CN114806032A - Thermoplastic prepreg, thermoplastic composite material, and method for producing same - Google Patents
Thermoplastic prepreg, thermoplastic composite material, and method for producing same Download PDFInfo
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- CN114806032A CN114806032A CN202210331286.6A CN202210331286A CN114806032A CN 114806032 A CN114806032 A CN 114806032A CN 202210331286 A CN202210331286 A CN 202210331286A CN 114806032 A CN114806032 A CN 114806032A
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- 239000003365 glass fiber Substances 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 13
- 239000012783 reinforcing fiber Substances 0.000 claims description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
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- 238000002791 soaking Methods 0.000 claims description 9
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- 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
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
- C08J2331/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to a thermoplastic prepreg, a thermoplastic composite material and a method for producing the same. The method comprises the steps of pre-polymerizing and impregnating the in-situ polymerized resin, polymerizing the resin pre-polymerization liquid to a solid state after impregnation, but not completely polymerizing the resin to the final high-rigidity resin, wherein the resin has certain flexibility, and simultaneously has few volatile micromolecules and monomers remained in the resin pre-polymerization liquid, so that the problems of poor forming property, high forming difficulty of complex-structure products and the like caused by rigidity of common thermoplastic prepregs are solved, and simultaneously, the problems that the existing in-situ polymerized thermoplastic prepregs with viscosity and drapability are not solidified due to the fact that the resin is not solidified, great environmental and safety hazards are brought in later-stage storage, particularly in the production process, great difficulty and inconvenience are brought to the subsequent manufacture of composite material products are also solved. The prepreg has few volatile micromolecules and monomers remained in the prepreg, does not need to be matched with a special gas treatment device and the like, and has good storage and production safety.
Description
Technical Field
The present invention relates to a resin-based composite material composed of reinforcing fibers and a resin, and more particularly to a thermoplastic prepreg and a thermoplastic composite material each of which comprises a thermoplastic resin as a matrix, and a method for producing the same. The thermoplastic prepreg and the thermoplastic composite material are particularly suitable for the production and manufacture of lightweight parts of aviation, automobile parts, sports equipment and industrial equipment.
Background
The fiber reinforced thermoplastic resin matrix composite material has excellent mechanical property, better interlayer strength and toughness than thermosetting resin matrix composite materials, and better recyclability, is a composite material meeting the requirements of sustainable development, and has wide application prospect in industrial equipment, automobiles and aerospace parts.
In the production of thermoplastic resin matrix composite material parts, thermoplastic prepregs are required to be subjected to hot press molding in most cases. A sheet-like fiber-reinforced thermoplastic resin composite obtained by impregnating a continuous fiber tape or fiber cloth with a thermoplastic resin is generally called a thermoplastic prepreg.
Generally, thermoplastic resin powder, resin film or extruded resin melt and a fiber belt or fiber felt are subjected to high-temperature hot pressing or rolling to impregnate the resin melt into a fiber bundle, and a sheet-shaped thermoplastic prepreg is formed after cooling and solidification (see chinese patents CN 104497414B and CN 106738447B). Due to the high viscosity of the thermoplastic melt, such methods are generally used for impregnating unidirectional fiber tapes or fiber mats and are difficult to completely impregnate into the internal interstices of the fiber tows, often with insufficient impregnation; in addition, the sheet-shaped thermoplastic prepreg has high rigidity, when composite material parts with complex structures are manufactured, the prepreg cannot be attached to a mold with the complex shape along a curved surface, shaping difficulty is high, the shapes of the composite material parts are greatly limited, many products with slightly complex structures are difficult to mold, or layers are easy to misplace when the prepreg is adopted for molding, fiber movement is large, even fiber damage is caused, and product performance cannot be guaranteed.
In order to improve the impregnation effect of the fibers and solve the problem of difficult shaping of the conventional thermoplastic prepreg, chinese patents CN 107118514 a and CN 108368280 a both disclose a method of in-situ polymerization, in which the fibers are impregnated with a partially polymerized solution of a thermoplastic polymer to form a thermoplastic prepreg having a certain viscosity and drapability. In the impregnation process, the incompletely polymerized resin solution is adopted and has certain fluidity, so that the impregnation effect on the fibers is better, and the mold shaping property is better. However, the resin in the prepreg prepared by the method is still in a liquid state, and the interior of the prepreg contains a large amount of oligomers and unpolymerized monomers, particularly bulk polymerized thermoplastic resins such as polystyrene, polymethyl methacrylate and the like, and the monomers and oligomers have strong volatility, and volatile gases are flammable and have high toxicity. Therefore, in the actual use process, such as the process of storing or producing composite material products, a large amount of volatile matters are generated in the links of cutting, heating and the like, and great potential safety hazards of environmental protection, production safety and life are brought. Besides the environmental protection and the potential safety hazard, the large amount of volatilization can cause the defects of reduction of resin among fibers, even formation of bubbles, gaps and the like, and the performance of a composite material product is reduced; in addition, because the polymerization degree of the resin in the prepreg is low, the resin can be completely polymerized by long-time heating during hot press molding, and the production efficiency of the thermoplastic resin matrix composite material product is greatly reduced.
Disclosure of Invention
The purpose of the invention is: in order to solve the technical problems of poor forming property and high forming difficulty of a composite material product with a complex structure caused by high rigidity of a thermoplastic prepreg prepared by a conventional method and the technical problems of environmental protection, potential safety hazards, poor performance of the thermoplastic resin matrix composite material product based on the potential safety hazard, low production efficiency and the like caused by a large amount of volatile components in the thermoplastic prepreg prepared by an in-situ polymerization method, the thermoplastic prepreg provided by the invention has strong adaptability of product structure, is environment-friendly, and is safe and reliable in storage and production; meanwhile, a thermoplastic composite material prepared based on the thermoplastic prepreg is also provided; in addition, a method for preparing the thermoplastic prepreg and a method for efficiently preparing a high-performance thermoplastic composite material product by using the thermoplastic prepreg are also provided.
The conception of the invention is as follows:
based on practical use experience of different thermoplastic prepregs and knowledge of inherent characteristics of polymers, the inventors found that the problems can be successfully solved by prepolymerizing and impregnating an in-situ polymerized resin, and further polymerizing a resin prepolymerization solution to a solid state but not completely polymerizing the resin prepolymerization solution to a final high-rigidity resin after impregnation, so that the resin in the prepreg is cured, but has low strength and certain flexibility.
The technical scheme of the invention is to provide a thermoplastic prepreg which mainly comprises reinforced fibers and in-situ polymerized thermoplastic resin and is characterized in that: the in-situ polymerized thermoplastic resin is polymerized to completely lose fluidity and viscosity, but the in-situ polymerized thermoplastic resin is not in a fully polymerized state, and the elastic modulus of the in-situ polymerized thermoplastic resin at 25 ℃ is a, wherein a is b/10000-b/10, and b is the elastic modulus of the in-situ polymerized thermoplastic resin after being completely and fully polymerized at 25 ℃. The thermoplastic resin in the thermoplastic prepreg is already cured, the residual volatile oligomer and residual monomer in the thermoplastic prepreg are extremely low, but the resin in the prepreg is low in strength and has certain flexibility because of incomplete full polymerization, and the prepreg has better mold forming property than the common rigid thermoplastic prepreg.
Further, the in-situ polymerized thermoplastic resin has an elastic modulus a of the resin in the prepreg at 25 ℃ of b/1000 to b/100.
In order to further improve the safety and environmental protection in the process of storing and processing the prepreg, a layer of thermoplastic resin-based film which is firmly and tightly combined with the surface of the reinforced fiber impregnated with the resin pre-polymerization liquid can be added on the upper surface and the lower surface of the thermoplastic prepreg; the thermoplastic film resin type is the same as the in-situ polymerized thermoplastic resin described above, and can prevent volatilization of a very small amount of residual oligomers in the thermoplastic prepreg resin. In order to further prevent the volatilization of a very small amount of residual oligomers in the thermoplastic resin, the thermoplastic resin-based film may be replaced with a thermoplastic resin-based film having a melting point 10 to 50 ℃ lower than the melting point of the resin in the in-situ polymerized thermoplastic resin.
Further, the thickness of the thermoplastic resin-based film is less than 1/5 the thickness of the thermoplastic prepreg.
Further, the thickness of the thermoplastic resin-based film is less than 1/10 the thickness of the thermoplastic prepreg. Thus, when a composite material product is manufactured by using the prepreg, if hot press molding is required, the hot press molding can be performed at a relatively low temperature.
Further, according to the requirements of different products, the content of the thermoplastic resin polymerized in situ in the thermoplastic prepreg is 20-60 wt%.
Further, in the above thermoplastic prepreg, the thermoplastic resin polymerized in situ includes polystyrene, polymethyl methacrylate, polymethacrylic acid, polyvinyl acetate or a copolymer thereof, or a modified polymer thereof.
Further, in the thermoplastic prepreg, the fibers in the reinforcing fibers are woven fabrics or fiber mats made of glass fibers, carbon fibers, quartz fibers and the like, wherein the fibers in the woven fabrics can be woven in a unidirectional, bidirectional or multidimensional manner; the reinforced fiber is a single-layer fiber woven fabric or a fiber felt, or a plurality of layers of fiber woven fabrics or fiber felts are directly paved together in the same or different directions, according to the structural characteristics of different composite material products, the thermoplastic prepreg can be directly prepared into a plurality of layers of fiber woven fabrics or fiber felts and the like, and the resin is directly polymerized and impregnated in situ into prepreg boards and prepreg blocks with different thicknesses, which is beneficial to improving the production efficiency and the overall mechanical property of subsequent composite material products.
The invention also provides a thermoplastic composite material, which is characterized in that: is prepared by combining any one of the thermoplastic prepregs or a plurality of different thermoplastic prepregs in multiple layers and fully polymerizing.
The invention also provides a preparation method of the thermoplastic prepreg, which is characterized by comprising the following steps:
step 1, adding a monomer and an initiator for synthesizing thermoplastic resin into a reactor, and performing prepolymerization to ensure that the viscosity of a resin prepolymerization solution is 100-10000 cps at a prepolymerization temperature;
step 2, putting the reinforced fibers into the resin pre-polymerization liquid, fully soaking, and continuing to polymerize the resin pre-polymerization liquid for soaking the reinforced fibers to ensure that the viscosity of the resin pre-polymerization liquid at the pre-polymerization temperature is 50000-500000 cps;
step 3, scraping out redundant resin pre-polymerization liquid, further polymerizing the resin pre-polymerization liquid impregnated with the reinforced fibers to ensure that the resin pre-polymerization liquid is polymerized to a state of losing fluidity and viscosity but not being fully polymerized, wherein the elastic modulus is 1/10000-1/10 of the elastic modulus of the resin after being fully polymerized; and then cooling and rolling to form the thermoplastic prepreg.
Further, in the step 3, the resin prepolymer is polymerized until the resin prepolymer loses fluidity and viscosity but is not completely polymerized, and the elastic modulus is 1/1000 to 1/100 of the elastic modulus of the resin after the resin is completely polymerized.
Further, in step 3, after the excess resin prepolymer liquid is scraped off, the thermoplastic resin-based film may be attached to the surface of the fiber woven fabric or fiber mat impregnated with the resin prepolymer liquid, and then further polymerized. The thermoplastic resin-based films are respectively added on the upper surface and the lower surface of the thermoplastic prepreg, so that the volatilization of the resin prepolymer liquid can be greatly reduced when the fiber woven fabric or the fiber felt impregnated with the resin prepolymer liquid is heated, thereby being beneficial to reducing the generation of prepreg resin gaps caused by volatilization on one hand, and reducing the environmental protection pressure and the safety pressure brought by volatile matters in the prepreg preparation process on the other hand.
The invention also provides a method for preparing a thermoplastic composite material product by adopting the thermoplastic prepreg, because the resin in the thermoplastic prepreg is not completely polymerized, the thermoplastic prepreg has certain flexibility and certain strength, and the thermoplastic composite material product with a simpler structure can be directly deformed by adopting a cold pressing mode, and the method is characterized by comprising the following steps of:
step 1, according to the structural characteristics of a product, cutting a thermoplastic prepreg containing single-layer or multi-layer fiber woven fabric or fiber felt or 3D woven fiber inside into a required prepreg block, laying the prepreg block in a normal-temperature mold, deforming the prepreg block to be attached to a molded surface of the mold as much as possible by adopting a manual or special tool, pressurizing the prepreg block through a press mold at normal temperature to deform the prepreg block to obtain a composite material product with lower rigidity, and demolding to take out the thermoplastic composite material product;
and 2, fixing the thermoplastic composite material product processed in the step 1 by using a simple tool, keeping the shape unchanged, putting the product with the fixing tool into an oven in batches, and further polymerizing to ensure that the thermoplastic resin in the product is completely and fully polymerized to obtain the final composite material product.
The invention also provides another method for preparing a thermoplastic composite material product by using the thermoplastic prepreg, wherein for the composite material product with a slightly complex part structure, the cold-pressed thermoplastic prepreg is directly adopted to have larger local deformation due to insufficient resin fluidity at normal temperature, and fiber breakage or excessive movement can be caused, so that the composite material product with the slightly complex structure can be formed by adopting a hot-pressing process, and the thermoplastic prepreg can also be subjected to hot-pressing forming at a relatively low temperature because the resin of the thermoplastic prepreg is not fully polymerized and the melting point is tens of degrees lower than the melting point of the resin after the resin is fully polymerized, and the method specifically comprises the following steps:
the method comprises the following steps of 1, quickly preheating a thermoplastic prepreg to a temperature 10-50 ℃ lower than the melting temperature of resin in the prepreg, enabling the temperature of a mold to be 10-20 ℃ lower than the softening temperature of the resin in the prepreg, laying the preheated thermoplastic prepreg on a mold using molded surface of the mold, manually or by a special tool in a bending area, deforming the prepreg to be attached to the mold using molded surface as much as possible, and then closing the mold;
step 2, keeping the temperature of the die basically unchanged, pressurizing the prepreg through a press, maintaining the pressure to shape the product, demolding and taking out the composite material product;
and 3, fixing the shape of the taken composite material sample by adopting a simple tool, putting the composite material sample into an oven in batches, and further heating to ensure that the resin in the composite material is completely and fully cured.
The invention also provides another method for preparing a thermoplastic composite material product by adopting the thermoplastic prepreg, a composite material sample is manufactured by laminating the prepregs with the thermoplastic resin-based film on the surface, and in the process, the prepregs are required to be heated to the temperature above the melting temperature of the thermoplastic resin-based film on the surface so as to be effectively hot-pressed and molded, and the manufacturing method comprises the following steps:
step 1, cutting the prepreg according to the structural characteristics of a product, quickly preheating to a temperature which is 5-20 ℃ higher than the melting temperature of a thermoplastic resin-based film on the surface of the prepreg, generally heating to the resin melting temperature for several minutes, further polymerizing the resin while melting to achieve the degree of complete and sufficient polymerization, wherein the temperature of a mold is 5-20 ℃ lower than the softening temperature of the prepreg resin, deforming the prepreg to be attached to the mold surface as much as possible by adopting a manual or special tool in a bending area corresponding to the product during laying, and then closing the mold;
step 2, keeping the temperature of the die basically unchanged, pressurizing the prepreg through a press, keeping the temperature and pressure to shape the product, demolding and taking out the composite material product;
and 3, putting the taken composite material samples into an oven in batches, and further heating to ensure that the resin in the composite material is completely and fully cured.
The invention has the beneficial effects that:
1. the resin in the prepreg is primarily cured but not fully cured to the final strength of the resin, has certain flexibility, simultaneously has few residual volatile micromolecules and monomers, overcomes the problems of poor forming property, large forming difficulty of complex structure products and the like caused by rigidity of the common thermoplastic prepreg, obtains the thermoplastic prepreg with certain flexibility, greatly improves the forming property, and can be used for producing the complex structure products; meanwhile, the problems that the existing thermoplastic prepreg with viscosity and drapability formed by in-situ polymerization contains a large amount of volatile micromolecules or even monomers because the resin is not cured, great environmental and safety hidden dangers are brought in later storage, particularly in the production process, great difficulty and inconvenience are brought to the subsequent manufacture of composite material products, and the like are solved. The prepreg has little volatile micromolecules and monomers remained in the prepreg, does not need to be matched with a special gas treatment device and the like, has good storage and production safety, can be used for molding composite material products by adopting various flexible manufacturing methods, for example, most products can be used for manufacturing the composite material products by adopting a cold press molding or batch heat treatment mode after hot press molding at a lower temperature, and greatly improves the performance of the composite material products.
2. The resin in the prepreg is subjected to primary curing, so that the complete polymerization can be achieved by heating in a shorter time compared with the conventional hot press molding during hot press molding, the actual production efficiency of the thermoplastic resin-based composite material product is greatly improved, and the energy consumption is remarkably reduced.
3. The invention can realize batch production;
when the thermoplastic composite material product is prepared, the mass production can be realized in the final curing process, and the actual production efficiency of the thermoplastic resin-based composite material product is further improved.
Drawings
FIG. 1 is a schematic representation of the main steps in the preparation of a prepreg according to the invention;
FIG. 2 is a schematic representation of the steps for making a composite article by a cold pressing process using the prepreg of the present invention;
FIG. 3 is a schematic representation of the steps for making a composite article by a relatively low temperature hot pressing process using the prepreg of the present invention;
FIG. 4 is a schematic representation of the steps of making a composite article by a conventional hot press process using a prepreg of the present invention;
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments accompanied with figures are described in detail below, and it is apparent that the described embodiments are a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in other embodiments" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The thermoplastic prepreg in the embodiment mainly comprises reinforcing fibers and an in-situ polymerized thermoplastic resin, wherein the in-situ polymerized thermoplastic resin is polymerized to a state of completely losing fluidity and viscosity but not achieving sufficient polymerization, and the elastic modulus of the in-situ polymerized thermoplastic resin at 25 ℃ is 1/10000-1/10, preferably 1/1000-1/100 of the elastic modulus of the in-situ polymerized thermoplastic resin after complete and sufficient polymerization at 25 ℃. The reinforcing fiber is glass fiber cloth, in other embodiments, the reinforcing fiber can be a unidirectional glass fiber tape or a glass fiber mat, or a bidirectional or multidimensional fiber woven fabric, a unidirectional fiber woven fabric or a fiber mat and the like made of fibers such as carbon fibers, quartz fibers or aramid fibers. The fiber woven fabric or the fiber felt can be a single layer, and can also be a plurality of layers of fiber woven fabrics or fiber felts which are directly paved together in the same or different directions. The thermoplastic resin for in situ polymerization is polystyrene, and in other embodiments, polymethyl methacrylate, polymethacrylic acid, polyvinyl acetate or copolymer thereof, or modified polymer thereof can be used. The content of the thermoplastic resin polymerized in situ is 20 to 60 weight percent.
Referring to fig. 1, this example prepares the above thermoplastic prepreg by the following process:
step one, prepolymerization: the raw materials comprise monomer styrene (industrial purity) of synthetic resin polymer and initiator Azobisisobutyronitrile (AIBN). Adding a styrene monomer and 0.1 wt% of AIBN (initiator) into a sealable groove-shaped reactor with a water bath for heating, heating the styrene solution in the reactor to 60-80 ℃, slowly stirring by a stirrer arranged on the reactor to perform polymerization reaction on the styrene monomer for 0.5-2 hours, wherein the viscosity of the styrene prepolymer solution is 100-10000 cps at the prepolymerization temperature.
Step two, impregnation and further polymerization: and (2) putting the loosely wound glass fiber cloth into the styrene pre-polymerization solution, fully soaking, and then continuously polymerizing the fiber-soaked styrene pre-polymerization solution for 0.5-1 hour at the temperature of 60-80 ℃ to ensure that the viscosity of the pre-polymerization solution is 50000-500000 cps at the pre-polymerization temperature. The hot water in the interlayer of the water bath reactor is changed into cold water, and the solution in the reactor is cooled to below 40 ℃, so that the pre-polymerized liquid is prevented from further reacting to cause the viscosity to be remarkably increased and even solidified.
Step three, further polymerizing, curing and rolling: the method comprises the steps of slowly taking out glass fiber cloth containing styrene pre-polymerized liquid from a reactor by adopting a winding device provided with a long heating box and a scraper, scraping the redundant styrene pre-polymerized liquid by the scraper, further polymerizing for 0.5-1 h at 80-100 ℃ through the long heating box to polymerize polystyrene resin until the polystyrene resin loses fluidity and viscosity but is not fully polymerized, controlling the elastic modulus at normal temperature to be 1/10000-1/10 of the elastic modulus (about 3GPa) of the normal fully polymerized polystyrene resin, preferably controlling the elastic modulus of the polystyrene in the prepreg to be 1/1000-1/100 of 3GPa and about 3 MPa-30 MPa, enabling the polymer in the prepreg to be close to the rigidity of soft rubber, enabling the obtained prepreg to have certain flexibility, and then winding to form the thermoplastic prepreg. Although the internal resin of the prepreg is not completely polymerized, the prepreg has extremely low internal residual oligomer, almost no residual monomer, and little volatile matter is generated during the later storage and secondary molding. In addition, the prepreg has certain flexibility, the subsequent forming die has good shaping property, and a composite material product can be produced by adopting a high-efficiency low-energy-consumption method.
And (3) adding comonomers such as acrylonitrile and butadiene or modifiers for flame retardance, ultraviolet resistance, toughening and the like into the styrene monomer in the step one.
In the second step, a plurality of layers of fiber cloth or thicker 3D fiber woven fabric blocks can be put into the pre-polymerization liquid for soaking, and the procedures of pre-polymerization and solidification are the same as the procedures of the pre-polymerization and solidification in the later period, so that a plurality of layers of prepregs or 3D woven fiber prepreg blocks with lower rigidity and certain flexibility at normal temperature are formed.
For composite material products with simpler structures, such as simple shells, reinforcing ribs with L-shaped sections and the like, the multilayer prepreg or 3D woven prepreg can be adopted, and the following processes are adopted to produce the products, as shown in FIG. 2: and (2) pressing the prepreg into the shape of a composite material product in a mould by using a press at normal temperature, fixing the cold-pressed composite material product by using a customized tool, putting the cold-pressed composite material product into an oven in batches, and heating the product at 100-120 ℃ for 12-24 hours to further completely cure the resin in the composite material product so as to achieve excellent mechanical properties.
For a composite material product with a slightly complex part structure, a cold-pressed prepreg is directly adopted, local deformation is large, the fluidity of the resin is insufficient at normal temperature, fibers are likely to be broken or moved too much, a hot-pressing process is needed for molding, the resin of the prepreg is not completely and fully polymerized, the average molecular weight is about 5000-20000, and the melting point is lower than that of ordinary polystyrene by tens of degrees, and the composite material can also be produced by a second composite material manufacturing method disclosed by the invention, as shown in fig. 3: carrying out hot press molding at a relatively low temperature, quickly preheating the cut prepreg to 150-180 ℃ in an infrared heating device, keeping the temperature of a mold at about 60-80 ℃, quickly carrying out die pressing and shaping, taking out and cooling the product, fixing the shape by adopting a simple tool according to needs, putting the product into an oven in batches, and heating the product at 100-120 ℃ for 12-24 hours to further completely cure the resin in the composite material product, thereby achieving excellent mechanical properties.
Example 2
In this embodiment, on the basis of embodiment 1, a layer of thermoplastic resin-based film firmly and tightly bonded to the thermoplastic prepreg is added on the surface of the thermoplastic prepreg, and the thickness of the layer of thermoplastic resin-based film may be 1/5, preferably 1/10.
In the preparation process, the prepolymerization, impregnation and further polymerization processes are the same as the first step and the second step in the example 1, after the glass fiber cloth is impregnated with the styrene prepolymer solution, the glass fiber cloth impregnated with the styrene prepolymer solution is slowly taken out of the reactor, excessive styrene prepolymer solution is scraped off by a scraper, an additional tool is adopted to attach ABS films with the thickness of 5-20 microns to two surfaces of the glass fiber cloth containing the styrene prepolymer solution, the resin solution is further polymerized synchronously through a long heating box, the resin is polymerized to completely lose the fluidity and the viscosity but not completely polymerized, the elastic modulus is only 1/10000-1/10 of the elastic modulus after the resin is completely polymerized, and then the resin is cooled and rolled to form the thermoplastic prepreg.
In the steps, the ABS films are respectively added on the two sides of the glass fiber cloth impregnated with the styrene pre-polymerization solution, so that the volatilization of the pre-polymerization solution during the subsequent heating and further polymerization is reduced, the product performances of the prepreg and the subsequent composite material are improved, and the environmental pollution and the potential safety hazard in the production are reduced. In addition, the ABS film has good toughness, and is beneficial to improving the interlayer mechanical property of the composite material product produced by the prepreg in the later period.
The prepreg with the ABS film on the surface is used for producing composite material products, and the production needs to be realized by adopting the following processes, as shown in figure 4, the prepreg is preheated to 5-20 ℃ above the melting temperature of the ABS film, the prepreg is heated to the melting temperature, the resin which is not fully polymerized is further polymerized, rapid hot press molding is carried out, the products are taken out and cooled, and then the products are put into an oven in batches to be heated for 6-12 hours at 100-120 ℃, so that the resin in the composite material products is ensured to be fully polymerized, and excellent mechanical properties are achieved.
In this example, according to different requirements of the performance of the final product, the ABS film on the surface of the prepreg can be replaced by a polystyrene film or other thermoplastic resin film with a lower melting point, such as a polypropylene film, but the temperature adopted in the later manufacturing of the composite material product needs to be adjusted, for example, if the surface of the prepreg is a polypropylene film, the prepreg can be hot-pressed at a relatively lower temperature, so as to reduce energy consumption and improve production efficiency.
Example 3
The difference between this embodiment and embodiment 1 is that polymethyl methacrylate is used as the thermoplastic resin for in-situ polymerization in the thermoplastic prepreg, and the thermoplastic prepreg can be specifically prepared by the following processes, with reference to fig. 1:
step one, prepolymerization: the raw materials comprise monomer methyl methacrylate (MMA, industrial purity) of synthetic polymer and initiator Azobisisobutyronitrile (AIBN). Adding an MMA monomer and 0.1 wt% of AIBN (initiator) into a tank-shaped reactor with a water bath heating function, heating an MMA solution in the reactor to 60-80 ℃, slowly stirring the MMA solution by a stirrer arranged on the reactor to enable the MMA monomer to carry out polymerization reaction for 0.5-2 hours, wherein the viscosity of an MMA prepolymer is 100-10000 cps at a prepolymerization temperature.
Step two, impregnation and further polymerization: and (3) placing the loosely wound glass fiber cloth into the prepolymerized resin liquid, fully soaking, and continuously polymerizing the MMA prepolymerized liquid for soaking the fibers at the temperature of 60-80 ℃ for 0.5-1 hour to ensure that the viscosity of the prepolymerized liquid is 50000-500000 cps at the prepolymerization temperature. The hot water in the interlayer of the water bath reactor is changed into cold water, and the solution in the reactor is cooled to below 40 ℃, so that the pre-polymerized liquid is prevented from further reacting to cause the viscosity to be remarkably increased and even solidified.
Step three, further polymerizing, curing and rolling: the method comprises the steps of slowly taking out glass fiber cloth containing MMA (methyl methacrylate) pre-polymerization liquid from a reactor by adopting a winding device provided with a long heating box and a scraper, scraping redundant resin by the scraper, further polymerizing for 0.5-1 h at 70-100 ℃ through the long heating box to polymerize polymethyl methacrylate (PMMA) resin until the resin loses fluidity and viscosity but is not fully polymerized, controlling the elastic modulus at normal temperature to be 1/10000-1/10 of the elastic modulus (about 3GPa) of the normal fully polymerized PMMA resin, preferably controlling the elastic modulus of PMMA in the prepreg to be 1/1000-1/100 of 3GPa and about 3 MPa-30 MPa, enabling the polymer in the prepreg to be close to the rigidity of soft rubber, enabling the obtained prepreg to have certain flexibility, and then winding to form thermoplastic prepreg. Although the resin in the prepreg is not fully polymerized, the prepreg has extremely low residual oligomer in the prepreg, almost no residual monomer, and few volatile matters are generated during later storage and secondary molding. In addition, the prepreg has certain flexibility, the subsequent forming mold has good shaping property, and a composite material product can be produced by adopting a high-efficiency low-energy-consumption method.
In other embodiments, the reinforcing fiber may also be a unidirectional glass fiber tape or a glass fiber mat, or a bidirectional or multidimensional fiber fabric, a unidirectional fiber fabric or a fiber mat made of fibers such as carbon fibers, quartz fibers or aramid fibers. In other embodiments, modifiers such as flame retardant, ultraviolet resistant, toughening and the like can also be added into the MMA monomer. In the second step, a plurality of layers of fiber cloth or thicker 3D fiber woven fabric blocks can be put into the pre-polymerization liquid for soaking, and the procedures of pre-polymerization and curing are the same as the procedures described above in the later period, so that a plurality of layers of prepregs or 3D fiber woven fabric blocks with lower rigidity and certain flexibility at normal temperature are formed.
For composite material products with simpler structures, such as simple shells, reinforcing ribs with L-shaped sections and the like, the multilayer prepreg or 3D woven prepreg can be adopted, and the first composite material manufacturing method is adopted to produce the products: pressing the prepreg into a shape of a composite material product at normal temperature, fixing the cold-pressed composite material product by using a customized tool, putting the cold-pressed composite material product into an oven in batches, and heating the product at 90-110 ℃ for 12-24 hours to further completely cure the resin in the composite material product, thereby achieving excellent mechanical properties.
For a composite material product with a slightly complex part structure, a cold-pressed prepreg is directly adopted, local deformation is large, the fluidity of the resin is insufficient at normal temperature, fibers are likely to be broken or moved too much, hot-pressing process molding is needed, and as the resin of the prepreg is not completely and fully polymerized, the average molecular weight is about 5000-20000, and the melting point is lower than that of ordinary PMMA by tens of degrees, the composite material manufacturing method II can be adopted to produce the product: carrying out hot press molding at a relatively low temperature, quickly preheating the cut prepreg to 140-160 ℃ in an infrared heating device, keeping the temperature of a mold at about 50-70 ℃, quickly carrying out die pressing and shaping, taking out and cooling the product, putting the product into an oven in batches, and heating the product at 90-110 ℃ for 12-24 hours, so that the resin in the composite material product is further completely cured, and excellent mechanical properties are achieved.
Claims (16)
1. A thermoplastic prepreg consisting essentially of reinforcing fibers and an in situ polymerized thermoplastic resin, characterized in that: the in-situ polymerized thermoplastic resin is polymerized to a state of completely losing fluidity and viscosity, but not achieving sufficient polymerization, and the elastic modulus of the in-situ polymerized thermoplastic resin at 25 ℃ is a, wherein a is b/10000-b/10, and b is the elastic modulus of the in-situ polymerized thermoplastic resin after complete and sufficient polymerization at 25 ℃.
2. The thermoplastic prepreg of claim 1, in which: the in-situ polymerized thermoplastic resin has an elastic modulus a of b/1000 to b/100 at 25 ℃.
3. The thermoplastic prepreg of claim 1, in which: thermoplastic resin-based films; the thermoplastic resin-based film is firmly and tightly bonded to the surface of the reinforcing fiber impregnated with the resin pre-polymerization liquid.
4. The thermoplastic prepreg of claim 3, in which: the thermoplastic resin-based film has the same resin type as the in-situ polymerized thermoplastic resin; or the thermoplastic resin-based film is different from the in-situ polymerized thermoplastic resin in resin type, and the melting point of the resin in the thermoplastic resin-based film is 10-50 ℃ lower than that of the in-situ polymerized thermoplastic resin.
5. The thermoplastic prepreg of claim 4, in which: the thickness of the thermoplastic resin-based film is less than 1/5 the thickness of the reinforcing fibers impregnated with the resin pre-polymerization liquid.
6. The thermoplastic prepreg of claim 5, in which: the thickness of the thermoplastic resin-based film is less than 1/10 the thickness of the reinforcing fibers impregnated with the resin pre-polymerization liquid.
7. The thermoplastic prepreg of any one of claims 1-6, wherein: the content of the in-situ polymerized thermoplastic resin is 20-60 wt%.
8. The thermoplastic prepreg of any one of claims 1-6, wherein: the in-situ polymerized thermoplastic resin comprises polystyrene, polymethyl methacrylate, polymethacrylic acid, polyvinyl acetate or a copolymer thereof, or a modified polymer thereof.
9. The thermoplastic prepreg of any one of claims 1-6, wherein: the fibers in the reinforced fibers are fiber braided fabrics or fiber felts made of glass fibers, carbon fibers or quartz fibers; wherein, the fiber in the fiber braided fabric is unidirectional, bidirectional or multidimensional braided; the reinforcing fiber is a single-layer fiber woven fabric or fiber felt, or a plurality of layers of fiber woven fabrics or fiber felts which are directly paved together in the same or different directions.
10. A thermoplastic composite characterized by: consisting essentially of a thermoplastic prepreg according to any one of claims 1 to 9 or a multilayer combination of several different thermoplastic prepregs and further fully polymerised.
11. A method of making a thermoplastic prepreg according to claim 1 comprising the steps of:
step 1, adding a monomer and an initiator for synthesizing thermoplastic resin into a reactor, and performing prepolymerization to ensure that the viscosity of a resin prepolymerization solution is 100-10000 cps at a prepolymerization temperature;
step 2, putting the reinforced fibers into the resin pre-polymerization liquid, fully soaking, and continuing to polymerize the resin pre-polymerization liquid for soaking the reinforced fibers to ensure that the viscosity of the resin pre-polymerization liquid at the pre-polymerization temperature is 50000-500000 cps;
step 3, scraping out redundant resin pre-polymerization liquid, further polymerizing the resin pre-polymerization liquid impregnated with the reinforced fibers to ensure that the resin pre-polymerization liquid is polymerized to a state of losing fluidity and viscosity but not being fully polymerized, wherein the elastic modulus is 1/10000-1/10 of the elastic modulus of the resin after being fully polymerized; and then cooling and rolling to form the thermoplastic prepreg.
12. The method of producing a thermoplastic prepreg according to claim 11, characterized in that: in the step 3, the resin pre-polymerization liquid is polymerized to a state of losing fluidity and viscosity but not being completely polymerized, and the elastic modulus is 1/1000-1/100 of the elastic modulus of the resin after being completely polymerized.
13. The method of producing a thermoplastic prepreg according to claim 11, characterized in that: and 3, after the excessive resin pre-polymerization liquid is scraped out, adhering the thermoplastic resin-based film to the surface of the fiber woven fabric or the fiber felt soaked with the resin pre-polymerization liquid, and then further polymerizing.
14. A method of making a thermoplastic composite article using a thermoplastic prepreg according to any one of claims 1 to 9, comprising the steps of:
step 1, cutting a thermoplastic prepreg into required prepreg blocks according to the structural characteristics of a product, laying the prepreg blocks in a normal-temperature mold, deforming the prepreg blocks to be attached to a molded surface of the mold as much as possible by adopting a manual or special tool, pressurizing the prepreg blocks through a press mold at normal temperature to deform the prepreg blocks to obtain a composite material product with lower rigidity, and demolding to take out the thermoplastic composite material product;
and 2, fixing the thermoplastic composite material product processed in the step 1 by using a simple tool, keeping the shape unchanged, putting the product with the fixing tool into an oven in batches, and further polymerizing to ensure that the thermoplastic resin in the product is completely and fully polymerized to obtain the final composite material product.
15. A method of making a thermoplastic composite article using a thermoplastic prepreg according to any one of claims 1 to 9, comprising the steps of:
the method comprises the following steps of 1, quickly preheating a thermoplastic prepreg to a temperature 10-50 ℃ lower than the melting temperature of resin in the prepreg, enabling the temperature of a mold to be 10-20 ℃ lower than the softening temperature of the resin in the prepreg, laying the preheated thermoplastic prepreg on a mold using molded surface of the mold, manually or by a special tool in a bending area, deforming the prepreg to be attached to the mold using molded surface as much as possible, and then closing the mold;
step 2, keeping the temperature of the die basically unchanged, pressurizing the prepreg through a press, maintaining the pressure to shape the product, demolding and taking out the composite material product;
and 3, fixing the shape of the taken composite material sample by adopting a simple tool, putting the composite material sample into an oven in batches, and further heating to ensure that the resin in the composite material is completely and fully cured.
16. A method of making a thermoplastic composite article using a thermoplastic prepreg according to any one of claims 1 to 9, comprising the steps of:
step 1, cutting the prepreg according to the structural characteristics of the product, quickly preheating to a temperature 5-20 ℃ higher than the melting temperature of a thermoplastic resin-based film on the surface of the prepreg, heating to the temperature of resin melting for several minutes, further polymerizing the resin while melting to a fully polymerized degree, wherein the temperature of a mold is 5-20 ℃ lower than the softening temperature of the prepreg resin, manually or by a special tool in a bending area corresponding to the product during laying, deforming the prepreg to be attached to the mold surface as much as possible, and then closing the mold,
step 2, keeping the temperature of the die basically unchanged, pressurizing the prepreg through a press, keeping the temperature and pressure to shape the product, demolding and taking out the composite material product;
and 3, putting the taken composite material samples into an oven in batches, and further heating to ensure that the resin in the composite material is completely and fully cured.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103009634A (en) * | 2011-09-26 | 2013-04-03 | 蓝星(北京)化工机械有限公司 | Thermoplastic resin composite material and preparation method thereof |
| CN106995533A (en) * | 2017-04-27 | 2017-08-01 | 武汉理工大学 | A kind of method that light-initiated in-situ polymerization prepares thermoplastic composite prepreg |
| JP2019210417A (en) * | 2018-06-07 | 2019-12-12 | サンコロナ小田株式会社 | Process for producing fiber reinforced composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103009634A (en) * | 2011-09-26 | 2013-04-03 | 蓝星(北京)化工机械有限公司 | Thermoplastic resin composite material and preparation method thereof |
| CN106995533A (en) * | 2017-04-27 | 2017-08-01 | 武汉理工大学 | A kind of method that light-initiated in-situ polymerization prepares thermoplastic composite prepreg |
| JP2019210417A (en) * | 2018-06-07 | 2019-12-12 | サンコロナ小田株式会社 | Process for producing fiber reinforced composite material |
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Application publication date: 20220729 |