CN110559487B - High-toughness thermosetting layered elastomer of poly citrate and preparation method thereof - Google Patents

High-toughness thermosetting layered elastomer of poly citrate and preparation method thereof Download PDF

Info

Publication number
CN110559487B
CN110559487B CN201910728807.XA CN201910728807A CN110559487B CN 110559487 B CN110559487 B CN 110559487B CN 201910728807 A CN201910728807 A CN 201910728807A CN 110559487 B CN110559487 B CN 110559487B
Authority
CN
China
Prior art keywords
citrate
poly
elastomer
layered
prepolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910728807.XA
Other languages
Chinese (zh)
Other versions
CN110559487A (en
Inventor
吉亚丽
谷少华
梁凯
孙宾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Donghua University
Original Assignee
Donghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Donghua University filed Critical Donghua University
Priority to CN201910728807.XA priority Critical patent/CN110559487B/en
Publication of CN110559487A publication Critical patent/CN110559487A/en
Application granted granted Critical
Publication of CN110559487B publication Critical patent/CN110559487B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/48—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with macromolecular fillers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58—Materials at least partially resorbable by the body
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention relates to a high-toughness thermosetting lamellar elastomer of poly-citrate and a preparation method thereof, which comprises the steps of respectively preparing a solution A dissolved with a poly-citrate prepolymer and a Pickering emulsion B taking chitin nano-whisker as an emulsifier to stabilize the emulsion of the poly-citrate prepolymer, alternately coating the solution A and the Pickering emulsion B on the surface of a substrate, and then carrying out vacuum curing to obtain the lamellar elastomer; the prepared elastomer is a layered composite material formed by alternately alternating soft phase layers (a poly-citrate elastomer in a three-dimensional cross-linked network structure) and hard phase layers (a compound of chitin nano crystal whiskers and the poly-citrate elastomer in a double-network cross-linked structure) and bonded through chemical bonds, the tensile strength of the composite material ranges from 15MPa to 170MPa, the strain range is 10% -50%, and the toughness of the composite material ranges from 7.5MJ/m to 17.2MJ/m3Elastic recovery rate>95 percent. The preparation method is simple, and the prepared layered elastomer has excellent mechanical property, strain and degradability.

Description

High-toughness thermosetting layered elastomer of poly citrate and preparation method thereof
Technical Field
The invention belongs to the technical field of artificial bone materials, and relates to a high-toughness thermosetting layered poly-citrate elastomer and a preparation method thereof.
Background
Bone tissue defects are important diseases affecting human health and life, particularly large-section bone defects cannot be healed only by means of the self-repairing capacity of bone tissues, and bone grafting operations are required, so that research and development of artificial bone biomaterials meeting clinical requirements become the key of the field of bone regeneration. It has been found that citric acid, which accounts for about 5 wt% of the organic components in bone, plays a role as a biomineralization regulator during bone formation and is an essential substance for bone regeneration. The poly citrate thermosetting elastomer prepared by copolycondensation of citric acid and diol monomer not only has good biocompatibility and mechanical property adjustability, but also has biodegradability, and citric acid molecules generated by degradation can promote bone repair, so that the poly citrate thermosetting elastomer has potential application value in the aspect of artificial bone materials. However, the mechanical properties of the poly-citrate are not yet satisfactory for artificial bone materials due to the chemical structure limitations of the poly-citrate itself.
The shell pearl shell is a hard phase (inorganic component)The layered composite material alternately alternated with soft phase (organic component) can cause a great deal of energy dissipation by inducing 'crack deflection', 'crack passivation', 'crack plastic deformation' and 'lamella extraction', thereby integrating high strength and high toughness into a whole and being an excellent structural form of the artificial bone material. At present, various layered composite materials are reported successively, which have inorganic sheet materials as hard phase layers and organic polymer materials as soft phase layers, wherein the inorganic materials mainly include alumina ceramics (Adv Mater,2016,28,5099), clay (Nano Lett,2010,10,2742), graphene (J Mater Chem a,2019,7,2787), and the like. Although the toughness and the strength of the inorganic-organic layered composite material are greatly improved, the tensile strength is up to 300MPa, and the toughness is up to 20MJ/m3However, all of them exhibit the characteristics of inorganic materials, i.e. the strain is low (generally less than 5%), which results in weak deformation bearing capacity of the materials, and because such inorganic materials have no biodegradability, the constructed layered composite materials are not suitable for bone tissue engineering substitutes. In addition, due to the great difference between the properties of the inorganic material and the organic polymer material, measures are required to overcome the defect of weak bonding force of the two-phase interface, such as introduction of a cross-linking agent to enhance the bonding force of the organic-inorganic two-phase interface (ACS Nano,2016,10,4816), but the complexity of system composition is increased, which is not beneficial to medical application.
Therefore, it is urgently needed to research an artificial bone material which is biodegradable, has good mechanical properties and has large strain.
Disclosure of Invention
The invention aims to solve the problem that an artificial bone material with biodegradability, excellent mechanical property and large strain is lacked in the prior art, and provides a biodegradable high-toughness thermosetting layered poly-citrate elastomer and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following scheme:
the high-toughness thermosetting layered elastomer of the poly citrate is a layered composite material with alternately alternated soft phase layers and hard phase layers;
the soft phase layer is a poly citrate elastomer and is in a three-dimensional cross-linked network structure;
the hard phase layer is a compound of the chitin nano crystal whisker and the poly citrate elastomer and is in a double-network cross-linked structure, and the double-network cross-linked structure is formed by mutually penetrating a three-dimensional leakage network structure formed by the chitin nano crystal whisker through the action of hydrogen bonds and a three-dimensional cross-linked network structure of the poly citrate elastomer;
the soft phase layer and the hard phase layer are combined through chemical bonds;
the tensile strength range of the high-toughness thermosetting layered elastomer of the poly-citrate is 15-170 MPa, which is enough to meet the requirement of practical application, the strain range is 10-50%, and the toughness (namely the energy consumed by tensile fracture) is 7.5-17.2 MJ/m3The elastic recovery rate is more than 95 percent.
The poly-citrate has biodegradability, and citric acid molecules generated by degradation can promote bone repair, so that the poly-citrate has potential application value in the aspect of artificial bone materials, but is limited by the chemical structure of the poly-citrate, has poor mechanical properties and is not enough to meet the requirements of practical application; in the prior art, the inorganic-organic layered composite structure can greatly improve the mechanical properties such as strength, toughness and the like of the material, but the hard phase layer is an inorganic material, so that the composite material has fatal defects, namely low strain (less than 5%), and poor material deformation bearing capacity, and in addition, the composite material is not biodegradable, so that the composite material is difficult to apply to the field of artificial bone materials;
the invention adopts degradable poly citrate with bone repair ability as main material to construct a layered composite structure, and prepares the artificial bone material with biodegradability, good mechanical property and larger strain, wherein, the soft phase layer is pure poly citrate, the hard phase layer is biodegradable chitin nano whisker/poly citrate nano composite with high strength and high modulus, and the used raw materials are all biodegradable materials, so the final product (poly citrate high-toughness thermosetting layered elastomer) has biodegradability; because of the layered composite structure, the final product has excellent mechanical properties; because the soft phase layer and the hard phase layer are both organic materials and are the same polymer, the interface bonding force is strong (bonding through chemical bonds), the final product has larger strain (10-50 percent, which is far higher than the prior art), can bear large deformation, and can meet the application requirements of the artificial bone material.
As a preferable scheme:
in the high-toughness thermosetting layered elastomer of the poly citrate, the single-layer thickness of a hard phase layer is 1-10 mu m, and the Young modulus is 10-200 MPa; the soft phase layer has a single layer thickness of 1 to 10 μm and a Young's modulus of 0.01 to 0.1 MPa.
According to the high-toughness thermosetting layered elastomer containing the poly-citrate, in all hard phase layers, the mass ratio of the chitin nano whiskers to the poly-citrate elastomer is the same, and the value range is 1-9: 1.
The high-toughness thermosetting layered elastomer of the poly-citrate is prepared by hydrolyzing chitin extracted from shrimp and crab shells with hydrochloric acid to obtain needle-rod-shaped nanoparticles, wherein the average length of the needle-rod-shaped nanoparticles is 300-500 nm, and the average diameter of the needle-rod-shaped nanoparticles is 15-20 nm.
In the high-toughness thermosetting layered elastomer containing the polycitrate, the polymerization degrees of the polycitrate elastomers in the soft phase layer and the hard phase layer are the same.
The invention also provides a method for preparing the high-toughness thermosetting layered elastomer of the poly-citrate, which comprises the steps of respectively preparing a solution A dissolved with a poly-citrate prepolymer and a Pickering emulsion B (the Pickering emulsion is an oil-water emulsion taking particles as an emulsifier) taking chitin nano-whisker as an emulsifier to stabilize the emulsion of the poly-citrate prepolymer, alternately coating the solution A and the Pickering emulsion B on the surface of a substrate (the specific mode can be spin coating, or other coating modes as long as uniform coating can be ensured), and then carrying out vacuum curing to obtain the high-toughness thermosetting layered elastomer of the poly-citrate. The poly citrate prepolymer is a substance generated by primary polymerization of citric acid containing tricarboxy and diol compound (or polyol compound) containing dihydroxy, in the vacuum curing process, the poly citrate prepolymer in the solution A is subjected to esterification reaction continuously to finally form poly citrate with a three-dimensional cross-linked network structure, while the poly citrate prepolymer in the Pickering emulsion B is subjected to esterification reaction continuously to form poly citrate with a three-dimensional cross-linked network structure, and meanwhile, the chitin nano whisker is self-assembled through hydrogen bond action to form a three-dimensional leakage network structure and penetrates through the network structure of the poly citrate to form a double-network cross-linked structure.
As a preferable scheme:
in the above-described method, all the citrate copolymer prepolymers are the melt reaction product of citric acid, 1, 8-octanediol and triblock polyether, and the preparation process is as follows: firstly, melting citric acid, 1, 8-octanediol and triblock polyether at a molar ratio of 1: 0.8-0.95: 0.2-0.05 at a temperature of 160 ℃, then reacting for 5-10 hours at a temperature of 135-145 ℃, and finally performing post-treatment (namely dialyzing by using deionized water and then freeze-drying to remove moisture), wherein the citric acid, the 1, 8-octanediol and the triblock polyether are mainly arranged to ensure that the molar ratio of carboxyl groups to hydroxyl groups is about 1: 1; the reaction temperature is preferably not too low at 135-145 ℃, otherwise the reaction temperature is difficult to melt sufficiently, and is not too high, otherwise the reaction temperature is serious in volatilization.
In the method, the solution A consists of a citrate prepolymer and a solvent, wherein the solvent is ethanol, 1, 4-dioxane or tetrahydrofuran, and the concentration of the solution A is 5-20 wt%;
the Pickering emulsion B is composed of a poly-citrate prepolymer, chitin nano-whiskers and water, wherein the solid content of the Pickering emulsion B is 5-20%, the mass ratio of the poly-citrate prepolymer to the chitin nano-whiskers is 1: 1-9, and the higher the content of the chitin nano-whiskers is, the higher the modulus of a hard phase layer is, and the higher the hardness is.
In the above method, the preparation process of the pickering emulsion B comprises the following steps: firstly, chitin nano crystal whisker is dispersed in water to form dispersion liquid, citrate prepolymer is dissolved in water to form emulsion, and then the dispersion liquid and the emulsion are mixed to form Pickering emulsion B.
In the method, the coating is carried out in a spin coater, the rotating speed is 500-; the vacuum curing is carried out in a vacuum drying oven, the curing temperature is 80-120 ℃, and the curing time is 2-10 days.
Has the advantages that:
(1) the high-toughness thermosetting layered elastomer of the poly-citrate adopts biodegradable poly-citrate and chitin nano crystal whisker as basic materials to construct a layered structure with alternate soft and hard materials, integrates high strength, high toughness and high elasticity, and is an excellent structural form of a biodegradable artificial bone material;
(2) unlike other layered composite materials, the high-toughness thermosetting layered elastomer of the poly-citrate adopts the same organic material as a matrix for both soft and hard phases, and the phase interfaces are combined through covalent bonds, so that the compatibility of the two phases is excellent, the binding force of the interfaces is enhanced, and the mechanical property of the material is greatly improved;
(3) the high-toughness thermosetting layered elastomer containing the poly-citrate has the tensile strength of 15-170 MPa, the strain of 10-50% and the toughness of 7.5-17.2 MJ/m3The rubber has good elasticity, and the elastic recovery rate is more than 95 percent;
(4) the high-toughness thermosetting layered elastomer containing the poly-citrate can obtain layered composite materials with different mechanical properties by changing the thickness of the layer, the proportion of the poly-citrate to the content of the chitin nano crystal whisker, the thermosetting time and the thermosetting temperature, and meet different use requirements;
(5) the preparation method of the high-toughness thermosetting lamellar elastomer of the poly-citrate does not use toxic and harmful reagents in the preparation process, is safe and environment-friendly, and has simple synthesis method.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A high-toughness thermosetting laminated polycitrate elastomer is prepared from the following steps:
(1) mixing citric acid with 1, 8-octanediol and triblock polyether according to a molar ratio of 1:0.8:0.2, melting at 160 ℃, reacting at 145 ℃ for 6 hours, dialyzing with deionized water, freeze-drying to remove water to obtain a poly-citrate prepolymer, and adding ethanol to obtain a poly-citrate prepolymer solution with the concentration of 5 wt%;
(2) dispersing chitin nano crystal whiskers with the average length of 300nm and the average diameter of 20nm in deionized water to form dispersion liquid;
(3) dissolving the poly citrate prepolymer obtained in the step (1) in water to form poly citrate prepolymer emulsion, adding the poly citrate prepolymer emulsion into the chitin nano whisker water dispersion formed in the step (2), and mixing to form chitin nano whisker/poly citrate prepolymer pickering emulsion with stable nano particles and 5 wt% of solid content, wherein the mass ratio of the chitin nano whisker to the poly citrate prepolymer is 9: 1;
(4) in a spin coater, on the surface of a substrate, alternately spin-coating an ethanol solution of a poly citrate prepolymer and a Pickering emulsion of chitin nano whisker/poly citrate prepolymer to a height of 0.5mm at a rotation speed of 500 rpm at a temperature of 30 ℃;
(5) and (3) placing the alternative spin-coating material prepared in the step (4) in a vacuum drying oven, and performing vacuum curing to obtain the high-toughness thermosetting layered poly-citrate elastomer, wherein the curing temperature is 120 ℃, the curing time is 10 days, and the vacuum degree is 200 Pa.
The finally prepared high-toughness thermosetting layered citrate elastomer is a layered composite material with alternately alternating soft phase layers and hard phase layers; the soft phase layer is a poly citrate elastomer, the single-layer thickness of the soft phase layer is 1 mu m, and the Young modulus is 0.1 MPa; the hard phase layer is a compound of chitin nano whiskers and a poly citrate elastomer, wherein in all the hard phase layers, the mass ratio of the chitin nano whiskers to the poly citrate elastomer is the same, the value is 9:1, the single-layer thickness of the hard phase layer is 1 micrometer, and the Young modulus is 200 MPa; and the elastomer consists of 250 hard phase layers and 250 layersThe soft phase layers are alternately combined, the tensile strength of the layered elastomer is 170MPa, the strain is 10 percent, and the toughness is 17.2MJ/m3The elastic recovery rate was 100%.
Example 2
A high-toughness thermosetting laminated polycitrate elastomer is prepared from the following steps:
(1) mixing citric acid with 1, 8-octanediol and triblock polyether according to a molar ratio of 1:0.8:0.2, melting at 160 ℃, reacting at 145 ℃ for 6 hours, dialyzing with deionized water, freeze-drying to remove water to obtain a poly-citrate prepolymer, and adding ethanol to obtain a poly-citrate prepolymer solution with the concentration of 10 wt%;
(2) dispersing chitin nano crystal whiskers with the average length of 300nm and the average diameter of 20nm in deionized water to form dispersion liquid;
(3) dissolving the poly citrate prepolymer obtained in the step (1) in water to form poly citrate prepolymer emulsion, adding the poly citrate prepolymer emulsion into the chitin nano whisker water dispersion formed in the step (2), and mixing to form chitin nano whisker/poly citrate prepolymer pickering emulsion with stable nano particles and a solid content of 10 wt%, wherein the mass ratio of the chitin nano whisker to the poly citrate prepolymer is 4: 1;
(4) in a spin coater, on the surface of a substrate, alternately spin-coating an ethanol solution of a poly-citrate prepolymer and a Pickering emulsion of chitin nano-whisker/poly-citrate prepolymer to a height of 1mm at a rotation speed of 4000 rpm at a temperature of 50 ℃;
(5) and (3) placing the alternative spin-coating material prepared in the step (4) in a vacuum drying oven, and performing vacuum curing to obtain the high-toughness thermosetting layered poly-citrate elastomer, wherein the curing temperature is 100 ℃, the curing time is 6 days, and the vacuum degree is 200 Pa.
The finally prepared high-toughness thermosetting layered citrate elastomer is a layered composite material with alternately alternating soft phase layers and hard phase layers; the soft phase layer is a poly citrate elastomer, the single-layer thickness of the soft phase layer is 5 mu m, and the Young modulus is 0.08 MPa; the hard phase layer is a compound of chitin nanowhiskers and a citrate polymer elastomer, whereinIn all hard phase layers, the mass ratio of the chitin nano crystal whiskers to the poly citrate elastomer is the same, the values are all 4:1, the single-layer thickness of the hard phase layer is 5 micrometers, and the Young modulus is 145 MPa; the elastomer is formed by alternately combining 100 hard phase layers and 100 soft phase layers, the tensile strength of the layered elastomer is 150MPa, the strain is 25 percent, and the toughness is 15.2MJ/m3The elastic recovery rate was 98%.
Example 3
A high-toughness thermosetting laminated polycitrate elastomer is prepared from the following steps:
(1) mixing citric acid with 1, 8-octanediol and triblock polyether according to a molar ratio of 1:0.8:0.2, melting at 160 ℃, reacting at 145 ℃ for 6 hours, dialyzing with deionized water, freeze-drying to remove water to obtain a poly-citrate prepolymer, and adding ethanol to obtain a poly-citrate prepolymer solution with the concentration of 15 wt%;
(2) dispersing chitin nano crystal whiskers with the average length of 300nm and the average diameter of 20nm in deionized water to form dispersion liquid;
(3) dissolving the poly citrate prepolymer obtained in the step (1) in water to form poly citrate prepolymer emulsion, adding the poly citrate prepolymer emulsion into the chitin nano whisker water dispersion formed in the step (2), and mixing to form chitin nano whisker/poly citrate prepolymer pickering emulsion with stable nano particles and 15 wt% of solid content, wherein the mass ratio of the chitin nano whisker to the poly citrate prepolymer is 3: 1;
(4) in a spin coater, alternately spin-coating an ethanol solution of a poly-citrate prepolymer and a Pickering emulsion of chitin nano-whisker/poly-citrate prepolymer on the surface of a substrate to a height of 1mm at a rotation speed of 5000 rpm and a temperature of 80 ℃;
(5) and (3) placing the alternative spin-coating material prepared in the step (4) in a vacuum drying oven, and performing vacuum curing to obtain the high-toughness thermosetting layered poly-citrate elastomer, wherein the curing temperature is 90 ℃, the curing time is 2 days, and the vacuum degree is 200 Pa.
The finally prepared high-toughness thermosetting laminated polycitrate elastomer is formed by crossing a soft phase layer and a hard phase layerAlternating layered composites; the soft phase layer is a poly citrate elastomer, the single-layer thickness of the soft phase layer is 10 mu m, and the Young modulus is 0.06 MPa; the hard phase layer is a compound of chitin nano whiskers and a poly citrate elastomer, wherein in all the hard phase layers, the mass ratio of the chitin nano whiskers to the poly citrate elastomer is the same, the value is 3:1, the single-layer thickness of the hard phase layer is 10 micrometers, and the Young modulus is 110 MPa; the elastic body is formed by alternately combining 50 hard phase layers and 50 soft phase layers, the tensile strength of the layered elastic body is 15MPa, the strain is 50 percent, and the toughness is 7.5MJ/m3The elastic recovery was 96%.
Example 4
A high-toughness thermosetting laminated polycitrate elastomer is prepared from the following steps:
(1) mixing citric acid with 1, 8-octanediol and triblock polyether according to a molar ratio of 1:0.8:0.2, melting at 160 ℃, reacting at 145 ℃ for 6 hours, dialyzing with deionized water, freeze-drying to remove water to obtain a poly-citrate prepolymer, and adding ethanol to obtain a poly-citrate prepolymer solution with the concentration of 20 wt%;
(2) dispersing chitin nano crystal whiskers with the average length of 300nm and the average diameter of 20nm in deionized water to form dispersion liquid;
(3) dissolving the poly citrate prepolymer obtained in the step (1) in water to form poly citrate prepolymer emulsion, adding the poly citrate prepolymer emulsion into the chitin nano whisker water dispersion formed in the step (2), and mixing to form chitin nano whisker/poly citrate prepolymer pickering emulsion with stable nano particles and 20wt% of solid content, wherein the mass ratio of the chitin nano whisker to the poly citrate prepolymer is 2: 1;
(4) in a spin coater, alternately spin-coating an ethanol solution of a poly-citrate prepolymer and a Pickering emulsion of chitin nano-whisker/poly-citrate prepolymer on the surface of a substrate to a height of 1mm at a rotating speed of 2000 rpm and a temperature of 60 ℃;
(5) and (3) placing the alternative spin-coating material prepared in the step (4) in a vacuum drying oven, and performing vacuum curing to obtain the high-toughness thermosetting layered poly-citrate elastomer, wherein the curing temperature is 80 ℃, the curing time is 5 days, and the vacuum degree is 200 Pa.
The finally prepared high-toughness thermosetting layered citrate elastomer is a layered composite material with alternately alternating soft phase layers and hard phase layers; the soft phase layer is a poly citrate elastomer, the single-layer thickness of the soft phase layer is 10 mu m, and the Young modulus is 0.04 MPa; the hard phase layer is a compound of chitin nano whiskers and a poly citrate elastomer, wherein in all the hard phase layers, the mass ratio of the chitin nano whiskers to the poly citrate elastomer is the same, the value is 2:1, the single-layer thickness of the hard phase layer is 10 micrometers, and the Young modulus is 75 MPa; the elastic body is formed by alternately combining 50 hard phase layers and 50 soft phase layers, the tensile strength of the layered elastic body is 110MPa, the strain is 35 percent, and the toughness is 13.7MJ/m3The elastic recovery was 95%.
Example 5
A high-toughness thermosetting laminated polycitrate elastomer is prepared from the following steps:
(1) mixing citric acid with 1, 8-octanediol and triblock polyether according to a molar ratio of 1:0.8:0.2, melting at 160 ℃, reacting at 145 ℃ for 6 hours, dialyzing with deionized water, freeze-drying to remove water to obtain a poly-citrate prepolymer, and adding ethanol to obtain a poly-citrate prepolymer solution with the concentration of 20 wt%;
(2) dispersing chitin nano crystal whiskers with the average length of 300nm and the average diameter of 20nm in deionized water to form dispersion liquid;
(3) dissolving the poly citrate prepolymer obtained in the step (1) in water to form poly citrate prepolymer emulsion, adding the poly citrate prepolymer emulsion into the chitin nano whisker water dispersion formed in the step (2), and mixing to form chitin nano whisker/poly citrate prepolymer pickering emulsion with stable nano particles and 20wt% of solid content, wherein the mass ratio of the chitin nano whisker to the poly citrate prepolymer is 1: 1;
(4) in a spin coater, alternately spin-coating an ethanol solution of a poly-citrate prepolymer and a Pickering emulsion of chitin nano-whisker/poly-citrate prepolymer on the surface of a substrate to a height of 1mm at a rotation speed of 800 rpm and a temperature of 40 ℃;
(5) and (3) placing the alternative spin-coating material prepared in the step (4) in a vacuum drying oven, and performing vacuum curing to obtain the high-toughness thermosetting layered poly-citrate elastomer, wherein the curing temperature is 80 ℃, the curing time is 3 days, and the vacuum degree is 200 Pa.
The finally prepared high-toughness thermosetting layered citrate elastomer is a layered composite material with alternately alternating soft phase layers and hard phase layers; the soft phase layer is a poly citrate elastomer, the single-layer thickness of the soft phase layer is 10 mu m, and the Young modulus is 0.01 MPa; the hard phase layer is a compound of chitin nano whiskers and a poly citrate elastomer, wherein in all the hard phase layers, the mass ratio of the chitin nano whiskers to the poly citrate elastomer is the same, the value is 1:1, the single-layer thickness of the hard phase layer is 10 micrometers, and the Young modulus is 10 MPa; the elastic body is formed by alternately combining 50 hard phase layers and 50 soft phase layers, the tensile strength of the layered elastic body is 50MPa, the strain is 45 percent, and the toughness is 11.9MJ/m3The elastic recovery was 95%.
Example 6
A high-toughness thermosetting laminated polycitrate elastomer is prepared from the following steps:
(1) mixing citric acid with 1, 8-octanediol and triblock polyether according to a molar ratio of 1:0.8:0.2, melting at 160 ℃, reacting at 135 ℃ for 10 hours, dialyzing with deionized water, freeze-drying to remove water to obtain a poly-citrate prepolymer, and adding 1, 4-dioxane to obtain a poly-citrate prepolymer solution with the concentration of 20 wt%;
(2) dispersing chitin nano crystal whiskers with the average length of 300nm and the average diameter of 15nm in deionized water to form dispersion liquid;
(3) dissolving the poly citrate prepolymer obtained in the step (1) in water to form poly citrate prepolymer emulsion, adding the poly citrate prepolymer emulsion into the chitin nano whisker water dispersion formed in the step (2), and mixing to form chitin nano whisker/poly citrate prepolymer pickering emulsion with stable nano particles and 20wt% of solid content, wherein the mass ratio of the chitin nano whisker to the poly citrate prepolymer is 9: 1;
(4) in a spin coater, on the surface of a substrate, alternately spin-coating an ethanol solution of a poly-citrate prepolymer and a Pickering emulsion of chitin nano-whisker/poly-citrate prepolymer to a height of 1mm at a rotation speed of 500 rpm at a temperature of 30 ℃;
(5) and (3) placing the alternative spin-coating material prepared in the step (4) in a vacuum drying oven, and performing vacuum curing to obtain the high-toughness thermosetting layered poly-citrate elastomer, wherein the curing temperature is 120 ℃, the curing time is 10 days, and the vacuum degree is 200 Pa.
The finally prepared high-toughness thermosetting layered citrate elastomer is a layered composite material with alternately alternating soft phase layers and hard phase layers; the soft phase layer is a poly citrate elastomer, the single-layer thickness of the soft phase layer is 10 mu m, and the Young modulus is 0.1 MPa; the hard phase layer is a compound of chitin nano whiskers and a poly citrate elastomer, wherein in all the hard phase layers, the mass ratio of the chitin nano whiskers to the poly citrate elastomer is the same, the value is 9:1, the single-layer thickness of the hard phase layer is 10 micrometers, and the Young modulus is 200 MPa; the elastic body is formed by alternately combining 50 hard phase layers and 50 soft phase layers, the tensile strength of the layered elastic body is 160MPa, the strain is 15 percent, and the toughness is 16.8MJ/m3The elastic recovery rate was 98%.
Example 7
A high-toughness thermosetting laminated polycitrate elastomer is prepared from the following steps:
(1) mixing citric acid with 1, 8-octanediol and triblock polyether according to a molar ratio of 1:0.8:0.2, melting at 160 ℃, reacting at 135 ℃ for 10 hours, dialyzing with deionized water, freeze-drying to remove water to obtain a poly-citrate prepolymer, and adding tetrahydrofuran to obtain a poly-citrate prepolymer solution with the concentration of 5 wt%;
(2) dispersing chitin nano crystal whiskers with the average length of 300nm and the average diameter of 15nm in deionized water to form dispersion liquid;
(3) dissolving the poly citrate prepolymer obtained in the step (1) in water to form poly citrate prepolymer emulsion, adding the poly citrate prepolymer emulsion into the chitin nano whisker water dispersion formed in the step (2), and mixing to form chitin nano whisker/poly citrate prepolymer pickering emulsion with stable nano particles and 5 wt% of solid content, wherein the mass ratio of the chitin nano whisker to the poly citrate prepolymer is 9: 1;
(4) in a spin coater, on the surface of a substrate, alternately spin-coating an ethanol solution of a poly citrate prepolymer and a Pickering emulsion of chitin nano whisker/poly citrate prepolymer to a height of 0.5mm at a rotation speed of 500 rpm at a temperature of 30 ℃;
(5) and (3) placing the alternative spin-coating material prepared in the step (4) in a vacuum drying oven, and performing vacuum curing to obtain the high-toughness thermosetting layered poly-citrate elastomer, wherein the curing temperature is 120 ℃, the curing time is 10 days, and the vacuum degree is 200 Pa.
The finally prepared high-toughness thermosetting layered citrate elastomer is a layered composite material with alternately alternating soft phase layers and hard phase layers; the soft phase layer is a poly citrate elastomer, the single-layer thickness of the soft phase layer is 1 mu m, and the Young modulus is 0.1 MPa; the hard phase layer is a compound of chitin nano whiskers and a poly citrate elastomer, wherein in all the hard phase layers, the mass ratio of the chitin nano whiskers to the poly citrate elastomer is the same, the value is 9:1, the single-layer thickness of the hard phase layer is 1 micrometer, and the Young modulus is 200 MPa; the elastomer is formed by alternately combining 250 hard phase layers and 250 soft phase layers, the tensile strength of the layered elastomer is 169MPa, the strain is 11 percent, and the toughness is 16.8MJ/m3The elastic recovery rate was 100%.
Example 8
A high-toughness thermosetting laminated polycitrate elastomer is prepared from the following steps:
(1) mixing citric acid with 1, 8-octanediol and triblock polyether according to a molar ratio of 1:0.8:0.2, melting at 160 ℃, reacting at 145 ℃ for 5 hours, dialyzing with deionized water, freeze-drying to remove water to obtain a poly-citrate prepolymer, and adding ethanol to obtain a poly-citrate prepolymer solution with the concentration of 20 wt%;
(2) dispersing chitin nano crystal whiskers with the average length of 400nm and the average diameter of 20nm in deionized water to form dispersion liquid;
(3) dissolving the poly citrate prepolymer obtained in the step (1) in water to form poly citrate prepolymer emulsion, adding the poly citrate prepolymer emulsion into the chitin nano whisker water dispersion formed in the step (2), and mixing to form chitin nano whisker/poly citrate prepolymer pickering emulsion with stable nano particles and 20wt% of solid content, wherein the mass ratio of the chitin nano whisker to the poly citrate prepolymer is 4: 1;
(4) in a spin coater, on the surface of a substrate, alternately spin-coating an ethanol solution of a poly-citrate prepolymer and a Pickering emulsion of chitin nano-whisker/poly-citrate prepolymer to a height of 1mm at a rotation speed of 4000 rpm at a temperature of 50 ℃;
(5) and (3) placing the alternative spin-coating material prepared in the step (4) in a vacuum drying oven, and performing vacuum curing to obtain the high-toughness thermosetting layered poly-citrate elastomer, wherein the curing temperature is 100 ℃, the curing time is 6 days, and the vacuum degree is 200 Pa.
The finally prepared high-toughness thermosetting layered citrate elastomer is a layered composite material with alternately alternating soft phase layers and hard phase layers; the soft phase layer is a poly citrate elastomer, the single-layer thickness of the soft phase layer is 10 mu m, and the Young modulus is 0.08 MPa; the hard phase layer is a compound of chitin nano whiskers and a poly citrate elastomer, wherein in all the hard phase layers, the mass ratio of the chitin nano whiskers to the poly citrate elastomer is the same, the value is 4:1, the single-layer thickness of the hard phase layer is 10 micrometers, and the Young modulus is 145 MPa; the elastic body is formed by alternately combining 50 hard phase layers and 50 soft phase layers, the tensile strength of the layered elastic body is 140MPa, the strain is 30 percent, and the toughness is 14.5MJ/m3The elastic recovery rate was 98%.
Example 9
A high-toughness thermosetting laminated polycitrate elastomer is prepared from the following steps:
(1) mixing citric acid with 1, 8-octanediol and triblock polyether according to a molar ratio of 1:0.8:0.2, melting at 160 ℃, reacting at 145 ℃ for 6 hours, dialyzing with deionized water, freeze-drying to remove water to obtain a poly-citrate prepolymer, and adding ethanol to obtain a poly-citrate prepolymer solution with the concentration of 20 wt%;
(2) dispersing chitin nano crystal whiskers with the average length of 500nm and the average diameter of 18nm in deionized water to form dispersion liquid;
(3) dissolving the poly citrate prepolymer obtained in the step (1) in water to form poly citrate prepolymer emulsion, adding the poly citrate prepolymer emulsion into the chitin nano whisker water dispersion formed in the step (2), and mixing to form chitin nano whisker/poly citrate prepolymer pickering emulsion with stable nano particles and 20wt% of solid content, wherein the mass ratio of the chitin nano whisker to the poly citrate prepolymer is 3: 1;
(4) in a spin coater, alternately spin-coating an ethanol solution of a poly-citrate prepolymer and a Pickering emulsion of chitin nano-whisker/poly-citrate prepolymer on the surface of a substrate to a height of 1mm at a rotation speed of 5000 rpm and a temperature of 80 ℃;
(5) and (3) placing the alternative spin-coating material prepared in the step (4) in a vacuum drying oven, and performing vacuum curing to obtain the high-toughness thermosetting layered poly-citrate elastomer, wherein the curing temperature is 90 ℃, the curing time is 2 days, and the vacuum degree is 200 Pa.
The finally prepared high-toughness thermosetting layered citrate elastomer is a layered composite material with alternately alternating soft phase layers and hard phase layers; the soft phase layer is a poly citrate elastomer, the single-layer thickness of the soft phase layer is 10 mu m, and the Young modulus is 0.06 MPa; the hard phase layer is a compound of chitin nano whiskers and a poly citrate elastomer, wherein in all the hard phase layers, the mass ratio of the chitin nano whiskers to the poly citrate elastomer is the same, the value is 3:1, the single-layer thickness of the hard phase layer is 10 micrometers, and the Young modulus is 110 MPa; the elastic body is formed by alternately combining 50 hard phase layers and 50 soft phase layers, the tensile strength of the layered elastic body is 16MPa, the strain is 48 percent, and the toughness is 7.9MJ/m3The elastic recovery was 95%.
Example 10
A high-toughness thermosetting laminated polycitrate elastomer is prepared from the following steps:
(1) mixing citric acid, 1, 8-octanediol and triblock polyether according to a molar ratio of 1:0.9:0.1, melting at 160 ℃, reacting at 145 ℃ for 8 hours, dialyzing with deionized water, freeze-drying to remove water to obtain a poly-citrate prepolymer, and adding ethanol to obtain a poly-citrate prepolymer solution with the concentration of 20 wt%;
(2) dispersing chitin nano crystal whiskers with the average length of 300nm and the average diameter of 20nm in deionized water to form dispersion liquid;
(3) dissolving the poly citrate prepolymer obtained in the step (1) in water to form poly citrate prepolymer emulsion, adding the poly citrate prepolymer emulsion into the chitin nano whisker water dispersion formed in the step (2), and mixing to form chitin nano whisker/poly citrate prepolymer pickering emulsion with stable nano particles and 20wt% of solid content, wherein the mass ratio of the chitin nano whisker to the poly citrate prepolymer is 2: 1;
(4) in a spin coater, alternately spin-coating an ethanol solution of a poly-citrate prepolymer and a Pickering emulsion of chitin nano-whisker/poly-citrate prepolymer on the surface of a substrate to a height of 1mm at a rotating speed of 2000 rpm and a temperature of 60 ℃;
(5) and (3) placing the alternative spin-coating material prepared in the step (4) in a vacuum drying oven, and performing vacuum curing to obtain the high-toughness thermosetting layered poly-citrate elastomer, wherein the curing temperature is 80 ℃, the curing time is 5 days, and the vacuum degree is 200 Pa.
The finally prepared high-toughness thermosetting layered citrate elastomer is a layered composite material with alternately alternating soft phase layers and hard phase layers; the soft phase layer is a poly citrate elastomer, the single-layer thickness of the soft phase layer is 10 mu m, and the Young modulus is 0.05 MPa; the hard phase layer is a compound of chitin nano whiskers and a poly citrate elastomer, wherein in all the hard phase layers, the mass ratio of the chitin nano whiskers to the poly citrate elastomer is the same, the value is 2:1, the single-layer thickness of the hard phase layer is 10 micrometers, and the Young modulus is 85 MPa; the elastic body is formed by alternately combining 50 hard phase layers and 50 soft phase layers, the tensile strength of the layered elastic body is 70MPa, the strain is 40 percent, and the toughness is 12.3MJ/m3The elastic recovery was 96%.
Example 11
A high-toughness thermosetting laminated polycitrate elastomer is prepared from the following steps:
(1) mixing citric acid with 1, 8-octanediol and triblock polyether according to a molar ratio of 1:0.95:0.05, melting at 160 ℃, reacting at 145 ℃ for 8 hours, dialyzing with deionized water, freeze-drying to remove water to obtain a poly-citrate prepolymer, and adding ethanol to obtain a poly-citrate prepolymer solution with the concentration of 20 wt%;
(2) dispersing chitin nano crystal whiskers with the average length of 300nm and the average diameter of 20nm in deionized water to form dispersion liquid;
(3) dissolving the poly citrate prepolymer obtained in the step (1) in water to form poly citrate prepolymer emulsion, adding the poly citrate prepolymer emulsion into the chitin nano whisker water dispersion formed in the step (2), and mixing to form chitin nano whisker/poly citrate prepolymer pickering emulsion with stable nano particles and 20wt% of solid content, wherein the mass ratio of the chitin nano whisker to the poly citrate prepolymer is 2: 1;
(4) in a spin coater, alternately spin-coating an ethanol solution of a poly-citrate prepolymer and a Pickering emulsion of chitin nano-whisker/poly-citrate prepolymer on the surface of a substrate to a height of 1mm at a rotating speed of 2000 rpm and a temperature of 60 ℃;
(5) and (3) placing the alternative spin-coating material prepared in the step (4) in a vacuum drying oven, and performing vacuum curing to obtain the high-toughness thermosetting layered poly-citrate elastomer, wherein the curing temperature is 80 ℃, the curing time is 5 days, and the vacuum degree is 200 Pa.
The finally prepared high-toughness thermosetting layered citrate elastomer is a layered composite material with alternately alternating soft phase layers and hard phase layers; the soft phase layer is a poly citrate elastomer, the single-layer thickness of the soft phase layer is 10 mu m, and the Young modulus is 0.06 MPa; the hard phase layer is a compound of chitin nano crystal whiskers and a poly citrate elastomer, wherein in all the hard phase layers, the mass ratio of the chitin nano crystal whiskers to the poly citrate elastomer is the same, the value is 2:1, the single-layer thickness of the hard phase layer is 10 micrometers, and the Young modulus is90 MPa; the elastic body is formed by alternately combining 50 hard phase layers and 50 soft phase layers, the tensile strength of the layered elastic body is 85MPa, the strain is 38 percent, and the toughness is 13.7MJ/m3The elastic recovery was 96%.

Claims (9)

1. The high-toughness thermosetting layered polycitrate elastomer is characterized by comprising the following components in parts by weight: is a layered composite material with alternately alternated soft phase layers and hard phase layers;
the soft phase layer is a poly citrate elastomer and is in a three-dimensional cross-linked network structure;
the hard phase layer is a compound of the chitin nano crystal whisker and the poly citrate elastomer and is in a double-network cross-linked structure, and the double-network cross-linked structure is formed by mutually penetrating a three-dimensional leakage network structure formed by the chitin nano crystal whisker through the action of hydrogen bonds and a three-dimensional cross-linked network structure of the poly citrate elastomer;
the soft phase layer and the hard phase layer are combined through chemical bonds; the polymerization degree of the citrate polymer elastomer in the soft phase layer and the hard phase layer is the same;
the high-toughness thermosetting layered elastomer containing the poly-citrate has the tensile strength ranging from 15MPa to 170MPa, the strain ranging from 10% to 50% and the toughness ranging from 7.5MJ/m to 17.2MJ/m3The elastic recovery rate is more than 95 percent.
2. The high-toughness thermosetting layered elastomer with citrate as claimed in claim 1, wherein in the high-toughness thermosetting layered elastomer with citrate, the single-layer thickness of the hard phase layer is 1-10 μm, and the Young modulus is 10-200 MPa; the soft phase layer has a single layer thickness of 1 to 10 μm and a Young's modulus of 0.01 to 0.1 MPa.
3. The high-toughness thermosetting layered elastomer with poly-citrate as claimed in claim 1, wherein the mass ratio of the chitin nanowhiskers to the poly-citrate elastomer in all the hard phase layers is the same, and the value range is 1-9: 1.
4. The high-toughness thermosetting layered elastomer with poly-citrate as claimed in claim 1, wherein the chitin nanowhisker is a needle-like nanoparticle obtained by hydrolyzing chitin extracted from shrimp and crab shells with hydrochloric acid, and has an average length of 300-500 nm and an average diameter of 15-20 nm.
5. A process for preparing a high-toughness thermosetting layered polycitrate elastomer as claimed in any one of claims 1 to 4, which comprises: respectively preparing a solution A dissolved with a poly-citrate prepolymer and a Pickering emulsion B taking chitin nano-whisker as an emulsifier to stabilize the poly-citrate prepolymer emulsion, alternately coating the solution A and the Pickering emulsion B on the surface of a substrate, and then carrying out vacuum curing to obtain the high-toughness thermosetting layered elastomer of the poly-citrate.
6. The method of claim 5 wherein all of the polycitrate prepolymers are the melt reaction product of citric acid, 1, 8-octanediol, and triblock polyether prepared by: firstly, citric acid, 1, 8-octanediol and triblock polyether in a molar ratio of 1: 0.8-0.95: 0.2-0.05 are melted, then reacted at a temperature of 135-145 ℃ for 5-10 hours, and finally post-treated.
7. The method of claim 5, wherein the solution A comprises a pre-polymer of poly-citrate and a solvent, the solvent is ethanol, 1, 4-dioxane or tetrahydrofuran, and the concentration of the solution A is 5-20 wt%;
the Pickering emulsion B is composed of a poly citrate prepolymer, chitin nanowhiskers and water, wherein the solid content of the Pickering emulsion B is 5-20%, and the mass ratio of the poly citrate prepolymer to the chitin nanowhiskers is 1: 1-9.
8. The method according to claim 7, wherein the pickering emulsion B is prepared by: firstly, chitin nano crystal whisker is dispersed in water to form dispersion liquid, citrate prepolymer is dissolved in water to form emulsion, and then the dispersion liquid and the emulsion are mixed to form Pickering emulsion B.
9. According to claim 5The method is characterized in that the coating is carried out in a spin coater, the rotating speed is 500-; the vacuum curing is carried out in a vacuum drying oven, and the curing temperature is 80-120 DEG CoAnd C, curing for 2-10 days.
CN201910728807.XA 2019-08-08 2019-08-08 High-toughness thermosetting layered elastomer of poly citrate and preparation method thereof Active CN110559487B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910728807.XA CN110559487B (en) 2019-08-08 2019-08-08 High-toughness thermosetting layered elastomer of poly citrate and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910728807.XA CN110559487B (en) 2019-08-08 2019-08-08 High-toughness thermosetting layered elastomer of poly citrate and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110559487A CN110559487A (en) 2019-12-13
CN110559487B true CN110559487B (en) 2020-11-24

Family

ID=68774763

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910728807.XA Active CN110559487B (en) 2019-08-08 2019-08-08 High-toughness thermosetting layered elastomer of poly citrate and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110559487B (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7641958B2 (en) * 2002-04-25 2010-01-05 Gore Enterprise Holdings, Inc. Membrane for use in sutured or sutureless surgical procedures
CN102580154A (en) * 2012-02-28 2012-07-18 淮阴工学院 Antifriction and toughening metal/ceramic bionic multilayer-film artificial joint
CN103909703A (en) * 2014-02-23 2014-07-09 青岛中科昊泰新材料科技有限公司 High-strength high-toughness polyvinyl chloride sheet material and production method thereof
CN103923383B (en) * 2014-04-01 2016-06-15 四川大学 A kind of polymer-based composite with excellent toughness and preparation method thereof
CN104927080B (en) * 2015-04-08 2018-01-30 北京航空航天大学 A kind of preparation method of the tough integrated conductive graphene composite of bionic laminar
CN108201632B (en) * 2016-12-20 2020-09-15 重庆润泽医药有限公司 Support for repairing articular cartilage
CN107596445A (en) * 2017-09-15 2018-01-19 东华大学 Poly- citrate performed polymer/chitin nano whisker slurry and preparation method thereof
CN107583106B (en) * 2017-09-15 2020-09-15 东华大学 Tissue engineering scaffold of nano-crystal whisker of poly citrate/chitin and preparation method thereof

Also Published As

Publication number Publication date
CN110559487A (en) 2019-12-13

Similar Documents

Publication Publication Date Title
Fu et al. The chitosan hydrogels: From structure to function
Zhu et al. Research progress in bio-based self-healing materials
Samadi et al. Self-healing and tough hydrogels with physically cross-linked triple networks based on Agar/PVA/Graphene
Hivechi et al. Drug release and biodegradability of electrospun cellulose nanocrystal reinforced polycaprolactone
Zhang et al. High performance PVA/lignin nanocomposite films with excellent water vapor barrier and UV-shielding properties
Xu et al. Bioinspired double network hydrogels: from covalent double network hydrogels via hybrid double network hydrogels to physical double network hydrogels
Shao et al. A self-healing cellulose nanocrystal-poly (ethylene glycol) nanocomposite hydrogel via Diels–Alder click reaction
Shao et al. Mimicking dynamic adhesiveness and strain-stiffening behavior of biological tissues in tough and self-healable cellulose nanocomposite hydrogels
Lee et al. Solution-blown core–shell self-healing nano-and microfibers
Mokhtari et al. An injectable mechanically robust hydrogel of Kappa-carrageenan-dopamine functionalized graphene oxide for promoting cell growth
Wen et al. Recent advancements in self-healing materials: Mechanicals, performances and features
Bian et al. Lignin nanoparticles as nano-spacers for tuning the viscoelasticity of cellulose nanofibril reinforced polyvinyl alcohol-borax hydrogel
Charreau et al. Nanocellulose patents trends: a comprehensive review on patents on cellulose nanocrystals, microfibrillated and bacterial cellulose
Islam et al. Progress and challenges in self-healing composite materials
Meng et al. Mechanical, hydrophobic and thermal properties of an organic-inorganic hybrid carrageenan-polyvinyl alcohol composite film
Chen et al. Modification and applications of bacterial celluloses in polymer science
Lei et al. Polysaccharide-based recoverable double-network hydrogel with high strength and self-healing properties
Wang et al. Mussel-inspired fabrication of konjac glucomannan/microcrystalline cellulose intelligent hydrogel with pH-responsive sustained release behavior
Zhong et al. A facile bottom-up route to self-assembled biogenic chitin nanofibers
Jiang et al. Preparation and characterization of hybrid double network chitosan/poly (acrylic amide-acrylic acid) high toughness hydrogel through Al3+ crosslinking
Wan et al. Recent progress in flexible nanocellulosic structures for wearable piezoresistive strain sensors
Zhang et al. Bioinspired polydopamine deposition and silane grafting modification of bamboo fiber for improved interface compatibility of poly (lactic acid) composites
Khattab et al. Cellulose nanocomposites: Opportunities, challenges, and applications
Sonseca et al. A comparative study of the mechanical, shape-memory, and degradation properties of poly (lactic acid) nanofiber and cellulose nanocrystal reinforced poly (mannitol sebacate) nanocomposites
CN110157170B (en) Polylactic acid/nano-cellulose/hydroxyapatite composite material and preparation thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant