CN109972397B - Preparation and application of in-situ synthesized nano-oxide reinforced carbon fiber sizing agent and basalt fiber impregnating compound - Google Patents
Preparation and application of in-situ synthesized nano-oxide reinforced carbon fiber sizing agent and basalt fiber impregnating compound Download PDFInfo
- Publication number
- CN109972397B CN109972397B CN201910224382.9A CN201910224382A CN109972397B CN 109972397 B CN109972397 B CN 109972397B CN 201910224382 A CN201910224382 A CN 201910224382A CN 109972397 B CN109972397 B CN 109972397B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- sizing agent
- nano
- carbon fiber
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/5013—Amines aliphatic containing more than seven carbon atoms, e.g. fatty amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
- D06M11/77—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 silicon or compounds thereof
- D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- 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
- D06M15/55—Epoxy resins
-
- 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
- D06M2101/40—Fibres of carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to a preparation method of a carbon fiber sizing agent and a basalt fiber/glass fiber impregnating compound for in-situ synthesis of nano-oxide reinforced epoxy resin, and a product and application thereof. The in-situ synthesized nano oxide reinforced epoxy resin emulsion has the advantages of self-emulsification, controllable emulsion micelle particle size, good emulsion storage stability, improved thermal stability, yellowing resistance and the like, is applied to epoxy resin type carbon fiber sizing agents and basalt fiber/glass fiber sizing agents, and can improve the processability and mechanical property of fibers and the interlaminar shear strength of fiber reinforced resin matrix composite materials.
Description
Technical Field
The invention belongs to the field of application of fiber interface modification auxiliary agents, relates to preparation of an in-situ synthesized nano oxide reinforced epoxy resin type carbon fiber sizing agent and a basalt fiber/glass fiber impregnating compound, and products and application thereof, and particularly relates to preparation of an in-situ synthesized nano oxide reinforced epoxy resin type carbon fiber sizing agent and a glass fiber/basalt fiber impregnating compound.
Background
The fiber interface modification auxiliary agent generally refers to a carbon fiber sizing agent, a glass fiber/basalt fiber impregnating compound and the like. The carbon fiber has the advantages of high axial strength and modulus, low density, high specific performance, no creep, good fatigue resistance, good corrosion resistance, good X-ray permeability, good electric and heat conductivity, good electromagnetic shielding performance and the like. The composite material made of carbon fiber has wide application prospect in civil industry such as aviation, aerospace, automobiles, electronic machinery, chemical engineering, light textile and the like and the fields of military affairs and high technology, and the carbon fiber is known as a novel material in the 21 st century. However, carbon fibers are brittle materials, and have the phenomena of easy friction and fluffing, monofilament fracture and the like in the production process, which greatly reduce the strength of the carbon fibers. Broken filaments can cause accidents such as circuit breaking of electrical equipment and instruments, seriously affect production safety and bring harm to the health of operators. In addition, the existence of the broken filaments can cause the resin matrix not to fully wet the carbon fibers, and pores are easily generated in the process of preparing the composite material, so that the mechanical property of the composite material is influenced. The carbon fiber is subjected to sizing treatment, so that the broken filament amount of the carbon fiber can be effectively reduced, and the compatibility of the carbon fiber and a resin matrix can be improved, so that the performance of the carbon fiber composite material is directly influenced by the quality of a sizing agent. The production process of the basalt fiber is pollution-free and harmless, is a green and environment-friendly material, and has wide application in the fields of friction materials, shipbuilding materials, automobile industry and the like. Glass fibers have many advantages such as good insulation properties, high heat resistance, and high mechanical strength, but also have disadvantages such as brittleness and poor abrasion resistance. The impregnating compound can greatly improve the surface properties of basalt fibers and glass fibers.
The epoxy resin contains two or more epoxy groups, the epoxy groups are cyclic structures formed by one oxygen atom and two carbon atoms, and the epoxy resin has high activity and can chemically react with various substances containing active hydrogen, such as amine, amide, phenol and the like. The epoxy resin has good cohesiveness and corrosion resistance, is easy to form a tough and firm film on the surface of the carbon fiber, and plays a role in protecting the carbon fiber to become the main component of most carbon fiber sizing agents. The nanometer oxide can be tightly combined with epoxy resin due to the special structure, so that the thermodynamic stability of the epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber sizing agent can be improved, the surface performance of the sized fiber can be optimized, and the performance of the fiber composite material is improved, thereby being widely concerned by people.
Chinese patent CN 1050404444 a (published japanese 2015.11.11) discloses a method for preparing a novel nano-silica water-based epoxy resin sizing agent for carbon fibers, which combines water-based modified epoxy resin with nano-silica sol, and adds aromatic amine curing agent, antioxidant and organic solvent to prepare the nano-water-based epoxy resin sizing agent, thereby improving the stability of emulsion and the toughness of sized carbon fibers. However, the prepared epoxy resin sizing agent adopts an external emulsifier, and has the defects of poor stability, easy demulsification and the like. The prepared modified epoxy resin is combined with the nano silicon dioxide prepared under the alkaline condition, the combination force of the modified epoxy resin and the nano silicon dioxide is not very strong, the preparation efficiency is low, high-temperature curing is required, precipitates are easy to generate, the stability is poor, and the cost is high.
Disclosure of Invention
Aiming at the dispersibility and storage stability of the nano oxide in the emulsion in the prior art; the invention aims to provide a method for preparing a nano-oxide reinforced epoxy resin type carbon fiber sizing agent and a basalt fiber/glass fiber impregnating compound by in-situ synthesis.
Another object of the present invention is to: provides the products of the in-situ synthesized nano oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a preparation method for in-situ synthesis of a nano-oxide reinforced epoxy resin type carbon fiber sizing agent and a basalt fiber/glass fiber impregnating compound is characterized by comprising the following synthesis steps:
(1) adding polyether amine and an amino organic compound into a solvent-1, dissolving for a period of time at a certain temperature under an inert atmosphere until all solids are completely dissolved, adding epoxy resin, gradually raising the temperature to a proper temperature, and reacting for a certain time at the temperature to obtain an amino modified epoxy resin intermediate;
(2) adding a solvent-2 into the intermediate prepared in the step (1) at a certain temperature under stirring to be fully and uniformly mixed, and then adding a certain amount of reagent-1 and deionized water to be fully hydrolyzed under an alkaline condition to form a nano oxide;
(3) adding a certain amount of acid to carry out salt forming reaction;
(4) adding distilled water, stirring and emulsifying for a certain time to prepare the in-situ synthesized nano oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound.
On the basis of the scheme, the amino organic compounds in the step (1) are primary amine and secondary amine, the polyether amine is amino polyethylene glycol monomethyl ether or methoxy polyethylene glycol amine, methoxy polyethylene glycol/polypropylene glycol amine, amino polyethylene glycol monoethyl ether, the molecular weight is 400-5000, and the molar ratio of the added polyether amine to the amino organic compounds is (0-10): (10-0).
Preferably, the best molar ratio of the added polyether amine to the amino organic compound is (0-2): 10-8.
Preferably, the primary and secondary amines are butylamine, hexylamine, octylamine, laurylamine and octadecylamine, aniline, cyclohexylamine, piperazine, but not limited to the amines listed.
Preferably, the primary and secondary amines are preferably octadecylamine and laurylamine.
Preferably, the polyether amine has an optimum molecular weight of 1000 to 2000.
On the basis of the scheme, the solvent-1 in the step (1) is an organic solvent which does not contain reactive hydrogen and can be mutually dissolved with water, and the dosage of the organic solvent is 5-50% of the total feeding amount; the certain temperature is 30-80 ℃, so that the charged amino organic compound is fully mixed and dissolved, and can be uniformly mixed with subsequently added epoxy resin, and the occurrence of heterogeneous reaction is prevented; the inert atmosphere is nitrogen or argon; the dissolving time is 20-30 minutes; the epoxy resin is bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, brominated epoxy resin, fluorinated epoxy resin, bifunctional aliphatic epoxy resin, linear bifunctional novolac epoxy resin and aliphatic epoxy resin, but is not limited to the listed epoxy resins, and the epoxy equivalent is 100-1000; the proper reaction temperature is 80-120 ℃; the reaction is carried out for a certain time of 2-6 hours.
Preferably, the organic solvent-1 is acetone, tetrahydrofuran, Dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO).
Preferably, the dosage of the solvent-1 is 0-50% of the total feeding materials, and the optimal range is 10-20%.
Preferably, the optimal proper reaction temperature is 100-110 ℃; the optimal reaction time is 2-4 hours.
On the basis of the scheme, the solvent-2 in the step (2) is acetone, tetrahydrofuran and absolute ethyl alcohol, and the dosage of the solvent is 5% -50% of that of the amino modified epoxy resin intermediate; the reagent-1 is a nanometer oxide precursor; the dosage of the reagent-1 is 0.1-200% of the mass of the intermediate, and the optimal range is 5-100%; the certain amount of deionized water is calculated according to (the adding amount of the nano oxide precursor/the molecular weight of the nano oxide precursor) multiplied by 2 multiplied by 18; the temperature is 40-60 ℃.
Preferably, the optimal dosage of the reagent-1 is 5-20% of the mass of the intermediate.
Preferably, the nano-oxide precursor is one or more of ethyl silicate (TEOS), tetrabutyl titanate, zinc acetylacetonate, copper acetylacetonate and other metal organic compounds, but is not limited to the listed precursors.
Based on the scheme, the acid in the step (3) is fatty acid or aromatic acid, and the optimal range is (60% -100%) calculated according to the molar weight of the amine input (0% -100%).
Preferably, the fatty acid in step (3) is formic acid, glacial acetic acid, propionic acid, butyric acid, oleic acid, and the aromatic acid is benzoic acid.
On the basis of the scheme, the certain reaction time in the step (4) is 4-5 hours.
The invention provides an in-situ synthesized nano-oxide reinforced epoxy resin type carbon fiber sizing agent and a basalt fiber/glass fiber impregnating compound, which are prepared according to any one of the methods.
The invention provides an application of in-situ synthesized nano-oxide reinforced epoxy resin type carbon fiber sizing agent and basalt fiber/glass fiber impregnating compound as carbon fiber sizing agent and basalt fiber/glass fiber impregnating compound in the industrial production of carbon fibers, basalt fibers and glass fibers.
The invention provides a method for preparing a nano-oxide reinforced epoxy resin type carbon fiber sizing agent and a glass fiber/basalt fiber impregnating compound through in-situ synthesis. Firstly, polyether amine, amino organic compound and epoxy resin are reacted to synthesize a modified epoxy resin intermediate, then a certain amount of nano oxide precursor such as ethyl silicate (TEOS), tetrabutyl titanate, zinc acetylacetonate and the like is added to hydrolyze under an alkaline condition, fatty acid or aromatic acid is added to perform a neutralization reaction, and distilled water is added to perform self-emulsification, so that the nano oxide modified carbon fiber sizing agent, the glass fiber and the basalt fiber impregnating compound are prepared. The sizing agent and the impregnating compound synthesized by the method have the following advantages: the preparation process is simple and the cost is low; the sizing agent/impregnating compound prepared by adopting the self-assembly and self-emulsification technologies has controllable particle size, high content of nano oxides, uniform dispersion of the nano oxides and high storage stability of emulsion; introducing a nanometer oxide precursor in situ, and hydrolyzing the nanometer oxide precursor by using ethyl silicate (TEOS), tetrabutyl titanate, zinc acetylacetonate, copper acetylacetonate and the like to prepare the nanometer oxide. Taking ethyl silicate as an example, TEOS hydrolyzes to generate silicon hydroxyl (Si-OH)/metal or nonmetal-hydroxide (M-OH) bonds, which is beneficial to the formation of organic-inorganic hybridization between nano-oxide and organic polymer to form core-shell structure emulsion micelles, thus improving the dispersibility and storage stability of nano-oxide in emulsion; the nano oxide reinforced epoxy resin sizing agent and the glass fiber/basalt fiber impregnating compound can greatly improve the mechanical property of the fiber and the interlaminar shear strength of the fiber reinforced resin matrix composite material; the preparation method can also improve the thermal stability and yellowing resistance of the sizing agent/impregnating compound.
The patent synthesizes nano-oxide in situ by a sol-gel method, applies the nano-oxide to the production of reinforced epoxy resin type carbon fiber sizing agent and basalt fiber/glass fiber soakage and the production field of carbon fiber, basalt fiber and glass fiber, and provides a novel and efficient preparation method of epoxy resin type carbon fiber sizing agent and basalt fiber/glass fiber soakage. Firstly, preparing an intermediate by adopting amino modified epoxy resin, then adding a nano oxide precursor, uniformly stirring, then adding a certain amount of water, hydrolyzing the nano oxide precursor under an alkaline condition, finally adding salifying reagent acid and distilled water, stirring and emulsifying for a certain time, and thus preparing the in-situ synthesized nano oxide reinforced epoxy resin emulsion. The nano oxide is embedded through in-situ hydrolysis reaction of a precursor sol-gel method, and forms organic-inorganic hybrid emulsion micelle with amino modified epoxy resin and a core-shell structure. The in-situ synthesized nano oxide reinforced epoxy resin emulsion has the advantages of self-emulsification, controllable emulsion micelle particle size, good stability and the like, and can improve the processability and mechanical property of fibers and the interlaminar shear strength of a fiber reinforced resin matrix composite material when being applied to the fields of epoxy resin type carbon fiber sizing agents and basalt fiber/glass fiber impregnating agents.
The invention discloses an in-situ synthesis technology for preparing a nano-oxide reinforced epoxy resin type carbon fiber sizing agent and a basalt fiber/glass fiber impregnating compound, wherein the nano-oxide comprises silicon dioxide, titanium dioxide, chromium dioxide, zinc oxide, copper oxide and the like. The reinforced epoxy resin type emulsion can effectively wrap the nano oxide in the polymer, obviously improve the thermal stability of the sizing agent and the impregnating compound, control the percentage content of the added nano oxide by adopting a self-assembly technology, and improve the storage stability of the sizing agent and the impregnating compound. In addition, the nano oxide is introduced into the epoxy resin type carbon fiber sizing agent, the basalt fiber and the glass fiber impregnating compound, so that the bonding strength between the fiber and the resin can be increased, and the surface properties of the carbon fiber, the glass fiber and the basalt fiber are improved.
The glass fiber/basalt fiber sizing agent has the advantage that the stability of the sizing agent is greatly improved by the amino modified epoxy resin intermediate synthesized by self-assembly. The nano oxide reinforced epoxy resin sizing agent and the glass fiber/basalt fiber sizing agent are controlled by adding ethyl silicate, tetrabutyl titanate, zinc acetylacetonate, copper acetylacetonate and the like, so that the mechanical property of the sized carbon fiber and the property of the composite material are greatly improved.
Drawings
The present invention is described in further detail below with reference to the attached drawings and examples, which are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way.
FIG. 1 shows a nano SiO2The particle size distribution diagram of the modified epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound.
Note that 5% is the data obtained by adding ethyl silicate accounting for 5% of the mass of the intermediate, 10% is the data obtained by adding ethyl silicate accounting for 10% of the mass of the intermediate, and measuring the data at 25 ℃ by using an OMNI particle size analyzer and a Zeta potential analyzer.
Detailed Description
Example 1:
adding 32.49 g of polyetheramine, 78.08 g of octadecylamine and 100 g of N-methylpyrrolidone into a reactor, reacting for 30 minutes under the conditions of 50 ℃ and nitrogen atmosphere and stirring, adding low-molecular-weight bisphenol A epoxy resin (epoxy equivalent of 175-208) and medium-and-high-molecular-weight bisphenol A epoxy resin (epoxy equivalent of 450-660) in a molar ratio of 8:2, gradually heating to 110 ℃, and reacting for 3 hours at the temperature to obtain the amino modified epoxy resin with the solid content of 75.09%. Installing a normal pressure reflux condensing device, adding 50 g of acetone, 9.39 g (5 percent of addition) of ethyl silicate and 1.6 g of distilled water at the temperature of 60 ℃ and the rotating speed of 40-50 r/min, stirring for 2-3 hours, then adding 19.49 g of glacial acetic acid and 438.03 g of distilled water, and reacting for 4 hours to obtain the nano SiO2Reinforced epoxy resin type carbon fiber sizing agent and basalt fiber/glass fiber impregnating compound.
Example 2:
adding 32.49 g of polyetheramine, 78.08 g of octadecylamine and 100 g of N-methylpyrrolidone into a reactor, reacting for 30 minutes at 50 ℃ under the condition of nitrogen atmosphere stirring, adding 138.71 g of bisphenol A epoxy resin (epoxy equivalent of 175-208), gradually heating to 110 ℃, and reacting for 3 hours at the temperature to obtain the amino modified epoxy resin with solid contentThe content was 75.09%. Installing a normal pressure reflux condensing device, adding 50 g of acetone, 18.77 g (10 percent of addition) of ethyl silicate and 3.25 g of distilled water at the temperature of 60 ℃ and the rotating speed of 40-50 r/min, stirring for 2-3 hours, then adding 19.49 g of glacial acetic acid and 438.03 g of distilled water, and reacting for 4 hours to obtain the nano SiO2Modified epoxy resin type carbon fiber sizing agent and basalt fiber/glass fiber impregnating compound.
Example 3:
adding 32.49 g of polyetheramine, 78.08 g of octadecylamine and 100 g of N-methylpyrrolidone into a reactor, reacting for 30 minutes at 50 ℃ under the condition of nitrogen atmosphere stirring, adding 138.71 g of bisphenol A epoxy resin (epoxy equivalent of 175-208), gradually heating to 110 ℃, and reacting for 3 hours at the temperature to obtain the amino modified epoxy resin with the solid content of 75.09%. Installing a normal pressure reflux condensing device, adding 50 g of acetone, 28.16 g (15 percent of addition) of ethyl silicate and 4.9 g of distilled water at the temperature of 60 ℃ and the rotating speed of 40-50 r/min, stirring for 2-3 hours, then adding 19.49 g of glacial acetic acid and 438.03 g of distilled water, and reacting for 4 hours to obtain the nano SiO2Modified epoxy resin type carbon fiber sizing agent and basalt fiber/glass fiber impregnating compound.
Example 4:
adding 32.49 g of polyetheramine, 78.08 g of octadecylamine and 100 g of N-methylpyrrolidone into a reactor, reacting for 30 minutes at 50 ℃ under the condition of nitrogen atmosphere stirring, adding 138.71 g of bisphenol A epoxy resin (epoxy equivalent of 175-208), gradually heating to 110 ℃, and reacting for 3 hours at the temperature to obtain the amino modified epoxy resin with the solid content of 75.09%. Installing a normal pressure reflux condensing device, adding 50 g of acetone, 37.55 g (20 percent of addition) of ethyl silicate and 6.5 g of distilled water at the temperature of 60 ℃ and the rotating speed of 40-50 r/min, stirring for 2-3 hours, adding 19.49 g of glacial acetic acid and 438.03 g of distilled water, and reacting for 4 hours to obtain the nano SiO2Modified epoxy resin type carbon fiber sizing agent and basalt fiber/glass fiber impregnating compound.
Comparative example 1
Adding 32.49 g of polyetheramine, 78.08 g of octadecylamine and 100 g of N-methylpyrrolidone into a reactor, reacting for 30 minutes under the conditions of 50 ℃, nitrogen atmosphere and stirring, then adding the materials according to the molar ratio of 8:2 of low-molecular-weight bisphenol A epoxy resin (epoxy equivalent 175-208) to medium-molecular-weight bisphenol A epoxy resin (epoxy equivalent 450-660), gradually heating to 110 ℃, and reacting for 3 hours at the temperature to obtain the amino modified epoxy resin with the solid content of 75.09%. And (3) installing a normal-pressure reflux condensing device, adding 50 g of acetone, 19.49 g of glacial acetic acid and 438.03 g of distilled water at the temperature of 60 ℃ and the rotating speed of 40-50 r/min, and reacting for 4 hours to obtain the amino modified epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound.
The embodiments described above are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications and improvements made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
TABLE 1 mechanical stability of nano-oxide reinforced epoxy resin type carbon fiber sizing agent, basalt fiber/glass fiber sizing agent and epoxy resin type carbon fiber sizing agent, basalt fiber/glass fiber sizing agent synthesized in situ
Note: sample No. 1 is an amino-modified epoxy resin type carbon fiber sizing agent, a basalt fiber/glass fiber wetting agent; sample No. 2 is an epoxy resin type carbon fiber sizing agent modified by adding nano silicon dioxide, a basalt fiber/glass fiber impregnating compound, and mechanical stability is tested by using a domestic high-speed centrifuge of HC-3018.
TABLE 2 amino-modified epoxy resin type carbon fiber sizing agent and nano SiO2Test result on production line of reinforced epoxy resin type carbon fiber sizing agent
Note: sample No. 1 is an amino-modified epoxy resin type carbon fiber sizing agent in comparative example 1, and relevant data on the production line is provided by Jilin Jinggong Co., Ltd; no. 2 is the carbon fiber sizing agent of the nano-silica reinforced epoxy resin type synthesized in situ in case 1, and the relevant data on the production line is provided by Jinggong carbon fiber Co., Ltd.
Claims (15)
1. A preparation method for in-situ synthesis of a nano-oxide reinforced epoxy resin type carbon fiber sizing agent and a basalt fiber/glass fiber impregnating compound is characterized by comprising the following synthesis steps:
(1) adding polyether amine and an amino organic compound into a solvent-1, dissolving for a period of time at a certain temperature under an inert atmosphere until all solids are completely dissolved, adding epoxy resin, gradually raising the temperature to a proper temperature, and reacting for a certain time at the temperature to obtain an amino modified epoxy resin intermediate;
(2) adding a solvent-2 into the intermediate prepared in the step (1) at a certain temperature under stirring to be fully and uniformly mixed, and then adding a certain amount of reagent-1 and deionized water to be fully hydrolyzed under an alkaline condition to form a nano oxide;
(3) adding a certain amount of acid to carry out salt forming reaction;
(4) adding distilled water, stirring and emulsifying for a certain time, and synthesizing in situ to prepare a nano oxide reinforced epoxy resin type carbon fiber sizing agent and a basalt fiber/glass fiber impregnating compound;
the solvent-1 in the step (1) is an organic solvent which does not contain reactive hydrogen and can be mutually dissolved with water, and the dosage of the organic solvent is 5-50% of the total feeding amount; the certain temperature is 30-80 ℃, so that the charged amino organic compound is fully mixed and dissolved, and can be uniformly mixed with subsequently added epoxy resin, and the occurrence of heterogeneous reaction is prevented; the inert atmosphere is nitrogen or argon; the dissolving time is 20-30 minutes; the epoxy resin is bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, brominated epoxy resin, fluorinated epoxy resin, bifunctional aliphatic epoxy resin and linear bifunctional novolac epoxy resin, and the epoxy equivalent value is 100-1000; the proper temperature is 80-120 ℃; the reaction is carried out for 2-6 hours;
the amino organic compounds in the step (1) are primary amine and secondary amine, the polyether amine is amino polyethylene glycol monomethyl ether or methoxy polyethylene glycol amine, methoxy polyethylene glycol/polypropylene glycol amine, amino polyethylene glycol monoethyl ether, and the molecular weight is 400-5000;
the primary amine is butylamine, hexylamine, octylamine, laurylamine and octadecylamine, the aniline, the cyclohexylamine and the diamine are piperazine;
the reagent-1 is a nanometer oxide precursor; the nano oxide precursor is one or more of ethyl silicate (TEOS), tetrabutyl titanate, zinc acetylacetonate and copper acetylacetonate.
2. The method for preparing the in-situ synthesized nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound according to claim 1, wherein the primary amine is octadecylamine and laurylamine.
3. The method for preparing the nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound for in-situ synthesis according to claim 1, wherein the polyether amine has an optimal molecular weight of 1000-2000.
4. The method for preparing the nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound for in-situ synthesis according to claim 1, wherein the solvent-1 is acetone, tetrahydrofuran, Dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO).
5. The method for preparing the in-situ synthesized nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound according to claim 1 or 4, wherein the dosage of the solvent-1 is 10-20% of the total feeding amount.
6. The method for preparing the nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound for in-situ synthesis according to claim 1, wherein the appropriate temperature is 100-110 ℃; the reaction is carried out for a certain time of 2-4 hours.
7. The method for preparing the nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound for in-situ synthesis according to claim 1, wherein the solvent-2 in the step (2) is acetone, tetrahydrofuran and absolute ethyl alcohol, and the dosage of the solvent-2 is 5% -50% of that of the amino modified epoxy resin intermediate; the dosage of the reagent-1 is 0.1-200% of the mass of the intermediate; the certain amount of deionized water is calculated according to (the adding amount of the nano oxide precursor/the molecular weight of the nano oxide precursor) multiplied by 2 multiplied by 18; the certain temperature is 40-60 ℃.
8. The method for preparing the nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound for in-situ synthesis according to claim 7, wherein the amount of the reagent-1 in the step (2) is 5-100% of the mass of the intermediate.
9. The method for preparing the nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound for in-situ synthesis according to claim 8, wherein the amount of the reagent-1 is 5-20% of the mass of the intermediate.
10. The method for preparing the nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound for in-situ synthesis according to claim 1, wherein the acid in the step (3) is a fatty acid or an aromatic acid.
11. The method for preparing the in-situ synthesized nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound according to claim 1 or 10, wherein the amount of the acid used in the step (3) is 60 to 100 percent of the molar amount of the amine used.
12. The method for preparing the nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound for in-situ synthesis according to claim 10, wherein the fatty acid in the step (3) is formic acid, glacial acetic acid, propionic acid, butyric acid or oleic acid, and the aromatic acid is benzoic acid.
13. The method for preparing the nano-oxide reinforced epoxy resin type carbon fiber sizing agent and the basalt fiber/glass fiber impregnating compound for in-situ synthesis according to claim 1, wherein the emulsification in the step (4) is carried out for a certain time of 4-5 hours.
14. An in-situ synthesized nano-oxide reinforced epoxy resin type carbon fiber sizing agent and a basalt fiber/glass fiber impregnating compound, which are characterized by being prepared according to the method of any one of claims 1 to 13.
15. Use of the in situ synthesized nano-oxide reinforced epoxy resin type carbon fiber sizing agent and basalt fiber/glass fiber sizing agent according to claim 14 as a carbon fiber sizing agent and basalt fiber/glass fiber sizing agent in the industrial production of carbon fibers, basalt fibers and glass fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910224382.9A CN109972397B (en) | 2019-03-25 | 2019-03-25 | Preparation and application of in-situ synthesized nano-oxide reinforced carbon fiber sizing agent and basalt fiber impregnating compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910224382.9A CN109972397B (en) | 2019-03-25 | 2019-03-25 | Preparation and application of in-situ synthesized nano-oxide reinforced carbon fiber sizing agent and basalt fiber impregnating compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109972397A CN109972397A (en) | 2019-07-05 |
| CN109972397B true CN109972397B (en) | 2021-07-13 |
Family
ID=67080209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910224382.9A Active CN109972397B (en) | 2019-03-25 | 2019-03-25 | Preparation and application of in-situ synthesized nano-oxide reinforced carbon fiber sizing agent and basalt fiber impregnating compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109972397B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548181A (en) * | 2020-06-01 | 2020-08-18 | 浙江华恒复合材料有限公司 | Vacuum composite heat insulation plate with multi-level hole structure and preparation method thereof |
| CN115521098B (en) * | 2022-10-21 | 2023-09-12 | 山东禹城丽富达公路工程有限公司 | Rapid repairing material for road concrete and preparation process thereof |
| CN115505138B (en) * | 2022-10-27 | 2023-05-30 | 济南新材料产业技术研究院 | Basalt short fiber reinforced polyamide imide resin and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670105A (en) * | 2004-03-19 | 2005-09-21 | 中国科学院理化技术研究院 | Modified epoxy resin adhesive used under low temperature |
| CN100348665C (en) * | 2006-04-28 | 2007-11-14 | 湘潭大学 | Process for in-situ polymerization preparation of nylon 6/epoxy resin/silicon dioxide nano composite materials |
| CN101864060B (en) * | 2010-06-03 | 2012-04-25 | 上海交通大学 | Preparation method of epoxy nanometer hybrid material with low surface energy |
| CN102675559B (en) * | 2012-05-22 | 2013-06-19 | 苏州巨峰电气绝缘系统股份有限公司 | Method for in-situ synthesis of epoxy group vacuum pressure impregnating resin hybridized by inorganic nanometer particles |
| MX358938B (en) * | 2014-01-21 | 2018-09-10 | Centro De Investig En Polimeros S A De C V | A cycloaliphatic resin, method for obtaining the same and its application in a high resistance coating. |
| CN105040444B (en) * | 2015-09-08 | 2018-04-20 | 威海诺葳信和新材料有限公司 | A kind of preparation method of nanometer waterborne epoxy resin sizing agent for carbon fiber |
| CN109251305B (en) * | 2018-07-10 | 2020-09-22 | 吉林乾仁新材料有限公司 | Self-assembly self-emulsifying amphiphilic water-based cationic epoxy resin type high-performance fiber sizing agent/impregnating agent/film-forming agent and preparation method thereof |
-
2019
- 2019-03-25 CN CN201910224382.9A patent/CN109972397B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109972397A (en) | 2019-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109972397B (en) | Preparation and application of in-situ synthesized nano-oxide reinforced carbon fiber sizing agent and basalt fiber impregnating compound | |
| CN102206919A (en) | Graphene modified carbon fiber emulsion sizing agent and preparation method thereof | |
| Zhang et al. | The modification of Kevlar fibers in coupling agents by γ-ray co-irradiation | |
| CN114045071B (en) | Building aluminum veneer curtain wall finish paint and preparation method thereof | |
| CN109972398B (en) | High-thermal-conductivity flexible epoxy resin insulating material and preparation method and application thereof | |
| CN113563577A (en) | Phenolphthalein modified polyaryletherketone water-based sizing agent and preparation method and application thereof | |
| CN111977991A (en) | Surface treating agent and method for preparing colored glass fiber by using same | |
| CN109608620B (en) | Flame-retardant degradable polyphosphazene type epoxy resin and preparation technology thereof | |
| CN111732871B (en) | Light high-heat-resistance coating and preparation method thereof | |
| CN112322244A (en) | High-temperature-resistant adhesive and preparation method thereof | |
| CN113003948B (en) | Basalt fiber sizing agent, preparation method thereof and basalt fiber composite material | |
| CN112574643A (en) | Flame-retardant water-based insulating paint and preparation method and application thereof | |
| CN116144210B (en) | High-flash-point fireproof coating based on modified cage-type silsesquioxane and preparation method thereof | |
| CN110258118B (en) | Water-soluble temperature-resistant carbon fiber sizing agent and preparation method thereof | |
| CN113652005B (en) | Polyborosiloxane modified ammonium polyphosphate and preparation method thereof | |
| CN109403028B (en) | Modification method of heterocyclic aramid fiber and modified heterocyclic aramid fiber | |
| CN114380958A (en) | High-thermal-conductivity epoxy VPI resin for high-voltage motor and preparation method and application thereof | |
| JP2009293140A (en) | Carbon filament bundle | |
| CN112647347A (en) | Preparation method of heat-resistant auxiliary agent for heat-resistant insulating paper | |
| CN114989759B (en) | Modified epoxy resin with low shrinkage, high toughness and low stress and preparation method thereof | |
| CN118186754A (en) | Carbon fiber sizing agent, preparation method thereof, carbon fiber material and carbon fiber reinforced resin composite material | |
| CN112341756B (en) | Organic silicon modified epoxy resin for robot insulating clothes and preparation method thereof | |
| CN114990925B (en) | Preparation method of heat-resistant auxiliary agent | |
| CN109853242B (en) | Carbon fiber sizing agent and preparation method thereof | |
| CN117988117A (en) | Aqueous carbon fiber sizing agent and preparation method 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 |