CN114043914B - Automobile carpet with composite fiber structure and preparation method thereof - Google Patents

Automobile carpet with composite fiber structure and preparation method thereof Download PDF

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Publication number
CN114043914B
CN114043914B CN202111433660.5A CN202111433660A CN114043914B CN 114043914 B CN114043914 B CN 114043914B CN 202111433660 A CN202111433660 A CN 202111433660A CN 114043914 B CN114043914 B CN 114043914B
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parts
carpet
foaming
fiber structure
composite fiber
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CN114043914A (en
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杜歆耘
皮佳鑫
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Ningbo Shangwei Automotive Trim Co ltd
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Ningbo Shangwei Automotive Trim Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60N—SEATS SPECIALLY ADAPTED FOR VEHICLES; VEHICLE PASSENGER ACCOMMODATION NOT OTHERWISE PROVIDED FOR
    • B60N3/00—Arrangements or adaptations of other passenger fittings, not otherwise provided for
    • B60N3/04—Arrangements or adaptations of other passenger fittings, not otherwise provided for of floor mats or carpets
    • B60N3/042—Arrangements or adaptations of other passenger fittings, not otherwise provided for of floor mats or carpets of carpets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D99/00—Subject matter not provided for in other groups of this subclass
    • B29D99/0057—Producing floor coverings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • 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
    • 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
    • C08J9/14—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 organic
    • C08J9/142—Compounds containing oxygen but no halogen atom
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
    • 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
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Transportation (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a preparation method of an automobile carpet with a composite fiber structure, which comprises the following steps of S1: carrying out secondary foaming on metallocene polyethylene resin, linear low-density polyethylene resin, ethylene propylene diene monomer, carbon nano tubes and polyethylene grafted maleic anhydride to obtain a porous foaming layer; s2: reacting terephthalic acid, dihydric alcohol, 2, 3-dihydroxylpropyl acrylate, 2-hydroxybutyl acrylate, an emulsifier and an initiator, adding Ag-MOFs, triethylamine and deionized water, and self-emulsifying to obtain a polyester prepolymer emulsion; then, carrying out polymerization of organic siloxane monomers to form an interpenetrating network polymer; adding the mixture into a solvent to form a spinning solution; s3: and receiving the obtained product on a porous foaming layer through electrostatic spinning, and treating to obtain the automobile carpet. The automobile carpet prepared by the invention not only has good sound absorption effect, but also has excellent flame retardant, antibacterial and self-cleaning performances and the like, and meets the high-performance requirements of people on the automobile carpet.

Description

Automobile carpet with composite fiber structure and preparation method thereof
Technical Field
The invention relates to the technical field of automotive interior trim, in particular to an automotive carpet with a composite fiber structure and a preparation method thereof.
Background
The automobile has entered into thousands of households, and becomes one of the necessary transportation means for people to go out daily. As one of the automotive interior parts, the automotive carpet has the advantages of full texture and gorgeous appearance, the ground can be modesty and splendid after being paved, the excellent decorative effect is obtained, and the automotive carpet is delightful and brings aesthetic enjoyment to people. In addition, the carpet is a fabric rich in elastic fibers, has plump, thick and soft texture, feels comfortable and soft, and is beneficial to eliminating fatigue and tension. However, the carpet made of the existing fiber structure has a further improved sound absorption effect, and in addition, the carpet has poor flame retardance and self-cleaning performance, so that the safety and comfort of the carpet as an automotive interior part are reduced, and the antibacterial property of the surface layer is poor, so that the high-performance requirement of people on the automotive carpet cannot be met.
Disclosure of Invention
In view of the defects of the prior art, the invention provides the automobile carpet with the composite fiber structure, so as to solve the problems of the existing automobile carpet in terms of sound absorption effect, flame retardance, antibacterial property and self-cleaning, and meet the requirement of people on high performance of the automobile carpet.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
a method of making an automotive carpet having a composite fiber structure, the method comprising the steps of:
step S1: weighing 55-65 parts by weight of metallocene polyethylene resin, 30-40 parts by weight of linear low-density polyethylene resin, 5-15 parts by weight of ethylene propylene diene monomer, 1.5-5.5 parts by weight of carbon nano tube and 2-7 parts by weight of polyethylene grafted maleic anhydride, mixing uniformly, slicing, placing in an autoclave for secondary foaming, and relieving pressure to obtain a porous foaming layer; according to the invention, metallocene polyethylene resin is used as a main raw material of the porous foaming layer, and linear low-density polyethylene resin is matched, so that the physical and mechanical properties of the porous foaming layer are improved; the addition of the ethylene propylene diene monomer makes the ethylene propylene diene monomer and the polyethylene resin have different expansion degrees in the secondary foaming process to form pore canals with different sizes; the carbon nano tube not only plays a role in reinforcement, but also is beneficial to forming another channel for sound transmission, and the sound absorption effect of the carpet is improved; in addition, the polyethylene grafted maleic anhydride added in the porous foaming layer further improves the binding force of the carpet surface layer and the porous foaming layer, so that the automobile carpet assembly is not easy to have the defects of layering, cracking and the like after being integrally molded.
Step S2: weighing 80-120 parts by weight of terephthalic acid monomer, 60-80 parts by weight of dihydric alcohol monomer, 10-30 parts by weight of 2, 3-dihydroxypropyl acrylate, 5-10 parts by weight of 2-hydroxybutyl acrylate, 20-30 parts by weight of emulsifier and 0.5-2.5 parts by weight of initiator, adding the mixture into a reaction kettle, reacting for 3-6 hours at the temperature of 60-90 ℃, then adding Ag-MOFs, triethylamine and deionized water, and strongly stirring and self-emulsifying to obtain a polyester prepolymer emulsion; carrying out polymerization of organic siloxane monomer in the obtained polyester prepolymer emulsion to form a polyester/polysiloxane interpenetrating network polymer; and adding the polyester/polysiloxane interpenetrating network polymer into a solvent, heating and stirring for 6-8 hours, and then continuously stirring for 6-8 hours at the temperature of 20-25 ℃ to form the polyester/polysiloxane interpenetrating network polymer spinning solution. Modifying polyester prepolymer emulsion obtained by polycondensation of terephthalic acid monomer and dihydric alcohol monomer through 2, 3-dihydroxypropyl acrylate and 2-hydroxybutyl acrylate, and further carrying out polymerization of organic siloxane monomer in the emulsion to obtain a polyester/polysiloxane interpenetrating network polymer; the composite fiber obtained by spinning the polymer has excellent mechanical properties, improves the heat resistance, oxidation resistance and self-cleaning performance of the automotive carpet, and further effectively avoids bacterial breeding on the surface layer of the automotive carpet.
Step S3: and (2) taking the porous foaming layer obtained in the step (S1) as a substrate layer, regulating and controlling the environmental humidity to 80 +/-1%, receiving the polyester/polysiloxane interpenetrating network polymer spinning solution obtained in the step (S2) onto the substrate layer in a sectional electrostatic spinning mode, and carding, folding and lapping, needle punching forming, napping and shaping, and irradiating by ultraviolet light to form a carpet surface layer on one surface of the porous foaming layer in situ to obtain the automobile carpet with the composite fiber structure. The surface density of the carpet surface layer is 400-600 g/m 2 . The sound of the sound enters a channel formed by countless continuous tiny holes through the synergistic action of the raised fabric layer and the porous foaming layer on the surface layer of the carpet, and composite fibers obtained by interpenetrating network polymer spinning are crossed and mixed together to form countless tiny gaps, so that the sound absorption effect of the automobile carpet assembly is effectively improved.
Preferably, the secondary foaming mode is as follows: firstly, introducing carbon dioxide gas, enabling the carbon dioxide gas to reach a supercritical state under a primary foaming condition, carrying out primary foaming on the mixed raw materials in a supercritical carbon dioxide gas environment, and relieving pressure to obtain a primary foaming intermediate; secondly, the primary foaming intermediate is placed in an autoclave again, and a physical foaming agent is introduced into the autoclave to carry out secondary foaming. More preferably, the primary foaming conditions include: the temperature is 20-50 ℃ lower than the melting point of the resin polymer, the pressure is 10-15 MPa, and the foaming time is 5-15 min. The secondary foaming conditions include: the temperature is 60-100 ℃, the pressure is 6-8 MPa, and the foaming time is 30-120 min. The polymer chip has a foaming ratio of 0.5 to 2 times and a pore size of 30 to 300 nm. According to the invention, through a secondary foaming mode, the internal communicated pore channels of the porous foaming layer are improved, and the pore channels in the porous foaming layer are different in size, so that the transmission distance of sound entering the carpet is prolonged, and the sound absorption effect of the automobile carpet is further improved.
Preferably, the diol consists of ethylene glycol and fluorine-containing diol; the molar ratio of the ethylene glycol to the fluorine-containing dihydric alcohol is 3-10: 1; the fluorine-containing dihydric alcohol is at least one of 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexanediol, 2,3,3,4, 4-hexafluoro-1, 5-pentanediol and 2,2,3, 3-tetrafluoro-1, 4-butanediol. Further, fluorine-containing diol is used for introducing fluorine-containing functional groups with good hydrophobic property into the polyester prepolymer emulsion, so that the self-cleaning property of the surface of the composite fiber is further improved.
Preferably, the emulsifier is one of sodium cetyl sulfate, polyvinylpyrrolidone or cetyltrimethylammonium bromide.
Preferably, the initiator is at least one of di-tert-butyl peroxide, dicumyl peroxide, potassium persulfate and sodium persulfate.
Preferably, the organosiloxane monomer is 3,3, 3-trifluoropropyltrimethoxysilane or methyl (3,3, 3-trifluoropropyl) diethoxysilane.
Preferably, the Ag-MOFs is a metal organic framework material with a network structure obtained by self-assembly combination of an organic ligand 2,4, 6-tris (4-carboxyphenoxy) -1,3, 5-triazine and metal silver ions through coordination bonds. According to the Ag-MOFs metal organic framework material, a plurality of carboxyl functional groups are arranged on the organic ligand, and the Ag-MOFs metal organic framework material can be coordinated with silver ions to form a network structure in a self-assembling manner, so that the silver ions are uniformly distributed in the surface layer of a carpet, and the overall antibacterial performance of the surface layer of the carpet is improved; meanwhile, the triazine structure in the center of the material is also beneficial to improving the weather resistance and the flame retardant property of the surface layer of the carpet, so that the long-term service life of the surface layer of the carpet under the severe condition is met.
Preferably, in the step S2, the organosiloxane monomer is added into the reaction kettle, and the polyester prepolymer emulsion in the reaction kettle is swelled, mixed uniformly, added with 0.5-2.5 parts of the initiator and 10-20 parts of the emulsifier, and reacted at 50-90 ℃ for 4-48 h.
Preferably, the sectional type electrostatic spinning process comprises a first spinning process which is 20-50 ℃ higher than the glass transition temperature of the polymer and a second spinning process which is at the glass transition temperature of the polymer, wherein the first period of time is set to be 10-30 min, and the first period of time is set to be 50-80 min. According to the invention, through the first stage of spinning process, the loose and disordered intermolecular force in the fiber amorphous region is quickly weakened to generate internal stress relaxation, and the composite fiber obtained by sectional type electrostatic spinning has abundant sound channels by utilizing the expansion effect during the extrusion of spinning dope, so that the sound absorption effect is further provided.
Preferably, the irradiation power of the ultraviolet irradiation is 10-30 kW, and the irradiation time is 6-40 min. Through the mode of ultraviolet illumination, further make composite fiber firmly combine on porous foaming layer, prolong car carpet life.
Preferably, the other side of the porous foaming layer is provided with a PE film layer and a carpet bottom layer. The carpet bottom layer is non-woven fabric or polypropylene fiber felt.
Another aspect of the present invention is to provide an automotive carpet having a composite fiber structure, which is prepared by the preparation method as described above.
The invention has the beneficial effects that:
compared with the existing automobile carpet with a fiber structure, the automobile carpet with the composite fiber structure obtains the composite fiber through polyester/polysiloxane interpenetrating network polymer spinning, is further combined on the porous foaming layer, has good mechanical property and sound absorption effect, has excellent comprehensive properties of flame retardance, antibiosis, self-cleaning and the like, improves the safety and comfort of the carpet as an automobile interior part, and meets the high-performance requirements of people on the automobile carpet.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
The preparation method of the automotive carpet with the composite fiber structure comprises the following steps:
step S1: weighing 55 parts by weight of metallocene polyethylene resin, 30 parts by weight of linear low-density polyethylene resin, 5 parts by weight of ethylene propylene diene monomer, 1.5 parts by weight of carbon nano tube and 2 parts by weight of polyethylene grafted maleic anhydride, mixing uniformly, slicing, placing in a high-pressure kettle for secondary foaming, and relieving pressure to obtain the porous foaming layer. The secondary foaming mode is as follows: firstly, introducing carbon dioxide gas, enabling the carbon dioxide gas to reach a supercritical state under a primary foaming condition, carrying out primary foaming on the mixed raw materials in a supercritical carbon dioxide gas environment, and relieving pressure to obtain a primary foaming intermediate; secondly, placing the primary foaming intermediate in a high-pressure kettle again, introducing a physical foaming agent obtained by compounding carbon dioxide and ethanol in a mass ratio of 1:1, and performing secondary foaming. The primary foaming conditions include: the temperature is 20 ℃ lower than the melting point of the resin polymer, the pressure is 10MPa, and the foaming time is 5 min. The secondary foaming conditions include: the temperature is 80 ℃, the pressure is 6MPa, and the foaming time is 30 min.
Step S2: weighing 80 parts of terephthalic acid monomer, 60 parts of dihydric alcohol monomer, 10 parts of 2, 3-dihydroxypropyl acrylate, 5 parts of 2-hydroxybutyl acrylate, 30 parts of emulsifier and 0.5 part of initiator according to parts by weight, adding into a reaction kettle, reacting at 60 ℃ for 6 hours, then adding Ag-MOFs, triethylamine and deionized water, and strongly stirring and self-emulsifying to obtain a polyester prepolymer emulsion; carrying out polymerization of organic siloxane monomer in the obtained polyester prepolymer emulsion to form a polyester/polysiloxane interpenetrating network polymer; and then adding the polyester/polysiloxane interpenetrating network polymer into 200 parts of toluene solvent, firstly heating and stirring for 6 hours, and then continuously stirring for 6 hours at the temperature of 20 ℃ to form the polyester/polysiloxane interpenetrating network polymer spinning solution. Further, in this step, an organosiloxane monomer was added to a reaction kettle, and the polyester prepolymer emulsion in the reaction kettle was swelled, mixed uniformly, added with 0.5 part of an initiator and 10 parts of an emulsifier, and reacted at 50 ℃ for 12 hours. The dihydric alcohol consists of ethylene glycol and fluorine-containing dihydric alcohol; the molar ratio of the ethylene glycol to the fluorine-containing diol is 3: 1; the fluorine-containing dihydric alcohol is 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexanediol. The emulsifier is sodium hexadecyl sulfate. The initiator is dicumyl peroxide. The organic siloxane monomer is 3,3, 3-trifluoropropyltrimethoxysilane. The Ag-MOFs is a metal organic framework material with a network structure, which is obtained by self-assembling and combining an organic ligand 2,4, 6-tris (4-carboxyphenoxy) -1,3, 5-triazine and metal silver ions through coordination bonds. The preparation method of the Ag-MOFs comprises the following steps: dissolving 0.3mol/L silver nitrate and 0.1 mol/L2, 4, 6-tri (4-carboxyl phenoxy) -1,3, 5-triazine in 200mL deionized water, and sealing and reacting at 110 ℃ for 24h to obtain the product.
Step S3: and (4) taking the porous foaming layer obtained in the step (S1) as a substrate layer, regulating and controlling the environmental humidity to 80% +/-1%, receiving the polyester/polysiloxane interpenetrating network polymer spinning solution obtained in the step (S2) onto the substrate layer in a sectional electrostatic spinning mode, and carding, folding and lapping, needle punching and forming, raising and shaping, and irradiating with ultraviolet light to form a carpet surface layer on one surface of the porous foaming layer in situ to obtain the automobile carpet with the composite fiber structure. The surface density of the carpet surface layer is 400g/m 2 . The sectional type electrostatic spinning process comprises a first stage of spinning process with the temperature 20 ℃ higher than the glass transition temperature of the polymer and a second stage of spinning process with the glass transition temperature of the polymer, wherein the first period of time is set to be 10min, and the first period of time is set to be 50 min. The irradiation power of the ultraviolet irradiation is 10kW, and the irradiation time is 40 min.
The other side of the porous foaming layer is provided with a PE film layer and a carpet bottom layer. The carpet bottom layer is non-woven fabric.
Example 2
The preparation method of the automotive carpet with the composite fiber structure comprises the following steps:
step S1: weighing 60 parts of metallocene polyethylene resin, 35 parts of linear low-density polyethylene resin, 10 parts of ethylene propylene diene monomer, 3.5 parts of carbon nano tube and 5 parts of polyethylene grafted maleic anhydride according to parts by weight, mixing uniformly, slicing, placing in a high-pressure kettle for secondary foaming, and relieving pressure to obtain the porous foaming layer. The secondary foaming mode is as follows: firstly, introducing carbon dioxide gas, enabling the carbon dioxide gas to reach a supercritical state under a primary foaming condition, carrying out primary foaming on the mixed raw materials in a supercritical carbon dioxide gas environment, and relieving pressure to obtain a primary foaming intermediate; secondly, placing the primary foaming intermediate into a high-pressure kettle again, introducing a physical foaming agent obtained by compounding carbon dioxide and ethanol in a mass ratio of 1:1, and carrying out secondary foaming. The primary foaming conditions include: the temperature is 30 ℃ lower than the melting point of the resin polymer, the pressure is 12MPa, and the foaming time is 10 min. The secondary foaming conditions include: the temperature is 80 ℃, the pressure is 7MPa, and the foaming time is 70 min.
Step S2: weighing 100 parts of terephthalic acid monomer, 70 parts of dihydric alcohol monomer, 20 parts of 2, 3-dihydroxypropyl acrylate, 7 parts of 2-hydroxybutyl acrylate, 25 parts of emulsifier and 1.5 parts of initiator according to parts by weight, adding into a reaction kettle, reacting at 70 ℃ for 4 hours, then adding Ag-MOFs, triethylamine and deionized water, and strongly stirring and self-emulsifying to obtain a polyester prepolymer emulsion; carrying out polymerization of organic siloxane monomers in the obtained polyester prepolymer emulsion to form a polyester/polysiloxane interpenetrating network polymer; and then adding the polyester/polysiloxane interpenetrating network polymer into 200 parts of toluene solvent, heating and stirring for 8 hours, and then continuously stirring for 6 hours at 25 ℃ to form the polyester/polysiloxane interpenetrating network polymer spinning solution. Further, in this step, an organosiloxane monomer was added to a reaction kettle, and the polyester prepolymer emulsion in the reaction kettle was swelled, mixed uniformly, added with 1.5 parts of an initiator and 15 parts of an emulsifier, and reacted at 60 ℃ for 24 hours. The dihydric alcohol consists of ethylene glycol and fluorine-containing dihydric alcohol; the molar ratio of the ethylene glycol to the fluorine-containing dihydric alcohol is 6: 1; the fluorine-containing dihydric alcohol is 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol. The emulsifier is polyvinylpyrrolidone. The initiator is di-tert-butyl peroxide. The organic siloxane monomer is methyl (3,3, 3-trifluoropropyl) diethoxysilane. The Ag-MOFs were the same as in example 1.
Step S3: and (4) taking the porous foaming layer obtained in the step (S1) as a substrate layer, regulating and controlling the environmental humidity to 80% +/-1%, receiving the polyester/polysiloxane interpenetrating network polymer spinning solution obtained in the step (S2) onto the substrate layer in a sectional electrostatic spinning mode, and carding, folding and lapping, needle punching and forming, raising and shaping, and irradiating with ultraviolet light to form a carpet surface layer on one surface of the porous foaming layer in situ to obtain the automobile carpet with the composite fiber structure. The surface density of the carpet surface layer is 500g/m 2 . The sectional type electrostatic spinning process comprises a first stage of spinning process with the temperature 30 ℃ higher than the glass transition temperature of the polymer and a second stage of spinning process with the glass transition temperature of the polymer, wherein the first stage of spinning process is set to be 20min, and the first stage of spinning process is set to be 60 min. The irradiation power of the ultraviolet irradiation is 20kW, and the irradiation time is 20 min.
The other side of the porous foaming layer is provided with a PE film layer and a carpet bottom layer. The bottom layer of the carpet is a polypropylene felt.
Example 3
The preparation method of the automotive carpet with the composite fiber structure comprises the following steps:
step S1: weighing 65 parts of metallocene polyethylene resin, 40 parts of linear low-density polyethylene resin, 15 parts of ethylene propylene diene monomer, 5.5 parts of carbon nano tube and 7 parts of polyethylene grafted maleic anhydride according to parts by weight, mixing uniformly, slicing, placing in a high-pressure kettle for secondary foaming, and relieving pressure to obtain the porous foaming layer. The secondary foaming mode is as follows: firstly, introducing carbon dioxide gas, enabling the carbon dioxide gas to reach a supercritical state under a primary foaming condition, carrying out primary foaming on the mixed raw materials in a supercritical carbon dioxide gas environment, and relieving pressure to obtain a primary foaming intermediate; secondly, placing the primary foaming intermediate into a high-pressure kettle again, introducing a physical foaming agent obtained by compounding carbon dioxide and ethanol in a mass ratio of 1:1, and carrying out secondary foaming. The primary foaming conditions include: the temperature is 50 ℃ lower than the melting point of the resin polymer, the pressure is 15MPa, and the foaming time is 5 min. The secondary foaming conditions include: the temperature is 100 ℃, the pressure is 8MPa, and the foaming time is 100 min.
Step S2: weighing 120 parts of terephthalic acid monomer, 80 parts of dihydric alcohol monomer, 30 parts of 2, 3-dihydroxypropyl acrylate, 10 parts of 2-hydroxybutyl acrylate, 30 parts of emulsifier and 2.5 parts of initiator according to parts by weight, adding into a reaction kettle, reacting for 6 hours at 90 ℃, then adding Ag-MOFs, triethylamine and deionized water, and strongly stirring and self-emulsifying to obtain a polyester prepolymer emulsion; carrying out polymerization of organic siloxane monomer in the obtained polyester prepolymer emulsion to form a polyester/polysiloxane interpenetrating network polymer; and then adding the polyester/polysiloxane interpenetrating network polymer into 200 parts of toluene solvent, heating and stirring for 8 hours, and then continuously stirring for 6 hours at 25 ℃ to form the polyester/polysiloxane interpenetrating network polymer spinning solution. Further, in this step, an organosiloxane monomer was added to a reaction kettle, and the polyester prepolymer emulsion in the reaction kettle was swelled, mixed uniformly, added with 2.5 parts of an initiator and 20 parts of an emulsifier, and reacted at 90 ℃ for 48 hours. The dihydric alcohol consists of ethylene glycol and fluorine-containing dihydric alcohol; the molar ratio of the ethylene glycol to the fluorine-containing diol is 10: 1; the fluorine-containing dihydric alcohol is 2,2,3, 3-tetrafluoro-1, 4-butanediol. The emulsifier is cetyl trimethyl ammonium bromide. The initiator is di-tert-butyl peroxide. The organic siloxane monomer is 3,3, 3-trifluoropropyltrimethoxysilane. The Ag-MOFs were the same as in example 1.
Step S3: taking the porous foaming layer obtained in the step S1 as a substrate layer, regulating and controlling the environmental humidity to 80% +/-1%, receiving the polyester/polysiloxane interpenetrating network polymer spinning solution obtained in the step S2 onto the substrate layer in a sectional electrostatic spinning mode, and carding, folding and lapping, needle punching and forming, raising and shaping, and carrying out purple spinningAnd after external illumination, forming a carpet surface layer on one surface of the porous foaming layer in situ to obtain the automobile carpet with the composite fiber structure. The surface density of the carpet surface layer is 600g/m 2 . The sectional type electrostatic spinning process comprises a first stage of spinning process with the temperature 50 ℃ higher than the glass transition temperature of the polymer and a second stage of spinning process with the glass transition temperature of the polymer, wherein the first period of time is set to be 30min, and the first period of time is set to be 80 min. The irradiation power of the ultraviolet irradiation is 30kW, and the irradiation time is 6 min.
The other side of the porous foaming layer is provided with a PE film layer and a carpet bottom layer. The carpet bottom layer is non-woven fabric.
Comparative example 1
The carpet tile having a conjugate fiber structure of this comparative example was manufactured substantially in the same manner as in example 1, except that, in the carpet tile having a conjugate fiber structure of this comparative example, the carpet tile was not subjected to the foaming treatment under the primary foaming condition, but was subjected to the foaming treatment under the secondary foaming condition only in step S1.
Comparative example 2
The carpet for an automobile having a composite fiber structure of the present comparative example was prepared substantially in the same manner as in example 1, except that in the carpet for an automobile having a composite fiber structure of the present comparative example, the Ag-MOFs metal organic framework material was not added to the polyester/polysiloxane interpenetrating network polymer in step S2.
Comparative example 3
The carpet tile having a conjugate fiber structure of this comparative example was manufactured in substantially the same manner as in example 1, except that, in the carpet tile having a conjugate fiber structure of this comparative example, the polyester/polysiloxane interpenetrating network polymer was added with nano-silver instead of the Ag-MOFs metal organic framework material in step S2, wherein the nano-silver was added in an amount equivalent to the amount of silver ions added in the Ag-MOFs metal organic framework material.
Comparative example 4
The carpet for an automobile having a conjugate fiber structure of the present comparative example was manufactured substantially in the same manner as in example 1, except that in the carpet for an automobile having a conjugate fiber structure of the present comparative example, PET polyester was used instead of the polyester/polysiloxane interpenetrating network polymer in step S2.
The automobile carpets with composite fiber structures prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to performance tests, and the performance results are shown in tables 1 and 2:
and (3) antibacterial property test: after the automobile carpet slices with the composite fiber structures prepared in the examples 1-3 and the comparative examples 1-4 are cut, gram-negative bacteria escherichia coli and gram-positive bacteria staphylococcus aureus are used as evaluation objects, the antibacterial performance of the sample slices is tested by adopting a shaking flask method, bacterial liquid and a sample are mixed and cultured in a shaking table for 24 hours, and the change of the bacterial concentration before and after culture is detected under the ultraviolet wavelength of 600nm, so that the antibacterial performance of the sample slices is evaluated.
TABLE 1
Figure BDA0003380981890000081
TABLE 2
Figure BDA0003380981890000082
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed.

Claims (10)

1. A method for preparing an automotive carpet having a composite fiber structure, characterized in that the method comprises the steps of:
step S1: weighing 55-65 parts by weight of metallocene polyethylene resin, 30-40 parts by weight of linear low-density polyethylene resin, 5-15 parts by weight of ethylene propylene diene monomer, 1.5-5.5 parts by weight of carbon nano tube and 2-7 parts by weight of polyethylene grafted maleic anhydride, mixing uniformly, slicing, placing in an autoclave for secondary foaming, and relieving pressure to obtain a porous foaming layer;
step S2: weighing 80-120 parts by weight of terephthalic acid monomer, 60-80 parts by weight of dihydric alcohol monomer, 10-30 parts by weight of 2, 3-dihydroxypropyl acrylate, 5-10 parts by weight of 2-hydroxybutyl acrylate, 20-30 parts by weight of emulsifier and 0.5-2.5 parts by weight of initiator, adding the mixture into a reaction kettle, reacting for 3-6 hours at the temperature of 60-90 ℃, then adding Ag-MOFs, triethylamine and deionized water, and strongly stirring and self-emulsifying to obtain a polyester prepolymer emulsion; carrying out polymerization of organic siloxane monomer in the obtained polyester prepolymer emulsion to form a polyester/polysiloxane interpenetrating network polymer; adding the polyester/polysiloxane interpenetrating network polymer into a solvent, heating and stirring for 6-8 hours, and then continuously stirring for 6-8 hours at the temperature of 20-25 ℃ to form a polyester/polysiloxane interpenetrating network polymer spinning solution;
step S3: and (4) taking the porous foaming layer obtained in the step (S1) as a substrate layer, regulating and controlling the environmental humidity to 80% +/-1%, receiving the polyester/polysiloxane interpenetrating network polymer spinning solution obtained in the step (S2) onto the substrate layer in a sectional electrostatic spinning mode, and carding, folding and lapping, needle punching and forming, raising and shaping, and irradiating with ultraviolet light to form a carpet surface layer on one surface of the porous foaming layer in situ to obtain the automobile carpet with the composite fiber structure.
2. The method for preparing an automotive carpet having a composite fiber structure according to claim 1, wherein the secondary foaming is performed by: firstly, introducing carbon dioxide gas, enabling the carbon dioxide gas to reach a supercritical state under a primary foaming condition, carrying out primary foaming on the mixed raw materials in a supercritical carbon dioxide gas environment, and relieving pressure to obtain a primary foaming intermediate; secondly, the primary foaming intermediate is placed in an autoclave again, and a physical foaming agent is introduced into the autoclave to carry out secondary foaming.
3. The method of making an automotive carpet having a composite fiber structure of claim 1 wherein the glycol is comprised of ethylene glycol and a fluorine-containing glycol; the fluorine-containing dihydric alcohol is at least one of 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexanediol, 2,3,3,4, 4-hexafluoro-1, 5-pentanediol and 2,2,3, 3-tetrafluoro-1, 4-butanediol.
4. The method of manufacturing an automotive carpet having a composite fiber structure according to claim 1, wherein the emulsifier is one of sodium cetyl sulfate, polyvinylpyrrolidone or cetyltrimethylammonium bromide.
5. The method of producing an automotive carpet having a conjugate fiber structure according to claim 1, wherein the initiator is at least one of di-t-butyl peroxide, dicumyl peroxide, potassium persulfate and sodium persulfate.
6. The method of claim 1, wherein the organosiloxane monomer is 3,3, 3-trifluoropropyltrimethoxysilane or methyl (3,3, 3-trifluoropropyl) diethoxysilane.
7. The method for preparing the automotive carpet with the composite fiber structure as claimed in claim 1, wherein the Ag-MOFs is organic ligand 2,4, 6-tris (4-carboxyphenoxy) -1,3, 5-triazine, and metal silver ions are combined by self-assembly through coordination bonds to obtain the metal-organic framework material with the network structure.
8. The method for preparing the automotive carpet having a composite fiber structure according to claim 1, wherein in step S2, the organosiloxane monomer is added into a reaction kettle, the polyester prepolymer emulsion in the reaction kettle is swelled, and the mixture is uniformly mixed, 0.5 to 2.5 parts of the initiator and 10 to 20 parts of the emulsifier are added, and the mixture is reacted at 50 to 90 ℃ for 4 to 48 hours.
9. The method for preparing the automotive carpet having a composite fiber structure according to claim 1, wherein the porous foam layer is provided with a PE film layer and a carpet backing layer on the other side.
10. An automotive carpet having a composite fiber structure, characterized in that it is produced by the production method according to any one of claims 1 to 9.
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GB1573778A (en) * 1976-11-04 1980-08-28 Mobay Chemical Corp Process for preparing polyurethane-backed carpet
JP2008110651A (en) * 2006-10-30 2008-05-15 Kaneka Corp Automobile interior trim material and automobile interior part
CN106188547A (en) * 2016-07-08 2016-12-07 山东大学 A kind of organosilicon damping additive and preparation method thereof
CN108749677A (en) * 2018-05-31 2018-11-06 江苏工程职业技术学院 Environmentally protective purification air Anti-bacterium, antiskid Car floor mat of one kind and preparation method thereof

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GB1573778A (en) * 1976-11-04 1980-08-28 Mobay Chemical Corp Process for preparing polyurethane-backed carpet
JP2008110651A (en) * 2006-10-30 2008-05-15 Kaneka Corp Automobile interior trim material and automobile interior part
CN106188547A (en) * 2016-07-08 2016-12-07 山东大学 A kind of organosilicon damping additive and preparation method thereof
CN108749677A (en) * 2018-05-31 2018-11-06 江苏工程职业技术学院 Environmentally protective purification air Anti-bacterium, antiskid Car floor mat of one kind and preparation method thereof

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