CN108360263B - High-activity interface reinforcing agent for rapid in-situ composite 3D printing composite material and preparation method thereof - Google Patents
High-activity interface reinforcing agent for rapid in-situ composite 3D printing composite material and preparation method thereof Download PDFInfo
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- CN108360263B CN108360263B CN201810124109.4A CN201810124109A CN108360263B CN 108360263 B CN108360263 B CN 108360263B CN 201810124109 A CN201810124109 A CN 201810124109A CN 108360263 B CN108360263 B CN 108360263B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Abstract
A high-activity interface reinforcing agent for a rapid in-situ composite 3D printing composite material and a preparation method thereof are used for realizing the interface strengthening and toughening in a rapid in-situ composite process by adopting a compound interface reinforcing agent system with high reaction activity aiming at the problem of poor bonding state of continuous fiber reinforced P L A and PA composite material 3D printing fiber-resin interface, wherein the interface reinforcing agent comprises 2-5 parts of carboxylate-containing polyurethane prepolymer, 0.01-0.03 part of carboxyl-containing carbon nano tube, 0.01-0.03 part of graphene oxide, 0.01-0.05 part of surfactant, 0.01-0.03 part of chain extender, 0.02-0.05 part of epoxy resin and 100 parts of deionized water.
Description
Technical Field
The invention relates to a preparation method of a high-activity interface reinforcing agent for rapid in-situ composite 3D printing P L A and PA composite materials, which aims at the problem of poor bonding state of continuous fiber reinforced P L A and PA composite material 3D printing fiber-resin interfaces, adopts a compound interface reinforcing agent system with high reaction activity to realize the strengthening and toughening of the interfaces in the rapid in-situ composite process.
Background
The P L A and PA resins are thermoplastic resins which are most applied to the current 3D printing technology, and are mainly applied to selective laser sintering (S L S) and fused deposition Forming (FDM) processes, but the mechanical property, creep resistance and structural stability of a single thermoplastic resin are poor, the fiber reinforced P L A and PA composite materials are effective technical approaches for solving the problems of the mechanical property, creep resistance and structural stability of the single thermoplastic resin, fiber reinforced PA composite materials are applied to parts such as automobile fuel tanks, engine oil nozzles, internal combustion engine synchronous driving gears, gears and pipe joints of heavy diesel engines in the United states, Europe, Japan and other countries, parts such as air window parts of boeing aircraft engines, cabin doors and the like are manufactured by adopting carbon fiber reinforced PA-66, engine parts of American MX are also manufactured by adopting carbon fiber reinforced PA-66, the continuous fiber 3D printing technology effectively combines the continuous fiber reinforced thermoplastic composite materials with the 3D printing technology, excessive dependence of the traditional process on process elements such as large-scale equipment, tooling molds is eliminated, high-precision integral manufacturing of complex structures and high-precision functions and integrated manufacturing of resin-based composite materials, and a fine manufacturing technology is provided.
The method for solving the interface problem aims at preparing the composite material by a hot pressing/mould pressing process, the method for solving the interface problem is that polymer coating treatment is carried out on the surface of carbon fiber, then good interface combination is realized through a preimpregnation process, and the design of a sizing agent/reinforcing agent matched with the resin is the key for improving the interface performance.
Disclosure of Invention
The invention provides a preparation method of a P L A and PA composite material high-activity interface reinforcing agent suitable for rapid in-situ compounding of continuous fiber 3D printing, and the preparation method has the characteristics of high reaction activity, good water solubility, environmental friendliness and the like.
The invention solves the technical problem that the bonding state of a fiber-resin interface of 3D printing of continuous fiber reinforced P L A and PA composite materials is poor, and the interface toughness of a rapid in-situ compounding process is realized by adopting a compound interface reinforcing agent system with high reaction activity.
The technical solution of the invention is as follows: a high-activity interface reinforcing agent for a rapid in-situ composite 3D printing composite material comprises the following components in percentage by mass:
further, the carboxylate-containing polyurethane prepolymer is prepared by pre-polymerizing dihydric alcohol, diisocyanate, 2-dihydroxy carboxylic acid and tertiary amine under the action of a catalyst, wherein the dihydric alcohol is a mixture of two or more of polyester dihydric alcohol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran glycol with the molecular weight of 400-1000; the diisocyanate compound is a mixture of two or more of diphenylmethane diisocyanate, toluene diisocyanate and isophorone diisocyanate; the dihydroxy carboxylic acid compound is one of 2, 2-dimethylolpropionic acid, 2, 2-dimethylolbutyric acid and 2, 2-dimethyloldodecanoic acid; the catalyst is dibutyltin dilaurate; the tertiary amine is one or a mixture of two of triethylamine, tripropylamine and tributylamine; the diluent is one or a mixture of two of acetone and butanone.
Furthermore, the carboxyl-containing carbon nano tube is a carboxylated multi-wall carbon nano tube, the diameter of the carbon nano tube is 10-20 nm, the length of the carbon nano tube is 10-30 mu, and the content of carboxyl is 2 +/-0.5 wt%.
Furthermore, the graphene oxide is 1-5 layers of graphene oxide, and the oxygen content is 30-45 at%.
Further, the chain extender is one or a mixture of two of ethylenediamine, propylenediamine, diethylenetriamine and triethylenetetramine.
Further, the epoxy resin is one or a mixture of two of E-51, E-44, AG-80, TDE-85, S-27, S-51, S-60, S-184, S-186, S-500M, S-510, S-610 and S-720.
Further, the surfactant is one or a mixture of two of triton-100 and sodium dodecyl benzene sulfonate.
The technical scheme of the method is as follows: a preparation method of a high-activity interface reinforcing agent for a rapid in-situ composite 3D printing composite material comprises the following steps:
(1) preparing a carbon nano particle monodisperse solution: grinding and mixing the surfactant and the carboxyl-containing carbon nano-tubes for at least 20min according to the mixture ratio in the claim; adding deionized water and few-layer graphene oxide, mechanically stirring for 30-50 min, and ultrasonically dispersing for at least 20 min; removing insoluble substances to obtain a carbon nanoparticle monodisperse solution;
(2) preparing a high-activity interface reinforcing agent: mixing the carboxylate-containing polyurethane prepolymer with the carbon nano particle monodisperse, and sequentially adding a chain extender and epoxy resin while shearing and stirring at a high speed; shearing and emulsifying for 60-100 min to obtain the high-activity interface reinforcing agent.
Further, the concrete prepolymerization step of the carboxylate-containing polyurethane prepolymer comprises the following steps: dehydrating the dihydric alcohol for at least 30min under the condition of 110-120 ℃ in vacuum; cooling to 50 +/-5 ℃, adding a diisocyanate compound, and reacting for 20-30 min; adding a dihydroxy carboxylic acid compound to react for 30-40 min; adding a catalyst, heating to 80-100 ℃, and continuing to react for 100-120 min; and finally adding tertiary amine and a diluent, stirring for 30 +/-5 min, and cooling to room temperature.
Further, the-OH group of the diol during the prepolymerization of the carboxylate-containing polyurethane prepolymer: the-CNO group of the diisocyanate compound: the molar ratio of-OH groups of the 2, 2-dihydroxycarboxylic acid compound is 1 (1.5-2.5) to 0.3-1; the content of the diisocyanate compound is 1.5 to 3 wt%.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, functional groups such as carboxyl, hydroxyl, epoxy group and isocyanate group are introduced to the surface of the fiber through the component compatibility of the reinforcing agent, and the fiber-resin interface bonding state is strengthened by chemical bonding, hydrogen bonding or polar action with P L A and PA end groups, the interface flexible buffer layer is constructed by adopting waterborne polyurethane as the main component of the reinforcing agent to improve the interface toughness, and the interface bonding strength is synergistically optimized by utilizing nano components such as modified carbon nanotubes and graphene.
(2) According to the invention, the waterborne polyurethane is used as the main component of the reinforcing agent, the interface flexible buffer layer is constructed to improve the interface toughness, the generation and the expansion of microcracks are further passivated and inhibited by utilizing the synergistic effect of the modified carbon nano tube, the graphene and other nano components in the interface layer, and the tensile strength and the bending strength of the composite material are improved by 20-30%.
(3) According to the invention, a small amount of epoxy resin is introduced, so that the infiltration capacity of the reinforcing agent on the fiber surface can be improved, the reinforcing agent and the terminal groups of nano particles, polyurethane and resin (P L A and PA) can be subjected to chemical reaction, and the sizing treatment speed of the reinforcing agent can be increased by 10-15%.
(4) The polyurethane molecular structure contains a certain hydrophilic group, and the carbon nano tube and the graphene also contain the hydrophilic group, so that the polyurethane molecular structure, the carbon nano tube and the graphene can be self-emulsified to form a stable monodisperse emulsion system, the dosage of an emulsifier is reduced, and the influence on the use effect caused by the over-complex reinforcing agent compounding system is avoided.
(5) The preparation method of the nano particle monodisperse liquid is simple, the equipment cost is low, the operation process is simple, the accumulated operation time is about 90min, and only common instruments and equipment such as a grinding mixer, a mechanical stirrer, ultrasonic dispersion and the like are needed.
(6) The preparation method of the carboxylate-containing polyurethane prepolymer is simple, the reaction condition is mild, the operability is strong, the maximum reaction temperature is lower than 120 ℃, the cumulative reaction time is 210-250 min, and the method has good economy and feasibility. (7) The preparation efficiency of the high-activity interface reinforcing agent is high, and only the carboxylate-containing polyurethane prepolymer and the carbon nano particle monodisperse are required to be mixed, the chain extender and the epoxy resin are sequentially added while high-speed shearing and stirring are carried out, and shearing emulsification is carried out for 60-100 min.
(8) The nano modified waterborne polyurethane high-activity interface reinforcing agent designed by the invention has the advantages of simple preparation process, high production efficiency and environmental friendliness, is the same as the existing universal fiber sizing agent sizing method, and is convenient for realizing large-scale industrial application.
Drawings
FIG. 1 is a flow chart of preparation of a nano-modified waterborne polyurethane high-activity interface enhancer
FIG. 2 is an infrared spectrum of the highly reactive interface enhancer of example 1.
FIG. 3 is an SEM image of the surface of carbon fibers impregnated with the highly reactive interfacial strength agent of example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, wherein the preparation process is as shown in FIG. 1:
1. a high-activity interface reinforcing agent for a rapid in-situ composite 3D printing composite material and a preparation method thereof are disclosed, wherein the high-activity interface reinforcing agent comprises the following components (by mass):
2. preparing a carbon nano particle monodisperse solution: grinding and mixing the surfactant and the carboxyl-containing carbon nano tube for at least 20 min; adding deionized water and graphene oxide, mechanically stirring for 30-50 min, and ultrasonically dispersing for at least 20 min; and removing insoluble substances by adopting a centrifugal machine to obtain the carbon nano particle monodisperse solution. The carboxyl-containing carbon nano tube is a carboxylated multi-wall carbon nano tube, the diameter of the carbon nano tube is 10-20 nm, the length of the carbon nano tube is 10-30 mu, and the content of carboxyl is 2 +/-0.5 wt%; the graphene oxide is 1-5 layers of graphene oxide, the average thickness is 5nm, and the oxygen content is 30-45 at%.
3. Preparation of carboxylate-containing polyurethane prepolymer: the prepolymer is prepared by the prepolymerization of dihydric alcohol, diisocyanate, 2-dihydroxy carboxylic acid and tertiary amine under the action of a catalyst, wherein the-OH group of the dihydric alcohol in the synthesis process of the carboxylate-containing polyurethane prepolymer is as follows: the-CNO group of the diisocyanate compound: the molar ratio of-OH groups of the 2, 2-dihydroxycarboxylic acid compound is 1: 1.5-2.5: 0.3-1; the content of the isocyanate compound is 1.5 to 3 wt%. The method comprises the following specific steps: dehydrating the dihydric alcohol for at least 30min under the condition of 110-120 ℃ in vacuum; cooling to 50 +/-5 ℃, adding a diisocyanate compound, and reacting for 20-30 min; adding a dihydroxy carboxylic acid compound to react for 30-40 min; adding a catalyst, heating to 80-100 ℃, and continuing to react for 100-120 min; and finally adding tertiary amine and a diluent, stirring for 30 +/-5 min, and cooling to room temperature. The dihydric alcohol is a mixture of two or more of polyester dihydric alcohol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran glycol with the molecular weight of 400-1000; the diisocyanate compound is a mixture of two or more of diphenylmethane diisocyanate, toluene diisocyanate and isophorone diisocyanate; the dihydroxy carboxylic acid compound is one of 2, 2-dimethylolpropionic acid, 2, 2-dimethylolbutyric acid and 2, 2-dimethyloldodecanoic acid; the catalyst is dibutyltin dilaurate; the tertiary amine is one or a mixture of two of triethylamine, tripropylamine and tributylamine; the diluent is one or a mixture of two of acetone and butanone.
4. Preparing a high-activity interface reinforcing agent: mixing the carboxylate-containing polyurethane prepolymer with the carbon nano particle monodisperse, and sequentially adding a chain extender and epoxy resin while shearing and stirring at a high speed; shearing and emulsifying for 60-100 min to obtain the high-activity interface reinforcing agent.
The chain extender is one or a mixture of two of ethylenediamine, propylenediamine, diethylenetriamine and triethylenetetramine; the epoxy resin is one or a mixture of two of E-51, E-44, AG-80, TDE-85, S-27, S-51, S-60, S-184, S-186, S-500M, S-510, S-610 and S-720; the surfactant is one or a mixture of two of triton-100 and sodium dodecyl benzene sulfonate.
The implementation method of the present invention is further described with reference to specific examples, which are only used to illustrate the implementation process of the present invention, and do not limit the scope of the present invention.
Example 1:
(1) weighing 10mg of carboxyl-containing carbon nano tube and 10mg of triton-100, and grinding in a glass grinding bowl for 20 min; then transferring the carbon nanotubes in the grinding bowl into a beaker, washing the residual carbon nanotubes in the grinding bowl for multiple times by using 50ml of deionized water, transferring the carbon nanotubes into the beaker, adding 10mg of graphene oxide and 50ml of deionized water, and mechanically stirring for 30 min; ultrasonic dispersing for 10 min; finally, the agglomerated insoluble substances are removed by centrifugation, and the monodisperse liquid with the carbon nano particle content of 0.02 percent is obtained.
(2) Vacuum dehydrating 6g of polypropylene glycol with average molecular weight of 600 and 5g of polyethylene glycol with average molecular weight of 400 at 110 deg.C for 30min until no bubbles emerge; cooling to 50 ℃, adding 6g of diphenylmethane diisocyanate and 1.9g of toluene diisocyanate, and reacting for 20 min; then adding 1.3g of 2, 2-dimethylolpropionic acid for reaction for 30 min; then adding a dibutyltin dilaurate catalyst, heating to 80 ℃, and continuing to react for 2 hours; finally, a solution of 1.1g triethylamine and 5ml acetone was added and the temperature was reduced to room temperature to obtain a carboxylate-containing polyurethane prepolymer having an isocyanate group content of 1.9 wt%.
(3) And (2) mixing 2g of the carboxylate-containing polyurethane prepolymer prepared in the step (2) with 100ml of the carbon nanoparticle monodisperse liquid prepared in the step (1), sequentially adding 0.012g of propylene diamine and 0.02g of epoxy resin (E-51) while carrying out high-speed shearing stirring, and carrying out shearing emulsification for 60min to obtain the nano modified waterborne polyurethane high-activity interface reinforcing agent.
The interface enhancement effect of the composite material verifies that the interlaminar shear performance of the continuous fiber 3D printed MT300-1K/P L A composite material unidirectional board is improved by 10%.
Example 2:
(1) weighing 25mg of carboxyl-containing carbon nano tube and 30mg of sodium dodecyl benzene sulfonate, and grinding in a glass grinding bowl for 20 min; then transferring the carbon nanotubes in the grinding bowl into a beaker, washing the residual carbon nanotubes in the grinding bowl for multiple times by using 50ml of deionized water, transferring the carbon nanotubes into the beaker, adding 15mg of graphene oxide and 50ml of deionized water, and mechanically stirring for 30 min; ultrasonic dispersing for 10 min; finally, the agglomerated insoluble substances are removed by centrifugation, and the monodisperse liquid with the carbon nano particle content of 0.04 percent is obtained.
(2) Vacuum dehydrating 6g of polyethylene glycol with average molecular weight of 400 and 4g of polytetrahydrofuran glycol with average molecular weight of 1000 at 110 deg.C for 30min until no bubbles emerge; cooling to 50 ℃, adding 2.8g of diphenylmethane diisocyanate and 4.3g of toluene diisocyanate, and reacting for 20 min; adding 2, 2-dimethylolbutyric acid 1g to react for 30 min; adding a dibutyltin dilaurate catalyst, heating to 80 ℃, and continuing to react for 2 hours; finally, a solution of 0.84g of triethylamine and 5ml of acetone is added and the temperature is reduced to room temperature, thus obtaining a carboxylate-containing polyurethane prepolymer with 2.2 wt% of isocyanate group.
(3) And (3) mixing the carboxylate-containing polyurethane prepolymer prepared in the step (2) with 100ml of carbon nanoparticle monodisperse liquid prepared in the step (1), sequentially adding 0.02g of ethylenediamine and 0.03g of epoxy resin (E-51) while stirring at a high speed, and shearing and emulsifying for 100min to obtain the nano modified waterborne polyurethane high-activity interface reinforcing agent.
The interface enhancement effect of the composite material verifies that the interlaminar shear performance of the continuous fiber 3D printed MT300-1K/P L A composite material unidirectional board is improved by 21%.
Example 3:
(1) weighing 25mg of carboxyl-containing carbon nano tube and 30mg of triton-100, and grinding in a glass grinding bowl for 20 min; then transferring the carbon nanotubes in the grinding bowl into a beaker, washing the residual carbon nanotubes in the grinding bowl for multiple times by using 50ml of deionized water, transferring the carbon nanotubes into the beaker, adding 25mg of graphene oxide and 50ml of deionized water, and mechanically stirring for 30 min; ultrasonic dispersing for 10 min; finally, the agglomerated insoluble substances are removed by centrifugation, and the monodisperse liquid with the carbon nano particle content of 0.05 percent is obtained.
(2) Vacuum dehydrating 4g of polyethylene glycol with average molecular weight of 400 and 6g of polytetrahydrofuran glycol with average molecular weight of 1000 at 110 deg.C for 30min until no bubbles emerge; cooling to 50 ℃, adding 6g of diphenylmethane diisocyanate and 3.0g of isophorone diisocyanate, and reacting for 20 min; then adding 1.3g of 2, 2-dimethylolpropionic acid for reaction for 30 min; then adding a dibutyltin dilaurate catalyst, heating to 80 ℃, and continuing to react for 2 hours; finally, a solution of 1.1g of triethylamine and 5ml of acetone is added and the temperature is reduced to room temperature, thus obtaining a carboxylate-containing polyurethane prepolymer with 2.5 wt% of isocyanate group.
(3) Mixing 4g of the carboxylate-containing polyurethane prepolymer prepared in the step (2) with 100ml of the carbon nanoparticle monodisperse liquid prepared in the step (1), and successively adding 0.02g of diethylenetriamine and 0.04g of epoxy resin (S-27) while stirring at a high speed; shearing and emulsifying for 100min to obtain the nano modified waterborne polyurethane high-activity interface reinforcing agent.
The interface enhancement effect of the composite material verifies that the interlaminar shear performance of the continuous fiber 3D printed MT300-1K/P L A composite material unidirectional board is improved by 25%.
Example 4:
(1) 30mg of carboxyl-containing carbon nano tube and 30mg of triton-100 are weighed and ground in a glass grinding bowl for 20 min; then transferring the carbon nanotubes in the grinding bowl into a beaker, washing the residual carbon nanotubes in the grinding bowl for multiple times by using 50ml of deionized water, transferring the carbon nanotubes into the beaker, adding 30mg of graphene oxide and 50ml of deionized water, and mechanically stirring for 30 min; ultrasonic dispersing for 10 min; finally, the agglomerated insoluble substances are removed by centrifugation, and the monodisperse liquid with the carbon nano particle content of 0.06 percent is obtained.
(2) Taking 6g of polyester glycol with the average molecular weight of 1000 and 4g of polyethylene glycol with the average molecular weight of 400, and carrying out vacuum dehydration for 30min at the temperature of 110 ℃ until no bubbles emerge; cooling to 50 ℃, adding 6g of diphenylmethane diisocyanate and 3.0g of isophorone diisocyanate, and reacting for 20 min; then adding 1.7g of 2, 2-dimethylol dodecanoic acid to react for 30 min; adding a dibutyltin dilaurate catalyst, heating to 80 ℃, and continuing to react for 2 hours; finally, a solution of 1.3g tripropylamine and 5ml acetone is added and the temperature is reduced to room temperature, giving a carboxylate-containing polyurethane prepolymer having an isocyanate group content of 2.5% by weight.
(3) Mixing 5g of the carboxylate-containing polyurethane prepolymer prepared in the step (2) with 100ml of the carbon nanoparticle monodisperse liquid prepared in the step (1), and successively adding 0.03g of triethylene tetramine and 0.05g of epoxy resin (S-27) while stirring at a high speed; shearing and emulsifying for 100min to obtain the nano modified waterborne polyurethane high-activity interface reinforcing agent.
The interface enhancement effect of the composite material verifies that the interlaminar shear performance of the continuous fiber 3D printed MT300-1K/P L A composite material unidirectional board is improved by 17%.
The invention has not been described in detail in part of the common general knowledge of those skilled in the art.
Claims (10)
1. A high-activity interface reinforcing agent for a rapid in-situ composite 3D printing composite material is characterized by comprising the following components in percentage by mass:
2. the reinforcing agent according to claim 1, characterized in that: the carboxylate-containing polyurethane prepolymer is prepared by pre-polymerizing dihydric alcohol, diisocyanate, 2-dihydroxy carboxylic acid and tertiary amine under the action of a catalyst, wherein the dihydric alcohol is a mixture of two or more of polyester dihydric alcohol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran glycol with the molecular weight of 400-1000; the diisocyanate compound is a mixture of two or more of diphenylmethane diisocyanate, toluene diisocyanate and isophorone diisocyanate; the dihydroxy carboxylic acid compound is one of 2, 2-dimethylolpropionic acid, 2, 2-dimethylolbutyric acid and 2, 2-dimethyloldodecanoic acid; the catalyst is dibutyltin dilaurate; the tertiary amine is one or a mixture of triethylamine, tripropylamine and tributylamine.
3. The reinforcing agent according to claim 1, characterized in that: the carboxyl-containing carbon nano tube is a carboxylated multi-wall carbon nano tube, the diameter of the carbon nano tube is 10-20 nm, the length of the carbon nano tube is 10-30 mu m, and the content of carboxyl is 2 +/-0.5 wt%.
4. The reinforcing agent according to claim 1, characterized in that: the graphene oxide is 1-5 layers of graphene oxide, and the oxygen content is 30-45 at%.
5. The reinforcing agent according to claim 1, characterized in that: the chain extender is one or a mixture of two of ethylenediamine, propylenediamine, diethylenetriamine and triethylenetetramine.
6. The reinforcing agent according to claim 1, characterized in that: the epoxy resin is one or a mixture of two of E-51, E-44, AG-80, TDE-85, S-27, S-51, S-60, S-184, S-186, S-500M, S-510, S-610 and S-720.
7. The reinforcing agent according to claim 1, characterized in that: the surfactant is one or a mixture of two of triton-100 and sodium dodecyl benzene sulfonate.
8. A preparation method of a high-activity interface reinforcing agent for a rapid in-situ composite 3D printing composite material is characterized by comprising the following steps:
(1) preparing a carbon nano particle monodisperse solution: grinding and mixing the surfactant and the carboxyl-containing carbon nano-tubes for at least 20min according to the mixture ratio in the claim 1; adding deionized water and graphene oxide, mechanically stirring for 30-50 min, and ultrasonically dispersing for at least 20 min; removing insoluble substances to obtain a carbon nanoparticle monodisperse solution;
(2) preparing a high-activity interface reinforcing agent: mixing the carboxylate-containing polyurethane prepolymer with the carbon nano particle monodisperse, and sequentially adding a chain extender and epoxy resin while shearing and stirring at a high speed; shearing and emulsifying for 60-100 min to obtain the high-activity interface reinforcing agent.
9. The method of claim 8, wherein: the concrete prepolymerization step of the carboxylate-containing polyurethane prepolymer comprises the following steps: dehydrating the dihydric alcohol for at least 30min under the condition of 110-120 ℃ in vacuum; cooling to 50 +/-5 ℃, adding a diisocyanate compound, and reacting for 20-30 min; adding a dihydroxy carboxylic acid compound to react for 30-40 min; adding a catalyst, heating to 80-100 ℃, and continuing to react for 100-120 min; finally, adding tertiary amine and a diluent, stirring for 30 +/-5 min, and cooling to room temperature; the diluent is one or a mixture of two of acetone and butanone.
10. The method of claim 9, wherein: the-OH group of the dihydric alcohol in the prepolymerization process of the carboxylate-containing polyurethane prepolymer: the-CNO group of the diisocyanate compound: the molar ratio of-OH groups of the 2, 2-dihydroxycarboxylic acid compound is 1 (1.5-2.5) to 0.3-1; the content of the diisocyanate compound is 1.5 to 3 wt%.
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| JP2005320641A (en) * | 2004-05-06 | 2005-11-17 | Toray Ind Inc | Sizing agent, carbon fiber and carbon fiber-reinforced composite material |
| CN102206919A (en) * | 2011-04-22 | 2011-10-05 | 中国科学院宁波材料技术与工程研究所 | Graphene modified carbon fiber emulsion sizing agent and preparation method thereof |
| RU2014127302A (en) * | 2011-12-05 | 2016-01-27 | Торэй Индастриз, Инк. | FORMING CARBON FIBERS RAW MATERIAL, FORMED MATERIAL AND CARBON FIBER REINFORCED COMPOSITE MATERIAL |
| JP6354763B2 (en) * | 2012-10-15 | 2018-07-11 | 東レ株式会社 | Fiber reinforced high modulus polymer composite with reinforced interfacial phase |
| JP6860774B2 (en) * | 2014-07-14 | 2021-04-21 | 学校法人同志社 | Fused Deposition Modeling Filament Manufacturing Method for 3D Printers |
| CN104264484B (en) * | 2014-09-26 | 2016-10-26 | 济南大学 | Emulsion type carbon fiber sizing agent and its preparation method and application |
| CN105862428B (en) * | 2016-05-05 | 2018-01-23 | 中国科学院宁波材料技术与工程研究所 | Preparation method of carbon fiber sizing agent that a kind of graphene is modified and products thereof |
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