CN110699960A - Sizing agent for thermoplastic resin reinforced fibers - Google Patents

Sizing agent for thermoplastic resin reinforced fibers Download PDF

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Publication number
CN110699960A
CN110699960A CN201910947222.7A CN201910947222A CN110699960A CN 110699960 A CN110699960 A CN 110699960A CN 201910947222 A CN201910947222 A CN 201910947222A CN 110699960 A CN110699960 A CN 110699960A
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resin
fiber
sizing agent
fibers
acid
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胡炜杰
纪红兵
程亮
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Guangdong University of Petrochemical Technology
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Guangdong University of Petrochemical Technology
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Priority to CN201910947222.7A priority Critical patent/CN110699960A/en
Publication of CN110699960A publication Critical patent/CN110699960A/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • 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
    • D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2246—Esters of unsaturated carboxylic acids
    • 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
    • D06M15/53—Polyethers
    • 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
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a sizing agent for thermoplastic resin reinforced fibers, which is a sizing agent for reinforced fibers consisting of acid modified polyolefin, a vinyl ester compound and water, wherein the weight ratio of the acid modified polyolefin resin to the vinyl ester compound is 1:9-1:1, the acid modified polyolefin is obtained by graft polymerization of at least one of polypropylene, an ethylene-propylene copolymer, a propylene-butylene copolymer and an ethylene-propylene-butylene copolymer and 0.1 ~ 20wt% of unsaturated carboxylic acid or anhydride thereof, fibers treated by the sizing agent have good fiber opening property and affinity with thermoplastic matrix resin, and the sizing agent also has excellent heat resistance and can resist the high-temperature forming process of the thermoplastic resin.

Description

Sizing agent for thermoplastic resin reinforced fibers
Technical Field
The invention relates to the technical field of fiber increase, in particular to a sizing agent for thermoplastic resin reinforced fibers.
Background
Fiber reinforced resin composite materials are used in large quantities in the fields of automobile manufacturing, aerospace, sports entertainment, general industry and the like. Examples of the reinforcing fiber used in the composite material include inorganic fibers such as carbon fibers, glass fibers, and ceramic fibers, and organic fibers such as aramid fibers, polyamide fibers, and polyethylene fibers. These synthetic fibers may be prepared as continuous long fibers into an intermediate material such as a unidirectional prepreg by a melt-impregnation method or the like, or may be processed into a woven fabric or cut into short fibers, and then subjected to various compounding and molding processes to prepare molded articles and parts.
In the field of advanced composite materials, thermosetting resins such as epoxy resins have been used as matrix materials in many cases, mainly because the cured thermosetting resins have more excellent mechanical properties. However, in recent years, from the viewpoints of molding efficiency, easy recycling, and suitability for large-scale industrial application, the range and scale of application of thermoplastic resin composites using a so-called thermoplastic resin such as a polyolefin resin, a polyamide resin, a polycarbonate resin, a polyacetal resin, an ABS resin, or a polyurethane resin as a base material have rapidly expanded.
The thermoplastic resin composite material is generally formed by cutting reinforcing fibers into short fibers having a length of 1 to 15mm, kneading the short fibers with a resin, and then extruding the mixture. When the chopped fibers are kneaded and pelletized with a thermoplastic resin, the fiber opening property of the chopped fibers is important, and if the chopped fibers are not well dispersed, the supply of the fibers becomes unstable, the dispersion in the resin becomes uneven, and the performance of the resulting composite material is poor.
In recent years, in order to further develop the mechanical properties such as tensile strength of reinforcing fibers, molding methods similar to thermosetting resin composite materials have been developed for thermoplastic resins, in which fibers are arranged unidirectionally or impregnated with a thermoplastic resin using a fiber fabric to obtain a so-called thermoplastic resin prepreg, which is then further molded into a part. In this case, it is very important to shorten the molding time and improve the physical properties of the composite material, since the molten resin can rapidly enter the fiber bundles and uniformly distribute in the fiber gaps during the preparation and molding of the prepreg.
In order to improve the bundling property of the reinforcing fibers and the affinity between the fibers and the matrix resin, the fibers are usually subjected to a sizing treatment using a sizing agent. The traditional sizing agent mainly takes epoxy resin as an effective component, and can endow fibers with better bundling property and good surface affinity with thermosetting resin base materials such as epoxy resin and the like. But it is difficult to satisfy the use requirements of the thermoplastic resin substrate. Particularly, when polyolefin resin is used as a resin base material, the molding temperature is far higher than the curing temperature of general thermosetting resin, so that high requirements are imposed on the heat resistance of the sizing agent, and if the heat resistance of the sizing agent is insufficient, the sizing agent is decomposed in the molding process, the bonding of fibers and resin is affected, and the performance and the grade of the composite material are reduced.
In addition, in general, in order to improve the film forming property, the main component of the sizing agent is mostly solid at normal temperature, and although the sizing agent is excellent in bundling property and is advantageous for processing when used for chopped fibers, when used in the form of long fibers, the sizing agent has a problem that the resin impregnation property is poor, that is, the resin cannot be rapidly introduced into the fiber bundle. In addition, in the process of manufacturing a prepreg, fibers are generally first split, and the splitting performance of a conventional sizing agent is poor. Therefore, in the field of thermoplastic resin composite materials, there is a need for a sizing agent that has good affinity with resins, that can impart good fiber opening properties to fibers, and that has good heat resistance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a fiber sizing agent which has excellent heat resistance, can enable fiber bundles to have good fiber opening performance and has good affinity with a thermoplastic resin matrix.
In order to achieve the purpose, the invention adopts the following technical scheme:
a sizing agent for thermoplastic resin reinforcing fibers is composed of an acid-modified polyolefin resin, a vinyl ester compound and water.
The sizing agent for reinforcing fibers in the present invention must contain the aforementioned acid-modified polyolefin, vinyl ester compound and water. Thus, the sizing agent can have good heat resistance, and can inhibit the decomposition of the sizing agent when the sizing agent is compounded with the thermoplastic resin at high temperature, and the fiber treated by the sizing agent has greatly improved fiber opening property and obviously improved affinity with the thermoplastic resin. Particularly, the bonding effect is the best for polyolefin resins.
The weight ratio of the acid-modified polyolefin resin to the vinyl ester compound (acid-modified polyolefin: vinyl ester compound) in the sizing agent is 1:9 to 1:1, preferably 1:4 to 9:11, more preferably 1:3 to 1:2, from the viewpoints of affinity with the matrix resin and fiber opening property.
In the sizing agent, the acid modified polyolefin and the vinyl ester compound are dispersed in water to form emulsion, and the average particle size of the emulsion is 1-5000 nm, preferably 10-1000 nm. If the particle diameter is less than 1nm, the acid-modified polyolefin resin particles easily penetrate the fiber bundle and hardly adhere to the fibers to a certain extent, and if the particle diameter exceeds 5000nm, the adhesion to the fibers is not uniform, the emulsion itself is poor in stability, and the emulsion is completely separated within several days, which is not favorable for practical storage and use.
The average particle diameter in the emulsion was measured using a laser particle sizer.
In addition to the above-mentioned essential components, various components such as a surfactant, a smoothing agent, an antioxidant, a flame retardant, an antibacterial agent, an antifoaming agent, and the like can be used in the sizing agent of the present invention. Particularly when the acid-modified polyolefin resin and the vinyl ester compound used are hardly soluble in water, a surfactant as an emulsifier is very important for forming a stable aqueous emulsion system. The weight ratio of the surfactant to the nonvolatile components of the sizing agent is 0.1 to 30%, preferably 5 to 20%, in view of the emulsification effect and the heat resistance.
The concentration of the nonvolatile component, i.e., the solid content of the sizing agent in the present invention is not particularly limited, but is preferably 10 to 60 wt%, more preferably 15 to 60 wt%, and still more preferably 20 to 50 wt%, in view of the stability of the emulsion, the viscosity during handling, the transportation cost, and the like.
The sizing agent of the present invention should have a mass reduction rate of the nonvolatile component at 400 ℃ of not more than 15%, preferably less than 10%. If it exceeds 15%, the sizing agent is significantly decomposed during the high-temperature molding, and the resulting decomposition products affect the bonding strength of the fibers to the resin.
As described above, the sizing agent aqueous emulsion contains as little solvent as possible other than water in view of safety to the human body, environmental friendliness, stability of the emulsion itself, and the like. If contained, the content thereof should not exceed 10% by weight, preferably 5% by weight, and most preferably not 1% by weight, relative to the sizing agent.
The method for producing the sizing agent of the present invention is not particularly limited, and various known methods can be used, for example, a method of adding each main component to warm water under stirring to disperse and emulsify, or emulsifying each component separately and then mixing, or mixing the main components, heating the mixture to a softening point or higher, then applying a shearing force using a homogenizer or the like, and slowly adding water to perform inversion emulsification.
Preferably, in the above-mentioned sizing agent: the acid-modified polyolefin resin is obtained by graft polymerization of at least one of polypropylene, an ethylene-propylene copolymer, a propylene-butene copolymer and an ethylene-propylene-butene copolymer with unsaturated carboxylic acid or anhydride thereof in a mass ratio of 100:1 to 5: 1.
In the main chain of the acid modified polyolefin, the propylene chain segment accounts for more than 50-98 mol%. If the proportion of the propylene segment is less than 50%, the affinity between the fiber and the thermoplastic resin is poor, and if it is more than 98%, the fiber becomes hard and loses flexibility after the treatment. If the main chain of the acid modified polyolefin is an ethylene-propylene-butylene copolymerization structure, the content of the butylene unit is less than 10 mol%.
The carbon number of the unsaturated carboxylic acid used for graft copolymerization in the acid modified polyolefin is 3-8. The unsaturated carboxylic acid may be an unsaturated monobasic acid, an unsaturated dibasic acid, or an ester derivative thereof. Specifically, maleic acid, maleic anhydride, fumaric acid, coated acid, acrylic acid, methacrylic acid ester, etc. Among them, maleic acid, acrylic acid, methacrylic acid and methacrylic acid ester are preferable. The proportion of the unsaturated carboxylic acid unit in the whole molecule should be 0.1 to 20wt%, preferably 1 to 15 wt%, more preferably 2 to 10 wt%. If the content is less than 0.1%, the affinity of the treated fiber with the resin is poor, and it is very difficult to exceed 20% under ordinary reaction conditions.
The unsaturated carboxylic acid compound is grafted to the polyolefin main chain, and a known method such as a solution polymerization method, a bulk polymerization method, or the like can be used.
The unsaturated carboxylic acid used in the acid-modified polyolefin resin may be completely or partially neutralized, and the basic substance used for neutralization may be an inorganic base such as sodium hydroxide, potassium hydroxide, or aluminum hydroxide, or an amine substance such as ammonia, methylamine, dimethylamine, trimethylamine, triethylamine, or tetramethylammonium hydroxide.
The weight average molecular weight of the acid-modified polyolefin resin is preferably 3000 to 200000, more preferably 5000 to 200000, and still more preferably 10000 to 150000. If the weight average molecular weight is less than 3000, the fiber after treatment has insufficient bundling property, which affects the workability of the subsequent processing, and if it exceeds 2000000, it is very difficult to disperse in water, and thus it is impossible to prepare an aqueous sizing agent, or even if it is dispersed in water, the particle size is very large, and the emulsion is very unstable, and thus it is impossible to store and use for a long time.
A reinforcing fiber bundle is prepared by treating the reinforcing fibers with the sizing agent.
The reinforcing fiber bundle in the present invention means a fiber bundle treated with the above-mentioned sizing agent and used for reinforcing a thermoplastic resin. Has excellent fiber opening property and affinity with resin. Meanwhile, the sizing agent has good heat resistance, so that the sizing agent cannot be decomposed in the high-temperature compounding process.
The attachment amount of the sizing agent on the fiber, namely the sizing amount, can be flexibly selected according to the actual situation and is usually between 0.5 and 5 percent. If the chopped fiber is used, the sizing amount is suitably increased and may be 1 to 10%. If the amount of sizing agent is too small, the main objects of the present invention, such as heat resistance of the fibers, resin impregnation property, and affinity with the resin, cannot be achieved, and if the amount of sizing agent is too large, the fiber bundle becomes rigid, the workability is deteriorated, and the resin impregnation property during molding is also deteriorated.
The method for manufacturing the synthetic fiber bundle mainly comprises a dilution process of diluting the sizing agent to 0.5-10%, and a sizing process of using the diluted sizing agent treatment liquid to perform sizing treatment on the raw material fiber bundle to achieve the sizing amount of 0.5-5%.
In the dilution process, the concentration of the sizing agent treatment solution is 1-10%, preferably 2-5%. The sizing step may be specifically performed by a known method such as a roller dipping method or a spraying method. The dipping method is preferable from the viewpoint of the uniformity of adhesion, cost, and the like.
The sized fiber bundle should be dried, and the drying method is not limited, and may be, for example, hot roll drying, hot air drying, etc.
The synthetic fibers to which the sizing agent of the present invention is applied include inorganic fibers such as carbon fibers, glass fibers, and ceramic fibers, and various organic fibers such as aramid fibers, polyethylene terephthalate (PET) fibers, polybutylene terephthalate (PBT) fibers, polyethylene naphthalate (PEN) fibers, polyacetal fibers, PBO fibers, polyarylate fibers, and polyketone fibers. From the viewpoint of the physical properties of the resulting composite material, the fibers are preferably carbon fibers, aramid fibers, polyethylene terephthalate (PET) fibers, polybutylene terephthalate (PBT) fibers, polyacetal fibers, PBO fibers, polyarylate fibers, and polyketone fibers, and particularly preferably carbon fibers.
Preferably, in the reinforcing fiber bundle described above: the reinforced fiber is carbon fiber, aramid fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyacetal fiber, PBO fiber or polyketone fiber.
A fiber reinforced resin matrix composite is formed by compounding the reinforced fiber bundles and thermoplastic resin. The fiber-reinforced composite material of the present invention is obtained by compounding the aforementioned reinforcing fiber with a thermoplastic resin as a matrix. By using the sizing agent, the reinforcing fiber and the resin matrix have good affinity, so that a composite material with excellent performance can be obtained.
The thermoplastic resin substrate used here may be any thermoplastic resin, and may be used alone or in combination of two or more. Specifically, polyolefin resin, polyamide resin, polycarbonate resin, polyester resin, ABS resin, polymethyl methacrylate resin, polyurethane resin, polyether ketone resin, etc. The polyolefin resin is a polymer material obtained by polymerizing olefin as a monomer, and may be a homopolymer or a copolymer.
The thermoplastic resin substrate may be modified as appropriate to improve the affinity with the fibers or the physical properties thereof.
The method for producing the composite material is not limited, and specific examples thereof include other molding methods such as extrusion molding after kneading chopped fibers and a resin, press molding using a UD unidirectional sheet or a woven fabric prepreg, and winding molding.
The content of the fibers in the composite material is not particularly limited, and is appropriately selected and adjusted depending on the form and type of the fibers, the type of the thermoplastic resin base material, and the like. The mass content of the fibers is preferably 5 to 70%, more preferably 20 to 60%, from the viewpoint of the reinforcing effect.
Preferably, in the above-mentioned sizing agent: the vinyl ester compound refers to a compound having both a vinyl group and an ester group at the molecular terminal, and a general vinyl ester resin is obtained by reacting an epoxy resin with an unsaturated carboxylic acid such as acrylic acid or methacrylic acid. The molecular structure of the compound may be an aromatic compound or an aliphatic compound.
The vinyl ester compound is preferably bisphenol a acrylate, bisphenol a methacrylate, ethoxylated bisphenol a acrylate, ethoxylated bisphenol a methacrylate, acrylic acid adduct of bisphenol a diglycidyl ether, methacrylic acid adduct of bisphenol a diglycidyl ether, acrylic acid adduct of ethoxylated bisphenol a diglycidyl ether, or methacrylic acid adduct of ethoxylated bisphenol a diglycidyl ether, from the viewpoint of heat resistance.
Compared with the prior art, the invention has the following beneficial effects:
the sizing agent for fibers of the present invention has excellent heat resistance, and the fiber bundle after treatment has excellent fiber opening performance and good affinity with thermoplastic resin. A fiber-reinforced thermoplastic resin composite material having excellent physical properties can be obtained.
Detailed Description
The present invention will be specifically described below with reference to examples. The percentages in the examples are percentages by mass or parts by mass. The measurement and evaluation methods are specifically as follows.
< affinity >
The affinity between the fibers and the resin was evaluated by using a composite material interface characteristic evaluation device HM410 manufactured by toyoho industries co.
Since all the fibers used in the examples were carbon fibers, carbon fiber monofilaments were fixed to the apparatus, and a molten polypropylene resin J-900GP was dropped onto the fibers from above, and cooled to room temperature to obtain test samples. Fixing the sample in a clamp, carrying out a pull-out test at the speed of 0.06mm/min, measuring the maximum tensile force F, and then calculating the interface shear strength tau according to the following formula to be used as an evaluation index of the affinity of the carbon fiber and the polypropylene resin.
Interfacial shear strength tau (MPa) ═ F/pi dl
Wherein F is the maximum pull-out load, d is the carbon fiber monofilament diameter, and l is the diameter of the droplet in the pull-out direction.
< fiber opening Property >
A carbon fiber having a fineness of 800tex, a number of filaments of 12000 and a sizing amount of 1.0% was used as a sample. The measurement was performed using a textile tester. The smaller the measured value, the better the fiber opening property.
Evaluation criteria:
a: less than 50g, the carbon fiber tow is soft and has very good fiber opening performance
B: 50-60 g, the carbon fiber tows are soft and have good fiber opening performance
C: 60g or more, the tow is stiff and has poor opening property
Rate of mass reduction
The sizing agent is thoroughly dried to constant weight at 105 ℃, a thermal analyzer is used, the temperature is raised to 500 ℃ at the temperature rise speed of 20 ℃/min under the air atmosphere, and the mass reduction rate of the sizing agent at 300 ℃ is obtained according to the thermal weight loss curve.
< particle size of emulsion >
The particle size of the emulsion was measured using a laser particle sizer.
< production of acid-modified polyolefin resin emulsions A1 to A4 >
(A1-1～A1-3)
100g of polypropylene resin and 400g of toluene were charged into a flask, and heated while stirring to dissolve the resin. And keeping the temperature above the melting point of the polypropylene resin, adding anhydrous maleic acid and methyl methacrylate, and carrying out graft polymerization on the polypropylene, the anhydrous maleic acid and the methyl methacrylate to obtain the acid modified polypropylene resin.
And stirring 245 parts by mass of the obtained acid-modified polypropylene resin, 20 parts by mass of aliphatic polyoxyethylene ether, 15 parts by mass of potassium hydroxide and 20 parts by mass of morpholine under the protection of nitrogen, heating to 170-180 ℃, slowly adding 700 parts by mass of water, and maintaining the temperature at 170-180 ℃ for two hours to completely and uniformly dissolve the acid-modified polypropylene resin. Cooling to normal temperature, and adding water to obtain acid modified polypropylene resin emulsion A1-1-A1-3 with the concentration of 30%.
The particle size was measured using a laser particle sizer and was 30 nm. The product is placed at the temperature of 50 ℃ for 1 month, has no flocculation, no layering and no floating oil, and has good stability. The specific properties of the three modified resins are as follows:
a1-1: polypropylene backbone, graft modification 5%, MW 4500
A1-2: polypropylene backbone, graft modification 5%, MW 28000
A1-3: polypropylene backbone, graft modification 15%, MW 37000
(A2-1～A2-3)
100g of an ethylene-propylene copolymer resin and 400g of toluene were charged into a flask, and the mixture was heated while stirring to dissolve the resin. Keeping the temperature above the melting point of the resin, adding anhydrous maleic acid and methyl methacrylate, and carrying out graft polymerization on the ethylene-propylene copolymer resin, the anhydrous maleic acid and the methyl methacrylate to obtain the acid modified polyolefin resin.
Stirring 250 parts by mass of the obtained acid modified polyolefin resin, 15 parts by mass of aliphatic polyoxyethylene ether, 15 parts by mass of potassium hydroxide and 20 parts by mass of morpholine under the protection of nitrogen, heating to 170-180 ℃, then slowly adding 700 parts by mass of water, and maintaining the temperature at 170-180 ℃ for two hours to completely and uniformly dissolve the acid modified polyolefin resin. Cooling to normal temperature, and adding water to obtain acid modified polyolefin resin emulsion A2-1-A2-3 with the concentration of 30%.
The particle size was measured using a laser particle sizer and was 20 nm. The product is placed at the temperature of 50 ℃ for 1 month, has no flocculation, no layering and no floating oil, and has good stability. The specific properties of the three acid-modified polyolefin resins are as follows:
a2-1: ethylene-propylene copolymer backbone with graft modification 3% MW 58000
A2-2: ethylene-propylene copolymer backbone, graft modification 5%, MW 63000
A2-3: ethylene-propylene copolymer backbone with 10% graft modification, MW 65000
(A3-1～A3-3)
100g of a propylene-butene copolymer resin and 400g of toluene were charged into a high-pressure flask, and dissolved by heating while stirring. The temperature was kept at the melting point of the resin or higher, and anhydrous maleic acid and methyl methacrylate were added to graft-polymerize the resin, the anhydrous maleic acid, and the methyl methacrylate, thereby obtaining an acid-modified polyolefin resin.
245 parts by mass of the obtained acid modified polyolefin resin, 15 parts by mass of aliphatic polyoxyethylene ether, 15 parts by mass of potassium hydroxide and 25 parts by mass of morpholine are stirred under the protection of nitrogen, the temperature is raised to 170-180 ℃, then 700 parts by mass of water is slowly added, and the temperature is maintained at 170-180 ℃ for two hours, so that the acid modified polyolefin resin is completely and uniformly dissolved. Cooling to normal temperature, and adding water to obtain acid modified polyolefin resin emulsion A3-1-A3-3 with the concentration of 30%.
The particle size was measured using a laser particle sizer and was 20 nm. The product is placed at the temperature of 50 ℃ for 1 month, has no flocculation, no layering and no floating oil, and has good stability. The specific properties of the three acid-modified polyolefin resins are as follows:
a3-1: propylene-butene copolymer backbone, graft modification 5%, MW 35000
A3-2: propylene-butene copolymer backbone with 10% graft modification, MW 60000
A3-3: propylene-butene copolymer backbone, graft modification 20%, MW 71000
(A4-1～A4-3)
100g of an ethylene-propylene-butene copolymer resin and 400g of toluene were charged into a flask, and the mixture was heated while stirring to dissolve the copolymer resin. Keeping the temperature above the melting point of the resin, adding anhydrous maleic acid and methyl methacrylate, and carrying out graft polymerization on the ethylene-propylene-butylene copolymer resin, the anhydrous maleic acid and the methyl methacrylate to obtain the acid modified polyolefin resin.
Stirring 250 parts by mass of the obtained acid modified polyolefin resin, 10 parts by mass of aliphatic polyoxyethylene ether, 15 parts by mass of potassium hydroxide and 25 parts by mass of morpholine under the protection of nitrogen, heating to 170-180 ℃, then slowly adding 700 parts by mass of water, and maintaining the temperature at 170-180 ℃ for two hours to completely and uniformly dissolve the acid modified polyolefin resin. Cooling to normal temperature, and adding water to obtain acid modified polyolefin resin emulsion A4-1-A4-3 with the concentration of 30%.
The particle size was measured using a laser particle sizer and was 20 nm. The product is placed at the temperature of 50 ℃ for 1 month, has no flocculation, no layering and no floating oil, and has good stability. The specific properties of the three acid-modified polyolefin resins are as follows:
a2-1: ethylene-propylene-butene copolymer backbone, graft modification 5%, MW 42000
A2-2: ethylene-propylene-butylene copolymer backbone with 10% graft modification, MW 62000
A2-3: ethylene-propylene-butylene copolymer backbone, graft modification 15%, MW 68000
< production of vinyl ester Compound emulsions B1 to B4 >
(B1)
Adding acrylic acid addition product of bisphenol A diglycidyl ether/castor oil polyoxyethylene (150) ether into an emulsifying device according to the mass ratio of 80/20, slowly adding water while stirring, and performing steering emulsification to obtain uniform emulsion B1, wherein the solid content of B1 is 40%.
The average grain diameter of the emulsion B1 is measured, the average grain diameter is 190nm, and the emulsion B1 has no flocculation, no layering and no floating oil and has good stability after being placed for 1 month at the temperature of 50 ℃.
(B2)
Adding (4) ethoxylated bisphenol A acrylate/castor oil polyoxyethylene (150) ether into an emulsifying device according to the mass ratio of 80/20, slowly adding water while stirring, and performing turning emulsification to obtain uniform emulsion B2, wherein the solid content of B2 is 40%.
The average grain diameter of the emulsion B2 is measured, the average grain diameter is 250nm, and the emulsion B2 has no flocculation, no delamination and no floating oil and has good stability after being placed for 1 month at the temperature of 50 ℃.
(B3)
Trimethylolpropane triacrylate/ethyl-propyl block polyether (MW15000, the ratio of propoxy to ethoxy is 20/80)/ethyl-propyl block polyether (MW2000, the ratio of propoxy to ethoxy is 60/40) are added into an emulsifying device according to the mass ratio of 70/15/15, water is slowly added while stirring, and turning emulsification is carried out to obtain uniform emulsion B4. the solid content of B4 is 40%.
The average grain diameter of the emulsion B1 is 210nm when the emulsion B1 is measured, and the emulsion B1 has no flocculation, no delamination and no floating oil and has good stability when placed for 1 month at the temperature of 50 ℃.
< examples 1 to 21, comparative examples 1 to 4>
The acid-modified polyolefin emulsion and the vinyl ester compound emulsion prepared as described above were mixed and stirred in the proportions shown in tables 1 to 3, and diluted with water to a sizing agent having a solid content of 10%. The obtained sizing agent was measured for its fiber-opening property and mass loss rate by the methods described above.
Carbon fibers (fineness 800tex, filament number 12K) that had not been sized were sized by the dipping method and dried to obtain carbon fiber bundles having a sizing amount of about 5%. The affinity with the resin was evaluated.
All results are shown in tables 1-3.
TABLE 1
Figure BDA0002224529710000101
TABLE 2
Figure BDA0002224529710000102
TABLE 3
Figure BDA0002224529710000111

Claims (8)

1. A sizing agent for thermoplastic resin reinforcing fibers, characterized in that: comprising an acid-modified polyolefin resin, a vinyl ester compound and water.
2. The sizing agent according to claim 1, characterized in that: the weight ratio of the acid-modified polyolefin resin to the vinyl ester compound is 1:9 to 1: 1.
3. The sizing agent according to claim 1, wherein the acid-modified polyolefin resin is obtained by graft-polymerizing at least one of polypropylene, an ethylene-propylene copolymer, a propylene-butene copolymer and an ethylene-propylene-butene copolymer with an unsaturated carboxylic acid or an anhydride thereof at a mass ratio of 100:1 ~ 5: 1.
4. The sizing agent according to claim 1, characterized in that: the vinyl ester compound is bisphenol A acrylate, bisphenol A methacrylate, ethoxylated bisphenol A acrylate, ethoxylated bisphenol A methacrylate, acrylic acid adduct of bisphenol A diglycidyl ether, methacrylic acid adduct of bisphenol A diglycidyl ether, acrylic acid adduct of ethoxylated bisphenol A diglycidyl ether, or methacrylic acid adduct of ethoxylated bisphenol A diglycidyl ether.
5. A reinforcing fiber bundle characterized by being obtained by treating reinforcing fibers with the sizing agent according to claim 1.
6. The reinforcing fiber bundle of claim 5, wherein: the reinforced fiber is carbon fiber, aramid fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyacetal fiber, PBO fiber or polyketone fiber.
7. A fiber-reinforced resin-based composite material characterized by being formed by compounding the reinforcing fiber bundles according to claim 4 with a thermoplastic resin.
8. The fiber reinforced resin based composite material according to claim 7, wherein: the thermoplastic resin is polyolefin resin, polyamide resin, polycarbonate resin, polyester resin, ABS resin, polymethyl methacrylate resin, polyurethane resin or polyether ketone resin.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4124688A1 (en) * 2021-07-30 2023-02-01 Formosa Plastics Corporation Method of sizing a carbon fiber bundle

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005256206A (en) * 2004-03-10 2005-09-22 Teijin Techno Products Ltd Carbon fiber, carbon fiber-reinforced thermoplastic resin and method for producing carbon fiber
WO2006101269A1 (en) * 2005-03-25 2006-09-28 Teijin Techno Products Limited Carbon fiber strand for reinforcing thermoplastic resins and method of producing the same
JP2006336131A (en) * 2005-05-31 2006-12-14 Teijin Techno Products Ltd Carbon fiber strand for reinforcing thermoplastic resin
JP2013067915A (en) * 2011-09-22 2013-04-18 Matsumoto Yushi Seiyaku Co Ltd Sizing agent for reinforced fiber and application thereof
CN104204341A (en) * 2012-03-29 2014-12-10 松本油脂制药株式会社 Sizing agent for reinforcing fibers, and use thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005256206A (en) * 2004-03-10 2005-09-22 Teijin Techno Products Ltd Carbon fiber, carbon fiber-reinforced thermoplastic resin and method for producing carbon fiber
WO2006101269A1 (en) * 2005-03-25 2006-09-28 Teijin Techno Products Limited Carbon fiber strand for reinforcing thermoplastic resins and method of producing the same
EP1862281A1 (en) * 2005-03-25 2007-12-05 Teijin Techno Products Limited Carbon fiber strand for reinforcing thermoplastic resins and method of producing the same
US20090062426A1 (en) * 2005-03-25 2009-03-05 Teijin Techno Products Limited Carbon Fiber Strand for Reinforcing Thermoplastic Resins and Method of Producing the Same
JP2006336131A (en) * 2005-05-31 2006-12-14 Teijin Techno Products Ltd Carbon fiber strand for reinforcing thermoplastic resin
JP2013067915A (en) * 2011-09-22 2013-04-18 Matsumoto Yushi Seiyaku Co Ltd Sizing agent for reinforced fiber and application thereof
CN104204341A (en) * 2012-03-29 2014-12-10 松本油脂制药株式会社 Sizing agent for reinforcing fibers, and use thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4124688A1 (en) * 2021-07-30 2023-02-01 Formosa Plastics Corporation Method of sizing a carbon fiber bundle

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