CN114085485A - Preparation of modified collagen fiber and application thereof in rubber - Google Patents
Preparation of modified collagen fiber and application thereof in rubber Download PDFInfo
- Publication number
- CN114085485A CN114085485A CN202111493276.4A CN202111493276A CN114085485A CN 114085485 A CN114085485 A CN 114085485A CN 202111493276 A CN202111493276 A CN 202111493276A CN 114085485 A CN114085485 A CN 114085485A
- Authority
- CN
- China
- Prior art keywords
- acrylate
- methacrylate
- metal
- solution
- rubber
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
-
- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention belongs to the technical field of composite materials, and discloses preparation of modified collagen fibers and application of the modified collagen fibers in rubber. According to the invention, the acrylic ester metal complex is used for modifying the collagen fiber, carbonyl in the acrylic ester is coordinated with metal ions, and then the metal ions in the obtained complex are further coordinated with amino, carboxyl and hydroxyl on the collagen fiber, so that the compatibility of the complex and the collagen fiber is ensured. The aliphatic chain of the acrylate has better compatibility with rubber materials, and unsaturated double bonds in the acrylate can participate in vulcanization reaction in the vulcanization process of the composite material to form covalent crosslinking with rubber, so that the compatibility of the acrylate and the rubber is further improved. Therefore, the acrylate metal complex plays a good role of a bridge between the collagen fiber and the rubber substrate, realizes the capacity-increasing modification of a composite system, and improves the mechanical property of the material.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method of modified collagen fibers and application of the modified collagen fibers in rubber.
Background
The collagen fiber as a reproducible natural fiber has higher strength, and the mechanical property of the rubber can be effectively improved theoretically by compounding the collagen fiber with a rubber material. However, because the compatibility between collagen fibers and rubber materials is poor, in many cases, the collagen fibers added into the rubber become stress concentration points instead, and the mechanical properties of the materials are affected.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of modified collagen fibers.
The second purpose of the invention is to provide the rubber composite material, the modified collagen fiber and the rubber are compounded to realize the compatibilization modification of the composite system, and the mechanical property of the composite material is obviously improved.
The third purpose of the present invention is to provide a rubber composite material, and simultaneously realize the modification of collagen fibers and the preparation of the composite material, and the mechanical properties of the obtained composite material are obviously improved.
In order to achieve the above object, the first technical solution adopted by the present invention is:
the preparation method of the modified collagen fiber comprises the following steps:
complexing acrylate with metal ions to prepare an acrylate metal complex; and
mixing the pretreated collagen fibers with an acrylate metal complex according to a weight ratio of 1: (0.01-2) mixing and reacting;
preferably, the weight ratio of the components is 1: (0.03-0.3) mixing and reacting.
Preferably, the method for preparing the acrylate metal complex specifically comprises:
dissolving a metal salt in a solvent with the pH value of-1-5 to obtain a metal salt solution; and
mixing a metal salt solution and acrylate, and carrying out a coordination reaction under the condition that the pH value is 2-6;
preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium, zinc, copper, vanadium, nickel, palladium, osmium, tungsten and molybdenum;
more preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium and zinc;
preferably, the molar ratio of the acrylate to the metal ions in the metal salt solution is 1: (0.5 to 4);
more preferably, the molar ratio of the acrylate to the metal ions in the metal salt solution is 1: (1-2.5).
Preferably, the solvent is any one of water and/or ethanol, a mixed solution of water and acetone, a mixed solution of ethanol and acetone, and a mixed solution of water, ethanol and acetone;
the content of acetone is less than or equal to 50 percent based on the total weight of the solvent.
Preferably, the acrylate comprises any one or more of acrylic acid, methacrylic acid, maleic anhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
More preferably, the acrylate comprises any one or more of acrylic acid, methacrylic acid and maleic acid.
Preferably, the acrylate comprises any one or more of methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate and isooctyl methacrylate.
More preferably, the acrylate comprises any one or more of n-butyl acrylate, isooctyl acrylate, n-butyl methacrylate and isooctyl methacrylate.
Preferably, the method of mixing the pretreated collagen fibers with the acrylate metal complex comprises:
soaking the pretreated collagen fibers in a solution, adjusting the pH for the first time, adding the acrylate metal complex, stirring for 0.5-24 h, adjusting the pH for the second time, continuously stirring for 0.5-24 h, and filtering; and
placing the obtained filtrate in an environment at 20-120 ℃ for 2-168 hours, cleaning and drying;
wherein the first pH adjustment and the second pH adjustment are determined according to the isoelectric point and the precipitation point of the complex;
the solution is any one of water and a mixed solution of water and ethanol;
the content of ethanol in the mixed solution of water and ethanol is less than or equal to 50 percent based on the total weight of the solution;
the weight ratio of the collagen fibers to the solution is 1: (2-10);
preferably, the weight ratio of the collagen fibers to the solution is 1: (3-5).
Preferably, the method of mixing the pretreated collagen fibers with the acrylate metal complex comprises:
soaking the pretreated collagen fibers in a solution, adjusting the pH for the first time, adding the acrylate metal complex, stirring for 0.5-24 h, adjusting the pH for the second time, continuously stirring for 0.5-24 h, and filtering; and
placing the obtained filtrate in an environment at 20-120 ℃ for 2-168 hours, cleaning and drying;
wherein the first pH adjustment and the second pH adjustment are determined according to the isoelectric point and the precipitation point of the complex;
the solution is a mixed solution of water and ethanol;
based on the total weight of the solution, the content of ethanol in the mixed solution of water and ethanol is 20-50%;
the weight ratio of the collagen fibers to the solution is 1: (2-10);
preferably, the weight ratio of the collagen fibers to the solution is 1: (3-5).
Preferably, the pretreatment of the collagen fiber comprises water washing, drying and pulverization;
preferably, the crushed collagen fibers are 10-1200 meshes;
more preferably, the crushed collagen fibers are 32-250 meshes;
preferably, the raw material of the collagen fiber is selected from any one or more of leather scraps and tanned leather.
The second technical scheme adopted by the invention is that the modified collagen fiber prepared by any one of the methods is adopted.
The third technical scheme adopted by the invention is as follows:
the rubber composite material comprises the modified collagen fiber and rubber of the second technical scheme, wherein the mass ratio of the modified collagen fiber to the rubber is (1-300): 100, respectively;
preferably, the mass ratio of the modified collagen fibers to the rubber is (3-40): 100.
the fourth technical scheme adopted by the invention is as follows: the method for preparing the composite material comprises the following steps: mixing the modified collagen fiber and rubber, adding a vulcanizing agent, blending, and vulcanizing and molding.
The fifth technical scheme adopted by the invention is as follows:
the rubber composite material comprises the following components in parts by weight (1-300): (0.3-150): 100 mixed pretreated collagen fibers, acrylate metal complex, rubber;
preferably, the weight ratio (5-40): (1.5-20): 100, mixing;
wherein the acrylate metal complex is obtained by complexing acrylate and metal.
Preferably, the acrylate comprises any one of acrylic acid, methacrylic acid, maleic anhydride, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, stearic acrylate, isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, isodecyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, lauryl methacrylate, stearic methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, isooctyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate;
preferably, the acrylate comprises any one or more of acrylic acid, methacrylic acid, maleic acid, n-butyl acrylate, isooctyl acrylate, n-butyl methacrylate, lauryl methacrylate, tert-butyl methacrylate and isooctyl methacrylate;
preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium, zinc, copper, vanadium, nickel, palladium, osmium, tungsten and molybdenum;
more preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium and zinc.
The sixth technical scheme provided by the invention is as follows:
a method for preparing the rubber composite material of the fifth technical scheme, which comprises the following steps:
complexing acrylate with metal to prepare acrylate metal complex; and
mixing the pretreated collagen fiber, the acrylate metal complex and the rubber, adding a vulcanizing agent, blending, and vulcanizing and molding.
Preferably, the method of preparing the acrylate metal complex comprises:
dissolving a metal salt in a solvent with the pH value of-1-5 to obtain a metal salt solution;
mixing a metal salt solution and acrylate, and carrying out a coordination reaction under the condition that the pH value is 2-6; and
and purifying the acrylate metal complex obtained by completing the coordination reaction by using extraction, liquid separation and recrystallization means.
Preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium, zinc, copper, vanadium, nickel, palladium, osmium, tungsten and molybdenum;
more preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium and zinc;
preferably, the molar ratio of the acrylate to the metal ions in the metal salt solution is 1: (0.5 to 4);
more preferably, the molar ratio of the acrylate to the metal ions in the metal salt solution is 1: (1-2.5).
Preferably, the solvent is any one of water and/or ethanol, a mixed solution of water and acetone, a mixed solution of ethanol and acetone, and a mixed solution of water, ethanol and acetone;
the content of acetone is less than or equal to 50 percent based on the total weight of the solvent.
Preferably, the pretreatment of the collagen fiber comprises water washing, drying and pulverization;
preferably, the crushed collagen fibers are 10-1200 meshes;
more preferably, the crushed collagen fibers are 32-250 meshes;
preferably, the raw material of the collagen fiber is selected from any one or more of leather scraps and tanned leather.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the acrylic ester metal complex can be used for modifying the collagen fiber, carbonyl in the acrylic ester is utilized to coordinate with metal ions, and then the metal ions in the obtained complex are further coordinated with amino, carboxyl and hydroxyl on the collagen fiber, so that the compatibility of the complex and the collagen fiber is ensured; and mixing the modified collagen fiber with rubber and vulcanizing. The invention can also directly mix and vulcanize the acrylate metal complex, the pretreated collagen fiber and the rubber. The aliphatic chain of the acrylate has better compatibility with rubber materials, in addition, in the vulcanization process of the composite material, unsaturated double bonds in the acrylate can participate in vulcanization reaction and form covalent crosslinking with rubber, and the compatibility of the unsaturated double bonds and the rubber can be improved. Therefore, the acrylate metal complex plays a good role of a bridge between the collagen fiber and the rubber substrate, realizes the capacity-increasing modification of a composite system, and improves the mechanical property of the material.
The invention fully utilizes the complexation characteristic of the collagen fiber and combines the essence of the vulcanization reaction to realize the compatibilization, reinforcement and modification of the collagen fiber/natural rubber composite system. Compared with the traditional 'similar compatibility' modification mode, the method for realizing compatibilization modification through coordination and covalent bonding can achieve better compatibilization effect in the reaction mechanism. The mechanical property of the collagen fiber/rubber composite material obtained by modification of the invention can be comparable to that of the composite material obtained under the traditional modification conditions.
Drawings
FIG. 1 is a schematic diagram of the reaction between collagen fibers, an acrylate metal complex and rubber.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts 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.
The preparation method of the rubber composite material is divided into two methods. Firstly, modifying collagen fibers by using an acrylate metal complex to obtain modified collagen fibers; then mixing and vulcanizing the modified collagen fibers and rubber to obtain a rubber composite material; this process may be referred to as a "two-step process". The second method is that the acrylate metal complex, the collagen fiber and the rubber are directly mixed and vulcanized to obtain the rubber composite material; this process may be referred to as a "one-step process".
The first embodiment of the present invention provides a method for preparing modified collagen fibers (i.e., the first step of the "two-step method" for preparing modified collagen fibers), comprising the steps of:
preparing an acrylate metal complex; and mixing the pretreated collagen fibers with an acrylate metal complex according to a weight ratio of 1: (0.01-2) mixing and reacting.
The invention uses the acrylate metal complex to modify the collagen fiber, and uses the carbonyl in the acrylate to coordinate with metal ions and further coordinate with amino, carboxyl and hydroxyl on the collagen fiber, thereby ensuring the compatibility of the complex and the collagen fiber.
In some preferred embodiments, the pretreated collagen fibers are mixed with the acrylate metal complex in a weight ratio of 1: (0.03-0.3) mixing and reacting.
It should be noted that the raw material of the collagen fibers according to the embodiment of the present invention is selected from any one or more of leather scraps and tanned leather. Wherein, the leather scraps refer to leather making leftover wastes generated by operations such as chipping, buffing, cutting and the like in the leather making process; tanning refers to the semi-finished product in the leather production process. The tanned leather is selected from any one or more of chrome tanned leather, aldehyde tanned leather, vegetable tanned leather, non-chrome metal tanned leather, organic tanned leather, combined tanned leather and the like.
The pretreatment of the collagen fiber comprises washing, drying and crushing, and the crushed collagen fiber is 10-1200 meshes, preferably 32-250 meshes.
Wherein, the washing is to wash the collagen fiber raw material by adopting water solution containing a surfactant; removing impurities such as grease, inorganic salt and the like in the raw materials by a water washing mode; the surfactant can be any common surfactant product on the market. The drying is carried out by using a conventional drying means, and a drying mode with the drying temperature of normal temperature to 80 ℃ is preferred. The pulverization is carried out by using a general-purpose pulverization apparatus, preferably a pulverization apparatus having a force chemical activation.
In some embodiments, a method of making an acrylate metal complex comprises:
dissolving a metal salt in a solvent with the pH value of-1-5 to obtain a metal salt solution; mixing the metal salt solution and the acrylate to perform a coordination reaction under the condition that the pH value is 2-6;
wherein the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium, zinc, copper, vanadium, nickel, palladium, osmium, tungsten and molybdenum; more preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium and zinc;
the molar ratio of the acrylate to the metal ions in the metal salt solution is 1: (0.5 to 4); preferably, the molar ratio of the acrylate to the metal ions in the metal salt solution is 1: (1-2.5).
The solvent is any one of water and/or ethanol, a mixed solution of water and acetone, a mixed solution of ethanol and acetone, and a mixed solution of water, ethanol and acetone; for example, the solvent may be water, ethanol, a mixture of water and acetone, a mixture of ethanol and acetone, or a mixture of water, ethanol and acetone, and when acetone is present in the solvent, the content of acetone is 50% or less based on the total weight of the solvent.
In some embodiments, a method of mixing pretreated collagen fibers with an acrylate metal complex comprises: soaking the pretreated collagen fibers in a solution, adjusting the pH for the first time, adding the acrylate metal complex, stirring for 0.5-24 h, adjusting the pH for the second time, continuously stirring for 0.5-24 h, and filtering; and placing the obtained filtrate in an environment at 20-120 ℃ for 2-168 hours, cleaning and drying. Wherein the weight ratio of the collagen fibers to the solution is 1: (2-10); preferably 1: (3-5).
The first pH adjustment is performed to avoid direct precipitation of the complex, and the second pH adjustment is performed to complete the complexation reaction. Therefore, the specific values of the first adjustment of pH and the second adjustment of pH need to be determined depending on the isoelectric point and precipitation point of the complex.
For pH adjustment with acids or bases, the acids or bases used include protic acids, lewis acids, protic bases, and lewis bases; more preferably, the acid or base used comprises magnesium oxide, formic acid and its aqueous solution, acetic acid and its aqueous solution, sodium carbonate and its aqueous solution, sodium bicarbonate and its aqueous solution, sodium hydroxide and its aqueous solution, ammonia, triethylamine.
It should be further noted that, when the acrylate is any one or more of acrylic acid, methacrylic acid, maleic anhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate, the solution in which the collagen fiber is soaked is any one of water, and a mixed solution of water and ethanol; for example, the water may be used, or the mixed solution of water and ethanol may be used, and the content of ethanol in the mixed solution of water and ethanol is 50% or less. When the acrylate is any one or more of methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate and isooctyl methacrylate, the solution for soaking the collagen fiber is a mixed solution of water and ethanol, and the content of the ethanol is 20-50%.
It should be noted that, in the actual production process, a polymerization inhibitor may be added after the acrylate metal complex and the collagen fiber are subjected to the coordination reaction. The reason is that the acrylate can be stored for a period of time for reuse after actual production, the acrylate has the possibility of self-polymerization under photo-thermal conditions during storage, double bonds in the complex are lost after self-polymerization occurs, and covalent bonds cannot be formed with rubber substrates during vulcanization, so that modification is influenced. Too much addition of inhibitor affects the subsequent vulcanization of the rubber, and too little is not enough to protect the complex. The amount of the polymerization inhibitor is generally 0.3 to 5%, preferably 0.5 to 1.5%.
The second embodiment of the invention provides a rubber composite material, which comprises the modified collagen fiber prepared by the first embodiment and rubber, wherein the mass ratio of the modified collagen fiber to the rubber is (1-300): 100, respectively; preferably, the mass ratio of the modified collagen fibers to the rubber is (3-40): 100.
the rubber composite material is prepared by mixing the modified collagen fiber and the rubber, adding a vulcanizing agent, and blending and molding. I.e. the second step of the "two-step process" is completed.
In a third embodiment of the invention, there is provided a rubber composite (i.e. a composite obtained by a "one-shot" process) comprising, by weight (1-300): (0.3-150): 100 mixed pretreated collagen fibers, acrylate metal complex, rubber; preferably, the weight ratio (5-40): (1.5-20): 100, and mixing. Wherein the acrylate metal complex is obtained by complexing acrylate and metal.
The preparation method of the rubber composite material is that the pretreated collagen fiber, the acrylate metal complex and the rubber are directly mixed, and then a vulcanizing agent is added for blending and forming.
In this embodiment, the raw material and pretreatment method of the collagen fiber, the raw material and production method of the acrylate metal complex are the same as those of the first embodiment. Meanwhile, in this embodiment, the acrylate complex prepared according to the first embodiment further requires removal of the solvent by recrystallization, liquid separation, rotary evaporation, or the like, before it can be blended with other raw materials.
The reaction generated in the preparation process of the rubber composite material is shown in figure 1, the collagen fiber is modified by the acrylate metal complex, and unsaturated double bonds contained in the collagen fiber can participate in the vulcanization reaction in the vulcanization process of the rubber to form copolymerization crosslinking with the rubber, so that the acrylate metal complex plays a role of a bridge between the collagen fiber and the rubber base material, the compatibilization modification of a composite system is realized, and the mechanical property of the material is improved.
In order to better understand the technical solution provided by the present invention, the following describes the method, composite material, and performance test for improving the compatibility of collagen fiber and rubber provided by the above embodiments of the present invention with a plurality of specific examples.
Some of the material information used in the embodiments of the present invention may be as follows:
non-chrome metal tanned leather is from Hebei Xinji Dongming leather Co., Ltd;
chrome tanned leather and leather scraps come from Fujian industry leather science and technology corporation, and the leather scraps are leather making corner wastes generated by slicing, grinding and cutting operations of the chrome tanned leather in the leather making process;
acrylic acid, methacrylic acid, n-butyl acrylate and isooctyl methacrylate are all analytical grade, and the manufacturer is the Aladdin chemical reagent (Shanghai) Co., Ltd;
ferric sulfate, ammonium bicarbonate, sodium hydroxide, chromium chloride, ethanol, aluminum chloride, magnesium chloride, sublimed sulfur and zinc oxide are all analytically pure, and the manufacturer is a metropolis chemical company Limited;
thermoplastic styrene butadiene rubber (SBS) manufactured by Zhongpetrochemical Balng petrochemical Co., Ltd., model YH-792(SBS 1401);
natural Rubber (NR), manufactured by Shenzhenxin synthetic rubber trade, Inc., model number Vietnam 3L;
ethylene Propylene Diene Monomer (EPDM), manufactured by the Dow chemical company, model number 4725P;
chloroprene Rubber (CR), model CR244, manufactured by shanxi rubber group ltd.
Example 1
(1) 100 parts of an acrylic acid solution (20% strength) was adjusted to pH 1.0, and then 93 parts of a pH-adjusted 1.0 aqueous iron sulfate solution (30% strength) was slowly added. Then, 30wt% of sodium hydroxide solution is used for adjusting the pH value to 2.0, and 0.2 part of hydroquinone is added and mixed evenly;
(2) selecting non-chrome metal tanned leather as a collagen fiber raw material, washing with water, drying, and crushing to 100 meshes by using a millstone type reactor with mechanochemical activation;
(3) soaking 100 parts of the collagen fibers obtained in the step (2) in 500 parts of 25 ℃ water, adjusting the pH value to 2.0, then adding 20 parts of the complex solution obtained in the step (1), stirring for 2 hours, adjusting the pH value to 4.0 by using a sodium bicarbonate solution (10%), continuing stirring for 1.5 hours, and filtering;
(4) sealing the filtrate obtained in the step (3), placing the filtrate in a drying oven at 35 ℃ for heating reaction for 60 hours, washing with water, drying, and crushing again with equipment by using common powder;
(5) and (3) uniformly mixing 100 parts of SBS, 4 parts of sulfur and 30 parts of the collagen fiber obtained in the step (4) on an open mill, and performing calendaring molding to obtain the acrylic acid metal complex modified collagen fiber/SBS composite material.
Example 2
(1) 100 parts of methacrylic acid was adjusted to pH-1 using NaOH, and 460 parts of a 0.5 chromic chloride ethanol solution (40% concentration) adjusted to pH was then slowly added. Then MgO is used for adjusting the pH value to 3.5, and 0.5 part of phenothiazine is added and mixed evenly;
(2) selecting leather scraps as a collagen fiber raw material, washing with water, drying, and crushing to 250 meshes by using a centrifugal reactor with a mechanochemical activation effect;
(3) soaking 100 parts of the collagen fibers obtained in the step (2) in 400 parts of water at 40 ℃, adjusting the pH value to 2.8, then adding 10 parts of the complex solution obtained in the step (1), stirring for 1.5h, adjusting the pH value to 4.2 by using a sodium carbonate solution (15%), continuing stirring for 0.5h, and filtering;
(4) sealing the filtrate obtained in the step (3), placing the filtrate in a 50 ℃ oven, heating for reaction for 48 hours, washing with water, drying, and crushing again with common powder;
(5) and (3) uniformly mixing 100 parts of NR, 5 parts of sulfur and 20 parts of the collagen fiber obtained in the step (4) in an internal mixer, and molding by using a press plate to obtain the acrylic acid metal complex modified collagen fiber/NR composite material.
Example 3
The difference from example 2 is that the complex obtained in step (1) is recrystallized and the preparation of the modified composite is carried out using a one-step process:
namely, 100 parts of NR, 5 parts of sulfur, 15 parts of collagen fiber and 2 parts of the complex solution obtained in example 2 (1) were mixed uniformly in an internal mixer, and then the mixture was molded with a platen to obtain an acrylic acid metal complex-modified collagen fiber/NR composite material.
Example 4
(1) 468 parts of aluminum chloride mixed solution (with the concentration of 20%) with the pH adjusted to 3.0 is added into 100 parts of n-butyl acrylate, then NaOH solution (with the concentration of 40%) is used for adjusting the pH to 3.8, 1 part of hydroquinone is added, liquid separation is carried out after uniform mixing, and oil phase solution is taken; the mixture ratio in the mixed solution is water: ethanol: acetone =30:50: 20;
(2) selecting a collagen fiber raw material as chrome tanned leather, washing, drying, and crushing to 150 meshes by using an engaged reactor with mechanochemical activation;
(3) uniformly mixing 100 parts of EPDM, 2 parts of sulfur, 10 parts of collagen fiber and 3 parts of the complex solution obtained in the step (1) in a screw extruder, and then obtaining the acrylic acid metal complex modified collagen fiber/EPAM composite material by using injection molding.
Example 5
(1) Adding 80 parts of magnesium chloride into 100 parts of isooctyl methacrylate, uniformly mixing, adding 2 parts of phenothiazine, continuously mixing, and taking an oil phase solution after liquid separation;
(2) selecting a collagen fiber raw material as chrome tanned leather, washing, drying, and crushing to 180 meshes by using an engaged reactor with mechanochemical activation;
(3) uniformly mixing 100 parts of CR, 0.5 part of zinc oxide, 5 parts of collagen fiber and 1 part of the complex solution obtained in the step (1) in an internal mixer, and vulcanizing and molding by using an air bed to obtain the acrylic acid metal complex modified collagen fiber/CR composite material.
Comparative examples 1 to 4 provide the preparation of collagen fiber/rubber composites without the addition of modifiers
Comparative example 1
Uniformly mixing 100 parts of SBS, 4 parts of sulfur and 30 parts of non-chrome metal tanning collagen fiber crushed to 100 meshes on an open mill, and calendering to obtain the collagen fiber/SBS composite material.
Comparative example 2
100 parts of NR, 5 parts of sulfur and 20 parts of leather scrap collagen fiber crushed to 250 meshes are uniformly mixed in an internal mixer, and then a pressing plate is used for molding to obtain the collagen fiber/NR composite material.
Comparative example 3
100 parts of EPDM, 2 parts of sulfur and 10 parts of chrome tanned leather collagen fiber crushed to 150 meshes are uniformly mixed in a screw extruder, and then the mixture is subjected to injection molding to obtain the collagen fiber/EPDM composite material.
Comparative example 4
100 parts of CR, 0.5 part of zinc oxide and 5 parts of chrome tanned leather collagen fiber crushed to 180 meshes are uniformly mixed in an internal mixer, and then vulcanized and molded by using an air bed to obtain the collagen fiber/CR composite material.
Comparative example 5 provides preparation of a sample of pure Natural rubber
After 100 parts of NR and 5 parts of sulfur were uniformly mixed in an internal mixer, a NR sample was obtained by molding with a press plate.
Comparative example 6 provides a conventional silane coupling agent-modified collagen fiber/NR composite
(1) Dissolving 15 parts of KH550 in 1500 parts of isopropanol-water (9: 1) mixed solvent, then adding 100 parts of leather scrap collagen fibers crushed to 250 meshes, stirring at room temperature for 6 hours, and adjusting the pH value with 0.1 mol/formic acid in the stirring process to stabilize the pH value of the suspension to 6.0-7.0; then adjusting the pH value to 4.0, continuously stirring for 2 hours at normal temperature, and filtering out;
(2) heating the filtrate obtained in the step (1) in a 120 ℃ oven for 18h, washing with 95% ethanol to remove unbound KH550, drying again, and pulverizing;
(3) mixing 100 parts of NR, 5 parts of sulfur and 20 parts of the collagen fiber obtained in the step (2) uniformly in an internal mixer, and molding the mixture by using a press plate to obtain the KH550 modified collagen fiber/NR composite material.
Experimental examples the composites were tested for mechanical properties according to ASTM D412, with the results given in the table below.
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 (17)
1. The preparation method of the modified collagen fiber is characterized by comprising the following steps:
complexing acrylate with metal ions to prepare an acrylate metal complex; and
mixing the pretreated collagen fibers with an acrylate metal complex according to a weight ratio of 1: (0.01-2) mixing and reacting;
preferably, the weight ratio of the components is 1: (0.03-0.3) mixing and reacting.
2. The method for preparing a modified collagen fiber according to claim 1, wherein the method for preparing the acrylate metal complex specifically comprises:
dissolving a metal salt in a solvent with the pH value of-1-5 to obtain a metal salt solution; and
mixing a metal salt solution and acrylate, and carrying out a coordination reaction under the condition that the pH value is 2-6;
preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium, zinc, copper, vanadium, nickel, palladium, osmium, tungsten and molybdenum;
more preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium and zinc;
preferably, the molar ratio of the acrylate to the metal ions in the metal salt solution is 1: (0.5 to 4);
more preferably, the molar ratio of the acrylate to the metal ions in the metal salt solution is 1: (1-2.5).
3. The method for producing a modified collagen fiber according to claim 2, wherein the solvent is any one of water and/or ethanol, a mixed solution of water and acetone, a mixed solution of ethanol and acetone, and a mixed solution of water, ethanol and acetone;
the content of acetone is less than or equal to 50 percent based on the total weight of the solvent.
4. The method for preparing modified collagen fiber according to any one of claims 1 to 3, wherein the acrylic acid ester comprises any one or more of acrylic acid, methacrylic acid, maleic anhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate;
preferably, the acrylate comprises any one or more of acrylic acid, methacrylic acid and maleic acid.
5. The method for preparing modified collagen fiber according to any one of claims 1 to 3, wherein the acrylic acid ester comprises any one or more of methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, isooctyl methacrylate;
preferably, the acrylate comprises any one or more of n-butyl acrylate, isooctyl acrylate, n-butyl methacrylate and isooctyl methacrylate.
6. The method for preparing modified collagen fiber according to claim 4, wherein the method of mixing the pretreated collagen fiber with the acrylate metal complex comprises:
soaking the pretreated collagen fibers in a solution, adjusting the pH for the first time, adding the acrylate metal complex, stirring for 0.5-24 h, adjusting the pH for the second time, continuously stirring for 0.5-24 h, and filtering; and
placing the obtained filtrate in an environment at 20-120 ℃ for 2-168 hours, cleaning and drying;
wherein the first pH adjustment and the second pH adjustment are determined according to the isoelectric point and the precipitation point of the complex;
the solution is any one of water and a mixed solution of water and ethanol;
the content of ethanol in the mixed solution of water and ethanol is less than or equal to 50 percent based on the total weight of the solution;
the weight ratio of the collagen fibers to the solution is 1: (2-10);
preferably, the weight ratio of the collagen fibers to the solution is 1: (3-5).
7. The method for preparing modified collagen fibers according to claim 5, wherein the method for mixing the pretreated collagen fibers with the acrylate metal complex comprises:
soaking the pretreated collagen fibers in a solution, adjusting the pH for the first time, adding the acrylate metal complex, stirring for 0.5-24 h, adjusting the pH for the second time, continuously stirring for 0.5-24 h, and filtering; and
placing the obtained filtrate in an environment at 20-120 ℃ for 2-168 hours, cleaning and drying;
wherein the first pH adjustment and the second pH adjustment are determined according to the isoelectric point and the precipitation point of the complex;
the solution is a mixed solution of water and ethanol;
based on the total weight of the solution, the content of ethanol in the mixed solution of water and ethanol is 20-50%;
the weight ratio of the collagen fibers to the solution is 1: (2-10);
preferably, the weight ratio of the collagen fibers to the solution is 1: (3-5).
8. The method for preparing modified collagen fiber according to claim 1, wherein the pretreatment of collagen fiber comprises washing with water, drying and pulverizing;
preferably, the crushed collagen fibers are 10-1200 meshes;
more preferably, the crushed collagen fibers are 32-250 meshes;
preferably, the raw material of the collagen fiber is selected from any one or more of leather scraps and tanned leather.
9. Modified collagen fibers obtained by the production method according to any one of claims 1 to 8.
10. A rubber composite material, characterized by comprising the modified collagen fibers and rubber according to claim 9, wherein the mass ratio of the modified collagen fibers to the rubber is (1-300): 100, respectively;
preferably, the mass ratio of the modified collagen fibers to the rubber is (3-40): 100.
11. a method of preparing a rubber composite as claimed in claim 10, comprising the steps of:
mixing the modified collagen fiber and rubber, adding a vulcanizing agent, blending, and vulcanizing and molding.
12. The rubber composite material is characterized by comprising the following components in parts by weight (1-300): (0.3-150): 100 mixed pretreated collagen fibers, acrylate metal complex, rubber;
preferably, the weight ratio (5-40): (1.5-20): 100, mixing;
wherein the acrylate metal complex is obtained by complexing acrylate and metal.
13. The rubber composite of claim 12, the acrylate comprises any one of acrylic acid, methacrylic acid, maleic anhydride, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, stearic acrylate, isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, isooctyl acrylate, isodecyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, lauryl methacrylate, stearic methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate;
preferably, the acrylate comprises any one or more of acrylic acid, methacrylic acid, maleic acid, n-butyl acrylate, isooctyl acrylate, n-butyl methacrylate, lauryl methacrylate, tert-butyl methacrylate and isooctyl methacrylate;
preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium, zinc, copper, vanadium, nickel, palladium, osmium, tungsten and molybdenum;
more preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium and zinc.
14. A process for preparing a rubber composite according to claim 12 or 13, comprising the steps of:
complexing acrylate with metal to prepare acrylate metal complex; and
mixing the pretreated collagen fiber, the acrylate metal complex and the rubber, adding a vulcanizing agent, blending, and vulcanizing and molding.
15. The method of claim 14, wherein the method of preparing the acrylate metal complex comprises:
dissolving a metal salt in a solvent with the pH value of-1-5 to obtain a metal salt solution;
mixing a metal salt solution and acrylate, and carrying out a coordination reaction under the condition that the pH value is 2-6; and
purifying the acrylate metal complex obtained by completing the coordination reaction by using extraction, liquid separation and recrystallization means;
preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium, zinc, copper, vanadium, nickel, palladium, osmium, tungsten and molybdenum;
more preferably, the metal comprises any one or more of chromium, zirconium, aluminum, titanium, iron, magnesium and zinc;
preferably, the molar ratio of the acrylate to the metal ions in the metal salt solution is 1: (0.5 to 4);
more preferably, the molar ratio of the acrylate to the metal ions in the metal salt solution is 1: (1-2.5).
16. The method according to claim 15, wherein the solvent is any one of water and/or ethanol, a mixed solution of water and acetone, a mixed solution of ethanol and acetone, and a mixed solution of water, ethanol and acetone;
the content of acetone is less than or equal to 50 percent based on the total weight of the solvent.
17. The method of claim 14, wherein the pretreatment of the collagen fibers comprises water washing, drying and pulverizing;
preferably, the crushed collagen fibers are 10-1200 meshes;
more preferably, the crushed collagen fibers are 32-250 meshes;
preferably, the raw material of the collagen fiber is selected from any one or more of leather scraps and tanned leather.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111493276.4A CN114085485B (en) | 2021-12-08 | 2021-12-08 | Preparation of modified collagen fiber and application thereof in rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111493276.4A CN114085485B (en) | 2021-12-08 | 2021-12-08 | Preparation of modified collagen fiber and application thereof in rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114085485A true CN114085485A (en) | 2022-02-25 |
| CN114085485B CN114085485B (en) | 2022-12-13 |
Family
ID=80306909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111493276.4A Active CN114085485B (en) | 2021-12-08 | 2021-12-08 | Preparation of modified collagen fiber and application thereof in rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114085485B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115505183A (en) * | 2022-10-27 | 2022-12-23 | 温州鞋革产业研究院 | Collagen fiber-based composite material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420949A (en) * | 1999-07-14 | 2003-05-28 | 钟渊化学工业株式会社 | Regenerated collagen fiber with excellent heat resistance |
| CN104788868A (en) * | 2015-04-24 | 2015-07-22 | 福建师范大学泉港石化研究院 | Method for preparing rubber from metal salt containing concentration water through coordination crosslinking |
| CN106117881A (en) * | 2016-07-05 | 2016-11-16 | 中山大学惠州研究院 | A kind of artificial leather 3D printed material and preparation method thereof |
| CN110229529A (en) * | 2019-06-27 | 2019-09-13 | 四川大学 | The method of the preparation method of materials with hide glue fibril based flameproofing and flame-retardant modified high polymer |
| CN110258111A (en) * | 2019-06-27 | 2019-09-20 | 四川大学 | The preparation method of modified abandoned collagenous fibres and its application in raising rubber mechanical property and self-cleaning performance |
| CN110957058A (en) * | 2019-12-25 | 2020-04-03 | 陕西科技大学 | Conductive leather and preparation method thereof |
| US20210181186A1 (en) * | 2017-11-03 | 2021-06-17 | Fluidigm Canada Inc. | Reagents and methods for elemental imaging mass spectrometry of biological samples |
-
2021
- 2021-12-08 CN CN202111493276.4A patent/CN114085485B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420949A (en) * | 1999-07-14 | 2003-05-28 | 钟渊化学工业株式会社 | Regenerated collagen fiber with excellent heat resistance |
| US6713537B1 (en) * | 1999-07-14 | 2004-03-30 | Kaneka Corporation | Regenerated collagen fiber with excellent heat resistance |
| CN104788868A (en) * | 2015-04-24 | 2015-07-22 | 福建师范大学泉港石化研究院 | Method for preparing rubber from metal salt containing concentration water through coordination crosslinking |
| CN106117881A (en) * | 2016-07-05 | 2016-11-16 | 中山大学惠州研究院 | A kind of artificial leather 3D printed material and preparation method thereof |
| US20210181186A1 (en) * | 2017-11-03 | 2021-06-17 | Fluidigm Canada Inc. | Reagents and methods for elemental imaging mass spectrometry of biological samples |
| CN110229529A (en) * | 2019-06-27 | 2019-09-13 | 四川大学 | The method of the preparation method of materials with hide glue fibril based flameproofing and flame-retardant modified high polymer |
| CN110258111A (en) * | 2019-06-27 | 2019-09-20 | 四川大学 | The preparation method of modified abandoned collagenous fibres and its application in raising rubber mechanical property and self-cleaning performance |
| CN110957058A (en) * | 2019-12-25 | 2020-04-03 | 陕西科技大学 | Conductive leather and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| LI SHUANGYANG等: "Natural Rubber-Based Elastomer Reinforced by Chemically Modified Multiscale Leather Collagen Fibers with Excellent Toughness", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
| 张颖鑫等: "皮胶原纤维/聚合物复合材料研究进展", 《皮革科学与工程》 * |
| 景松岩等: "《毛皮学》", 31 December 1993, 东北林业大学出版社 * |
| 李升等: "ART丙烯酸树脂鞣剂对铬鞣革改性机理研究", 《中国皮革》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115505183A (en) * | 2022-10-27 | 2022-12-23 | 温州鞋革产业研究院 | Collagen fiber-based composite material and preparation method and application thereof |
| CN115505183B (en) * | 2022-10-27 | 2024-01-19 | 温州鞋革产业研究院 | Collagen fiber-based composite material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114085485B (en) | 2022-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114085485B (en) | Preparation of modified collagen fiber and application thereof in rubber | |
| CN102363820B (en) | Reutilization method of chromium-containing leather production sludge | |
| CN102040766A (en) | Low-odor scratch-resistant ore filled polypropylene compound and preparation method thereof | |
| CA3028368C (en) | A bioplastic composition comprising biomass as a component and a production process | |
| JP2002060608A (en) | Thermosetting resin composition for vehicle body outer panel | |
| CN104789715A (en) | Salt-free, pickling-free, short-process and little-chromium tanning method | |
| CN107903505A (en) | A kind of method for compounding nucleator tenacity-increased profax | |
| CN110229529B (en) | Preparation method of collagen fiber-based flame retardant and method for flame-retarding modified high polymer | |
| CN100475827C (en) | Method for preparing composite metal salt adhesion improver | |
| Lu et al. | The reaction of vegetable tannin-aldehyde-collagen: A further understanding of vegetable tannin-aldehyde combination tannage | |
| CN109294245B (en) | Method for preparing protein plastic by using chromium-containing waste leather scraps | |
| CN112176128B (en) | Method for synthesizing ZnZr-MOF-LDH nano tanning agent based on template-oriented method | |
| CN103665553A (en) | Modified polypropylene material for automobile ceiling and preparation method thereof | |
| CN102295802A (en) | High-toughness and high-strength polypropylene composition, and preparation method thereof | |
| CN109852742B (en) | Application method of modified collagen polypeptide tanning filler | |
| CN103665554A (en) | Heat-resistant polypropylene material for automobile interior trim parts and preparation method thereof | |
| CN111424437B (en) | Fiber leather and preparation method thereof | |
| CN107349918A (en) | A kind of preparation method of diatomite aids,filter | |
| CN108219337B (en) | Waste high impact polystyrene composite material modified by ceramic waste residue and preparation method thereof | |
| CN106147189A (en) | A kind of plastic material and preparation method thereof | |
| AU2020103418A4 (en) | The Preparation Method of an Electroplating Grade ABS/TPU Alloy Material with High Fluidity | |
| CN104311936A (en) | High-elasticity low-hardness synthetic rubber for color selector and preparation method thereof | |
| TWI419976B (en) | Method of manufacturing protein filling agent by using chromium-containing leather waste | |
| Gomes | Evaluation of Different Pre-treatments of Chromium Leather Waste and Their Use in Biogas Production | |
| CN110655680B (en) | Mixed anion zinc monomer, and composition and application 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 |