CN111171513A - Method for toughening thermosetting resin by using collagen fibers and modified thermosetting resin - Google Patents
Method for toughening thermosetting resin by using collagen fibers and modified thermosetting resin Download PDFInfo
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Abstract
The invention relates to the technical field of biomass material toughening modified thermosetting resin, in particular to a method for toughening thermosetting resin by using hide collagen fiber and modified thermosetting resin. The method for toughening the thermosetting resin by using the collagen fibers comprises the following steps: and uniformly mixing the thermosetting resin prepolymer and the collagen fibers, and then carrying out curing reaction. The invention utilizes collagen fiber to toughen and modify thermosetting resin so as to realize toughening effect and improve the modulus of the thermosetting resin. And as a renewable natural fiber, the collagen fiber has wide sources and low price, and has lower cost compared with the existing toughening method.
Description
Technical Field
The invention relates to the technical field of biomass material toughening modified thermosetting resin, in particular to a method for toughening thermosetting resin by using hide collagen fiber and modified thermosetting resin.
Background
The thermosetting resin is a polymer material with a three-dimensional cross-linked network structure, has the remarkable advantages of high hardness, corrosion resistance, high bonding strength, flame retardancy, good thermal stability and the like, and is widely applied to the fields of machinery, electrical appliances, aviation, adhesives, coatings and the like. However, thermosetting resins have inherent defects, and the characteristics of poor toughness and high brittleness limit the application of thermosetting resins in various fields. In recent decades, a large number of scholars have been engaged in toughening and modifying thermosetting resins, and the adopted methods generally include five methods, namely toughening with rigid fillers (including nano rigid particles, thermotropic liquid crystals, etc.), toughening with flexible fillers (rubber particles, thermoplastic resins, etc.), toughening with fibers (glass fibers, lignin fibers, etc.), toughening with structures (constructing interpenetrating network structures, "networks" - "spherulite" structures, constructing resin internal cavity structures, novel hyperbranched polymers, etc.), and toughening with molecular main chain modification (introducing long chains between crosslinking groups, introducing flexible long-chain branches into rigid main chains, etc.). However, most thermosetting resins are general-purpose resins with low price, most toughening materials adopted at present are higher in price than the thermosetting resins, and the preparation process of part of toughening materials with excellent performance is more complicated. And the introduction of some flexible fillers, flexible chains and active groups can also reduce the flame retardancy of the thermosetting resin to a certain extent. In addition, most of the prior toughening technologies for thermosetting resins can increase the toughness of the thermosetting resins and simultaneously cause the modulus of the thermosetting resins to be reduced.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a method for toughening thermosetting resin by collagen fiber, so as to solve the technical problem that the toughening and modulus improvement of thermosetting resin cannot be achieved at the same time in the prior art.
The second purpose of the invention is to provide a modified thermosetting resin obtained by modifying collagen fibers, wherein the modified thermosetting resin has better toughness and higher modulus.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the method for toughening the thermosetting resin by the collagen fiber comprises the following steps:
and uniformly mixing the thermosetting resin prepolymer and the collagen fibers, and then carrying out curing reaction.
The invention utilizes the collagen fiber to toughen and modify the thermosetting resin so as to realize the toughening effect and simultaneously improve the modulus of the thermosetting resin. And the collagen fiber is used as a renewable natural fiber, has wide sources and low price, and has lower cost compared with the existing toughening method.
The collagen fibril adopted by the invention is a multilevel structure aggregate which is formed by sequentially assembling collagen molecules of three-strand helix into collagen micro-element fiber, collagen fibril and collagen fiber, and can still show excellent toughness even in the liquid nitrogen atmosphere.
In addition, the molecular structure surface of the collagen fiber contains a large number of reactive amino groups, carboxyl groups, and hydroxyl groups. Most thermosetting resins polymerize by reacting amino, carboxyl, hydroxyl, anhydride, acid chloride, and ester groups in the molecular structure. The introduction of the molecules of the collagen fibers can introduce flexible chain segments between rigid structures of the thermosetting resin, so that the toughening of the thermosetting resin is realized. And the collagen fiber is a flexible fiber easy to deform, and is filled into thermosetting resin, so that the transfer energy can be absorbed, and the function of preventing the silver line from being converted into the crack is generated. Meanwhile, the collagen fiber is a macromolecule with high specific surface area, and the entanglement among molecules of the collagen fiber is beneficial to forming a semi-interpenetrating network (semi-IPN) structure in the thermosetting resin, so that the energy is conveniently transferred in the whole material, and the modification effect of structural toughening is achieved; furthermore, the modulus of the resin is improved while toughening by utilizing the high strength and high modulus of the collagen fiber.
In addition, the thermosetting resin toughened by the percutaneous collagen fibers does not reduce the flame retardancy of the thermosetting resin.
In a specific embodiment of the present invention, the collagen fibers are pretreated by subjecting a collagen fiber raw material to an activation treatment and/or a micro-denaturation treatment.
The method has the advantages that the collagen fiber raw material is activated, so that more functional group structures are exposed on the collagen fiber, and the collagen fiber is better compatible and reactive with thermosetting resin; by a micro-denaturing treatment to increase the flexibility of the collagen fibers.
In one embodiment of the present invention, the pretreatment method comprises activating the collagen fiber raw material and then performing a micro-denaturation treatment. If the collagen fiber material is subjected to the activation treatment and the micro-denaturation treatment, the activation treatment step precedes the micro-denaturation treatment step.
In one embodiment of the present invention, the thermosetting resin prepolymer includes an active group capable of reacting with an amino group, a carboxyl group and/or a hydroxyl group. Specifically, the reactive group that can react with an amino group, a carboxyl group, and/or a hydroxyl group includes, but is not limited to, any one or more of an amino group, a carboxyl group, a hydroxyl group, an acid anhydride, an acid chloride, and an ester group.
In one embodiment of the present invention, the mixing method includes: and mixing the solution containing the linear resin prepolymer with the pretreated collagen fibers and then performing precuring. Wherein the pre-curing method comprises the following steps: one or more of changing the pH, raising the temperature, or adding a cross-linking agent. The solution containing the linear resin prepolymer is pre-cured to obtain the thermosetting resin prepolymer mixed with the skin collagen fibers.
In one embodiment of the present invention, the curing reaction comprises: and heating the pre-cured material in a mold to perform a curing reaction. Wherein the transfer to different molds can be performed depending on the conditions such as whether foaming is required.
In one embodiment of the present invention, when the thermosetting resin prepolymer is a meltable thermosetting resin prepolymer, the mixing manner includes: directly mixing the meltable thermosetting resin prepolymer with the pretreated collagen fibers, and uniformly mixing the mixture by a mixer.
In one embodiment of the present invention, the curing reaction comprises: and heating and hot-pressing the directly mixed materials in a hot press to perform a curing reaction.
In one embodiment of the present invention, a curing agent may be added during the curing reaction to accelerate the curing reaction or improve the curing efficiency. The type of the curing agent can be selected according to the type of the actual thermosetting resin prepolymer, so that the efficient proceeding of the curing reaction is ensured.
In a specific embodiment of the present invention, the thermosetting resin includes any one or more of melamine formaldehyde resin, dicyandiamide formaldehyde resin, urea formaldehyde resin, phenol formaldehyde resin, epoxy resin, polyurethane and unsaturated polyester.
In a specific embodiment of the invention, the raw material of the hide collagen fibers is selected from any one or more of waste leather scraps and tanned leather. Wherein, the waste leather scraps refer to leather making leftover wastes generated by operations of chipping, buffing, cutting and the like in the leather making process; tanning refers to the semi-finished product in the leather production process.
In a particular embodiment of the invention, the tanned leather is selected from any one or more of wet blue leather, wet white leather, aldehyde tanned leather, vegetable tanned leather, non-chrome metal tanned leather, combination tanned leather and the like.
In one embodiment of the present invention, the raw material of the collagen fiber is subjected to a water washing treatment and a pulverization treatment before the activation treatment.
In one embodiment of the present invention, the water washing treatment comprises: and cleaning the collagen fiber raw material by adopting an aqueous solution containing a surfactant. Impurities such as fats and oils and inorganic salts in the raw materials are removed by washing with water. Wherein, the surfactant can be any surfactant which is commercially available and used for cleaning the collagen fiber raw material.
In one embodiment of the present invention, the collagen fiber raw material is pulverized to have a particle size of 10 to 5000 mesh, preferably 32 to 800 mesh.
As in the different embodiments, the collagen fiber raw material may be pulverized to a particle size of 10 mesh, 20 mesh, 30 mesh, 32 mesh, 50 mesh, 100 mesh, 120 mesh, 200 mesh, 300 mesh, 400 mesh, 500 mesh, 600 mesh, 700 mesh, 800 mesh, or the like.
In a specific embodiment of the present invention, the activation treatment includes any one or more of a mechanochemical milling treatment, a microwave treatment and a swelling treatment.
In one embodiment of the present invention, the mechanochemical polishing process is performed using a mechanochemical apparatus.
Optionally, the mechanochemical reaction equipment comprises any one or more of a screw type mechanochemical reactor, a millstone type mechanochemical reactor, a centrifugal type mechanochemical reactor, a mesh type mechanochemical reactor, a hammer type mechanochemical reactor, a cutting type mechanochemical reactor, a gas flow crusher, a dry ball mill and a wet ball mill. Through mechanochemical grinding, the structure of the collagen fiber bundle is loosened, partial peptide bonds and hydrogen bonds are broken, and more reactive amino groups, hydroxyl groups, carboxyl groups and the like on collagen molecules are exposed.
In one embodiment of the present invention, the swelling treatment comprises: and (3) carrying out impregnation treatment by adopting ethanol and/or acetone. The solution can be used for cleaning materials again, and can also be used for properly destroying the hydrogen bond function, swelling collagen molecules and loosening the fiber bundle structure. Wherein the dosage of the ethanol and/or the acetone is 50-800 percent of the mass of the collagen fiber raw material, and the dipping time is 30 min-30 d.
In one embodiment of the present invention, the microwave treatment comprises: soaking the collagen fiber in water, and treating with microwave in a microwave reactor. Wherein the using amount of the water is preferably 50-800% of the mass of the collagen fiber; the water is preferably deionized water.
Preferably, the microwave treatment time is 5s to 1800s, and the microwave power is 50W to 3000W.
In one embodiment of the present invention, the swollen or microwave-treated collagen fibers are dried and then pulverized again to 10 to 5000 mesh, preferably 32 to 800 mesh.
The skin collagen fiber after the activation treatment, in particular the mechanical chemical grinding, the microwave treatment or the swelling treatment and the crushing treatment has the defibration rate of more than 50 percent, and the water absorption rate of 12 to 30 percent after the air conditioning in the standard temperature and humidity atmosphere (the temperature is 25 ℃ and the humidity is 50 percent) for 48 hours. Wherein, the calculation formula of the defibration rate is as follows: the number of collagen fiber single fibers in the sample per unit mass/(the number of collagen fiber single fibers + the number of collagen fiber bundles).
In one embodiment of the present invention, the micro-denaturing treatment comprises: dry heat denaturation treatment and/or wet heat denaturation treatment. The flexibility of the collagen fiber is increased by performing micro-modification treatment on the collagen fiber.
Optionally, the dry heat denaturation treatment comprises: drying the collagen fiber, and then heating to 120-200 ℃ for treatment for 5-120 min.
Optionally, the wet heat denaturation treatment comprises: heating the collagen fiber in a solvent to 60-110 ℃ for 5-120 min. Wherein the solvent comprises any one or more of water, glycerol, petroleum ether and simethicone.
In a specific embodiment of the present invention, the method further includes: and (3) cleaning the skin collagen fibers subjected to the damp-heat denaturation treatment.
In a specific embodiment of the invention, the amount of the collagen fiber is 0.5-30% of the mass of the thermosetting resin prepolymer.
The invention also provides the modified thermosetting resin obtained by adopting the method for toughening the thermosetting resin by using any one of the collagen fibers.
The modified thermosetting resin has low cost, obviously improved toughness, and improved strength and modulus.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention utilizes the collagen fiber to toughen and modify the thermosetting resin so as to realize the toughening effect and simultaneously improve the modulus of the thermosetting resin;
(2) the skin collagen fiber adopted by the invention is used as a renewable natural fiber, has wide source and low price, and has lower cost compared with the existing toughening method;
(3) the modified thermosetting resin obtained by the invention has higher toughness, strength and modulus, and has wide application prospect.
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 graph comparing the dynamic loss modulus results of MF resins of different treatments provided by examples and comparative examples of the present invention;
fig. 2 is a graph comparing the dynamic loss angle results of MF resins treated differently according to the present invention and comparative example.
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.
Some of the reagent information used in embodiments of the invention may be as follows:
the white wet leather is from Hebei Xinji Dongming leather Co Ltd;
the waste leather scraps come from the Henning Rexingx leather company Limited and are leather-making corner wastes generated by slicing, grinding and cutting operations of the blue wet leather in the leather-making process;
the melamine linear prepolymer in the solution system is self-synthesized by using melamine, formaldehyde and triethylamine as raw materials, reagents are all analytically pure, and a manufacturer is a metropolis chemical company Limited;
the thermoplastic melamine formaldehyde resin prepolymer is made by Chengjie plastic raw material Co., Ltd, Dongguan, and has the model number DY 104D;
surfactant, the manufacturer is Sichuan Dawei science and technology Co., Ltd, and the model is FG-B;
the phenolic aldehyde linear prepolymer is self-synthesized by using phenol, formaldehyde and sodium hydroxide as raw materials, reagents are analytically pure, and a manufacturer is a metropolis Kolon chemical Co., Ltd;
the acrylonitrile fiber is manufactured by Yangzhou Tianhao textile Co.Ltd, and the type of the acrylonitrile fiber is polypropylene filament;
the glass fiber is manufactured by Changzhou build Wei building materials GmbH, and the model is alkali-free chopped 6 mm;
carbon black, the manufacturer is Shanghai Kayin chemical Co., Ltd, model N330;
lignin fiber, type SMA, from hebei shenpeng chemical ltd;
vulcanized rubber, model number TV6001, available from jejia plastics science and technology ltd, dongguan.
Example 1
The embodiment provides a method for toughening thermosetting resin by using collagen fibers, which comprises the following steps:
(1) mixing 100 weight parts of waste leather scraps, 400 weight parts of water and 0.5 weight part of FG-B at 25 ℃ for 2 hours, filtering water, mixing with 400 weight parts of water at 25 ℃ for 2 hours, and filtering water;
(2) fully drying the waste leather scraps washed by water in the step (1) at 80 ℃, and then crushing the waste leather scraps to 120 meshes to obtain collagen fiber powder with the defibration rate of about 24%;
(3) mixing 126 parts by weight of melamine powder and 158 parts by weight of formaldehyde solution with the concentration of 38% and the pH value of 10.5 at 85 ℃ for 3 hours to obtain melamine formaldehyde resin prepolymer solution;
(4) mixing 5 parts by weight of the collagen fiber powder obtained in the step (2) with 100 parts by weight of the melamine formaldehyde resin prepolymer solution obtained in the step (3) for 1 hour, then adjusting the pH value to 6.5, and pouring; after the temperature is kept at 40 ℃ for 24h, the temperature is raised to 95 ℃ and the temperature is kept for 9h to obtain the collagen fiber modified melamine formaldehyde resin.
Wherein, the water is filtered after being mixed with water and/or surfactant for a plurality of times in the step (1), the purpose is to clean the waste leather scraps, and the use amount of the water and the surfactant is not limited to the above, and can be adjusted according to the actual situation.
Example 2
This example refers to the preparation of example 1, with the only difference that: the used leather collagen fiber raw material is wet white leather, and the defibration rate of the obtained collagen fiber is about 17.8 percent.
Example 3
The embodiment provides a method for toughening thermosetting resin by using collagen fibers, which comprises the following steps:
(1) mixing 100 weight parts of waste leather scraps, 400 weight parts of water and 0.5 weight part of FG-B at 25 ℃ for 2 hours, filtering water, mixing with 400 weight parts of water at 25 ℃ for 2 hours, and filtering water;
(2) fully drying the waste leather scraps washed by water in the step (1) at 80 ℃, and then crushing the waste leather scraps to 120 meshes to obtain collagen fiber powder with the defibration rate of about 24%;
(3) activating the collagen fiber powder obtained in the step (2) in a 36-tooth staggered-blade centrifugal type mechanochemical reactor for 2 times at 2400rpm, wherein the mesh opening is 0.12mm, and the activated collagen fiber powder is obtained through trapezoidal holes, the defibering rate of the activated collagen fiber powder is about 70%, and the water absorption rate of the activated collagen fiber powder is about 17.3% after air conditioning in a standard temperature and humidity atmosphere (the temperature is 25 ℃ and the humidity is 50%) for 48 hours;
(4) mixing 126 parts by weight of melamine powder and 158 parts by weight of formaldehyde solution with the concentration of 38% and the pH value of 10.5 at 85 ℃ for 3 hours to obtain melamine formaldehyde resin prepolymer solution;
(5) mixing 10 parts by weight of the collagen fiber powder obtained in the step (3) with 100 parts by weight of the melamine formaldehyde resin prepolymer solution obtained in the step (4) for 1 hour, then adjusting the pH value to 6.5, and pouring; after the temperature is kept at 40 ℃ for 24h, the temperature is raised to 95 ℃ and the temperature is kept for 9h to obtain the collagen fiber modified melamine formaldehyde resin.
Example 4
The embodiment provides a method for toughening thermosetting resin by using collagen fibers, which comprises the following steps:
(1) mixing 100 weight parts of waste leather scraps, 400 weight parts of water and 0.5 weight part of FG-B at 25 ℃ for 2 hours, filtering water, mixing with 400 weight parts of water at 25 ℃ for 2 hours, and filtering water;
(2) fully drying the waste leather scraps washed by water in the step (1) at 80 ℃, and then crushing the waste leather scraps to 120 meshes to obtain collagen fiber powder with the defibration rate of about 24%;
(3) fully drying the collagen fiber powder obtained in the step (2), and heating to 160 ℃ for treatment for 30min to obtain collagen fiber powder subjected to micro-modification treatment;
(4) mixing 126 parts by weight of melamine powder and 158 parts by weight of formaldehyde solution with the concentration of 38% and the pH value of 10.5 at 85 ℃ for 3 hours to obtain melamine formaldehyde resin prepolymer solution;
(5) mixing 2 parts by weight of the collagen fiber powder obtained in the step (3) with 100 parts by weight of the melamine formaldehyde resin prepolymer solution obtained in the step (4) for 1 hour, then adjusting the pH value to 6.5, and pouring; after the temperature is kept at 40 ℃ for 24h, the temperature is raised to 95 ℃ and the temperature is kept for 9h to obtain the collagen fiber modified melamine formaldehyde resin.
Example 5
The embodiment provides a method for toughening thermosetting resin by using collagen fibers, which comprises the following steps:
(1) mixing 100 weight parts of waste leather scraps, 400 weight parts of water and 0.5 weight part of FG-B at 25 ℃ for 2 hours, filtering water, mixing with 400 weight parts of water at 25 ℃ for 2 hours, and filtering water;
(2) fully drying the waste leather scraps washed by water in the step (1) at 80 ℃, and then crushing the waste leather scraps to 120 meshes to obtain collagen fiber powder with the defibration rate of about 24%;
(3) activating the collagen fibers obtained in the step (2) in an airflow crusher for 1h, wherein the atmosphere is air, the air pressure of a cavity is 1.1MPa, so as to obtain activated collagen fiber powder, the defibration rate of the activated collagen fiber powder is about 62%, and the water absorption rate of the activated collagen fiber powder is about 18.6% after air conditioning in a standard temperature and humidity atmosphere (the temperature is 25 ℃ and the humidity is 50%) for 48 h;
(4) soaking the collagen fiber powder obtained in the step (3) in 95 ℃ glycerol for 20min, and washing and drying to obtain collagen fiber powder subjected to micro-modification treatment;
(5) mixing 126 parts by weight of melamine powder and 158 parts by weight of formaldehyde solution with the concentration of 38% and the pH value of 10.5 at 85 ℃ for 3 hours to obtain melamine formaldehyde resin prepolymer solution;
(6) mixing 5 parts by weight of the collagen fiber powder obtained in the step (4) with 100 parts by weight of the melamine formaldehyde resin prepolymer solution obtained in the step (5) for 1 hour, then adjusting the pH value to 6.5, and pouring; after the temperature is kept at 40 ℃ for 24h, the temperature is raised to 95 ℃ and the temperature is kept for 9h to obtain the collagen fiber modified melamine formaldehyde resin.
Example 6
The embodiment provides a method for modifying thermoplastic resin by using collagen fibers, which comprises the following steps:
(1) mixing 100 weight parts of waste leather scraps, 400 weight parts of water and 0.5 weight part of FG-B at 25 ℃ for 2 hours, filtering water, mixing with 400 weight parts of water at 25 ℃ for 2 hours, and filtering water;
(2) fully drying the waste leather scraps washed by water in the step (1) at 80 ℃, and then crushing the waste leather scraps to 120 meshes to obtain collagen fiber powder with the defibration rate of about 24%;
(3) soaking the collagen fiber obtained in the step (2) in acetone with the weight of 400% for 7d, drying and crushing to obtain activated collagen fiber powder, wherein the defibration rate is about 76%, and the water absorption rate is about 21.1% after air conditioning in a standard temperature and humidity atmosphere (the temperature is 25 ℃ and the humidity is 50%) for 48 h;
(4) and (3) uniformly mixing 100 parts by weight of thermoplastic melamine formaldehyde resin prepolymer and 10 parts by weight of collagen fiber powder obtained in the step (3), and vulcanizing and molding on a flat plate hot press to obtain the collagen fiber modified thermosetting melamine formaldehyde resin, wherein the hot pressing temperature is 130 ℃, the pressure is 1.5MPa, and the time is 30 min.
Example 7
The embodiment provides a method for toughening thermosetting resin by using collagen fibers, which comprises the following steps:
(1) mixing 100 weight parts of waste leather scraps, 400 weight parts of water and 0.5 weight part of FG-B at 25 ℃ for 2 hours, filtering water, mixing with 400 weight parts of water at 25 ℃ for 2 hours, and filtering water;
(2) fully drying the waste leather scraps washed by water in the step (1) at 80 ℃, and then crushing the waste leather scraps to 120 meshes to obtain collagen fiber powder with the defibration rate of about 24%;
(3) mixing 100 parts by weight of phenol and 100 parts by weight of formaldehyde solution with the concentration of 38% and the pH value of 11 at 60 ℃ for 2 hours to obtain phenolic resin prepolymer solution;
(4) mixing 3 parts by weight of the collagen fiber powder obtained in the step (2) with 100 parts by weight of the phenolic resin prepolymer solution obtained in the step (3) for 1 hour, and pouring; keeping the temperature at 60 ℃ for 24h to obtain the collagen fiber modified phenolic resin.
Comparative example 1
Comparative example 1 provides a blank melamine formaldehyde resin:
mixing 126 parts by weight of melamine powder and 158 parts by weight of 38% formaldehyde solution with a pH of 10.5 at 85 ℃ for 3h, then adjusting the pH to 6.5, and casting; after the temperature is kept at 40 ℃ for 24h, the temperature is raised to 95 ℃ and the temperature is kept for 9h to obtain the melamine formaldehyde resin.
Comparative example 2
Comparative example 2 provides a melt-prepared blank melamine formaldehyde resin:
100 parts by weight of thermoplastic melamine formaldehyde resin prepolymer is vulcanized and molded on a flat plate hot press, the temperature is 130 ℃, the pressure is 1.5MPa, and the time is 30min to obtain the melamine formaldehyde resin.
Comparative example 3
Comparative example 3 provides a blank phenolic resin:
mixing 100 parts by weight of phenol and 100 parts by weight of formaldehyde solution with the concentration of 38% and the pH value of 11 at 60 ℃ for 3 hours, and pouring; keeping the temperature at 60 ℃ for 24h to obtain the phenolic resin.
Comparative example 4
Comparative example 4 provides an acrylonitrile fiber-modified resin comprising the steps of:
(1) crushing acrylonitrile fiber to 120 meshes to obtain acrylonitrile fiber powder;
(2) mixing 126 parts by weight of melamine powder and 158 parts by weight of formaldehyde solution with the concentration of 38% and the pH value of 10.5 at 85 ℃ for 3 hours to obtain melamine formaldehyde resin prepolymer solution;
(3) mixing 5 parts by weight of the acrylonitrile fiber powder obtained in the step (1) with 100 parts by weight of the melamine formaldehyde resin prepolymer solution obtained in the step (3) for 1 hour, then adjusting the pH value to 6.5, and pouring; after the temperature is kept at 40 ℃ for 24h, the temperature is raised to 95 ℃ and the temperature is kept for 9h to obtain the melamine formaldehyde resin modified by the acrylonitrile fiber.
Comparative example 5
Comparative example 5 the preparation process of comparative example 4 was referenced, with the only difference that: the acrylonitrile fibers were replaced with carbon black.
Comparative example 6
Comparative example 6 the preparation process of comparative example 4 was referenced, with the only difference that: the acrylic fiber is replaced by glass fiber.
Comparative example 7
Comparative example 7 the preparation process of comparative example 4 was referenced, with the only difference that: the acrylonitrile fiber is replaced by lignin fiber.
Comparative example 8
Comparative example 8 the preparation process of comparative example 4 was referenced, with the only difference that: the acrylonitrile fiber is replaced by vulcanized natural rubber.
Experimental example 1
In order to comparatively illustrate the toughening effect, strength and other properties of the resin materials obtained in different examples and comparative examples of the present invention, the resin materials obtained in different examples and comparative examples were tested, and the test standards refer to ASTM D638, ASTM D256 and ASTM D790, and the test results are shown in table 1.
TABLE 1 results of Performance test of different resin materials
As can be seen from the above table, the modified thermosetting resin prepared by the toughening method of the present invention can improve the modulus of the resin while achieving toughening.
FIGS. 1 and 2 are graphs comparing the results of dynamic loss modulus and dynamic loss angle for differently treated resins provided in example 1 of the present invention and comparative example.
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 (10)
1. The method for toughening the thermosetting resin by using the collagen fibers is characterized by comprising the following steps of:
uniformly mixing the thermosetting resin prepolymer and the collagen fibers, and then carrying out curing reaction;
optionally, the amount of the collagen fiber is 0.5-30% of the mass of the thermosetting resin prepolymer.
2. The method for toughening a thermosetting resin with collagen fibers according to claim 1, wherein the collagen fibers are pretreated, and the pretreatment method comprises subjecting a collagen fiber raw material to an activation treatment and/or a micro-denaturation treatment.
3. The method for toughening thermosetting resin with collagen fiber according to claim 2, wherein the pretreatment comprises activating the collagen fiber raw material and then performing a micro-modification treatment.
4. The method for toughening a thermosetting resin by using collagen fibers according to claim 1, wherein the thermosetting resin prepolymer comprises an active group capable of reacting with an amino group, a carboxyl group and/or a hydroxyl group;
preferably, the thermosetting resin includes any one or more of melamine formaldehyde resin, dicyandiamide formaldehyde resin, urea formaldehyde resin, phenol formaldehyde resin, epoxy resin, polyurethane and unsaturated polyester.
5. The method for toughening a thermosetting resin with collagen fibers according to claim 1, wherein the mixing comprises: mixing the solution containing the linear resin prepolymer with the pretreated collagen fibers and then performing precuring;
preferably, the pre-curing method comprises: pre-curing by any one or more of changing the pH, raising the temperature or adding a cross-linking agent;
preferably, the curing reaction comprises: and heating the pre-cured material in a mold to perform a curing reaction.
6. The method for toughening a thermosetting resin with collagen fibers according to claim 1, wherein the mixing comprises: directly mixing the meltable thermosetting resin prepolymer with the pretreated collagen fibers;
preferably, the curing reaction comprises: and heating and hot-pressing the directly mixed materials in a hot press to perform a curing reaction.
7. The method for toughening thermosetting resin with collagen fibers according to any one of claims 1 to 6, wherein the collagen fiber raw material is selected from any one or more of waste leather scraps and tanned leather;
preferably, the tanned leather is selected from any one or more of wet blue leather, wet white leather, aldehyde tanned leather, vegetable tanned leather, non-chrome metal tanned leather, combination tanned leather;
more preferably, the raw material of the collagen fiber is pulverized to 10 to 5000 mesh in advance.
8. The method for toughening a thermosetting resin with collagen fibers according to claim 2 or 3, wherein the activation treatment comprises any one or more of a mechanochemical grinding treatment, a microwave treatment and a swelling treatment;
preferably, mechanochemical equipment is adopted to carry out the mechanochemical grinding treatment;
optionally, the mechanochemical reaction equipment comprises any one or more of a screw type mechanochemical reactor, a millstone type mechanochemical reactor, a centrifugal type mechanochemical reactor, a mesh type mechanochemical reactor, a hammer type mechanochemical reactor, a cutting type mechanochemical reactor, an airflow crusher, a dry ball mill and a wet ball mill;
preferably, the microwave treatment comprises: soaking the collagen fiber in water, and performing microwave treatment by using a microwave reactor;
more preferably, the microwave treatment time is 5s to 1800s, and the microwave power is 50W to 3000W;
preferably, the swelling treatment comprises: adopting ethanol and/or acetone for impregnation treatment;
preferably, the swollen or microwaved collagen fibers are dried and pulverized.
9. The method for toughening a thermosetting resin with collagen fibers according to claim 2 or 3, wherein the micro-modification treatment comprises: dry heat denaturation treatment and/or wet heat denaturation treatment;
preferably, the dry heat denaturation treatment comprises: drying the collagen fiber, heating to 120-200 ℃, and treating for 5-120 min;
preferably, the wet heat denaturation treatment comprises: heating the collagen fiber in a solvent to 60-110 ℃ and treating for 5-120 min;
more preferably, the solvent includes any one or more of water, glycerol, petroleum ether and simethicone;
more preferably, the method further comprises the following steps: and (3) cleaning the skin collagen fibers subjected to the damp-heat denaturation treatment.
10. A modified thermosetting resin obtained by the method for toughening a thermosetting resin with collagen fibers according to any one of claims 1 to 9.
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| CN114085446A (en) * | 2021-12-08 | 2022-02-25 | 四川大学 | Creep-resistant composite material and preparation method thereof |
| CN115464818A (en) * | 2022-08-10 | 2022-12-13 | 四川大学 | Method for preparing composite regenerated plastic product by using waste leather material |
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