CN114946786A - Glass fiber toughened light fishing rod and preparation method thereof - Google Patents

Glass fiber toughened light fishing rod and preparation method thereof Download PDF

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Publication number
CN114946786A
CN114946786A CN202210769116.6A CN202210769116A CN114946786A CN 114946786 A CN114946786 A CN 114946786A CN 202210769116 A CN202210769116 A CN 202210769116A CN 114946786 A CN114946786 A CN 114946786A
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glass fiber
fishing rod
cloth
toughened
liquid
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CN114946786B (en
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马国栋
马国梁
马奎
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Anhui Bojia Fishing Tackle Co ltd
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Anhui Bojia Fishing Tackle Co ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01K—ANIMAL HUSBANDRY; CARE OF BIRDS, FISHES, INSECTS; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K87/00—Fishing rods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0013—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using multilayer webs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/045—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyolefin or polystyrene (co-)polymers
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/143—Inert, i.e. inert to chemical degradation, corrosion resistant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
    • Y02A40/81—Aquaculture, e.g. of fish

Abstract

The invention discloses a glass fiber toughened light fishing rod and a preparation method thereof, and relates to the technical field of high-performance fishing rods. The invention is used for solving the technical problems that the hierarchical structure and the preparation method need to be further improved to reduce the content of bubbles, so that the finished product with the same weight has larger fishing weight and more excellent toughness, interlaminar shear strength and corrosion resistance; the finished fishing rod has better toughness, interlaminar shear strength and corrosion resistance, and the fishing rod with the same weight has larger fishing weight.

Description

Glass fiber toughened type light fishing rod and preparation method thereof
Technical Field
The invention relates to the technical field of high-performance fishing rods, in particular to a glass fiber toughened light fishing rod and a preparation method thereof.
Background
The strength and toughness of the existing common fishing rod are reduced quickly when the common fishing rod is used for a long time under the condition of high strength and high frequency, the resistance to instantaneous small-angle force is low, the service life of the product is short, the rigidity can be reduced after the common fishing rod is used for a long time, and the common fishing rod does not meet the requirements of use under the conditions of high strength and high frequency after being used for a period of time.
The prior art (CN108000916B) discloses a preparation method of a single-layer porous graphene reinforced carbon fiber fishing rod, which comprises the steps of firstly stripping expanded graphite into graphene microchip dispersion liquid, spraying and drying to obtain graphene microchip powder, carrying out microwave treatment in NMP dispersion liquid after oxidation to obtain a single-layer porous graphene precursor, finally carrying out activation treatment on the precursor by using strong base to obtain single-layer porous graphene with rich holes and larger pore diameter, compounding the single-layer porous graphene with carbon fibers to obtain a carbon fiber cloth material, and finally cutting the carbon fiber cloth material into the fishing rod; the single-layer porous graphene can easily coat carbon fibers, and meanwhile provides enough channels for the circulation of resin among carbon fiber cloth in the curing process of the fishing rod, so that organic integrity with good continuity is formed among the graphene, the carbon fibers and the carbon fibers, the tensile bending strength of the carbon fiber fishing rod is greatly improved, and the fishing rod fishing weight is remarkably increased. However, the following technical problems are found: further improvements in the layered structure and manufacturing process are needed to reduce the bubble content, resulting in a product of equivalent weight with greater fishing weight and better toughness, interlaminar shear strength and corrosion resistance.
A solution is now proposed to address the technical drawback in this respect.
Disclosure of Invention
The invention aims to provide a glass fiber toughened light fishing rod and a preparation method thereof, which are used for solving the technical problems that in the prior art, the hierarchical structure and the preparation method need to be further improved to reduce the content of bubbles, so that a finished product with the same weight has larger fishing weight and has better toughness, interlaminar shear strength and corrosion resistance.
The purpose of the invention can be realized by the following technical scheme:
a glass fiber toughening type light fishing rod takes carbon fiber cloth as prepreg cloth, a fishing rod blank is obtained by sequentially carrying out resin prepreg liquid treatment, glass fiber cloth wrapping, modified toughening glass fiber liquid treatment, curing cutting, pipe coiling, belt winding fastening and demolding on the prepreg cloth, and the fishing rod blank is polished, coated and assembled to obtain a finished fishing rod product;
the preparation method of the resin prepreg liquid comprises the following steps:
step one, sequentially adding 2, 4-pentanediol, adipic acid and cobalt iso-octoate into a reaction kettle provided with a condensation reflux pipe and a mechanical stirrer, heating to 205-220 ℃, stirring at a rotating speed of 80-120 rpm until a solution is clear, cooling to 145-155 ℃, dropwise adding maleic anhydride into a constant-pressure dropping funnel, heating to 210-225 ℃ after dropwise adding is finished, stirring to react until the acid value is less than 10, adding ethyl acetate, naturally cooling to room temperature, filtering, and carrying out reduced pressure concentration to remove the ethyl acetate to obtain unsaturated polyester resin;
and step two, adding azodiisobutyronitrile into the unsaturated polyester resin, heating to reflux, dropwise adding butyl acrylate, continuously stirring for 1-2 hours after dropwise adding is finished, and adding dimethylethanolamine for neutralization reaction after the temperature of the reaction liquid is reduced to 40-50 ℃ to obtain the resin preimpregnation liquid.
The theoretical reaction mechanism of the resin prepreg is as follows:
Figure BDA0003726722770000031
the resin prepreg liquid takes saturated dibasic acid adipic acid, saturated dihydric alcohol 2, 4-pentanediol and maleic anhydride as raw materials, linear unsaturated polyester resin with ester bonds and unsaturated double bonds is obtained through condensation polymerization under the catalysis of cobalt iso-octoate, the unsaturated polyester resin and acrylic acid monomer butyl acrylate are subjected to grafting reaction under the catalysis of free radical initiator azobisisobutyronitrile, and the reaction mechanism of the grafting reaction is theoretically analyzed to graft the butyl acrylate monomer on the carbon-carbon double bonds; the adipic acid and the 2, 4-pentanediol have longer carbon chains, the high molecular weight unsaturated polyester resin formed by polycondensation with the maleic anhydride improves the corrosion resistance and the heat resistance, and the grafting of the butyl acrylate introduces carbon chain ester groups, so that the defect of poor adhesive force of the unsaturated polyester resin is overcome, the adhesion of resin prepreg liquid with carbon fiber cloth and glass fiber cloth is facilitated, and the smoothness of the modified toughened glass fiber liquid after treatment is maintained.
According to a further improved scheme of the invention, the mass ratio of the 2, 4-pentanediol to the adipic acid to the cobalt isooctanoate to the maleic anhydride is 6-10: 1-3: 0.012-0.035: 0.6 to 2.5; the using amount of the ethyl acetate is 3-5 times of the mass of the adipic acid.
As a further improved scheme of the invention, the mass ratio of the unsaturated polyester resin to the azodiisobutyronitrile and the butyl acrylate is 1: 0.02-0.06: 0.4-0.7, wherein the dosage of the dimethylethanolamine is 6-15% of the mass of the unsaturated polyester resin.
As a further improved scheme of the invention, the preparation method of the modified toughened glass fiber liquid comprises the following steps:
adding 36-55 parts by weight of random copolymer polypropylene, 6-11 parts by weight of basic magnesium sulfate whisker, 3-8 parts by weight of styrene-butadiene-styrene block copolymer, 3.5-6.5 parts by weight of maleic anhydride grafted polypropylene, 1.5-3.5 parts by weight of ethylene bis stearamide and 0.3-0.8 part by weight of phosphite antioxidant into a mixer, heating to 78-85 ℃, and mixing at the rotating speed of 800-1200 rpm to obtain a toughened polypropylene mixture;
and secondly, adding 12-26 parts of silicon dioxide hollow microspheres and 1.2-2.5 parts of silane coupling agent into 100 parts of toughened polypropylene mixture according to parts by weight, heating to 90-106 ℃, mixing at 560-800 rpm, adding 15-32 parts of alkali-free chopped glass fibers, uniformly mixing, feeding into a double-screw extruder, carrying out melt extrusion, and adding 3-5 times of ethanol into the extruded material to obtain the modified toughened glass fiber liquid.
The modified toughened glass fiber liquid is prepared by mixing and heating random copolymerization polypropylene serving as a matrix, a low-density reinforced filler basic magnesium sulfate whisker, a toughening agent styrene-butadiene-styrene block copolymer, a compatilizer maleic anhydride grafted polypropylene, a lubricant ethylene bis stearamide and a phosphite antioxidant to obtain a toughened polypropylene mixture; the random copolymerization polypropylene has better shock resistance and lower melting temperature due to the introduction of different monomer molecules in a high molecular chain, and can be well bonded with the styrene-butadiene-styrene block copolymer and well mixed with the phosphite antioxidant under the action of improving the bonding property and compatibility of the compatilizer maleic anhydride grafted polypropylene; the silicon dioxide hollow microspheres have good specific surface area, heat insulation performance and smaller density, and the silane coupling agent improves the bonding strength of the silicon dioxide hollow microspheres, so that the silicon dioxide hollow microspheres are well dispersed in the toughened polypropylene mixture and wrap the alkali-free chopped glass fibers; the modified toughening glass fiber liquid is coated on the periphery of the composite toughening cloth, so that the alkali-free chopped glass fibers are effectively prevented from leaking, and the toughness, strength, heat-insulating property and durability of the composite toughening cloth are obviously improved by matching the alkali-free chopped glass fibers with the silicon dioxide hollow microspheres.
As a further improvement of the present invention, the density of the random copolymerized polypropylene is 0.91g/cm 3 Tensile yield strength of 285kg/cm 3 The thermal deformation temperature is 95 ℃ and the Vicat softening point is 125 ℃; the specific surface area of the silicon dioxide hollow microspheres is 200 +/-20 m 2 The silica content is more than or equal to 99.8 percent, and the tap density is 45-55 g/dm 3 (ii) a The fiber diameter of the alkali-free chopped glass fiber is 8-12 mu m, and the elongation at break is 2.45%; the temperature of melt extrusion is 190-230 ℃.
A preparation method of a glass fiber toughened light fishing rod comprises the following steps:
s1, arranging carbon fibers in the resin preimpregnation liquid, carrying out ultrasonic treatment at 45-55 ℃ for 20-30 min, standing for 15-22 h, and curing at 95-106 ℃ for 30-40 min to obtain preimpregnated carbon fiber cloth;
s2, wrapping the glass fiber cloth on the periphery of the preimpregnated carbon fiber cloth, and extruding by an external force of 10-20 kPa to enable the glass fiber cloth and the carbon fiber cloth to be tightly adhered to obtain composite toughening cloth;
s3, coating modified toughened glass fiber liquid on the periphery of the composite toughened cloth, extruding and removing bubbles through an external force of 5-10 kPa, repeating for 3-5 times, standing for 30-50 min at normal temperature, drying for 2-3 hours at 45-65 ℃, and cooling to obtain a cloth finished product;
s4, curing and cutting the cloth finished product, coiling the pipe, fastening the winding belt, and demolding to obtain a fishing rod blank;
and S5, polishing, coating and assembling the fishing rod blank to obtain the finished fishing rod.
As a further improved scheme of the invention, the compression strength of the carbon fiber cloth is 3000MPa, the bending strength is 600MPa, and the interlaminar shear strength is 38.5 MPa; the curing process of step S4 is specifically baking at 65-85 ℃ for 30-50 min, heating to 120-135 ℃ and curing for 2-3 hours.
The invention has the following beneficial effects:
1. according to the glass fiber toughened light fishing rod, carbon fiber cloth with excellent compression resistance, bending resistance and interlaminar shear strength is used as prepreg cloth, high-molecular chain resin with good flexibility, chemical corrosion resistance and good adhesion is filled in the surface and the holes of the carbon fiber cloth through resin prepreg liquid treatment, the glass fiber cloth is wrapped to increase the toughness and the interlaminar shear strength of the carbon fiber cloth, and the modified toughened glass fiber liquid treatment enables a modified toughened molecular structure to be embedded into the surface and the holes of the glass fiber cloth and well combined with the high-molecular chain resin to form a smooth and compact surface, so that the toughness and the interlaminar shear strength of the carbon fiber cloth are improved while the density is reduced; compared with the toughening type light fishing rod in the prior art, the finished fishing rod obtained by polishing, coating and assembling has better toughness, interlaminar shear strength and corrosion resistance, and the fishing rod with the same weight has larger fishing weight.
2. The invention relates to a preparation method of a glass fiber toughening type light fishing rod, which is obtained by treating carbon fiber cloth with resin preimpregnation liquid, wrapping the glass fiber cloth, treating modified toughening glass fiber liquid, curing and cutting, coiling, fastening a winding tape, demoulding, polishing, coating and assembling, wherein micro bubbles in the resin preimpregnation liquid are removed through vibration in ultrasonic treatment, so that the bubbles are prevented from remaining in the preimpregnated carbon fiber cloth after curing; the glass fiber cloth is wrapped and external force extrusion with certain strength is kept in the coating process of the modified toughened glass fiber liquid, so that the structural adhesion in the cloth finished product is tighter, the bubble content is smaller, and the toughness, the interlayer shear strength and the corrosion resistance of the fishing rod finished product are guaranteed.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Example 1
The embodiment provides a glass fiber toughened light fishing rod, which is characterized in that carbon fiber cloth is used as prepreg cloth, the carbon fiber cloth is sequentially subjected to resin prepreg liquid treatment, glass fiber cloth wrapping, modified toughened glass fiber liquid treatment, curing cutting, pipe coiling, belt winding fastening and demoulding to obtain a fishing rod blank, and the fishing rod blank is polished, coated and assembled to obtain a finished fishing rod product.
The preparation method of the resin prepreg liquid comprises the following steps:
step one, adding 756g of 2, 4-pentanediol, 250g of adipic acid and 2.8g of cobalt isooctanoate into a reaction kettle provided with a condensation reflux pipe and mechanical stirring in sequence, heating to 216 ℃, stirring at a rotating speed of 110rpm until the solution is clear, cooling to 152 ℃, dropping 185g of maleic anhydride into a constant-pressure dropping funnel, heating to 217 ℃ after dropping, stirring to react until the acid value is less than 10, adding 875g of ethyl acetate, naturally cooling to room temperature, filtering, concentrating under reduced pressure to remove the ethyl acetate to obtain unsaturated polyester resin;
and step two, adding 4.8g of azodiisobutyronitrile into 100g of unsaturated polyester resin, heating to reflux, dropwise adding 56g of butyl acrylate, continuously stirring for 1.6 hours after dropwise adding is finished, and adding 12g of dimethylethanolamine for neutralization reaction after the reaction liquid is cooled to 46 ℃ to obtain the resin prepreg liquid.
The preparation method of the modified toughened glass fiber liquid comprises the following steps:
step one, adding 52g of random copolymer polypropylene, 9g of basic magnesium sulfate whisker, 7g of styrene-butadiene-styrene block copolymer, 4.6g of maleic anhydride grafted polypropylene, 2.3g of ethylene bis stearamide and 0.6g of phosphite antioxidant into a mixer, heating to 83 ℃, and mixing at the rotating speed of 1100rpm to obtain a toughened polypropylene mixture;
and step two, adding 18g of silicon dioxide hollow microspheres and 2.2g of silane coupling agent into 100g of toughened polypropylene mixture, heating to 97 ℃, mixing at the rotating speed of 670rpm, adding 26g of alkali-free chopped glass fibers, uniformly mixing, feeding into a double-screw extruder, melting and extruding, and adding 3.6 times of ethanol into the extruded materials to obtain the modified toughened glass fiber liquid. Wherein the density of the random copolymerization polypropylene is 0.91g/cm 3 Tensile yield strength of 285kg/cm 3 The thermal deformation temperature is 95 ℃ and the Vicat softening point is 125 ℃; the specific surface area of the silica hollow microspheres is 210m 2 The silica content is more than or equal to 99.8 percent, and the tap density is 48g/dm 3 (ii) a The fiber diameter of the alkali-free chopped glass fiber is 10 mu m, and the elongation at break is 2.45%; the melt extrusion temperature was 215 ℃.
The preparation method of the glass fiber toughened light fishing rod comprises the following steps:
s1, arranging the carbon fibers in the resin preimpregnation liquid, carrying out ultrasonic treatment at 52 ℃ for 25min, standing for 20 hours, and curing at 103 ℃ for 38min to obtain preimpregnated carbon fiber cloth; wherein the compression strength of the carbon fiber cloth is 3000MPa, the bending strength is 600MPa, and the interlaminar shear strength is 38.5 MPa;
s2, wrapping the glass fiber cloth on the periphery of the preimpregnated carbon fiber cloth, and extruding by an external force of 16kPa to enable the glass fiber cloth and the carbon fiber cloth to be tightly adhered to obtain the composite toughening cloth;
s3, coating the modified toughened glass fiber liquid on the periphery of the composite toughened cloth, extruding and removing bubbles through an external force of 8kPa, repeating the steps for 4 times, standing at normal temperature for 40min, drying at 56 ℃ for 2.6 hours, and cooling to obtain a cloth finished product;
s4, baking the cloth finished product at 78 ℃ for 46min, heating to 132 ℃ for curing for 2.2 hours, cutting, coiling, winding a belt, fastening, and demolding to obtain a fishing rod blank;
s5, polishing, coating and assembling the fishing rod blank to obtain the finished fishing rod.
Example 2
The embodiment provides a glass fiber toughened light fishing rod, which is characterized in that carbon fiber cloth is used as prepreg cloth, the carbon fiber cloth is sequentially subjected to resin prepreg liquid treatment, glass fiber cloth wrapping, modified toughened glass fiber liquid treatment, curing cutting, pipe coiling, belt winding fastening and demoulding to obtain a fishing rod blank, and the fishing rod blank is polished, coated and assembled to obtain a finished fishing rod product.
The preparation method of the resin prepreg liquid comprises the following steps:
step one, adding 862g of 2, 4-pentanediol, 195g of adipic acid and 2.8g of cobalt isooctanoate into a reaction kettle provided with a condensation reflux pipe and mechanical stirring in sequence, heating to 217 ℃, stirring at a rotating speed of 115rpm until the solution is clear, cooling to 149 ℃, dropwise adding maleic anhydride into a constant-pressure dropping funnel, heating to 220 ℃ after dropwise adding, stirring to react until the acid value is less than 10, adding 780g of ethyl acetate, naturally cooling to room temperature, filtering, and concentrating under reduced pressure to remove the ethyl acetate to obtain unsaturated polyester resin;
and step two, adding 5.5g of azodiisobutyronitrile into 100g of unsaturated polyester resin, heating to reflux, dropwise adding 65g of butyl acrylate, continuously stirring for 1.8 hours after dropwise adding is finished, and adding 10g of dimethylethanolamine for neutralization reaction after the reaction liquid is cooled to 46 ℃ to obtain the resin prepreg liquid.
The preparation method of the modified toughened glass fiber liquid comprises the following steps:
adding 49g of random copolymer polypropylene, 10g of basic magnesium sulfate whisker, 7g of styrene-butadiene-styrene block copolymer, 6.2g of maleic anhydride grafted polypropylene, 2.7g of ethylene bis stearamide and 0.6g of phosphite antioxidant into a mixer, heating to 84 ℃, and mixing at 1120rpm to obtain a toughened polypropylene mixture;
and step two, adding 23g of silicon dioxide hollow microspheres and 2.3g of silane coupling agent into 100g of toughened polypropylene mixture, heating to 102 ℃, mixing at the rotating speed of 760rpm, adding 29g of alkali-free chopped glass fibers, uniformly mixing, feeding into a double-screw extruder, melting and extruding, and adding 4.2 times of ethanol into the extruded materials to obtain the modified toughened glass fiber liquid. Therein, noneThe density of the regular copolymerized polypropylene is 0.91g/cm 3 Tensile yield strength of 285kg/cm 3 The thermal deformation temperature is 95 ℃ and the Vicat softening point is 125 ℃; the specific surface area of the silica hollow microspheres is 195m 2 The silica content is more than or equal to 99.8 percent, and the tap density is 50g/dm 3 (ii) a The fiber diameter of the alkali-free chopped glass fiber is 9 mu m, and the elongation at break is 2.45 percent; the melt extrusion temperature was 215 ℃.
The preparation method of the glass fiber toughened light fishing rod comprises the following steps:
s1, arranging carbon fibers in the resin prepreg, carrying out ultrasonic treatment at 47 ℃ for 26min, standing for 19 hours, and curing at 104 ℃ for 36min to obtain prepreg carbon fiber cloth; wherein the compression strength of the carbon fiber cloth is 3000MPa, the bending strength is 600MPa, and the interlaminar shear strength is 38.5 MPa;
s2, wrapping the glass fiber cloth on the periphery of the preimpregnated carbon fiber cloth, and extruding by an external force of 16kPa to enable the glass fiber cloth and the carbon fiber cloth to be tightly adhered to obtain the composite toughening cloth;
s3, coating the modified toughened glass fiber liquid on the periphery of the composite toughened cloth, extruding and removing bubbles through an external force of 9kPa, repeating the steps for 3 times, standing at normal temperature for 46min, drying at 64 ℃ for 2.5 hours, and cooling to obtain a cloth finished product;
s4, baking the cloth finished product at 82 ℃ for 47min, heating to 132 ℃ for curing for 2.6 hours, cutting, coiling, winding a belt for fastening, and demolding to obtain a fishing rod blank;
s5, polishing, coating and assembling the fishing rod blank to obtain the finished fishing rod.
Example 3
The embodiment provides a glass fiber toughened light fishing rod, which is characterized in that carbon fiber cloth is used as prepreg cloth, the carbon fiber cloth is sequentially subjected to resin prepreg liquid treatment, glass fiber cloth wrapping, modified toughened glass fiber liquid treatment, curing cutting, pipe coiling, belt winding fastening and demoulding to obtain a fishing rod blank, and the fishing rod blank is polished, coated and assembled to obtain a finished fishing rod product.
The preparation method of the resin prepreg liquid comprises the following steps:
step one, adding 925g of 2, 4-pentanediol, 267g of adipic acid and 3.3g of cobalt isooctanoate into a reaction kettle provided with a condensation reflux pipe and mechanical stirring in sequence, heating to 216 ℃, stirring at a rotating speed of 115rpm until the solution is clear, cooling to 153 ℃, dropwise adding 165g of maleic anhydride into a constant-pressure dropping funnel, heating to 220 ℃ after dropwise adding, stirring to react until the acid value is less than 10, adding 1121g of ethyl acetate, naturally cooling to room temperature, filtering, and concentrating under reduced pressure to remove the ethyl acetate to obtain unsaturated polyester resin;
and step two, adding 5.2g of azodiisobutyronitrile into 100g of unsaturated polyester resin, heating to reflux, dropwise adding 65g of butyl acrylate, continuously stirring for 1.6 hours after dropwise adding is finished, and adding 13g of dimethylethanolamine for neutralization reaction after the temperature of the reaction liquid is reduced to 50 ℃ to obtain the resin prepreg liquid.
The preparation method of the modified toughened glass fiber liquid comprises the following steps:
adding 48g of random copolymer polypropylene, 10g of basic magnesium sulfate whisker, 6g of styrene-butadiene-styrene block copolymer, 5.8g of maleic anhydride grafted polypropylene, 3.3g of ethylene bis stearamide and 0.6g of phosphite antioxidant into a mixer, heating to 85 ℃, and mixing at the rotating speed of 1160rpm to obtain a toughened polypropylene mixture;
and step two, adding 20g of silicon dioxide hollow microspheres and 1.7g of silane coupling agent into 100g of toughened polypropylene mixture, heating to 98 ℃, mixing at the rotating speed of 780rpm, adding 25g of alkali-free chopped glass fibers, uniformly mixing, feeding into a double-screw extruder, melting and extruding, and adding 4.2 times of ethanol into the extruded materials to obtain the modified toughened glass fiber liquid. Wherein the density of the random copolymerization polypropylene is 0.91g/cm 3 Tensile yield strength of 285kg/cm 3 The thermal deformation temperature is 95 ℃ and the Vicat softening point is 125 ℃; the specific surface area of the silica hollow microspheres is 215m 2 The silica content is more than or equal to 99.8 percent, and the tap density is 53g/dm 3 (ii) a The fiber diameter of the alkali-free chopped glass fiber is 12 mu m, and the elongation at break is 2.45 percent; the melt extrusion temperature was 225 ℃.
The preparation method of the glass fiber toughened light fishing rod comprises the following steps:
s1, arranging carbon fibers in the resin prepreg, carrying out ultrasonic treatment at 48 ℃ for 24min, standing for 22 h, and curing at 100 ℃ for 40min to obtain prepreg carbon fiber cloth; wherein the compression strength of the carbon fiber cloth is 3000MPa, the bending strength is 600MPa, and the interlaminar shear strength is 38.5 MPa;
s2, wrapping the glass fiber cloth on the periphery of the preimpregnated carbon fiber cloth, and extruding by an external force of 15kPa to enable the glass fiber cloth and the carbon fiber cloth to be tightly adhered to obtain the composite toughening cloth;
s3, coating the modified toughening glass fiber liquid on the periphery of the composite toughening cloth, extruding by using an external force of 8kPa to remove bubbles, repeating for 5 times, standing at normal temperature for 40min, drying at 58 ℃ for 2.8 hours, and cooling to obtain a cloth finished product;
s4, baking the cloth finished product at 77 ℃ for 50min, heating to 135 ℃ for curing for 2.2 hours, cutting, coiling, winding a belt for fastening, and demolding to obtain a fishing rod blank;
s5, polishing, coating and assembling the fishing rod blank to obtain the finished fishing rod.
Example 4
The embodiment provides a glass fiber toughened light fishing rod, which is characterized in that carbon fiber cloth is used as prepreg cloth, the carbon fiber cloth is sequentially subjected to resin prepreg liquid treatment, glass fiber cloth wrapping, modified toughened glass fiber liquid treatment, curing cutting, pipe coiling, belt winding fastening and demoulding to obtain a fishing rod blank, and the fishing rod blank is polished, coated and assembled to obtain a finished fishing rod product.
The preparation method of the resin prepreg liquid comprises the following steps:
step one, adding 786g of 2, 4-pentanediol, 198g of adipic acid and 2.9g of cobalt isooctanoate into a reaction kettle provided with a condensation reflux pipe and mechanical stirring in sequence, heating to 213 ℃, stirring at a rotating speed of 110rpm until the solution is clear, cooling to 149 ℃, dropping 226g of maleic anhydride into a constant-pressure dropping funnel, heating to 217 ℃ after dropping, stirring to react until the acid value is less than 10, adding 831.6g of ethyl acetate, naturally cooling to room temperature, filtering, and concentrating under reduced pressure to remove the ethyl acetate to obtain unsaturated polyester resin;
and step two, adding 4.3g of azodiisobutyronitrile into 100g of unsaturated polyester resin, heating to reflux, dropwise adding 53g of butyl acrylate, continuously stirring for 1.4 hours after dropwise adding is finished, and adding 8g of dimethylethanolamine for neutralization reaction after the reaction liquid is cooled to 43 ℃ to obtain the resin prepreg liquid.
The preparation method of the modified toughened glass fiber liquid comprises the following steps:
adding 53g of random copolymer polypropylene, 9g of basic magnesium sulfate whisker, 7g of styrene-butadiene-styrene block copolymer, 4.9g of maleic anhydride grafted polypropylene, 3.1g of ethylene bis stearamide and 0.5g of phosphite antioxidant into a mixer, heating to 82 ℃, and mixing at the rotating speed of 1080rpm to obtain a toughened polypropylene mixture;
and step two, adding 22g of silicon dioxide hollow microspheres and 1.9g of silane coupling agent into 100g of toughened polypropylene mixture, heating to 104 ℃, mixing at a rotating speed of 690rpm, adding 28g of alkali-free chopped glass fibers, uniformly mixing, feeding into a double-screw extruder, melting and extruding, and adding 4.5 times of ethanol into the extruded materials to obtain the modified toughened glass fiber liquid. Wherein the density of the random copolymerization polypropylene is 0.91g/cm 3 Tensile yield strength of 285kg/cm 3 The thermal deformation temperature is 95 ℃ and the Vicat softening point is 125 ℃; the specific surface area of the silicon dioxide hollow microspheres is 215m 2 The silica content is more than or equal to 99.8 percent, and the tap density is 53g/dm 3 (ii) a The fiber diameter of the alkali-free chopped glass fiber is 12 mu m, and the elongation at break is 2.45 percent; the melt extrusion temperature was 225 ℃.
The preparation method of the glass fiber toughened light fishing rod comprises the following steps:
s1, arranging carbon fibers in the resin prepreg, carrying out ultrasonic treatment at 52 ℃ for 28min, standing for 21 h, and curing at 102 ℃ for 36min to obtain prepreg carbon fiber cloth; wherein the compression strength of the carbon fiber cloth is 3000MPa, the bending strength is 600MPa, and the interlaminar shear strength is 38.5 MPa;
s2, wrapping the glass fiber cloth on the periphery of the preimpregnated carbon fiber cloth, and extruding by an external force of 18kPa to enable the glass fiber cloth and the carbon fiber cloth to be tightly adhered to obtain the composite toughening cloth;
s3, coating the modified toughened glass fiber liquid on the periphery of the composite toughened cloth, extruding and removing bubbles through an external force of 9kPa, repeating the steps for 4 times, standing at normal temperature for 46min, drying at 62 ℃ for 3 hours, and cooling to obtain a cloth finished product;
s4, baking the cloth finished product at 82 ℃ for 45min, heating to 132 ℃ for curing for 2.6 hours, cutting, coiling, winding a belt for fastening, and demolding to obtain a fishing rod blank;
s5, polishing, coating and assembling the fishing rod blank to obtain the finished fishing rod.
Comparative example 1
This comparative example differs from example 1 in that the resin prepreg was replaced with an unsaturated polyester resin prepared according to step one.
Comparative example 2
The difference between the comparative example and the example 1 is that the alkali-free chopped glass fiber is not added in the modified toughening glass fiber liquid.
Comparative example 3
This comparative example differs from example 1 in that step S1 of the production method is not subjected to ultrasonic treatment.
Performance testing
Fishing rods of examples 1-3 and comparative examples 1-3 are prepared into fishing rods with 8 sections, 6.2 meters and weights of 150-180 g, fishing weight tests are carried out on the fishing rods by adopting standard QBT1476-2004, and the bending strength, the bending modulus and the interlaminar shear strength are tested, and the specific test results are shown in the following table:
Figure BDA0003726722770000131
Figure BDA0003726722770000141
as can be seen from the above table, the fishing rod prepared in the examples of the present invention has better fishing weight, bending strength, bending modulus and interlaminar shear strength than the fishing rod prepared in the comparative examples under the premise of controlling the number of knots, length and weight, which indicates that the fishing rod prepared in the examples satisfies the requirements of light weight, toughness and high fishing weight. In the comparative example 1, the unsaturated polyester resin and the acrylic acid monomer butyl acrylate do not have a grafting reaction under the catalysis of the free radical initiator azobisisobutyronitrile, so that the adhesion of the resin prepreg liquid to the carbon fiber cloth and the glass fiber cloth is not facilitated, and the fishing weight and the toughness of the finished fishing rod are reduced; in comparative example 2, the alkali-free chopped glass fiber is not added during the preparation of the modified toughened glass fiber liquid, so that the alkali-free chopped glass fiber cannot be wrapped by the silica hollow microspheres, and the fishing weight and the toughness are obviously reduced; comparative example 3 because ultrasonic treatment was not performed, air bubbles remained in the preimpregnated carbon fiber cloth after curing, and the internal structure cohesiveness of the fishing rod was reduced, so that the fishing weight and toughness of the finished fishing rod were slightly reduced.
The foregoing is merely illustrative and explanatory of the present invention, and various modifications, additions or substitutions as would be apparent to one skilled in the art to the specific embodiments described are possible without departing from the invention as claimed herein or beyond the scope thereof.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (7)

1. A glass fiber toughening type light fishing rod is characterized in that carbon fiber cloth is used as prepreg cloth, and is sequentially subjected to resin prepreg liquid treatment, glass fiber cloth wrapping, modified toughening glass fiber liquid treatment, curing cutting, pipe coiling, belt winding fastening and demolding to obtain a fishing rod blank, and the fishing rod blank is subjected to polishing, coating and assembling to obtain a fishing rod finished product;
the preparation method of the resin prepreg liquid comprises the following steps:
step one, sequentially adding 2, 4-pentanediol, adipic acid and cobalt isooctanoate into a reaction kettle provided with a condensing reflux pipe and a mechanical stirrer, heating to 205-220 ℃, stirring at a rotating speed of 80-120 rpm until a solution is clear, cooling to 145-155 ℃, dropwise adding maleic anhydride into a constant-pressure dropping funnel, heating to 210-225 ℃ after dropwise adding, stirring to react until the acid value is less than 10, adding ethyl acetate, naturally cooling to room temperature, filtering, and concentrating under reduced pressure to remove the ethyl acetate to obtain unsaturated polyester resin;
and step two, adding azodiisobutyronitrile into the unsaturated polyester resin, heating to reflux, dropwise adding butyl acrylate, continuously stirring for 1-2 hours after dropwise adding is finished, and adding dimethylethanolamine for neutralization reaction after the temperature of the reaction liquid is reduced to 40-50 ℃ to obtain the resin preimpregnation liquid.
2. The glass fiber toughened light fishing rod as claimed in claim 1, wherein the mass ratio of 2, 4-pentanediol, adipic acid, cobalt isooctanoate and maleic anhydride is 6-10: 1-3: 0.012-0.035: 0.6 to 2.5; the using amount of the ethyl acetate is 3-5 times of the mass of the adipic acid.
3. The glass fiber toughened type light fishing rod as claimed in claim 1, wherein the mass ratio of the unsaturated polyester resin to the azodiisobutyronitrile and butyl acrylate is 1: 0.02-0.06: 0.4-0.7, wherein the dosage of the dimethylethanolamine is 6-15% of the mass of the unsaturated polyester resin.
4. The glass fiber toughened type light fishing rod as claimed in claim 1, wherein the preparation method of the modified toughened glass fiber liquid comprises the following steps:
adding 36-55 parts by weight of random copolymer polypropylene, 6-11 parts by weight of basic magnesium sulfate whisker, 3-8 parts by weight of styrene-butadiene-styrene block copolymer, 3.5-6.5 parts by weight of maleic anhydride grafted polypropylene, 1.5-3.5 parts by weight of ethylene bis stearamide and 0.3-0.8 part by weight of phosphite antioxidant into a mixer, heating to 78-85 ℃, and mixing at the rotating speed of 800-1200 rpm to obtain a toughened polypropylene mixture;
and secondly, adding 12-26 parts of silicon dioxide hollow microspheres and 1.2-2.5 parts of silane coupling agent into 100 parts of toughened polypropylene mixture according to parts by weight, heating to 90-106 ℃, mixing at 560-800 rpm, adding 15-32 parts of alkali-free chopped glass fibers, uniformly mixing, feeding into a double-screw extruder, carrying out melt extrusion, and adding 3-5 times of ethanol into the extruded material to obtain the modified toughened glass fiber liquid.
5. The glass fiber toughened light fishing rod of claim 4, wherein the density of the polypropylene random copolymer is 0.91g/cm 3 Tensile yield strength of 285kg/cm 3 The thermal deformation temperature is 95 ℃ and the Vicat softening point is 125 ℃; the specific surface area of the silicon dioxide hollow microspheres is 200 +/-20 m 2 The silica content is more than or equal to 99.8 percent, and the tap density is 45-55 g/dm 3 (ii) a The fiber diameter of the alkali-free chopped glass fiber is 8-12 mu m, and the elongation at break is 2.45%; the temperature of melt extrusion is 190-230 ℃.
6. The preparation method of the glass fiber toughened light fishing rod is characterized by comprising the following steps:
s1, arranging carbon fibers in the resin pre-impregnation liquid, carrying out ultrasonic treatment at 45-55 ℃ for 20-30 min, standing for 15-22 h, and curing at 95-106 ℃ for 30-40 min to obtain pre-impregnated carbon fiber cloth;
s2, wrapping the glass fiber cloth on the periphery of the preimpregnated carbon fiber cloth, and extruding by an external force of 10-20 kPa to enable the glass fiber cloth and the carbon fiber cloth to be tightly adhered to obtain composite toughening cloth;
s3, coating the modified toughened glass fiber liquid on the periphery of the composite toughened cloth, extruding and removing bubbles through an external force of 5-10 kPa, repeating for 3-5 times, standing for 30-50 min at normal temperature, drying for 2-3 hours at 45-65 ℃, and cooling to obtain a cloth finished product;
s4, curing and cutting the cloth finished product, coiling the pipe, fastening the winding belt, and demolding to obtain a fishing rod blank;
s5, polishing, coating and assembling the fishing rod blank to obtain the finished fishing rod.
7. The method for preparing a glass fiber toughened type light fishing rod as claimed in claim 6, wherein the carbon fiber cloth has a compression strength of 3000MPa, a bending strength of 600MPa, and an interlaminar shear strength of 38.5 MPa; the curing process of step S4 is specifically baking at 65-85 ℃ for 30-50 min, heating to 120-135 ℃ and curing for 2-3 hours.
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