examples of the functional group capable of forming a complex with these multivalent ions include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
  • endothelial cells can be attached to the surface and allowed to proliferate. Therefore, by selecting the type of the non-crosslinked polymer that governs the physical properties of the surface layer of the semi-interpenetrating network structure in the gel according to the present invention, or by chemically modifying the side chain of the non-crosslinked polymer, An extremely durable substrate for cell culture can be obtained.
  • a non-crosslinked polymer having high flexibility satisfying a predetermined condition penetrates into a rigid network structure including a crosslinked polymer and in which cavities are scattered.
  • the mechanical strength and durability of these industrial materials can be improved by using the gel of the present invention to constitute a water-absorbent resin, a lubricant, a cell culture substrate and the like.
  • the method for producing a gel having a semi-interpenetrating network structure according to the present invention is not particularly limited! /, But first, radically copolymerization of monomers having different reactivities to disperse the cavities. Next, the cross-linked polymer is formed, and then the cross-linked polymer does not contain a cross-linking agent, and the monomer solution force is immersed in the monomer solution while the non-cross-linked polymer is entangled with the cross-linked polymer by radical polymerization. Legal is preferred.
  • a monomer having a different reactivity is radically copolymerized to form a polymer, and another crosslinking agent is added to the polymer solution.
  • a method of further polymerizing the polymers by gamma ray irradiation or the like is preferable.
  • the gel having the semi-interpenetrating network structure may be further immersed in another monomer solution, and the third and fourth non-crosslinked polymers may be entangled with the gel.
  • a crosslinking agent 0.001 to 0.1 mol times dibule monomer is added as a crosslinking agent to an appropriate concentration of electrolyte bulule monomer, and these are combined with radicals. It is preferable to polymerize.
  • the cross-linking agent include N, N′-methylene bisacrylamide (MBAA) and ethylene glycol dimetatalylate.
  • non-uniformity of the network structure composed of the crosslinked polymer can be enhanced.
  • non-uniformity of the network structure may be increased by mixing fine particles inside the network structure and removing the fine particles by dissolution after the formation of the network structure. .
  • the crosslinked polymer when the non-crosslinked polymer is entangled with the network structure composed of the crosslinked polymer by using the sequential polymerization method, the crosslinked polymer may be equilibrated and swollen even if the solvent is removed or just after the synthesis. It may be. Furthermore, after the crosslinked polymer is immersed in the monomer solution of the non-crosslinked polymer and becomes in an equilibrium swelling state, that is, after the monomer concentration is almost equal between the inside and the outside of the network structure, the polymerization of the monomer is not performed for the first time. It is preferable that the In this monomer solution, the concentration of the cross-linking agent such as dibule monomer with respect to the monomer needs to be less than 0. 01 mol%.
  • the non-crosslinked polymer is polymerized in a state where the crosslinked polymer is sufficiently swollen, even if the non-crosslinked polymer is entangled with the crosslinked polymer, the volume increase rate remains at most several tens of percent. .
  • the third and fourth polymers are further entangled with this semi-interpenetrating network structure.
  • the same means as the polymerization means for the non-crosslinked polymer described above may be used.
  • the gel produced by the above-mentioned method was once vacuum dried and then dried. Soak the gel in a solution containing multivalent ions.
  • a frame with an outer length of 80 X 80 mm and a width of 5 mm was cut out from a 100 X 100 X 2 mm silicone resin board with a cutter, and a 3 mm groove was made in one part of the frame.
  • the silicone resin frame was sandwiched between two 100 ⁇ 100 ⁇ 3 mm glass plates to assemble a polymerization vessel.
  • the gel having a semi-interpenetrating network structure obtained in this manner was subjected to equilibrium swelling again in pure water.
  • the weight content of the crosslinked polymer is 1.5%
  • the weight content of the non-crosslinked polymer is 12.5%
  • the weight content of pure water is 86%.
  • the equilibrium swelling degree of the crosslinked polymer was 44
  • the equilibrium swelling degree of the gel itself was 7.4.
  • a gel having a semi-interpenetrating network structure was obtained in the same manner as in Comparative Example 1 except that the formation of the interpenetrating network structure or semi-interpenetrating network structure> was changed as follows.
  • a gel having a semi-interpenetrating network structure was prepared in the same manner as in Comparative Example 1 except that the formation of an interpenetrating network structure or a semi-interpenetrating network structure> was changed as follows. Obtained.
  • the immersion solution strength gel is taken out and cut into an appropriate size, and then the gel is used with two glass plates of 100 X 100 X 3mm so that air bubbles are not mixed between the glass plates. I pinched it.
  • ultraviolet rays were irradiated for 10 hours at room temperature using a 365 nm wavelength UV lamp (30W, 0.68A).
  • a gel having a semi-interpenetrating network structure was obtained by polymerizing the AAm monomer diffused in the gel to produce a non-crosslinked polymer.
  • the initial elastic modulus of the gel was calculated from the slope of the curve in the region where the strain of the strain-stress curve obtained by the compression test was less than 10% and high in linearity by the following equation.
  • the compressive strength of the gel is the stress when the slope of the strain-stress curve output to the monitor changes in real time during the measurement due to the gel being destroyed, or the strain-stress curve output to the monitor. Even if the slope of the film did not change, the following formula was calculated from the stress and the surface area when the fracture of the gel was confirmed.
  • the weight average molecular weight M of the non-crosslinked polymer in the semi-interpenetrating network structure is
  • the Hyde Mouth Gel according to the present invention is transparent with high mechanical strength and fracture strength, and has flexibility, substance permeability and impact resistance.
  • Materials building materials, communication materials (e.g. bearings, cables and joints), soil modifiers, contact lenses, intraocular lenses, hollow fibers, artificial cartilage, artificial joints, artificial organs (e.g. artificial blood vessels and artificial skins) ), Fuel cell materials, knottery separators, bedsore prevention mats, cushions, lubricants, lotions and other stabilizers and thickeners, cell culture substrates, drug delivery systems (DDS), It can be used as a drug carrier, a sensor for a specific substance, or a software computer used at the tip of a force tail.
  • DDS drug delivery systems

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Abstract

Technique par laquelle la résistance d'un gel peut être améliorée sans dégrader les excellentes propriétés du gel, telles qu'une flexibilité élevée et une rétention d'eau élevée ; et différents usages du gel. Dans le gel, un polymère réticulé constitue le squelette de base du gel et forme une structure de réseau rigide ayant des parties vides distribuées de façon éparpillée qui sont des parties extrêmement clairsemées dans le réseau, alors qu'un polymère non réticulé se situe dans ces parties vides et qu'il est physiquement emmêlé au niveau de ses extrémités avec la structure de réseau du polymère réticulé tout en conservant sa flexibilité. Dans le gel ayant une structure de réseaux semi-intercalés, la propagation de fissures sur une grande distance ne peut pas avoir lieu tant qu'on n'applique pas une force extérieure extrêmement grande dépassant les contraintes diffusibles par le polymère non réticulé. Même si une cassure a lieu de façon microscopique, elle ne devient pas une cassure macroscopique dans ces conditions. Ce gel ne se casse jamais sauf si on applique une force extérieure extraordinairement grande, parce que la valeur critique conduisant à une cassure macroscopique est extrêmement élevée.
PCT/JP2005/011469 2004-06-25 2005-06-22 Gel, procédé servant à produire celui-ci, résine absorbant l'eau, matière lubrifiante et substrat pour la culture de cellules WO2006001313A1 (fr)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006213868A (ja) * 2005-02-04 2006-08-17 Hokkaido Univ ゲルおよびその製造方法
JP2006249258A (ja) * 2005-03-10 2006-09-21 Fuji Xerox Co Ltd 高分子ゲル組成物、高分子ゲル組成物の製造方法、及び光学素子
WO2008065756A1 (fr) 2006-11-29 2008-06-05 National University Corporation Hokkaido University Agent de remplissage osseux pour un traitement de régénération de tissu cartilagineux
JP2009051087A (ja) * 2007-08-27 2009-03-12 Three M Innovative Properties Co 高分子ゲル構造体及びその製造方法
JP2010174063A (ja) * 2009-01-27 2010-08-12 Mitsubishi Rayon Co Ltd ゲルおよびその製造方法
EP2353609A1 (fr) 2010-02-04 2011-08-10 Sanofi Pasteur Compositions et procédés d'immunisation
JP2011236311A (ja) * 2010-05-10 2011-11-24 Institute Of Physical & Chemical Research 導電性ハイドロゲル、導電性乾燥ゲル、および導電性ハイドロゲルの製造方法
JP2012001596A (ja) * 2010-06-15 2012-01-05 Mitsubishi Rayon Co Ltd ゲルおよびその製造方法
JP2013533356A (ja) * 2010-07-09 2013-08-22 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド アクリルコポリマー増粘剤のブレンド
JP2015096560A (ja) * 2013-11-15 2015-05-21 東亞合成株式会社 高強度ゲル
JP2015138192A (ja) * 2014-01-23 2015-07-30 株式会社リコー 手技練習用臓器モデル
JP2018127551A (ja) * 2017-02-09 2018-08-16 国立大学法人山形大学 低摩擦化された表面を有する高強度ゲルの製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001525464A (ja) * 1997-12-05 2001-12-11 エシロール アテルナジオナール カンパニー ジェネラーレ デ オプティック タンパク質の付着に対して抵抗性のある光透過性ポリマー材料の製造方法、その方法により得られる材料、その材料から生産されるコンタクトレンズおよび眼内レンズ
JP2002212452A (ja) * 2001-01-22 2002-07-31 Hokkaido Technology Licence Office Co Ltd 直鎖状高分子を有する低摩擦ハイドロゲルおよびその製造方法
WO2003093337A1 (fr) * 2002-05-01 2003-11-13 Hokkaido Technology Licensing Office Co., Ltd. Hydrogel a structure de reseau a semi-interpenetration et procede de production associe

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001525464A (ja) * 1997-12-05 2001-12-11 エシロール アテルナジオナール カンパニー ジェネラーレ デ オプティック タンパク質の付着に対して抵抗性のある光透過性ポリマー材料の製造方法、その方法により得られる材料、その材料から生産されるコンタクトレンズおよび眼内レンズ
JP2002212452A (ja) * 2001-01-22 2002-07-31 Hokkaido Technology Licence Office Co Ltd 直鎖状高分子を有する低摩擦ハイドロゲルおよびその製造方法
WO2003093337A1 (fr) * 2002-05-01 2003-11-13 Hokkaido Technology Licensing Office Co., Ltd. Hydrogel a structure de reseau a semi-interpenetration et procede de production associe

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006213868A (ja) * 2005-02-04 2006-08-17 Hokkaido Univ ゲルおよびその製造方法
JP2006249258A (ja) * 2005-03-10 2006-09-21 Fuji Xerox Co Ltd 高分子ゲル組成物、高分子ゲル組成物の製造方法、及び光学素子
WO2008065756A1 (fr) 2006-11-29 2008-06-05 National University Corporation Hokkaido University Agent de remplissage osseux pour un traitement de régénération de tissu cartilagineux
US9539366B2 (en) 2006-11-29 2017-01-10 National University Corporation Hokkaido University Method for inducing regeneration of cartilage
JP5166282B2 (ja) * 2006-11-29 2013-03-21 国立大学法人北海道大学 軟骨組織再生治療用骨充填剤
US9453084B2 (en) 2007-08-27 2016-09-27 3M Innovative Properties Company Polymer gel structure and method for producing the same
JP2009051087A (ja) * 2007-08-27 2009-03-12 Three M Innovative Properties Co 高分子ゲル構造体及びその製造方法
JP2010174063A (ja) * 2009-01-27 2010-08-12 Mitsubishi Rayon Co Ltd ゲルおよびその製造方法
EP2353609A1 (fr) 2010-02-04 2011-08-10 Sanofi Pasteur Compositions et procédés d'immunisation
JP2011236311A (ja) * 2010-05-10 2011-11-24 Institute Of Physical & Chemical Research 導電性ハイドロゲル、導電性乾燥ゲル、および導電性ハイドロゲルの製造方法
JP2012001596A (ja) * 2010-06-15 2012-01-05 Mitsubishi Rayon Co Ltd ゲルおよびその製造方法
JP2013533356A (ja) * 2010-07-09 2013-08-22 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド アクリルコポリマー増粘剤のブレンド
JP2015096560A (ja) * 2013-11-15 2015-05-21 東亞合成株式会社 高強度ゲル
JP2015138192A (ja) * 2014-01-23 2015-07-30 株式会社リコー 手技練習用臓器モデル
JP2018127551A (ja) * 2017-02-09 2018-08-16 国立大学法人山形大学 低摩擦化された表面を有する高強度ゲルの製造方法

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