CN113463385B - High-strength and high-toughness collagen fiber matrix, framework material, structural material and preparation method thereof - Google Patents

High-strength and high-toughness collagen fiber matrix, framework material, structural material and preparation method thereof Download PDF

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CN113463385B
CN113463385B CN202110813301.6A CN202110813301A CN113463385B CN 113463385 B CN113463385 B CN 113463385B CN 202110813301 A CN202110813301 A CN 202110813301A CN 113463385 B CN113463385 B CN 113463385B
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toughness
collagen fiber
strength
collagen
tannin
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CN113463385A (en
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李双洋
石碧
周建飞
许维星
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Sichuan University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/238—Tannins, e.g. gallotannic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71—Salts of phosphoric acids
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/325—Calcium, strontium or barium phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/14—Collagen fibres

Abstract

The invention relates to the technical field of composite materials, in particular to a high-toughness collagen fiber matrix, a framework material, a structural material and a preparation method thereof. The high-strength and high-toughness collagen fiber matrix comprises tannin modified collagen fibers and inorganic mineral crystals growing on the tannin modified collagen fibers in situ. The high-toughness collagen fiber framework material is mainly obtained by performing orientation control on a high-toughness collagen fiber matrix. The high-toughness collagen fiber structural material comprises a high-toughness collagen fiber framework material and a high polymer material filled in the framework material. The invention provides crystal growth sites by utilizing the electrostatic interaction and the complexing interaction of phenolic hydroxyl groups on tannin modified collagen fibers and metal ions, so that inorganic mineral crystals can uniformly and biomimetically mineralized and grow on the collagen fibers. The bionic structural material can be prepared by performing orientation control on the high-strength and high-toughness collagen fiber matrix to obtain a collagen fiber framework with a layered structure and adding a small amount of high polymer, and has the properties of light weight, high strength and toughness.

Description

High-strength and high-toughness collagen fiber matrix, framework material, structural material and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a high-toughness collagen fiber matrix, a framework material, a structural material and a preparation method thereof.
Background
Structural materials play a key role in modern society by providing functions such as load bearing in buildings, automobiles, electronic substrates, packaging, and many other structures. Mechanical strength and material weight (or density) are two important factors in engineering applications, especially when energy efficiency must be considered, such as in the fields of light vehicles, aircraft and high-rise building materials. Traditional structural materials (e.g., steel, concrete, brick, and petroleum-based composites) play a dominant role in the engineering field (e.g., construction and automotive). However, with the emphasis on the development of green and low-carbon economy, the development of renewable bio-source materials is imminent. In addition, in order to meet the demand for higher energy efficiency, it is of great interest to develop structural materials that are both lightweight and have high toughness.
Biogenic materials are attractive alternatives to structural applications due to their sustainability and renewability. In order to seek lighter, stiffer and stronger materials, a common approach is to pack bio-based materials (such as natural fibers) as reinforcing materials into polymers to obtain lightweight structural materials with high stiffness and strength. However, in conventional composites, it is very difficult to simultaneously increase the strength and toughness of the material, since most of the dissipative plastic deformation occurs in the polymer matrix, and although high loadings of reinforcement materials can generally achieve higher strength, toughness is generally poor. Therefore, there is a need for simple and efficient design and engineering strategies to improve the strength and toughness of bio-based structural materials for modern engineering applications.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a highly tough collagen fiber matrix to solve the technical problems of the prior art that strength, toughness and the like cannot be simultaneously achieved.
The second purpose of the invention is to provide a preparation method of the collagen fiber matrix with high toughness.
The third purpose of the invention is to provide a highly tough collagen fiber skeleton material.
A fourth object of the present invention is to provide a highly tough collagen fiber structural material.
The fifth purpose of the invention is to provide a preparation method of the collagen fiber structural material with high toughness.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a high strength and toughness collagen fiber matrix comprising tannin modified collagen fibers and inorganic mineral crystals grown in situ on the tannin modified collagen fibers.
In a specific embodiment of the present invention, the content of the inorganic mineral crystals in the matrix is 30% to 70%.
In a specific embodiment of the present invention, the inorganic mineral crystals include any one or more of aragonite crystals, calcium phosphate crystals and kaolinite crystals.
In a specific embodiment of the present invention, the method for preparing the tannin modified collagen fibers comprises: mixing tannin and collagen fibers in a liquid environment with the pH value of 5-6, reacting, washing and drying.
In a specific embodiment of the invention, the mass ratio of the tannin to the collagen fibers is 1: 2-4.
In the specific embodiment of the invention, the aqueous solution of tannin and the aqueous dispersion of collagen fibers are mixed, and then the pH is adjusted to 5-6 by alkali for reaction.
In practice, the aqueous solution of tannin is added to the aqueous dispersion of collagen fibers and mixed.
In a specific embodiment of the present invention, the mixing reaction time is 1 to 10 hours, preferably 2 to 8 hours.
In a specific embodiment of the present invention, the drying conditions include: drying for 10-30 h at 60-90 ℃.
The invention also provides a preparation method of any one of the high-toughness collagen fiber matrixes, which comprises the following steps:
the tannin modified collagen fibers and calcium carbonate and/or calcium chloride and/or kaolinite are in a solution system, and inorganic mineral crystals are grown on the tannin modified collagen fibers in situ.
According to the classical nucleation theory, mineral crystals form crystals after homogeneous or heterogeneous nucleation in sequence.
In the specific implementation mode of the invention, when the aragonite crystal is grown, the mixed system is heated at 45-55 ℃ to enable the inorganic mineral crystal to grow on the tannin modified collagen fiber in situ; when growing calcium phosphate crystals, stirring the mixed system at the temperature of 1-20 ℃ to enable inorganic mineral crystals to grow on the tannin modified collagen fibers in situ; when growing the kaolinite crystal, adjusting the pH value of the mixed system to 8.5-9.5, and heating at 40-70 ℃ to enable the inorganic mineral crystal to grow on the tannin modified collagen fiber in situ.
In a particular embodiment of the invention, when growing an aragonite crystal: and heating the tannin modified collagen fibers and calcium carbonate in a solution system at 45-55 ℃ to enable inorganic mineral crystals to grow on the tannin modified collagen fibers in situ. Further, the time of the heating treatment is 24-60 hours.
In a particular embodiment of the invention, when growing an aragonite crystal: besides calcium carbonate, the solution also comprises NaCl and Na2SO4、NaHCO3、MgCl2·6H2O、CaCl2And KCl.
In a particular embodiment of the invention, when growing an aragonite crystal: the mass ratio of the tannin modified collagen fibers to the calcium carbonate is 1: 1-3; the dispersion concentration of the calcium carbonate in the solution system is 8-12 g/L.
In a specific embodiment of the present invention, when growing calcium phosphate crystals: and stirring the tannin modified collagen fibers and calcium chloride in a solution system at the temperature of 1-20 ℃ to enable inorganic mineral crystals to grow on the tannin modified collagen fibers in situ. Further, the stirring time is 60-120 min; the stirring speed is 800-1200 r/min.
In a specific embodiment of the present invention, when growing calcium phosphate crystals: besides calcium chloride, the solution also comprises KH2PO4And Na2HPO4·12H2O。
In a specific embodiment of the present invention, when growing calcium phosphate crystals: the mass ratio of the tannin modified collagen fibers to the calcium chloride is 1: 1-2; the concentration of the calcium chloride in the solution system is 5-10 g/L.
In a particular embodiment of the invention, when growing kaolinite crystals: and in a solution system, regulating the pH value of the mixed system to 8.5-9.5, and heating at 40-70 ℃ to enable inorganic mineral crystals to grow on the tannin modified collagen fibers in situ. Further, the mass ratio of the tannin modified collagen fibers to the kaolinite is 1: 1-3; the concentration of the kaolinite in the solution system is 4-13 g/L.
In a specific embodiment of the invention, the pH of the tannin modified collagen fibers is adjusted to 7-9 in advance.
The invention also provides a high-toughness collagen fiber framework material which is mainly obtained by performing orientation control treatment on any one of the high-toughness collagen fiber matrixes.
In a specific embodiment of the present invention, the orientation regulating treatment includes any one or more of a freezing orientation, a water evaporation induced orientation, and a magnetic induced orientation.
In a specific embodiment of the invention, the frozen orientation comprises: and the high-strength and high-toughness collagen fiber matrix is immersed in a system at the temperature of-60 to-90 ℃ in a mould at the speed of 0.5 to 1.5cm/min and is kept for 5 to 20 min.
After the freezing orientation, performing freeze-drying. In practice, the freeze drying is carried out under conventional freeze drying conditions, and for example, the freeze drying may be carried out at a temperature of-20 ℃ or lower and in a vacuum of 0.1Pa or lower to remove water.
In a specific embodiment of the invention, the water evaporation induced orientation comprises: and putting the suspension of the high-toughness collagen fiber matrix in a mould, and drying the liquid in a drying oven at the temperature of 20-50 ℃.
In a specific embodiment of the invention, the magnetically induced orientation comprises: adding magnetic nanoparticles such as iron oxide nanoparticles and/or carbon nanotubes into the suspension of the high-toughness collagen fiber matrix, and keeping the suspension at room temperature under the action of an external stable magnetic field until the suspension is completely dried. Furthermore, the strength of the magnetic field can be 0.1-1T.
The invention also provides a high-toughness collagen fiber structural material which comprises a high-toughness collagen fiber framework material and a high polymer material filled in the framework material.
In a specific embodiment of the invention, the mass ratio of the framework material to the polymer material is (7-8): 2-3.
In a specific embodiment of the present invention, the polymer material includes at least one of a natural polymer material and a synthetic polymer material.
In a specific embodiment of the present invention, the natural polymer material includes any one or more of chitosan, starch and sodium alginate.
In a specific embodiment of the present invention, the synthetic polymer material includes any one or more of an epoxy resin, a phenolic resin, an unsaturated polyester resin, an acrylic resin, and an amino resin.
The invention also provides a preparation method of any one of the high-toughness collagen fiber structural materials, which comprises the following steps:
and high-molecular polymer is filled in the high-toughness collagen fiber framework material and is subjected to hot-pressing solidification.
In a specific embodiment of the present invention, the method of filling comprises: injecting the macromolecular prepolymer into the backbone; or spraying the high molecular polymer on the framework.
In a specific embodiment of the present invention, the viscosity of the high molecular prepolymer is 10 to 8000mpa · s.
In a specific embodiment of the invention, the hot-press curing temperature is 50-150 ℃, the hot-press curing pressure is 4-50 MPa, and the hot-press curing time is 2-48 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, collagen fibers are used as raw materials, and the complexation of phenolic hydroxyl groups on tannin modified collagen fibers and metal ions in inorganic minerals is utilized to provide crystal growth sites, so that inorganic mineral crystals can uniformly grow on the collagen fibers;
(2) according to the invention, the orientation of the high-strength and high-toughness collagen fiber matrix is regulated to obtain the collagen fiber skeleton with a laminated structure, and a small amount of high polymer is added to prepare a corresponding structural material with light weight, high strength and toughness;
(3) the structural material of the invention takes collagen fiber as a main material and high molecular polymer as an auxiliary material, thereby ensuring the sustainability and the reproducibility of the material and meeting the requirements of green low-carbon economic development.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a physical diagram and an SEM diagram of a high-toughness collagen fiber scaffold material provided in an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
A high strength and toughness collagen fiber matrix comprising tannin modified collagen fibers and inorganic mineral crystals grown in situ on the tannin modified collagen fibers.
In a specific embodiment of the present invention, the inorganic mineral crystals include any one or more of aragonite crystals, calcium phosphate crystals and kaolinite crystals.
The nacreous layer produced in mollusk shells attracts widespread attention because of its excellent properties of high hardness, high strength and high toughness. Due to the effect of the aragonite crystals in the nacreous layer assembling on the macromolecular structure of the organic matrix and forming mineral bridges between the inorganic layers, the aragonite flakes and the organic layers are alternately stacked with a unique "brick-mortar" microstructure that gives it an order of magnitude higher fracture toughness than the fracture toughness of pure aragonite crystals. The simulation of the microstructure of the pearl layer is an effective strategy for designing and preparing the high-toughness material.
The collagen fiber is a natural polymer material with wide sources, mainly comes from skins of livestock animals such as cattle, sheep, pigs and the like, and has the density of one sixth of that of steel. Collagen fibers are supramolecular structures formed by the self-assembly of collagen molecules. The collagen molecular structure contains various functional groups including-COOH, -OH and-NH2、-CONH2and-CONH-, in principle, many chemical reactions can be carried out. This provides a large number of in situ growth points for the inorganic crystals.
According to the invention, collagen fibers are used as raw materials, and the complexation of phenolic hydroxyl groups on tannin modified collagen fibers and inorganic matters is utilized to increase crystal growth sites, so that mineral crystals can uniformly grow on the collagen fibers, and further, the strength and the toughness are improved.
In a specific embodiment of the present invention, the content of the inorganic mineral crystals in the matrix is 30% to 70%.
In a specific embodiment of the present invention, the method for preparing the tannin modified collagen fibers comprises: mixing tannin and collagen fibers in a liquid environment with the pH value of 5-6, reacting, washing and drying.
In a particular embodiment of the invention, the tannin comprises any one or more of myricetin, cercis tannin, larch tannin, quebracho tannin and majestic tannin, preferably myricetin.
In a specific embodiment of the invention, the mass ratio of the tannin to the collagen fibers is 1: 2-4. As in the different embodiments, the ratio of tannins to collagen fibres can be 1: 2, 1: 2.5, 1: 3, 1: 3.5, 1: 4, etc.
In the specific embodiment of the invention, the aqueous solution of tannin and the aqueous dispersion of collagen fibers are mixed, and then the pH is adjusted to 5-6 by alkali for reaction. As in various embodiments, the pH of the liquid environment may be 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, and so forth.
In practice, the aqueous solution of tannin is added to the aqueous dispersion of collagen fibers and mixed. Under the condition that the pH value is 5-6, effective combination of tannin and collagen fibers can be promoted, and a plurality of tannin structures are modified on the collagen fibers.
In a specific embodiment of the invention, in the aqueous solution of tannin, the mass fraction of tannin is 10% -20%; the mass ratio of the collagen fibers to water in the aqueous dispersion of collagen fibers is 1(40 to 60), for example, 1: 50.
In practical operation, the pH can be adjusted to 5-6 by using an aqueous solution of sodium bicarbonate, but the pH is not limited to the above, and the pH can be adjusted by using a conventional alkali.
In a specific embodiment of the present invention, the mixing reaction time is 1 to 10 hours, preferably 2 to 8 hours.
In a specific embodiment of the invention, the washing comprises: and (3) carrying out solid-liquid separation on the materials after the mixing reaction, collecting the solid, and washing the solid by adopting ethanol. Further, the washing is repeated for 1-3 times. The solid was washed with ethanol to remove unreacted tannin.
In a specific embodiment of the present invention, the drying conditions include: drying for 10-30 h at 60-90 ℃.
In one embodiment of the present invention, the collagen fibers are prepared mainly from waste leather scraps after pretreatment. Further, the waste leather scrap includes metal tanned waste leather scrap. Wherein the waste leather shavings include, but are not limited to, blue leather shavings. The waste leather scraps are used as raw materials, the source is wide, the cost is low, and the resource utilization of the tanning solid waste can be realized.
In a specific embodiment of the present invention, the pre-treatment comprises: the waste leather scraps are dehydrated and crushed. Further, the preprocessing comprises: washing the waste leather scraps with water, adjusting the pH value, washing with water, soaking in ethanol, filtering, drying and crushing.
In practical practice, the dehydration manner includes any one or more of natural drying, heat drying, ethanol dehydration, freeze drying and vacuum drying.
In a preferred embodiment of the present invention, the collagen fibers after the pulverization have a particle size of 40 to 500 mesh, preferably 40 to 100 mesh.
The invention also provides a preparation method of any one of the high-toughness collagen fiber matrixes, which comprises the following steps:
the tannin modified collagen fibers and calcium carbonate and/or calcium chloride and/or kaolinite are in a solution system, and inorganic mineral crystals are grown on the tannin modified collagen fibers in situ.
In a particular embodiment of the invention, when growing an aragonite crystal: and heating the tannin modified collagen fibers and calcium carbonate in a solution system at 45-55 ℃ to enable inorganic mineral crystals to grow on the tannin modified collagen fibers in situ. Further, the time of the heating treatment is 24-60 hours.
As in the different embodiments, the temperature of the heat treatment can be 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃ and so on.
In a specific embodiment of the present invention, the time of the heat treatment is 24 to 60 hours.
As in the different embodiments, the time of the heat treatment may be 24h, 28h, 32h, 36h, 42h, 48h, 54h, 60h, and the like.
In the specific embodiment of the invention, the heat treatment is carried out for 48 +/-2 h at the temperature of 51 +/-1 ℃.
In a particular embodiment of the invention, when growing an aragonite crystal: besides calcium carbonate, the solution also comprises NaCl and Na2SO4、NaHCO3、MgCl2·6H2O、CaCl2And KCl. Further, the pH value of the tannin modified collagen fibers is adjusted to 7-9 in advance.
Further, when growing aragonite crystals: in the solution system, NaCl and Na2SO4、NaHCO3、MgCl2·6H2O、CaCl2And the concentration of KCl is respectively 3.8-4.2 g/L, 0.08-0.12 g/L, 0.28-0.32 g/L and 0.18-0.22 g/L.
In actual operation, the tannin modified collagen fibers can be pre-dispersed in water, the pH is adjusted to 7-9, and then calcium carbonate, NaCl and Na are added in proportion2SO4、NaHCO3、MgCl2·6H2O、CaCl2And KCl to obtain a suspension system, and heating to grow aragonite crystals on the tannin modified collagen fibers in situ.
In a specific embodiment of the present invention, the mass ratio of the tannin-modified collagen fibers to the calcium carbonate is 1: 3 (1: 3), preferably 1: 1.5 to 2.5, and more preferably 1: 2. In various embodiments, the mass ratio of the tannin-modified collagen fibers to calcium carbonate can be 1: 1.2, 1: 1.4, 1: 1.6, 1: 1.8, 1: 2, 1: 2.2, 1: 2.4, 1: 2.6, 1: 2.8, 1: 3, and the like.
In a specific embodiment of the invention, the dispersion concentration of the calcium carbonate in the solution system is 8-12 g/L, preferably 9-11 g/L, and more preferably 10 g/L.
In a specific embodiment of the present invention, when growing calcium phosphate crystals: and stirring the tannin modified collagen fibers and calcium chloride in a solution system at the temperature of 1-20 ℃ to enable inorganic mineral crystals to grow on the tannin modified collagen fibers in situ. Further, the stirring time is 60-120 min; the stirring speed is 800-1200 r/min.
In the inventionIn a specific embodiment, when growing calcium phosphate crystals: besides calcium chloride, the solution also comprises KH2PO4And Na2HPO4·12H2And O. Further, the pH value of the tannin modified collagen fibers is adjusted to 7-9 in advance.
Further, when growing calcium phosphate crystals: in the solution system, KH2PO4And Na2HPO4·12H2The concentration of O is 1.5-2.0 g/L and 15-18 g/L respectively.
In a specific embodiment of the present invention, when growing calcium phosphate crystals: the mass ratio of the tannin modified collagen fibers to the calcium chloride is 1: 1-2; the concentration of the calcium chloride in the solution system is 5-10 g/L.
In a particular embodiment of the invention, when growing kaolinite crystals: and in a solution system, regulating the pH value of a mixed system to 8.5-9.5, and heating at 40-70 ℃ to enable inorganic mineral crystals to grow on the tannin modified collagen fibers in situ. Further, the pH value of the mixed system is adjusted to 8.5-9.5 by adopting a sodium hydroxide aqueous solution, and for example, the sodium hydroxide aqueous solution can be 1 mol/L.
In a specific embodiment of the invention, when the kaolinite crystal grows, the mass ratio of the tannin modified collagen fibers to the kaolinite is 1: 1-3; the concentration of the kaolinite in the solution system is 4-13 g/L.
The invention also provides a high-toughness collagen fiber framework material which is mainly obtained by performing orientation control treatment on any one of the high-toughness collagen fiber matrixes.
In a specific embodiment of the present invention, the orientation regulation includes any one or more of a freezing orientation, a water evaporation induced orientation, and a magnetic induced orientation.
In a specific embodiment of the invention, the frozen orientation comprises: and the high-strength and high-toughness collagen fiber matrix is immersed in a system at the temperature of-60 to-90 ℃ in a mould at the speed of 0.5 to 1.5cm/min and is kept for 5 to 20 min.
As in various embodiments, the speed at which the mold is immersed can be 0.5cm/min, 0.6cm/min, 0.7cm/min, 0.8cm/min, 0.9cm/min, 1cm/min, 1.1cm/min, 1.2cm/min, 1.3cm/min, 1.4cm/min, 1.5cm/min, and the like.
In a specific embodiment of the invention, the system may be liquid nitrogen refrigerated ethanol.
As in the different embodiments, the temperature of the ethanol may be-60 deg.C, -65 deg.C, -70 deg.C, -75 deg.C, -80 deg.C, -85 deg.C, -90 deg.C, and so forth. In actual practice, the system temperature is maintained constant during the immersion.
In actual operation, the whole mould is immersed in the system and then kept for 5-20 min. As in the different embodiments, the holding time may be 5min, 10min, 15min, 20min, and so on.
In practice, the frozen oriented frozen sample is freeze-dried under conventional freeze-drying conditions, for example, under an environment of a vacuum degree of 0.1Pa or less at a temperature of-20 ℃ or less, to remove water.
The invention adopts a freezing orientation technology, the tannin modified collagen fiber matrix suspension with inorganic mineral crystals grown in situ is placed in a temperature field for cooling, a solvent (usually water) is gradually solidified along the temperature gradient along with the reduction of the temperature, an ice crystal column generated by solidification extrudes, discharges and embeds collagen fibers between the ice crystal columns, and the ice crystals are removed through freezing drying to obtain the corresponding framework material.
In a specific embodiment of the invention, the water evaporation induced orientation comprises: and (3) keeping the high-strength and high-toughness collagen fiber matrix in a mold at the temperature of 20-50 ℃ until the matrix is dried. Specifically, the mold can be placed in an oven at 20-50 ℃ until the liquid is dried.
In a specific embodiment of the invention, the magnetically induced orientation comprises: the high-strength and high-toughness collagen fiber matrix is mixed with the magnetic nanoparticles, and is placed at room temperature under the action of an external magnetic field until the collagen fiber matrix is completely dried. Specifically, the magnetic nanoparticles include iron oxide nanoparticles and/or carbon nanotubes and the like. Furthermore, the strength of the magnetic field can be 0.1-1T.
The invention also provides a high-toughness collagen fiber structural material which comprises a high-toughness collagen fiber framework material and a high polymer material filled in the framework material.
In a specific embodiment of the invention, the mass ratio of the framework material to the polymer material is (7-8): 2-3.
In the structural material, the ratio of the high polymer material is 20-30%, the ratio of the framework material is 70-80%, the collagen fiber framework material is used as the main material, the high polymer material is used as the auxiliary material, the dosage of the biological source material is increased, the sustainability and the reproducibility of the material are ensured, and the strength and the toughness can be improved at the same time.
In a specific embodiment of the present invention, the polymer material includes at least one of a natural polymer material and a synthetic polymer material.
In a specific embodiment of the present invention, the natural polymer material includes any one or more of chitosan, starch and sodium alginate.
In a specific embodiment of the present invention, the synthetic polymer material includes any one or more of an epoxy resin, a phenolic resin, an unsaturated polyester resin, an acrylic resin, and an amino resin.
Further, the acrylic resin includes, but is not limited to, PMMA resin, and the amino resin includes, but is not limited to, urea resin.
The invention also provides a preparation method of any one of the high-toughness collagen fiber structural materials, which comprises the following steps:
and high-molecular polymer is filled in the high-toughness collagen fiber framework material and is subjected to hot-pressing solidification.
In a specific embodiment of the present invention, the method of filling comprises: injecting the macromolecular prepolymer into the backbone; or spraying the high molecular polymer on the framework. In practice, the prepolymer of the macromolecule is injected into the backbone at a temperature below the curing temperature.
In a specific embodiment of the present invention, the viscosity of the polymer prepolymer is 10 to 8000mpa · s.
As in the different embodiments, the viscosity of the high molecular prepolymer may be 10 mPa.s, 50 mPa.s, 100 mPa.s, 200 mPa.s, 300 mPa.s, 400 mPa.s, 500 mPa.s, 600 mPa.s, 700 mPa.s, 800 mPa.s, 900 mPa.s, 1000 mPa.s, 1100 mPa.s, 1200 mPa.s, 1300 mPa.s, 1400 mPa.s, 1500 mPa.s, 1600 mPa.s, 1700 mPa.s, 1800 mPa.s, 1900 mPa.s, 2000 mPa.s, or the like. By adopting the prepolymer with the viscosity, the prepolymer can be fully filled in the framework material, so that the problems of uneven filling caused by overlarge viscosity and poor fluidity and the problems of too small viscosity, too good mobile phase and incapability of being filled and remained in the framework material are avoided.
In actual operation, the high molecular polymer can be prepared into a solution state and the like, and the high molecular polymer is sprayed on the framework by adopting a conventional spraying mode. The concentration of the solution is not limited, the spraying process can be realized, and the high molecular polymer can be uniformly sprayed on the framework.
In actual operation, the temperature of the hot-pressing curing can be adjusted according to actual requirements, so as to ensure that the high-molecular prepolymer is cured, for example, the temperature reaches the initiation temperature of the initiator, can initiate free radical polymerization, or the temperature reaches the temperature at which the prepolymer and the curing agent can react and cure, and the like.
In one embodiment of the invention, the hot-press curing temperature is 50-150 ℃, the hot-press curing pressure is 4-50 MPa, and the hot-press curing time is 2-48 h.
In actual operation, the filled material can be placed in a steel die, hot pressing is carried out at 90-110 ℃, constant pressure of 4-6 MPa is applied for 5-24 hours, and hot pressing solidification is completed.
And the filled material can be preheated and pressed for 5-24 hours at 50-70 ℃ and 4-6 MPa, and then hot-pressed for 20-24 hours at 75-85 ℃ and 20-30 MPa. Further, the skeleton may be cut in advance, a high molecular polymer may be sprayed on the surface of the skeleton, and then the material sprayed with the high molecular polymer may be stacked and laminated, and then the pre-heat press treatment and the heat press treatment may be performed.
The collagen fibers used in the following examples can be prepared from, but are not limited to, blue shavings by the following methods:
adding blue leather scraps (waste materials of leather factories) into deionized water, adjusting the pH value to 6 by using 1mol/L sodium bicarbonate aqueous solution, filtering, dehydrating by using ethanol, recovering the ethanol, cooling by using liquid nitrogen, grinding by using an ultracentrifugal pulverizer, and sieving by using a 40-mesh screen to obtain the collagen fiber.
Example 1
The embodiment provides a preparation method of a high-toughness collagen fiber matrix, which comprises the following steps:
(1) preparation of tannin modified collagen fiber
Dissolving 100g of myricetin in 500g of deionized water, and stirring until the myricetin is completely dissolved to obtain a myricetin aqueous solution for later use;
placing 300g collagen fiber in a beaker, adding 15kg deionized water, stirring, adding the prepared myricetin water solution when the collagen fiber is uniformly dispersed in water, and adding 0.1mol/L NaHCO3Adjusting the pH value of the solution to 5.4-5.8, keeping the solution stable, mechanically stirring for 5 hours, filtering by using a Buchner funnel, washing the reacted materials by using absolute ethyl alcohol, repeating for 3 times, and removing unreacted myricetin; drying at 80 + -2 deg.C for 24 hr to obtain myricetin modified collagen fiber.
(2) Preparation of high-strength and high-toughness collagen fiber matrix
Adding 10g of myricetin modified collagen fiber into 2L of water, adjusting the pH to 7.8-8.2, and adding CaCO3、NaCl、Na2SO4、NaHCO3、MgCl2·6H2O、CaCl2And KCl with respective concentration regulated to 10 g.L-1、4g·L-1、0.1g·L-1、0.3g·L-1、0.3g·L-1、0.3g·L-1、0.2g·L-1Obtaining suspension;
and (3) heating the suspension at 51 ℃ for 48h to grow aragonite crystals on the tannin modified collagen fibers in situ, and removing the supernatant to obtain the high-strength and high-toughness collagen fiber matrix.
Example 2
The embodiment provides a preparation method of a high-toughness collagen fiber matrix, which comprises the following steps:
(1) preparation of tannin modified collagen fiber
The same as in example 1.
(2) Preparation of high-strength and high-toughness collagen fiber matrix
Adding 12g of CaCl2Dissolving in 0.4L deionized water to obtain CaCl2An aqueous solution; adding 10g of myricetin modified collagen fiber into 1.4L of water, adjusting the pH value to 7.8-8.2, and adding 3.3g of KH2PO4And 30.384g Na2HPO4·12H2O, obtaining a suspension containing collagen fibers; adding CaCl2Placing the aqueous solution and the suspension containing collagen fibers in a water bath at 2 deg.C for 30min, and adding CaCl2Pouring the water solution into the suspension containing the collagen fiber, and stirring for about 90min at 1000r/min to obtain the high-strength and high-toughness collagen fiber matrix with the calcium phosphate crystal growing.
Example 3
This example refers to the preparation of the high tenacity collagen fiber matrix of example 1, with the only differences being: in the step (2), the dosage of the myricetin modified collagen fiber is 20 g.
Example 4
This example refers to the preparation of the high tenacity collagen fiber matrix of example 1, with the only differences being: in the step (2), the dosage of the myricetin modified collagen fiber is 7 g.
Example 5
This example refers to the preparation of the high tenacity collagen fiber matrix of example 1, with the only differences being: in step (2), the suspension was heat treated at 45 ℃ for 48 h.
Example 6
This example refers to the preparation of the high tenacity collagen fiber matrix of example 1, with the only differences being: in step (2), the suspension was heat treated at 55 ℃ for 48 h.
Examples 7 to 11
The embodiment provides a preparation method of a high-toughness collagen fiber framework material, which comprises the following steps:
pouring the high-strength and high-toughness collagen fiber matrix into a polydimethylsiloxane mold, slowly putting the mold into ethanol refrigerated by liquid nitrogen at the speed of 1cm/min, keeping the temperature of the ethanol constant at-75 ℃, and freezing for 10 min;
then the frozen sample is subjected to freeze drying treatment to remove water; wherein, the conditions of the freeze drying treatment comprise: freeze drying at-35 deg.C under 0.1kPa for 72 h.
The high-toughness collagen fiber scaffold materials of examples 7 to 11 were prepared from the high-toughness collagen fiber matrices of examples 1 and 3 to 6, respectively.
Example 12
The embodiment provides a preparation method of a high-toughness collagen fiber framework material, which comprises the following steps:
pouring the high-strength and high-toughness collagen fiber matrix obtained in the example 2 into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold into an oven at the temperature of 30 ℃, performing water evaporation induced self-assembly, and obtaining a dry pearl-like layer film with calcium phosphate crystals grown after about 24 hours.
Examples 13 to 17
The embodiment provides a preparation method of a high-toughness collagen fiber structure material, which comprises the following steps:
(1) adding 0.03g of initiator AIBN to 3g of Methyl Methacrylate (MMA) to obtain a mixture, mixing the mixture with toluene at a mass ratio of 1: 2, and heating at 70 deg.C and N2Heating for 1min under the atmosphere to complete the first prepolymerization reaction; a second free-radical polymerization step was then carried out with a further addition of 0.5% by weight of AIBN, based on the mass of the initial MMA, to give a prepolymer.
(2) Injecting the prepolymer obtained in the step (1) into a high-strength and high-toughness collagen fiber framework material at the temperature of 50 ℃ until the framework material is completely impregnated, then placing the framework material into a steel die, carrying out a hot-pressing process at the temperature of 100 ℃, and applying a constant pressure of 5MPa for 2 hours to complete solidification, thereby obtaining the high-strength and high-toughness collagen fiber structural material;
the mass ratio of the injected prepolymer to the high-strength and high-toughness collagen fiber framework material is 2: 8.
The high-toughness collagen fiber skeleton materials used in the high-toughness collagen fiber structural materials of examples 13 to 17 were the high-toughness collagen fiber skeleton materials of examples 7 to 11, respectively.
Example 18
The embodiment provides a preparation method of a high-toughness collagen fiber structural material, which comprises the following steps:
(1) dissolving chitosan powder in an acetic acid solution with the mass fraction of 1% to obtain a chitosan solution with the mass fraction of 1 wt.%.
(2) Cutting the nacreous layer-imitated film obtained in example 12 into pieces with the same size, and spraying a layer of chitosan solution on the surface of each piece; the mass ratio of the chitosan to the collagen fiber skeleton is 1: 30. the individual chips were then stacked and laminated and pre-pressed at 60 ℃ for 12h with 5 MPa.
(3) Then immerging the massive material obtained after prepressing into CaCl2Aqueous solution (1mol L)-1) Neutralizing for 2 hours, and then washing for 3 times by using deionized water; then applying 25MPa pressure at 80 ℃ and keeping for 24h to prepare the high-strength and high-toughness collagen fiber structural material.
Example 19
The embodiment provides a preparation method of a high-toughness collagen fiber structure material, which comprises the following steps:
(1) 3g of phenolic resin (type: E51) was taken, and 0.06g of a curing agent (type: 731) was added to obtain a mixture.
(2) Injecting the mixture obtained in the step (1) into the high-strength and high-toughness collagen fiber framework material obtained in the embodiment 7 at the temperature of 50 ℃ until the framework material is completely impregnated, then placing the framework material into a steel die, carrying out a hot-pressing process at the temperature of 100 ℃, and applying a constant pressure of 10MPa for 4 hours to finish curing to obtain the high-strength and high-toughness collagen fiber structural material; wherein, the mass ratio of the injected mixture to the high-strength and high-toughness collagen fiber framework material is 1: 8.
Comparative example 1
Comparative example 1 provides a method of preparing a composite material comprising the steps of:
tannin-modified collagen fibers (containing no aragonite crystals, step (1) of preparation reference example 1) were blended with the prepolymer, placed in a steel mold, and then subjected to hot press curing to obtain a composite material. Wherein the prepolymer and the thermocompression curing are the same as those described in example 13; the mass ratio of the collagen fibers to the prepolymer is 8: 2.
Comparative example 2
The composite material of comparative example 2 is referred to comparative example 1 except that the collagen fiber of comparative example 1 is replaced with the myricetin-modified collagen fiber of example 1.
Comparative example 3
The composite material of comparative example 3 is referred to comparative example 1 except that the tannin-modified collagen fibers of comparative example 1 are replaced with aragonite crystals; and blending the aragonite crystal and the prepolymer, placing the mixture in a steel die, and then performing hot-pressing curing to obtain the composite material. The mass ratio of aragonite crystals to prepolymer was 5: 3.
Experimental example 1
Fig. 1 is a physical diagram and an SEM diagram of a high-toughness collagen fiber scaffold material provided in example 6 of the present invention. As can be seen from the figure, in the framework material of the present invention, tannin-modified collagen fibers with aragonite crystals grown in situ form parallel layers.
Experimental example 2
To illustrate the differences in strength and toughness of the materials of the different examples and comparative examples, the strength and toughness of the materials of examples 13, 15, 17-19 and comparative examples 1-3 were tested according to ASTM D7264/D7264M-2015, and the test results are shown in Table 1.
Table 1 strength and modulus test results for different materials
Figure BDA0003169255370000181
Figure BDA0003169255370000191
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (12)

1. The high-strength and high-toughness collagen fiber matrix is characterized by comprising tannin modified collagen fibers and inorganic mineral crystals growing on the tannin modified collagen fibers in situ;
the inorganic mineral crystals comprise any one or two of aragonite crystals and kaolinite crystals;
the preparation method of the high-strength and high-toughness collagen fiber matrix comprises the following steps:
in a solution system, the tannin modified collagen fibers and calcium carbonate and/or kaolinite enable inorganic mineral crystals to grow on the tannin modified collagen fibers in situ;
when the aragonite crystal grows, heating the mixed system at 45-55 ℃ to enable an inorganic mineral crystal to grow on the tannin modified collagen fiber in situ, wherein the heating time is 24-60 hours;
or when growing the kaolinite crystal, adjusting the pH value of the mixed system to 8.5-9.5, and heating at 40-70 ℃ to enable the inorganic mineral crystal to grow on the tannin modified collagen fiber in situ; when growing the kaolinite crystal, heating for 2-5 h;
the mass ratio of the tannin modified collagen fibers to the calcium carbonate is 1: 1-3;
the dispersion concentration of the calcium carbonate in the solution system is 8-12 g/L;
or the mass ratio of the tannin modified collagen fibers to the kaolinite is 1: 1-3;
the concentration of the kaolinite in the solution system is 4-13 g/L.
2. The high strength and toughness collagen fiber matrix as claimed in claim 1, wherein the content of said inorganic mineral crystal in said matrix is 30-70%.
3. The high-toughness collagen fiber matrix as claimed in claim 1, wherein the preparation method of the tannin-modified collagen fiber comprises: mixing tannin and collagen fibers in a liquid environment with the pH value of 5-6, reacting, washing and drying.
4. The high-toughness collagen fiber skeleton material is characterized in that the high-toughness collagen fiber skeleton material is mainly obtained by performing orientation control treatment on the high-toughness collagen fiber matrix according to claim 1 or 2.
5. The high-toughness collagen fiber skeleton material according to claim 4, wherein the orientation control treatment comprises any one or more of a freezing orientation, a water evaporation induced orientation and a magnetic induced orientation;
the frozen orientation comprises: immersing the high-strength and high-toughness collagen fiber matrix in a system at-60 to-90 ℃ at a speed of 0.5 to 1.5cm/min in a mold, and keeping for 5 to 20 min;
the water evaporation induced orientation comprises: the high-strength and high-toughness collagen fiber matrix is placed in a mold and kept at the temperature of 20-50 ℃ until being dried;
the magnetically induced orientation comprises: the high-strength and high-toughness collagen fiber matrix is mixed with the magnetic nanoparticles and kept at room temperature under the action of an external magnetic field until the collagen fiber matrix is completely dried.
6. The high-toughness collagen fiber structural material is characterized by comprising the high-toughness collagen fiber framework material as defined in claim 4 or 5 and a polymer material filled in the framework material.
7. The high strength and toughness collagen fiber structural material according to claim 6, wherein the mass ratio of the framework material to the polymer material is (7-8): 2-3.
8. The high strength and toughness collagen fiber structure material according to claim 6, wherein said polymer material comprises at least one of natural polymer material and synthetic polymer material.
9. The preparation method of the high-toughness collagen fiber structural material as claimed in any one of claims 6 to 8, which is characterized by comprising the following steps: and high-molecular polymer is filled in the high-toughness collagen fiber framework material and is subjected to hot-pressing solidification.
10. The method for preparing the high-toughness collagen fiber structural material according to claim 9, wherein the filling method comprises: injecting a prepolymer of the high molecular polymer into the skeleton, or spraying the high molecular polymer onto the skeleton.
11. The method for preparing the high-toughness collagen fiber structural material according to claim 10, wherein the viscosity of the prepolymer of the high molecular polymer is 10-8000 mpa-s.
12. The preparation method of the high-strength and high-toughness collagen fiber structural material according to claim 9, wherein after the filling, the temperature of the hot-pressing curing is 50-150 ℃, the pressure of the hot-pressing curing is 4-50 MPa, and the time of the hot-pressing curing is 2-48 h.
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