CN113121988B - Composite material and foam prepared from same - Google Patents

Composite material and foam prepared from same Download PDF

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CN113121988B
CN113121988B CN202010123354.0A CN202010123354A CN113121988B CN 113121988 B CN113121988 B CN 113121988B CN 202010123354 A CN202010123354 A CN 202010123354A CN 113121988 B CN113121988 B CN 113121988B
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acrylate
weight
fiber
composite
oligomer
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CN113121988A (en
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郑舜文
张胜隆
吴志郎
赵英捷
刘信助
梁文忠
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Industrial Technology Research Institute ITRI
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0085—Use of fibrous compounding ingredients
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—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
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/14—Homopolymers or copolymers of styrene with unsaturated esters
    • 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
    • C08J2427/00—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 a halogen; Derivatives of such polymers
    • C08J2427/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A composite material and a foam prepared by using the composite material. The composite material comprises a network polymer, a fluorine-containing polymer fiber (fluoroine-containing polymer fiber) and a reinforcing fiber. The network polymer is a cross-linking reaction product of a polymer and an oligomer, wherein the polymer is polyamide, polyester, polyurethane or a combination of the above; and, the oligomer is a vinyl aromatic-acrylate oligomer (vinyl aromatic-co-acrylate oligomer) having an epoxy functionality, wherein the weight percent of the oligomer is from 1% to 10% based on the weight of the network polymer; and the ratio of the weight of the reinforcing fiber to the total weight of the network polymer and the fluoropolymer fiber is 1:9 to 4:6.

Description

Composite material and foam prepared from same
Technical Field
The invention relates to a composite material and a foam prepared from the composite material.
Background
Synthetic resins reinforced with fibers are lightweight and have high mechanical strength, and therefore, have been increasingly used in recent years in fields requiring lightweight and high mechanical strength, such as automobiles, ships, aviation, medical treatment, and construction. The fiber-reinforced synthetic resin (fiber-reinforced synthetic resin) sheet is generally produced by impregnating a base material with a resin, which is a woven or nonwoven fabric comprising fibers having excellent strength such as glass fibers. Accordingly, the fiber-reinforced resin sheet has superior strength compared to a general resin sheet not reinforced with fibers.
The automobile is a main transportation means at present, and is also a large pollution source, and the main reason is the exhaust gas and energy consumption of the automobile. In view of the above, the weight reduction of automobiles has become an important improvement, and the weight of the automobile body is reduced by reducing the materials, so that the fuel consumption is reduced, and the exhaust emission is promoted to be improved.
In order to further produce a fiber-reinforced resin composite material having both excellent strength and light weight, a method of forming a fiber-reinforced resin foam molded body by adding a foaming agent has been proposed. However, due to the low melt strength (melt strength) and bubble retention (bubble retention) of the conventional resin material, the formed foam has defects such as surface air explosion (surface explosion) or bubble floating (formation of surface voids or inner voids). In addition, when the supercritical fluid (supercritical fluid) is used as the foaming agent, the phase separation phenomenon in the composite material causes the formed foam to have a large difference in cell size, resulting in a significant decrease in physical properties of the foam.
Disclosure of Invention
The present invention provides a composite material. According to embodiments of the present invention, the composite material comprises a network polymer, a fluoropolymer fiber, and a reinforcing fiber. The network polymer is a cross-linked reaction product of a polymer and an oligomer, wherein the polymer is polyamide, polyester, polyurethane or a combination thereof. The oligomer is a vinyl aromatic-acrylate oligomer having an epoxy functionality, wherein the weight percent of the oligomer is about 1% to 10% based on the weight of the network polymer. The weight ratio of reinforcing fibers to the total weight of the network polymer and the fluoropolymer fibers is about 1:9 to 4:6.
The invention also provides a foam which can be prepared from the composite material. According to an embodiment of the present invention, the foam may be composed of the above composite material and a plurality of cells, wherein the plurality of cells are disposed in the composite material.
Drawings
FIGS. 1 to 11 are scanning electron microscope (scanning electron microscope, SEM) spectra of the foams (1) to (11), respectively.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
The composite material and the foam of the present invention are described in detail below. It is to be understood that the following description provides many different embodiments, or examples, for implementing different forms of the invention. The specific components and arrangements described below are only a brief description of the present invention. These are, of course, merely examples and are not intended to be limiting. Furthermore, repeated reference numerals or designations may be used in the various embodiments. These repetition are for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In the present invention, the term "about" means that the specified amount may be increased or decreased by an amount that would be recognized by those skilled in the art as being of a general and reasonable size.
The invention provides a composite material and a foam formed by using the same. According to embodiments of the present invention, the composite material comprises a network polymer, a fluoropolymer, and a reinforcing fiber. By the specific configuration (for example, fiber shape (having an aspect ratio of 50 or more)) and content of the fluoropolymer, when a foam is formed using the composite material, the fluoropolymer can uniformly adsorb and disperse the blowing agent introduced into the composite material, and thus a foam having a relatively uniform cell size (for example, a difference between the cell pore size distribution D90 and the cell pore size distribution D10 of 20 μm to 35 μm) can be formed, and defects such as surface air explosion (surface explosion) or bubble floating (formation of surface voids or inner voids) can be avoided. Further, the foam formed from the composite material of the present invention can achieve the technical object of light weight and high mechanical strength. In addition, since the network polymer and the fluorine-containing polymer (fluorine-containing polymer) can form a half of interpenetrating polymer network (semi-interpenetrating polymer network), the melt strength of the composite material can be improved.
According to embodiments of the present invention, the composite material comprises a network polymer, a fluoropolymer fiber, and a reinforcing fiber. According to an embodiment of the invention, the average length of the reinforcing fibers in the composite is between about 0.01mm and 1mm, for example 0.02mm, 0.05mm, 0.1mm, 0.2mm, 0.5mm or 0.8mm. The reinforcing fibers may comprise glass fibers, carbon fibers, or a combination thereof.
According to the embodiment of the invention, the network polymer (network polymer) and the fluorine-containing polymer fiber (fluorine-containing polymer fiber) can form a semi-interpenetrating polymer network (semi-interpenetrating polymer network), wherein the reinforcing fiber is uniformly dispersed in the semi-interpenetrating polymer network. In the present invention, a semi-interpenetrating polymer network refers to a network of fluoropolymer fibers and network polymers, wherein the network polymers are crosslinked and the fluoropolymer fibers are not crosslinked. The network polymer and fluoropolymer fibers are not simply blended together, but rather are more intimately associated with each other, i.e., the crosslinked network polymer is physically entangled with at least a portion of the non-crosslinked fluoropolymer fibers. Because the fluoropolymer fiber has hydrophobic properties and high cohesion, when the composite material of the present invention is subjected to a foaming process, the fluoropolymer fiber allows the introduced foaming agent to form smaller cells and adhere to the fluoropolymer fiber, thus forming a foam having a more uniform cell size and a higher cell density, and reducing the occurrence of defects.
According to some embodiments of the invention, the composite material is composed of a network polymer, a fluoropolymer fiber, and a reinforcing fiber. According to embodiments of the present invention, the ratio of the weight of the reinforcing fiber to the total weight of the network polymer and the fluoropolymer fiber is about 1:9 to 4:6, such as 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, or 1:2. If the amount of the reinforcing fiber is too low, the thermal stability effect of physical strength reinforcement is not obvious, and the dimensional shrinkage is too high; and, if the amount of reinforcing fibers is too high, the fibers easily pass through the surface of the composite material, affecting the flatness of the material surface and the processing characteristics of the material, resulting in limited applications of the finished product obtained from the composite material.
According to embodiments of the present invention, the fluoropolymer fiber may be Polytetrafluoroethylene (PTFE) fiber, polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) fiber, perfluoroalkoxyalkane (perfluoroalkoxy alkane, PFA) fiber, fluorinated ethylene propylene copolymer (fluorinated ethylene propylene, FEP) fiber, or a combination thereof. According to embodiments of the present invention, the fluoropolymer fiber may have a number average molecular weight of about 5,000 to 500,000, such as 10,000, 20,000, 50,000, 80,000, 100,000, 200,000, 300,000, or 400,000. In accordance with embodiments of the present invention, the fluoropolymer fibers may have an average aspect ratio of greater than 5, such as 5 to 2000, 10 to 2000, 20 to 2000, or 10 to 1500, in order that the fluoropolymer fibers may be more intimately bonded to the network polymer, even physically entangled to form a semi-interpenetrating polymer network. According to embodiments of the present invention, the weight percent of the fluoropolymer fiber may be about 0.1wt% to 2wt%, such as 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, or 1.9wt% based on the total weight of the network polymer, the fluoropolymer fiber, and the reinforcing fiber. If the weight percentage of the fluoropolymer fiber is too low, the amount of the fluoropolymer fiber adsorbing the blowing agent is too low, so that the blowing agent is easily phase separated from the composite material, which leads to a wide cell distribution and the occurrence of bubbles (bubbles) in addition to defects. If the weight percentage of the fluoropolymer fiber is too high, the fluoropolymer fiber tends to aggregate in the composite, resulting in poor processability of the resulting composite.
According to certain embodiments of the present invention, the weight percent of the fluoropolymer fiber may be about 0.1wt% to 2wt% based on the total weight of the semi-interpenetrating polymer network and reinforcing fiber.
According to the embodiment of the invention, the network polymer is a polymer and an oligomer which are crosslinked. According to embodiments of the present invention, the polymer may be a polyamide, a polyester, a polyurethane, or a combination thereof. The polymer may have a number average molecular weight of about 5,000 to 500,000, such as 7500, 10,000, 20,000, 50,000, 80,000, 100,000, 200,000, 300,000, or 400,000. According to embodiments of the invention, the polyamide may be polycaprolactam, polyhexamethylene adipamide (polyhexamethylene adipamide), polylaurolactam (ppolyaurolactam), polydodeoxycapramide, polybutyrolactam (polybutyrolactam), polydodecylhexamethylenediamine (polyhexamethylene dodecanoamide), polyundecanamide (polyundecanamide), polydecanoyl hexamethylenediamine (polyhexamethylene sebacamide), or polydecanoyl sebacamide (polydecamethylene sebacamide). According to embodiments of the invention, the polyester may be polyethylene terephthalate (polyethylene terephthalate, PET), polybutylene terephthalate (polybutylene terephthalate, PBT), cyclohexanediol copolyester (polyethylene terephthalate glycol, PETG), polyethylene terephthalate cyclohexane dimethanol ester (polycyclohexylenedimethylene terephthalate glycol, PCTG), polybutylene terephthalate (Polybutylene terephthalate, PBT), polycyclohexane dimethanol ester (polycyclohexylenedimethylene terephthalate, PCT), polyethylene naphthalate (polyethylene naphthalate, PEN), or polypropylene terephthalate (polytrimethylene terephthalate, PTT).
According to an embodiment of the invention, the oligomer may be a vinyl aromatic-co-acrylate oligomer oligomer having an epoxy functionality (epoxy functional group). According to embodiments of the invention, the oligomer may have a molecular weight (e.g., number average molecular weight) of about 200 to 65,000, such as 250 to 65,000, 1,000 to 65,000, 2,000 to 65,000, 3,000 to 65,000, 4,000 to 65,000, 5,000 to 60,000, 1,000 to 50,000, 2,000 to 50,000, 3,000 to 50,000, 4,000 to 50,000, or 2,000 to 30,000. According to embodiments of the present invention, the oligomer may have an epoxy equivalent weight of about 200 to 2,000, such as 250 to 2,000, 300 to 2,000, 350 to 2,000, 300 to 1,800, or 300 to 1,600.
According to an embodiment of the present invention, the vinyl aromatic-acrylate oligomer having an epoxy functional group may be a copolymer of a vinyl aromatic monomer and an acrylate monomer, wherein the acrylate monomer at least comprises an acrylate monomer having an epoxy functional group. According to embodiments of the present invention, the acrylate monomer having an epoxy functionality may be, for example, glycidyl acrylate (glycidyl acrylate), glycidyl methacrylate (glycidyl methacrylate), methyl 3,4-epoxybutyl acrylate (3, 4-epoxybutyl methacrylate), 3,4-epoxybutyl acrylate (3, 4-epoxybutyl acrylate), or a combination thereof. According to an embodiment of the present invention, the vinyl aromatic monomer may be styrene (styrene), methyl styrene (methyl styrene), ethyl styrene (ethyl styrene), propyl styrene (propyl styrene), cyclohexyl styrene (cyclohexyl styrene), vinyl biphenyl (vinyl biphenyl), or a combination thereof. According to an embodiment of the present invention, the acrylate monomer may further include methyl acrylate (methyl acrylate), methyl methacrylate (methyl methacrylate), ethyl acrylate (ethyl acrylate), ethyl methacrylate (ethyl methacrylate), n-butyl acrylate (n-butyl acrylate), n-butyl methacrylate (n-butyl methacrylate), sec-butyl acrylate (sec-butyl acrylate), sec-butyl methacrylate (sec-butyl methacrylate), third butyl acrylate (tert-butyl acrylate), third butyl methacrylate (tert-butyl methacrylate), cyclohexyl acrylate (cyclohexyl acrylate), cyclohexyl methacrylate (cyclohexyl methacrylate), or a combination thereof.
Since the oligomer of the present invention has an epoxy functional group (epoxy functional group), a network polymer can be formed by a crosslinking reaction of the epoxy functional group with a polymer (i.e., polyamide, polyester, or polyurethane). The degree of crosslinking of the network polymer of the present invention can be adjusted by the ratio of the number of repeating units having epoxy functionality (e.g., derived from acrylate monomers having epoxy functionality) to the number of repeating units having no epoxy functionality (e.g., derived from vinyl aromatic monomers and from acrylate monomers having no epoxy functionality). In addition, since the oligomer has repeating units derived from a vinyl aromatic monomer, aromatic ring groups of the repeating units can assist in adsorbing the blowing agent, the formed foam has a more uniform cell size and a higher cell density, and can reduce the occurrence of defects.
In accordance with embodiments of the present invention, the oligomers used to form the network polymer may have a weight percent of about 1% to 10% (e.g., 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%) based on the total weight of the polymer and oligomer (i.e., about the weight of the network polymer). If the amount of oligomer is too low, the melt strength of the resulting composite material cannot be improved, which is disadvantageous for the subsequent foaming process. If the oligomer is used in too high an amount, the composite may not be melted due to too high a degree of crosslinking of the network polymer, resulting in the composite not being applicable to the formation of foam.
According to an embodiment of the present invention, the vinyl aromatic-acrylate oligomer having an epoxy functional group may be a copolymer of a vinyl aromatic monomer and an acrylate monomer having an epoxy functional group. In addition, according to the embodiment of the invention, the vinyl aromatic-acrylate oligomer with epoxy functional group can be a copolymer of vinyl aromatic monomer, first acrylate monomer and second acrylate monomer, wherein the first acrylate monomer is acrylate monomer with epoxy functional group, and the second acrylate monomer is different from the first acrylate monomer. According to an embodiment of the present invention, the second acrylate monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, or a combination thereof.
According to embodiments of the present invention, the vinyl aromatic-acrylate oligomer having epoxy functionality may have
Figure BDA0002393667770000071
Is->
Figure BDA0002393667770000072
Repeating units, where the repeating units may be arranged in a block, alternating or random manner, where R 1 、R 2 、R 4 、R 6 Or R 7 Independently hydrogen or C 1-6 Alkyl of (a); r is R 3 Is hydrogen, C 1-6 Alkyl, C of (2) 5-7 Cycloalkyl or benzene ring; r is as follows 5 Is C 1-6 Alkyl or C of (2) 5-7 Cycloalkyl groups of (a). According to an embodiment of the invention, C 1-6 Alkyl groups may be straight or branched (linear or branched) chain alkyl groups. For example, C 1-6 The alkyl group may be methyl (methyl), ethyl (ethyl), propyl (propyl), butyl (butyl), pentyl (pentayl), hexyl (hexyl) or an isomer (isomer) thereof. According to an embodiment of the invention, C 5-7 The cycloalkyl group of (c) may be cyclopentyl (cyclyl), hexyl (cyclohexyl) or cycloheptyl (cycloheptyl).
According to embodiments of the present invention, the vinyl aromatic-acrylate oligomer having epoxy functionality may have x
Figure BDA0002393667770000081
Repeat unit, y->
Figure BDA0002393667770000082
Repeat unit, z->
Figure BDA0002393667770000083
Repeating units, wherein x, y and z may each independently be an integer from 1 to 30, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28 or 29. According to embodiments of the invention, z (x+y) may be 2:1 to 20:1. If the ratio of z to x+y is too low, the number of epoxy functional groups available for crosslinking is low, resulting in a reduced degree of crosslinking of the resulting network polymer, affecting the melting of the resulting composite Melt strength. If the ratio of z to x+y is too high, the number of epoxy functional groups available for crosslinking is too high, resulting in too high a crosslinking density affecting the processing characteristics.
According to an embodiment of the present invention, the method for preparing the composite material may include the following steps. First, a composition is provided, wherein the composition may comprise a polymer (i.e., polyamide, polyester, polyurethane, or a combination thereof), an oligomer, and a fluoropolymer (in the form of particles, which may have a particle size of 1 μm to 200 μm). According to some embodiments of the invention, the composition may optionally further comprise an additive, such as a processing oil, an initiator, a stabilizer, a melt strength enhancer, an antioxidant, an anti-adhesive, an antistatic agent, or a combination thereof. The amount of the additive is not limited and may be adjusted according to actual needs by those of ordinary skill in the art. In the composition, the weight percent of the oligomer is 1wt% to 10wt%, based on the total weight of the polymer and oligomer. Next, the composition is fed into a twin-screw extruder (the aspect ratio may be 40 to 60), and melt-kneading is performed, wherein the screw rotation speed is set to 60 to 300rpm, and the screw temperature is set to 180℃to 220 ℃. In this stage, the polymer pair undergoes a cross-linking reaction with the oligomer to form a network polymer. Then, after 0.1 to 5 minutes of melt-kneading, the temperature of the twin-screw extruder was raised from 250℃to 265℃by a gradient temperature-raising method, and melt-kneading was performed for 0.1 to 5 minutes. In this stage, the fluoropolymer is gradually converted from particulate fluoropolymer to fluoropolymer fibers as a result of the increase in temperature and shear forces, and further physically entangled with the network polymer to form a semi-interpenetrating polymer network. Then, the reinforcing fiber is added into a double-screw extruder, and extrusion bracing granulation is carried out to obtain the composite master batch. The amount of fluoropolymer fiber in the composite is about 0.1wt% to 2wt% based on the weight of the composite.
According to an embodiment of the present invention, the present invention also provides a foam, wherein the foam is prepared by using the composite material of the present invention, and a plurality of cells are configured in the composite material. According to an embodiment of the invention, the foam obtained by the composite material of the inventionAverage pore size of cells of the body (D avg ) Can be controlled to about 10 μm to 50 μm, and the difference between the cell pore size distribution D90 and the cell pore size distribution D10 of the foam is 20 μm to 35 μm (e.g., 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm or 34 μm). According to embodiments of the present invention, the smaller the difference between the cell pore size distribution D90 and the cell pore size distribution D10 of the foam, the more consistent the cell size of the resulting foam. Here, the cell pore size distribution D90 means that 90% of the total volume of the cells have a diameter smaller than the value defined by the D90; and, the cell pore size distribution D10 means that 10% of the total volume of the cells have a diameter smaller than the value defined by D10. According to an embodiment of the invention, the cell pore size distribution D90 and the cell pore size distribution D10 are determined according to the method specified in ISO 13322-1:2014. According to embodiments of the present invention, the foam has a cell pore size distribution D90 of 50 μm or less (e.g., 45 μm or less) to avoid the reduction of mechanical strength or the creation of defects (e.g., cell collapse) due to large cell formation. Further, the foam formed from the composite material of the present invention can achieve the technical object of light weight and high mechanical strength.
According to embodiments of the present invention, the composite material of the present invention may have a melt index of 0.7 to 20, such as 1 to 6, 1 to 5.5, 1 to 5, 1 to 4.5, 1 to 4, 1 to 3.5, or 1 to 3. Melt index was measured in accordance with ASTM-D-1238 (275 ℃ C., under a 2.16kg weight).
According to an embodiment of the present invention, the method for preparing a foam using the composite material according to the present invention comprises the following steps. First, the composite master batch is dried at 80 to 100 ℃ for 8 to 12 hours. And then, carrying out a microcellular foaming process on the dried composite master batch to obtain a foam. The foaming process uses a supercritical foaming injection molding machine to foam at a temperature of 200 ℃ to 300 ℃, a gas pressure of 1000psi to 3000psi, and a ratio of nitrogen to carbon dioxide of 10:1 to 6:4.
In order to make the above and other objects, features and advantages of the present invention more comprehensible, several embodiments accompanied with figures are described in detail below:
table 1 shows materials according to examples of the present invention
TABLE 1
Figure BDA0002393667770000101
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Figure BDA0002393667770000111
Figure BDA0002393667770000121
Preparation of composite master batch
Example 1
67.32 parts by weight of polyamide (1), 0.68 part by weight of oligomer (1), 2 parts by weight of Polytetrafluoroethylene (PTFE) and 0.1 part by weight of processing oil were fed into a twin-screw extruder (twin screw extruder) (model ZSK-25, L/D value 40) to melt-knead, wherein the screw rotation speed was set at 200rpm and the screw temperature was set at 220℃to react polyamide (1) with oligomer (1). Then, the temperature of the twin-screw extruder was increased from 220℃to 280℃by means of a gradient temperature increase. After melt kneading for 1.5 minutes, the granular polytetrafluoroethylene was softened and stretched into fibrous polytetrafluoroethylene. Next, 30 parts by weight of glass fiber was fed into a twin screw extruder. After melt kneading for 1.5 minutes, the pellets were extruded and pelletized by a pelletizer (model GZML-110L-150) at a temperature of 50 to 100℃and a screw speed of 20rpm, to obtain a composite master batch (1).
Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (1) were measured, and the results are shown in table 1. Melt index is measured in accordance with the manner specified in ASTM-D-1238; tensile strength is measured in accordance with the manner specified in ASTM D412; and impact strength is measured in accordance with ASTM D-638. The average aspect ratio of the fibrous polytetrafluoroethylene in the obtained composite master batch (1) was measured, and the results are shown in table 1.
Example 2
Example 2 was conducted as described in example 1 except that the weight of polyamide (1) was reduced from 67.32 parts by weight to 66.64 parts by weight, and the weight of oligomer (1) was increased from 0.68 parts by weight to 1.36 parts by weight, to obtain composite master batch (2). Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (2) were measured, and the results are shown in table 1. The average aspect ratio of the fibrous polytetrafluoroethylene in the obtained composite master batch (2) was measured, and the results are shown in table 1.
Example 3
Example 3 was conducted as described in example 1 except that the weight of polyamide (1) was reduced from 67.32 parts by weight to 66 parts by weight, and the weight of oligomer (1) was increased from 0.68 parts by weight to 2 parts by weight, to obtain composite master batch (3). Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (3) were measured, and the results are shown in table 1. The average aspect ratio of the fibrous polytetrafluoroethylene in the obtained composite master batch (3) was measured, and the results are shown in Table 1.
Example 4
Example 4 was conducted as described in example 1 except that the weight of polyamide (1) was reduced from 67.32 parts by weight to 64.6 parts by weight, and the weight of oligomer (1) was increased from 0.68 parts by weight to 3.4 parts by weight, to obtain composite master batch (4). Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (4) were measured, and the results are shown in table 1. The average aspect ratio of the fibrous polytetrafluoroethylene in the obtained composite master batch (4) was measured, and the results are shown in Table 1.
Example 5
Example 5 the procedure of example 1 was followed, except that the weight of polyamide (1) was reduced from 67.32 parts by weight to 62.56 parts by weight, and the weight of oligomer (1) was increased from 0.68 parts by weight to 5.44 parts by weight, to obtain composite master batch (5). Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (5) were measured, and the results are shown in table 1. The average aspect ratio of the fibrous polytetrafluoroethylene in the obtained composite master batch (5) was measured, and the results are shown in Table 1.
Example 6
Example 6 was conducted as described in example 1 except that the weight of polyamide (1) was reduced from 67.32 parts by weight to 61.2 parts by weight, and the weight of oligomer (1) was increased from 0.68 parts by weight to 6.8 parts by weight, to obtain composite master batch (6). Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (6) were measured, and the results are shown in table 1. The average aspect ratio of the fibrous polytetrafluoroethylene in the obtained composite master batch (6) was measured, and the results are shown in Table 1.
Comparative example 1
68 parts by weight of polyamide (1), 2 parts by weight of Polytetrafluoroethylene (PTFE) and 0.1 part by weight of processing oil were fed into a twin-screw extruder (twin screw extruder) (model ZSK-25, L/D value 40) to melt-knead, wherein the screw rotation speed was set at 200rpm and the screw temperature was set at 220 ℃. After melt kneading for 1.5 minutes, the granular polytetrafluoroethylene was softened and stretched into fibrous polytetrafluoroethylene. Next, 30 parts by weight of glass fiber was fed into a twin screw extruder. After melt kneading for 1.5 minutes, the pellets were extruded and pelletized by a pelletizer (model GZML-110L-150) at a temperature of 50 to 100℃and a screw speed of 20rpm, to obtain composite master batch (7).
Next, the Melt Index (MI), tensile strength (tensile strength), and impact strength (impact strength) of the obtained composite master batch (7) were measured, and the results are shown in table 1.
TABLE 1
Figure BDA0002393667770000141
Since comparative example 1 did not add a styrene-acrylate oligomer having an epoxy functional group to react with polyamide to form a polymer network, the polyamide in the composite master batch obtained in comparative example 1 did not form a semi-interpenetrating polymer network with polytetrafluoroethylene fibers. As shown in table 1, the composite master batch obtained in comparative example 1 had a higher melt index, which means that the composite had a lower melt strength, which is not beneficial to the subsequent foaming process. In addition, since the styrene-acrylate oligomer having an epoxy functional group is added to react with the polyamide to form a network polymer in examples 1 to 6, the modified polyamide (network polymer) in the composite master batch obtained in examples 1 to 6 can form a semi-interpenetrating polymer network with polytetrafluoroethylene fiber, further improving the melt strength of the composite.
Example 7
68.11 parts by weight of polyamide (1), 1.39 parts by weight of oligomer (1), 0.5 part by weight of Polytetrafluoroethylene (PTFE) and 0.1 part by weight of processing oil were fed into a twin-screw extruder (twin screw extruder) (model ZSK-25, L/D value 40) to melt-knead, wherein the screw rotation speed was set at 200rpm and the screw temperature was set at 220℃to react polyamide (1) with oligomer (1). Then, the temperature of the twin-screw extruder was increased from 220℃to 280℃by means of a gradient temperature increase. After melt kneading for 1.5 minutes, the granular polytetrafluoroethylene was softened and stretched into fibrous polytetrafluoroethylene. Next, 30 parts by weight of glass fiber was fed into a twin screw extruder. After melt kneading for 1.5 minutes, the pellets were extruded and pelletized by a pelletizer (model GZML-110L-150) at a temperature of 50 to 100℃and a screw speed of 20rpm, to obtain a composite master batch (8). Wherein the polytetrafluoroethylene fiber is present in an amount of about 0.5 weight percent based on the weight of the composite masterbatch (8).
Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (8) were measured, and the results are shown in table 2.
Example 8
Example 8 the procedure of example 7 was followed, except that the weight of polyamide (1) was reduced from 68.11 parts by weight to 67.62 parts by weight, the weight of oligomer (1) was reduced from 1.39 parts by weight to 1.38 parts by weight, and the weight of polytetrafluoroethylene was increased from 0.5 parts by weight to 1 part by weight, to obtain composite master batch (9). Wherein the amount of polytetrafluoroethylene fibers is about 1 wt.% based on the weight of the composite masterbatch (9). Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (9) were measured, and the results are shown in table 2.
Example 9
Example 9 was conducted as described in example 7 except that the weight of polyamide (1) was reduced from 68.11 parts by weight to 67.13 parts by weight, the weight of oligomer (1) was reduced from 1.39 parts by weight to 1.37 parts by weight, and the weight of polytetrafluoroethylene was increased from 0.5 parts by weight to 1.5 parts by weight, to obtain composite master batch (10). Wherein the polytetrafluoroethylene fiber is present in an amount of about 1.5 weight percent based on the weight of the composite masterbatch (10). Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (10) were measured, and the results are shown in table 2.
Comparative example 2
Comparative example 2 was conducted as described in example 7, except that the weight of polyamide (1) was increased from 68.11 parts by weight to 68.6 parts by weight, the weight of oligomer (1) was increased from 1.39 parts by weight to 1.4 parts by weight, and the weight of Polytetrafluoroethylene (PTFE) was reduced from 0.5 parts by weight to 0 parts by weight, to obtain composite master batch (11) (containing no polytetrafluoroethylene). Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (11) were measured, and the results are shown in table 2.
Comparative example 3
66.15 parts by weight of polyamide (1), 1.35 parts by weight of oligomer (1), 2.5 parts by weight of Polytetrafluoroethylene (PTFE) and 0.1 part by weight of processing oil were fed into a twin-screw extruder (twin screw extruder) (model ZSK-25, L/D value 40) to melt-knead, wherein the screw rotation speed was set at 200rpm and the screw temperature was set at 220℃to react polyamide (1) with oligomer (1). Then, the temperature of the twin-screw extruder was increased from 220℃to 280℃by means of a gradient temperature increase. After melt kneading for 1.5 minutes, the granular polytetrafluoroethylene was softened and stretched into fibrous polytetrafluoroethylene. Next, 30 parts by weight of glass fiber was fed into a twin screw extruder. After melt kneading for 1.5 minutes, extrusion bracing was performed. Here, the phenomenon that the product after melt kneading is not easily pulled and broken during the pulling process by extrusion was observed, indicating that the processability of the obtained product was poor. Granulating by a granulator (model GZML-110L-150) at 50-100deg.C and screw rotation speed of 20rpm to obtain composite master batch (12). Wherein the polytetrafluoroethylene fiber is present in an amount of about 2.5 weight percent based on the weight of the composite masterbatch (12).
Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (12) were measured, and the results are shown in table 2.
Comparative example 4
65.66 parts by weight of polyamide (1), 1.34 parts by weight of oligomer (1), 3 parts by weight of Polytetrafluoroethylene (PTFE) and 0.1 part by weight of processing oil were fed into a twin-screw extruder (twin screw extruder) (model ZSK-25, L/D value 40) to melt-knead, wherein the screw rotation speed was set at 200rpm and the screw temperature was set at 220℃to react polyamide (1) with oligomer (1). Then, the temperature of the twin-screw extruder was increased from 220℃to 280℃by means of a gradient temperature increase. After melt kneading for 1.5 minutes, the granular polytetrafluoroethylene was softened and stretched into fibrous polytetrafluoroethylene. Next, 30 parts by weight of glass fiber was fed into a twin screw extruder. After melt kneading for 1.5 minutes, extrusion bracing was performed. Here, the phenomenon that the product after melt kneading is not likely to be pulled or broken during the pulling process by extrusion was observed, indicating that the processability of the obtained product was poor. Granulating by a granulator (model GZML-110L-150) at 50-100deg.C and screw rotation speed of 20rpm to obtain composite master batch (13). Wherein the polytetrafluoroethylene fiber is present in an amount of about 2.5 weight percent based on the weight of the composite masterbatch (13).
Next, the Melt Index (MI), tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (13) were measured, and the results are shown in table 2.
TABLE 2
Figure BDA0002393667770000171
Figure BDA0002393667770000181
As shown in Table 2, when the amount of polytetrafluoroethylene added is more than 2% by weight, poor processability of the resulting composite material is observed because excessive polytetrafluoroethylene aggregates to cause phase separation, which is disadvantageous for mass production of the composite material.
Example 10
66.5 parts by weight of polyamide (1), 2 parts by weight of oligomer (1), 1.5 parts by weight of Polytetrafluoroethylene (PTFE) and 0.1 part by weight of processing oil were fed into a twin-screw extruder (twin screw extruder) (model ZSK-25, L/D value 40) to melt-knead, wherein the screw rotation speed was set at 200rpm and the screw temperature was set at 220℃to react polyamide (1) with oligomer (1). Then, the temperature of the twin-screw extruder was increased from 220℃to 280℃by means of a gradient temperature increase. After melt kneading for 1.5 minutes, the granular polytetrafluoroethylene was softened and stretched into fibrous polytetrafluoroethylene. Next, 30 parts by weight of glass fiber was fed into a twin screw extruder. After melt kneading for 1.5 minutes, the pellets were extruded and pelletized by a pelletizer (model GZML-110L-150) at a temperature of 50 to 100℃and a screw speed of 20rpm, to obtain composite master batch (14).
Then, the tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (14) were measured, and the results are shown in Table 3.
Example 11
Example 11 was conducted as described in example 10 except that polyamide (1) was replaced with polyamide (2) to obtain a composite master batch (15). Then, the tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (15) were measured, and the results are shown in Table 3.
Example 12
Example 12 was performed as described in example 10, except that polyamide (1) was replaced with polyethylene terephthalate (polyethylene terephthalate, PET) to give composite masterbatch (16). Then, the tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (16) were measured, and the results are shown in Table 3.
Example 13
Example 13 was conducted as described in example 10 except that polyamide (1) was replaced with a thermoplastic polyester elastomer (TPEE) to give a composite masterbatch (17). Then, the tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (17) were measured, and the results are shown in Table 3.
Comparative example 5
96.5 parts by weight of a thermoplastic polyester elastomer (TPEE), 2 parts by weight of an oligomer (1), 1.5 parts by weight of Polytetrafluoroethylene (PTFE) and 0.1 part by weight of a processing oil were fed into a twin screw extruder (twin screw extruder) (model ZSK-25, l/D value 40) to melt-knead, wherein the screw rotation speed was set to 200rpm and the screw temperature was set to 220 ℃, and the thermoplastic polyester elastomer (TPEE) was reacted with the oligomer (1). Then, the temperature of the twin-screw extruder was increased from 220℃to 280℃by means of a gradient temperature increase. After melt kneading for 1.5 minutes, the granular polytetrafluoroethylene was softened and stretched into fibrous polytetrafluoroethylene. Next, extrusion bracing was performed, and pelletization was performed by a pelletizer (model GZML-110L-150) at a temperature of 50 to 100℃and a screw rotation speed of 20rpm, to obtain a composite master batch (18).
Then, the tensile strength (tensile strength) and impact strength (impact strength) of the obtained composite master batch (18) were measured, and the results are shown in Table 3.
TABLE 3 Table 3
Figure BDA0002393667770000191
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Figure BDA0002393667770000201
Preparation of foam
Examples 14 to 19 and comparative example 6
The composite master batches (1) to (7) obtained in examples 1 to 6 and comparative example 1 were each dried at 100℃for 12 hours. And then, respectively carrying out microcellular foaming processes on the dried composite master batches (1) - (7) to obtain the foam bodies (1) - (7). The foaming process was performed using a supercritical foaming injection molding machine (J450 EL-MuCell, manufactured by Japan Steel Works ltd.) at a temperature of 300 ℃, a gas pressure of 2000psi, and a nitrogen to carbon dioxide ratio of 7:3.
Next, the obtained foams (1) - (5) and (7) were subjected to measurement of tensile strength (tensile strength), impact strength (impact strength), and cell size, cell density and foam density were measured by nondestructive stereotomography analysis (X-Ray Computerize Tomography, X-Ray CT), and the results are shown in Table 4. Next, the obtained foam (1) to (7) was observed by a scanning electron microscope (scanning electron microscope, SEM), and the results are shown in FIGS. 1 to 7, respectively.
TABLE 4 Table 4
Figure BDA0002393667770000202
Figure BDA0002393667770000211
Since the composite master batch (7) used in comparative example 6 had a low melt strength, the foam (7) produced therefrom was remarkably observed to have surface bubbles and internal bubbles (i.e., cells having a size of more than 100 μm) (as shown in fig. 7), resulting in deterioration of properties (e.g., a decrease in tensile strength) of the resultant foam (as shown in table 4). In addition, as can be seen from FIGS. 1 to 6, the foams (1) to (6) produced in examples 14 to 19 had fewer defects (surface bubbles, internal bubbles) and the cell sizes were also more uniform. When the weight ratio of oligomer to polyamide reaches 10:90, a significant increase in cell size and a decrease in cell density of the foamed body (6) can be observed.
Examples 20 to 22 and comparative example 7
The composite master batches (8) - (11) obtained in examples 7-9 and comparative example 2 were each dried at 100℃for 12 hours. And then, respectively carrying out microcellular foaming processes on the dried composite master batches (8) - (11) to obtain the foaming bodies (8) - (11). The foaming process was performed using a supercritical foaming injection molding machine (J450 EL-MuCell, manufactured by Japan Steel Works ltd.) at a temperature of 300 ℃, a gas pressure of 2000psi, and a nitrogen to carbon dioxide ratio of 7:3.
Next, the obtained foams (8) - (11) were subjected to measurement of tensile strength (tensile strength) and impact strength (impact strength), and measurement of cell size and cell density were measured by non-destructive stereotomography (X-Ray Computerize Tomography, X-Ray CT), and the results are shown in Table 5. Next, the obtained foam (8) - (11) was observed by a scanning electron microscope (scanning electron microscope, SEM), and the results are shown in FIGS. 8-11, respectively.
TABLE 5
Figure BDA0002393667770000212
Figure BDA0002393667770000221
Since the composite master batch (11) used in comparative example 7 was not added with Polytetrafluoroethylene (PTFE), the foam (11) prepared therefrom was clearly observed to have surface cells and internal cells (as in fig. 11), and the cell distribution was too wide (the cell size difference was large), resulting in the resultant foam having poor performance (e.g., the tensile strength fall before and after foaming was too large). In addition, as can be seen from FIGS. 8 to 10, the foams (8) - (10) prepared in examples 20-22 had fewer defects (surface bubbles, internal bubbles) and the cell sizes were also more uniform. Furthermore, the cell size of the foam decreased with increasing polytetrafluoroethylene usage, as shown in Table 5.
Examples 23 to 26
The composite master batches (14) - (17) obtained in examples 10-13 were each dried at 100℃for 12 hours. And then, respectively carrying out microcellular foaming processes on the dried composite master batches (14) - (17) to obtain the foam bodies (12) - (15). The foaming process was performed using a supercritical foaming injection molding machine (J450 EL-MuCell, manufactured by Japan Steel Works ltd.) at a temperature of 300 ℃, a gas pressure of 2000psi, and a nitrogen to carbon dioxide ratio of 7:3.
Next, the obtained foams (12) to (15) were measured for tensile strength (tensile strength) and impact strength (impact strength), and the results are shown in Table 6.
TABLE 6
Figure BDA0002393667770000222
As can be seen from tables 3 and 6, various polyamides or polyesters can be used to prepare the composites of the present invention and can be further used to form foams.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.

Claims (17)

1. A composite material comprising a network polymer, a fluoropolymer fiber, and a reinforcing fiber, wherein the network polymer is the cross-linked reaction product of a polymer and an oligomer, wherein the polymer is a polyamide, a polyester, a polyurethane, or a combination thereof; and, the oligomer is a vinyl aromatic-acrylate oligomer having an epoxy functionality, wherein the weight percent of the oligomer is from 1wt% to 10wt%, based on the weight of the network polymer; and the ratio of the weight of the reinforcing fiber to the total weight of the network polymer and the fluoropolymer fiber is 1:9 to 4:6;
wherein the weight percent of the fluoropolymer fiber is 0.1wt% to 2wt%, based on the total weight of the network polymer, the fluoropolymer fiber, and the reinforcing fiber.
2. The composite material of claim 1, wherein the network polymer and the fluoropolymer fiber comprise a semi-interpenetrating polymer network.
3. The composite of claim 1, wherein the composite has a melt index of 0.7 to 20.
4. The composite of claim 1, wherein the polyamide is polycaprolactam, polyhexamethylene adipamide (polyhexamethylene adipamide), polylauryllactam, polydodectam, polybutyrolactam, polydodecanoyl hexamethylenediamine (polyhexamethylene dodecanoamide), polyundecanamide, polydecanoyl hexamethylenediamine (polyhexamethylene sebacamide), polydecanoyl sebacamide (polydecamethylene sebacamide), or a combination thereof.
5. The composite of claim 1, wherein the polyester is polyethylene terephthalate (polyethylene terephthalate, PET), cyclohexanediol copolyester (polyethylene terephthalate glycol, PETG), polyethylene terephthalate cyclohexanedimethanol ester (polycyclohexylenedimethylene terephthalate glycol, PCTG), polybutylene terephthalate (Polybutylene terephthalate, PBT), polycyclocyclohexanedimethanol ester (polycyclohexylenedimethylene terephthalate, PCT), polyethylene naphthalate (polyethylene naphthalate, PEN), polypropylene terephthalate (polytrimethylene terephthalate, PTT), or a combination thereof.
6. The composite of claim 1, wherein the vinyl aromatic-acrylate oligomer having epoxy functionality is a copolymer of a vinyl aromatic monomer and an acrylate monomer, wherein the acrylate monomer comprises an acrylate monomer having epoxy functionality.
7. The composite material of claim 6, wherein the vinyl aromatic monomer is styrene (styrene), methyl styrene (methyl styrene), ethyl styrene (propyl styrene), cyclohexyl styrene (cyclohexyl styrene), vinyl biphenyl (vinyl biphenyl), or a combination thereof.
8. The composite of claim 6, wherein the acrylate monomer having an epoxy functionality is glycidyl acrylate (glycidyl acrylate), glycidyl methacrylate (glycidyl methacrylate), methyl 3,4-epoxybutyl acrylate (3, 4-epoxybutyl methacrylate), 3,4-epoxybutyl acrylate (3, 4-epoxybutyl acrylate), or a combination thereof.
9. The composite of claim 6, wherein the acrylate monomer further comprises methyl acrylate (methyl acrylate), methyl methacrylate (methyl methacrylate), ethyl acrylate (ethyl acrylate), ethyl methacrylate (ethyl methacrylate), n-butyl acrylate (n-butyl acrylate), n-butyl methacrylate (n-butyl methacrylate), sec-butyl acrylate (sec-butyl acrylate), sec-butyl methacrylate (sec-butyl methacrylate), third butyl acrylate (tert-butyl acrylate), third butyl methacrylate (tert-butyl methacrylate), cyclohexyl acrylate (cyclohexyl acrylate), cyclohexyl methacrylate (cyclohexyl methacrylate), or a combination thereof.
10. The composite material of claim 1, wherein the vinyl aromatic-acrylate oligomer having epoxy functionality has
Figure FDA0004147169530000021
Is->
Figure FDA0004147169530000031
Repeating units arranged in blocks, alternating or random fashion, wherein R 1 、R 2 、R 4 、R 6 Or R is 7 Independently hydrogen or C 1-6 Alkyl of (a); r is R 3 Is hydrogen, C 1-6 Alkyl, C of (2) 5-7 Cycloalkyl or benzene ring; r is as follows 5 Is C 1-6 Alkyl or C of (2) 5-7 Cycloalkyl groups of (a).
11. The composite material of claim 10, wherein the vinyl aromatic-acrylate oligomer having epoxy functionality has x number of
Figure FDA0004147169530000032
Repeat unit, y->
Figure FDA0004147169530000033
Repeating units and z
Figure FDA0004147169530000034
Repeating units wherein x, y and z are independently integers from 1 to 30.
12. The composite material of claim 11, wherein z (x+y) is 2:1 to 20:1.
13. The composite material of claim 1, wherein the fluoropolymer fiber is Polytetrafluoroethylene (PTFE) fiber, polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) fiber, perfluoroalkoxyalkane (perfluoroalkoxy alkane, PFA) fiber, fluorinated ethylene propylene copolymer (fluorinated ethylene propylene, FEP) fiber, or a combination thereof.
14. The composite material of claim 1, wherein the fluoropolymer fiber has an aspect ratio of 5 to 2000.
15. A foam comprising the composite of claim 1 and a plurality of cells disposed in the composite.
16. The foam of claim 15, wherein the foam has an average cell size of 10 to 50 microns.
17. The foam of claim 15, wherein the foam has a cell size distribution D90 and a cell size distribution D10 that differ by 20 μιη to 35 μιη.
CN202010123354.0A 2019-12-31 2020-02-27 Composite material and foam prepared from same Active CN113121988B (en)

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