CN116199966A - Flame-retardant cable material and preparation method thereof - Google Patents

Flame-retardant cable material and preparation method thereof Download PDF

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CN116199966A
CN116199966A CN202310227886.2A CN202310227886A CN116199966A CN 116199966 A CN116199966 A CN 116199966A CN 202310227886 A CN202310227886 A CN 202310227886A CN 116199966 A CN116199966 A CN 116199966A
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cable material
prepolymer
group
source
flame
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CN116199966B (en
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李娟�
张迪
夏衍
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Zhejiang University of Science and Technology ZUST
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • 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
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables

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  • Spectroscopy & Molecular Physics (AREA)
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  • Organic Insulating Materials (AREA)

Abstract

The application discloses a flame-retardant cable material and a preparation method thereof, wherein the flame-retardant cable material comprises the following components: a cable material matrix comprising an ethylene-vinyl acetate copolymer and a linear low density polyethylene; the prepolymer is a reaction product of an acid source and an oxygen-surrounding source under the action of a catalyst, wherein the reaction product comprises a cross-linked structure formed by transesterification of an epoxy group and a carboxyl group, and at least one of the acid source or the oxygen-surrounding source contains a P element; and a product of a partial reaction of the prepolymer with the ethylene-vinyl acetate copolymer, wherein the product is a polymer containing an ester group and a phosphaphenanthrene compound or a polymer containing an ester group and a phosphonate group. The cable composite material has high flame retardant grade and good mechanical property and physical property, and can reach the cable fireproof standard.

Description

Flame-retardant cable material and preparation method thereof
Technical Field
The application relates to the field of chemical polyester fibers, in particular to a flame-retardant cable material and a preparation method thereof.
Background
The wire and cable are indispensable transmission arteries in the current society, and the life of people is indispensible from the cable. However, because the circuit heats and the cable material is not flame retardant, fire hazards exist, and life and property safety of people are threatened, so the safety measure adopted internationally is to flame retardant the cable material. At present, PVC material occupies the position of a cable material tap, and with the enhancement of environmental awareness, halogen flame retardants are gradually abandoned and forbidden.
In recent years, ethylene-vinyl acetate copolymer (EVA) can satisfy the severe requirements of the cable material matrix because of its good heat resistance, aging resistance, and the like. EVA is an olefin polymer copolymerized from ethylene (E) -Vinyl Acetate (VA). EVA has good heat resistance, weather resistance, ozone resistance, electrical property, surface gloss, aging resistance and other properties, and is safe and nontoxic. EVA has irreplaceable advantages over conventional cable materials, and has been increasingly dominant in cable materials in recent years. But its flammability limits its widespread use in the field of cable materials. At present, a large amount of inorganic flame retardants (such as aluminum hydroxide, magnesium hydroxide and the like) are often added in EVA flame retardance, however, the mechanical properties of the EVA flame retardants are likely to be reduced by adding a large amount of inorganic flame retardants, and the processing process of the EVA flame retardants is affected. Therefore, new flame retardant needs to be synthesized and added into EVA, so that the flame retardant property of EVA is further improved, and the application field of EVA is expanded.
Disclosure of Invention
The technical problem to be solved by the technical scheme is to provide the cable material with better flame retardant property, mechanical property and physical property and the preparation method thereof.
One aspect of the present application provides a flame retardant cable material comprising: a cable material matrix comprising an ethylene-vinyl acetate copolymer and a linear low density polyethylene; the prepolymer is a reaction product of an acid source and an oxygen-surrounding source under the action of a catalyst, wherein the reaction product comprises a cross-linked structure formed by transesterification of an epoxy group and a carboxyl group, and at least one of the acid source or the oxygen-surrounding source contains a P element; and a product of a partial reaction of the prepolymer with the ethylene-vinyl acetate copolymer, wherein the product is a polymer containing an ester group and a phosphaphenanthrene compound or a polymer containing an ester group and a phosphonate group.
In some embodiments of the present application, the cable material matrix is 65% to 76% by mass, the prepolymer is 1% to 10% by mass, and the prepolymer is 10% to 25% by mass of the product of the partial reaction with the ethylene-vinyl acetate copolymer.
In some embodiments of the present application, the flame retardant cable material further comprises a compatibilizer, which is a maleic anhydride grafted ethylene vinyl acetate copolymer, and a catalytic carbon former, which is a silicone.
In some embodiments of the present application, the compatibiliser is 4% to 6% by mass and the catalytic char-forming agent is 0% to 3% by mass.
In some embodiments of the present application, the reaction product of the acid source and the cyclic oxygen source under the action of the catalyst is
Figure BDA0004119078480000021
Wherein X and Y are natural numbers, the range of X is between 40 and 60, and the range of Y is between 3 and 10.
In some embodiments of the present application, the mole percent range of the source of cyclic oxygen, the source of acid, and the catalyst to form the prepolymer is 1 (1-1.05): (0.05-0.15).
In some embodiments of the present application, the acid source comprises a compound of formula (i):
Figure BDA0004119078480000031
wherein R of formula (I) is selected from C 2 -C 10 A group or a furan ring-containing or DOPO structure-containing group, the C 2 -C 10 The group comprises linear alkane, cycloalkane and aromatic ring; the DOPO structural group is a group containing one or two DOPO structures.
In some embodiments of the present application, the acid source comprises any one or more of succinic acid, 1, 4-cyclohexanedicarboxylic acid, furandicarboxylic acid, 5-norbornene-2, 3 dicarboxylic acid, DOPO-ITA, terephthalic acid, TPNA, and DMZH, wherein the structural formulas of DOPO-ITA, TPNA, and DMZH are:
Figure BDA0004119078480000032
in some embodiments of the present application, the epoxy source comprises a compound of formula (II):
Figure BDA0004119078480000041
wherein R1 of formula (II) is selected from C10-C30 ether epoxy groups or phosphonate structure-containing groups; the ether group of C10-C30 is glycidyl ether group containing at least two aromatic rings; the phosphonate structural group refers to a group containing at least one benzene ring structure and containing only one phosphonate structure and having carbon atoms within 25.
In some embodiments of the present application, the epoxy source comprises any one or more of EDPDO, soy epoxy, and DGEBA, wherein the structural formula of EDPDO, soy epoxy, and DGEBA is:
Figure BDA0004119078480000042
in some embodiments of the present application, the catalyst comprises 1,5, 7-triazabicyclo [4, 0] dec-5-ene (TBD) or zinc acetate.
In some embodiments of the present application, the mass ratio of the ethylene-vinyl acetate copolymer to the linear low density polyethylene in the cable material matrix is between 1.5 and 4.
In another aspect, the present application further provides a method for preparing a flame retardant cable material, including: melting an epoxy source, adding an acid source into the molten epoxy source, uniformly mixing, adding a catalyst, and pre-reacting for a specific time in a specific temperature range to form a prepolymer, wherein the prepolymer comprises a cross-linked structure formed by transesterification of epoxy groups and carboxyl groups, and at least one of the acid source or the epoxy source contains P element; and fully mixing the prepolymer with a cable material matrix, and then carrying out melt blending granulation to form the flame-retardant cable material, wherein the cable material matrix is a mixture of an ethylene-vinyl acetate copolymer and linear low-density polyethylene, and in the process of melt blending granulation, the prepolymer and the ethylene-vinyl acetate copolymer partially react to form a product which is a polymer containing ester groups and phosphaphenanthrene compounds or a polymer containing ester groups and phosphonate groups.
In some embodiments of the present application, the pre-reaction temperature is 140 ℃ to 170 ℃; the process conditions for mixing the prepolymer and the mixture of ethylene-vinyl acetate copolymer and linear low density polyethylene are: stirring for 15-30 min by a double-screw extruder at the rotating speed of 40-60 r/min and the temperature of 170-200 ℃, wherein the length-diameter ratio of the screw of the double-screw extruder is 40:1.
In some embodiments of the present application, in the step of thoroughly mixing the prepolymer and the cable material matrix plus the auxiliary material, the mass percent of the cable material matrix is 68% to 76%, and the mass percent of the prepolymer is 17% to 26%; during melt blending granulation, the prepolymer is partially reacted with the ethylene-vinyl acetate copolymer to give a product of 10 to 25 mass%.
In some embodiments of the present application, the melt blending granulation process further comprises a compatibilizer and a catalytic carbonizing agent, wherein the compatibilizer is a maleic anhydride grafted ethylene vinyl acetate copolymer, and the catalytic carbonizing agent is an organosilicon, wherein the compatibilizer is well mixed with the prepolymer and the cable material matrix flame retardant cable material.
In some embodiments of the present application, the compatibiliser is 4% to 6% by mass and the catalytic char-forming agent is 0% to 3% by mass.
In some embodiments of the present application, the mole percent range of the source of cyclic oxygen, the source of acid, and the catalyst to form the prepolymer is 1 (1-1.05): (0.05-0.15).
In some embodiments of the present application, the acid source comprises a compound of formula (i):
Figure BDA0004119078480000061
wherein R of formula (I) is selected from C 2 -C 10 A group or a furan ring-containing or DOPO structure-containing group, the C 2 -C 10 The group comprises linear alkane, cycloalkane and aromatic ring; the DOPO structural group is a group containing one or two DOPO structures;
the epoxy source includes a compound having the structural formula (II):
Figure BDA0004119078480000062
wherein R1 of formula (II) is selected from C10-C30 ether epoxy groups or phosphonate structure-containing groups; the ether group of C10-C30 is glycidyl ether group containing at least two aromatic rings; the phosphonate structural group refers to a group containing at least one benzene ring structure and only one phosphonate structure and having carbon atoms within 25;
the catalyst comprises 1,5, 7-triazabicyclo [4, 0] dec-5-ene (TBD) or zinc acetate.
Compared with the prior art, the technical scheme of the application has the following beneficial effects:
according to the flame-retardant cable, ethylene-vinyl acetate copolymer EVA/Linear Low Density Polyethylene (LLDPE) is used as a cable material matrix, a prepolymer with a cross-linked structure formed by transesterification of epoxy groups and carboxyl groups is added, and a compatilizer and a catalytic carbonizing agent are assisted to synergistically improve the flame retardance of the cable material matrix. On one hand, the high flame retardant grade of the cable can be maintained, the addition amount is low, and on the other hand, the prepolymer (Vitrimer) can be crosslinked through esterification reaction and EVA, so that the reduction of the mechanical property and the physical property of the cable composite material is avoided to a great extent. The cable composite material has high flame retardant grade, good mechanical property and physical property, can reach the cable fireproof standard, and has good industrial application prospect.
Detailed Description
The following description provides specific applications and requirements to enable any person skilled in the art to make and use the teachings of the present application. Various modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the application. Thus, the present application is not limited to the embodiments shown, but is to be accorded the widest scope consistent with the claims.
The phosphorus-containing flame retardant has better flame retardant effect, is low in toxicity and even nontoxic, and is a preferable alternative to halogen flame retardants. The Vitrimer is a high molecular polymer containing reversible covalent cross-linked network, can perform reversible exchange reaction through bond exchange, rearranges the topological network structure of the Vitrimer, so that the material has viscoelasticity and fluidity, has plasticity and reworkability under the condition of keeping the chemical structure and the performance of the material intact, belongs to an environment-friendly material, and accords with the environmental protection concept. The glass polymer flame retardant can effectively exert the advantages of the glass polymer, and improves the flame retardant property.
However, polyester belongs to inflammable materials, and has certain potential safety hazards, and flame retardance is an important and necessary guarantee for guaranteeing the safety of the polyester in the use process. Although the current flame-retardant polyester fiber technology is mature, the thermal property and chemical property of the low-melting polyester sheath resin and the core resin are different, and the flame-retardant polyester technology cannot be used for flame-retardant cable materials through simple transplanting, so that the flame-retardant cable materials on the market are scarce.
Based on this, the application provides a flame retardant cable material, comprising: a cable material matrix comprising an ethylene-vinyl acetate copolymer and a linear low density polyethylene; the prepolymer is a reaction product of an acid source and an oxygen-surrounding source under the action of a catalyst, wherein the reaction product comprises a cross-linked structure formed by transesterification of an epoxy group and a carboxyl group, and at least one of the acid source or the oxygen-surrounding source contains a P element; and a product of a partial reaction of the prepolymer with the ethylene-vinyl acetate copolymer, wherein the product is a polymer containing an ester group and a phosphaphenanthrene compound or a polymer containing an ester group and a phosphonate group.
Ethylene-vinyl acetate copolymer (EVA), a general purpose high molecular polymer, linear Low Density Polyethylene (LLDPE) is a molecular structure with very short and small comonomer branches on the backbone of linear ethylene formed by copolymerization of ethylene with small amounts of alpha-olefins. In some embodiments of the present application, the cable material matrix is a mixture of an ethylene-vinyl acetate copolymer and a linear low density polyethylene, wherein the mass ratio of the ethylene-vinyl acetate copolymer to the linear low density polyethylene is between 1.5 and 4, such as 2,2.5,3,3.5,3.8 and the like. Optionally, other modifying substances can be added into the cable material matrix.
In the flame-retardant cable material formed by the application, the mass percent of the cable material matrix is 65-76%, such as 68%,70%,72%, 74% and the like.
In the flame-retardant cable material formed by the application, the flame-retardant cable material also comprises 1 to 10 percent of prepolymer by mass, wherein the prepolymer is the reaction product of the acid source and the cyclic oxygen source under the action of a catalyst, and in some embodiments of the application, the molecular formula of the prepolymer is
Figure BDA0004119078480000081
Wherein X and Y are natural numbers, the range of X is between 40 and 60, and the range of Y is between 3 and 10. That is, under the action of the catalyst, the epoxy group in the source of the cyclic oxygen and the carboxyl group in the source of the acid undergo transesterification to form a crosslinked structure containing P.
In some embodiments of the present application, the cyclic oxygen source, acid source, and catalyst forming the prepolymer are in the range of 1 (1-1.05) mole percent: (0.05-0.15). Optionally, the mole percentage of the cyclic oxygen source and the acid source is 1:1.
in some embodiments of the present application, a molar ratio of 1:1, then melting the epoxy source at 140-170 ℃, adding the acid source into the molten oxygen source, uniformly mixing, adding a catalyst, and pre-reacting at 150 ℃ for 1-3 hours to form the prepolymer.
In some embodiments of the present application, the acid source comprises a compound of formula (i):
Figure BDA0004119078480000091
wherein R of formula (I) is selected from C 2 -C 10 A group or a furan ring-containing or DOPO structure-containing group, the C 2 -C 10 The group comprises linear alkane, cycloalkane and aromatic ring; the DOPO structural group is a group containing one or two DOPO structures, and the molecular formula of the DOPO structure is that
Figure BDA0004119078480000092
The DOPO group can play a role in gas-phase flame retardance in the combustion process of the flame-retardant cable material, and PO is released to interrupt chain reaction.
Optionally, the acid source includes any one or more of succinic acid, 1, 4-cyclohexanedicarboxylic acid, furandicarboxylic acid, 5-norbornene-2, 3 dicarboxylic acid, DOPO-ITA, terephthalic acid, TPNA, and DMZH, wherein the structural formulas of DOPO-ITA, TPNA, and DMZH are respectively:
Figure BDA0004119078480000093
Figure BDA0004119078480000101
in some embodiments of the present application, the epoxy source comprises a compound of formula (II):
Figure BDA0004119078480000102
wherein R1 of formula (II) is selected from C10-C30 ether epoxy groups or phosphonate structure-containing groups; the ether group of C10-C30 is glycidyl ether group containing at least two aromatic rings; the phosphonate structural group refers to a group containing at least one benzene ring structure and containing only one phosphonate structure and having carbon atoms within 25.
In some embodiments of the present application, the epoxy source comprises any one or more of EDPDO, soy epoxy, and DGEBA, wherein the structural formula of EDPDO, soy epoxy, and DGEBA is:
Figure BDA0004119078480000111
in some embodiments of the present application, the catalyst comprises 1,5, 7-triazabicyclo [4, 0] dec-5-ene (TBD) or zinc acetate.
The prepolymer in the embodiment of the application is a cross-linked structure formed by transesterification reaction of epoxy groups and carboxyl groups in a molar ratio of 1:1-1:1.05 under the action of a catalyst. When the acid source contains flame retardant P element, the epoxy source compound reacted with the flame retardant P element may or may not contain P element; when the epoxy source contains flame-retardant P element, the acid source compound which reacts with the epoxy source may or may not contain P element; in order to ensure flame retardant effect, one of the acid source and the cyclic oxygen source must contain P element.
The flame-retardant cable material also comprises a product of partial reaction of the prepolymer and the ethylene-vinyl acetate copolymer, wherein the product is a polymer containing ester groups and phosphaphenanthrene compounds or a polymer containing ester groups and phosphonate groups. Wherein the prepolymer is partially reacted with the ethylene-vinyl acetate copolymer at a mass percent of from 10% to 25%, such as 15%,19%,23%, etc. The prepolymer is crosslinked through esterification reaction and EVA, so that the reduction of mechanical properties and physical properties of the cable material is avoided to a great extent. The cable material has high flame retardant grade and good mechanical property and physical property, can reach the cable fireproof standard, and can be applied in market.
In some embodiments of the present application, the flame retardant cable material further comprises a compatibilizer, which is a maleic anhydride grafted ethylene vinyl acetate copolymer, and a catalytic carbon former, which is a silicone. The compatilizer improves the fusion and reaction capacity of the prepolymer and the cable material matrix, and the catalytic carbon forming agent is organic silicon, can catalyze the matrix material to form carbon and promote the formation of a high-quality carbon layer.
In some embodiments of the present application, the compatibilizing agent is 4% to 6% by mass, e.g., 4.5%,5%,5.5%, etc., and the catalytic char-forming agent is 0 to 3% by mass, e.g., 0.1%,1%,2%, etc.
The flame retardant cable material of the present application may further include one or more of stabilizers, processing aids, fuels, and the like.
In another aspect, the present application further provides a method for preparing a flame retardant cable material, including: melting an epoxy source, adding an acid source into the molten epoxy source, uniformly mixing, adding a catalyst, and pre-reacting for a specific time in a specific temperature range to form a prepolymer, wherein the prepolymer comprises a cross-linked structure formed by transesterification of epoxy groups and carboxyl groups, and at least one of the acid source or the epoxy source contains P element; and fully mixing the prepolymer with a cable material matrix, and then carrying out melt blending granulation to form the flame-retardant cable material, wherein the cable material matrix is a mixture of an ethylene-vinyl acetate copolymer and linear low-density polyethylene, and in the process of melt blending granulation, the prepolymer and the ethylene-vinyl acetate copolymer partially react to form a product which is a polymer containing ester groups and phosphaphenanthrene compounds or a polymer containing ester groups and phosphonate groups.
In some embodiments of the present application, the pre-reaction temperature is 140 ℃ to 170 ℃, e.g., 150 ℃,160 ℃,165 ℃, etc.; the mole percentage of the cyclic oxygen source, the acid source and the catalyst for forming the prepolymer is in the range of 1 (1-1.05): (0.05-0.15). In some embodiments of the present application, a molar ratio of 1:1.03 acid source and epoxy source, then at a temperature of 165 DEG CUnder the condition, firstly melting the epoxy source, then adding the acid source into the molten oxygen source, uniformly mixing, and finally adding the epoxy source and the acid source in a molar ratio of 1:0.1 pre-reacted at a temperature of 150 ℃ for 1 to 3 hours to form the prepolymer. The prepolymer may have the formula, for example
Figure BDA0004119078480000131
Wherein X and Y are natural numbers, the range of X is between 40 and 60, and the range of Y is between 3 and 10.
In some embodiments of the present application, the acid source comprises a compound of formula (i):
Figure BDA0004119078480000132
wherein R of formula (I) is selected from C 2 -C 10 A group or a furan ring-containing or DOPO structure-containing group, the C 2 -C 10 The group comprises linear alkane, cycloalkane and aromatic ring; the DOPO structural group is a group containing one or two DOPO structures;
the epoxy source includes a compound having the structural formula (II):
Figure BDA0004119078480000133
wherein R1 of formula (II) is selected from C10-C30 ether epoxy groups or phosphonate structure-containing groups; the ether group of C10-C30 is glycidyl ether group containing at least two aromatic rings; the phosphonate structural group refers to a group containing at least one benzene ring structure and only one phosphonate structure and having carbon atoms within 25; the catalyst comprises 1,5, 7-triazabicyclo [4, 0] dec-5-ene (TBD) or zinc acetate.
And then, fully mixing the prepolymer and the cable material matrix, and performing melt blending granulation to form the flame-retardant cable material, wherein the process conditions for mixing the prepolymer and the cable material matrix (comprising a mixture of an ethylene-vinyl acetate copolymer and linear low-density polyethylene) are as follows: stirring for 15-30 min by a double-screw extruder at the rotating speed of 40-60 r/min and the temperature of 170-200 ℃, wherein the length-diameter ratio of the screw of the double-screw extruder is 40:1.
In some embodiments of the present application, the mass percent of the product of the partial reaction of the prepolymer with the ethylene-vinyl acetate copolymer in the melt blending granulation process is from 10% to 25%. In the step of fully mixing the prepolymer and the cable material matrix, the mass percent of the cable material matrix is 68-76%, the mass percent of the prepolymer is 17-26%, and the mass percent of auxiliary materials (including compatilizer and catalytic carbonizing agent) is 4-9%. . That is, the mass percentage of the cable material matrix is 68% to 76% before the melt blending granulation process, and after the melt blending granulation, the resulting flame-retardant cable material further comprises 65% to 76% of the cable material matrix because a part of EVA in the cable material matrix reacts with the copolymer. After melt blending granulation, the mass percentage of the prepolymer is also reduced from 17 to 26% before reaction to 1 to 10% after reaction.
In some embodiments of the present application, the melt blending granulation process further comprises a compatibilizer and a catalytic carbonizing agent, wherein the compatibilizer is a maleic anhydride grafted ethylene vinyl acetate copolymer, and the catalytic carbonizing agent is an organosilicon, wherein the compatibilizer is well mixed with the prepolymer and the cable material matrix flame retardant cable material.
In some embodiments of the present application, the compatibiliser is 4% to 6% by mass and the catalytic char-forming agent is 0% to 3% by mass.
In the process of melt blending granulation, the prepolymer and the ethylene-vinyl acetate copolymer partially react to form a product which is a polymer containing ester groups and phosphaphenanthrene compounds or a polymer containing ester groups and phosphonate groups. The product avoids the reduction of the mechanical property and the physical property of the cable composite material.
Compared with the prior art, the technical scheme of the application has the following beneficial effects:
according to the flame-retardant cable, ethylene-vinyl acetate copolymer EVA/Linear Low Density Polyethylene (LLDPE) is used as a cable material matrix, a prepolymer with a cross-linked structure formed by transesterification of epoxy groups and carboxyl groups is added, and a compatilizer and a catalytic carbonizing agent are assisted to synergistically improve the flame retardance of the cable material matrix. On one hand, the high flame retardant grade of the cable can be maintained, the addition amount is low, and on the other hand, the prepolymer (Vitrimer) can be crosslinked through esterification reaction and EVA, so that the reduction of the mechanical property and the physical property of the cable composite material is avoided to a great extent. The cable composite material has high flame retardant grade, good mechanical property and physical property, can reach the cable fireproof standard, and has good industrial application prospect.
The product properties of the present application are analyzed in detail below in connection with the preparation examples and examples.
Preparation example 1
Adipic acid (acid source), EDPDO (epoxy source) and TBD (catalyst) in the molar ratio of 1:1:0.14 are weighed, the EDPDO is melted at 140 ℃, then adipic acid is added after the EDPDO is melted and mixed uniformly, and finally the catalyst TBD is added for pre-reaction for 2 hours at the temperature of 150 ℃ to obtain the prepolymer 1.
Preparation example 2
Succinic acid, EDPDO and TBD with the molar ratio of 1:1.02:0.12 are weighed, and prepolymer 2 is obtained in the same treatment process as in preparation example 1.
Preparation example 3
1, 4-cyclohexanedicarboxylic acid, EDPDO and TBD were weighed in a molar ratio of 1:1:0.08, and prepolymer 3 was obtained in the same procedure as in preparation example 1.
Preparation example 4
Furandicarboxylic acid, EDPDO and TBD were weighed in a molar ratio of 1.03:1:0.1, and prepolymer 4 was obtained in the same procedure as in preparation example 1.
Preparation example 5
5-norbornene-2, 3-dicarboxylic acid, EDPDO and TBD were weighed out in a molar ratio of 1:1:0.1, and prepolymer 5 was obtained by the same procedure as in preparation example 1.
Preparation example 6
DOPO-ITA, EDPDO and TBD were weighed in a molar ratio of 1.05:1:0.1, and prepolymer 6 was obtained in the same procedure as in preparation example 1.
Preparation example 7
Terephthalic acid, EDPDO and TBD in a molar ratio of 1:1:0.1 were weighed and treated in the same manner as in preparation example 1 to obtain prepolymer 7.
Preparation example 8
TPNA, EDPDO and TBD in a molar ratio of 1:1:0.1 were weighed out and treated in the same manner as in preparation example 1 to obtain prepolymer 8.
Preparation example 9
DMZH, EDPDO and TBD were weighed in a molar ratio of 1:1:0.05, and prepolymer 9 was obtained in the same procedure as in preparation example 1.
Preparation example 10
DOPO-ITA, soybean epoxy and TBD were weighed in a molar ratio of 1:1:0.1, and the same procedure as in preparation example 1 was conducted to obtain prepolymer 10.
PREPARATION EXAMPLE 11
TPNA, soybean epoxy and TBD were weighed in a molar ratio of 1.05:1:0.1, and prepolymer 11 was obtained by the same procedure as in preparation example 1.
Preparation example 12
DMZH, soy epoxy and TBD were weighed in a molar ratio of 1:1:0.05 and treated in the same manner as in preparation example 1 to give prepolymer 12.
Preparation example 13
DOPO-ITA, DGEBA and TBD were weighed in a molar ratio of 1:1:0.1, and prepolymer 13 was obtained in the same procedure as in preparation example 1.
PREPARATION EXAMPLE 14
TPNA, DGEBA and TBD were weighed in a molar ratio of 1:1:0.1 and treated in the same manner as in preparation example 1 to obtain prepolymer 14.
Preparation example 15
DMZH, DGEBA and TBD were weighed in a molar ratio of 1:1:0.05, and prepolymer 15 was obtained in the same procedure as in preparation example 1.
PREPARATION EXAMPLE 16
Succinic acid, EDPDO and zinc acetate were weighed in a molar ratio of 1:1:0.15, and prepolymer 16 was obtained in the same procedure as in preparation example 1.
Preparation example 17
TPNA, soybean epoxy and zinc acetate were weighed in a molar ratio of 1:1:0.15, and prepolymer 17 was obtained in the same procedure as in preparation example 1.
Examples
Example 1
Prepolymer 1 (22 Kg), EVA/LLDPE (69 Kg), compatilizer (maleic anhydride grafted ethylene vinyl acetate copolymer) (6 Kg) and organosilicon (3 Kg) in the mass ratio of 22:69:6:3 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The length-diameter ratio of the screw of the selected double-screw extruder is 40:1.
Example 2
Prepolymer 2 (25 Kg), EVA/LLDPE (68 Kg), a compatilizer (4 Kg) and organosilicon (3 Kg) in a mass ratio of 25:68:4:3 are weighed, stirred for 30min at a rotating speed of 40r/min and a temperature of 190 ℃, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 3
Prepolymer 3 (22 Kg), EVA/LLDPE (72 Kg) and a compatilizer (6 Kg) with the mass ratio of 22:72:6 are weighed, stirred for 25min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 4
Prepolymer 4 (21 Kg), EVA/LLDPE (73 Kg) and a compatilizer (6 Kg) with the mass ratio of 21:73:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 5
Prepolymer 5 (24 Kg), EVA/LLDPE (70 Kg) and a compatilizer (6 Kg) with the mass ratio of 24:70:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 6
Prepolymer 6 (19 Kg), EVA/LLDPE (72 Kg), a compatilizer (6 Kg) and organosilicon (3 Kg) in a mass ratio of 19:72:6:3 are weighed, stirred for 30min at a rotating speed of 50r/min and a temperature of 200 ℃, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1. .
Example 7
Prepolymer 7 (21 Kg), EVA/LLDPE (73 Kg) and a compatilizer (6 Kg) with the mass ratio of 21:73:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 8
Prepolymer 8 (18 Kg), EVA/LLDPE (76 Kg) and a compatilizer (6 Kg) with the mass ratio of 18:76:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 9
Prepolymer 9 (17 Kg), EVA/LLDPE (77 Kg) and a compatilizer (6 Kg) with the mass ratio of 17:77:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 10
The prepolymer 10 (22 Kg), EVA/LLDPE (72 Kg) and a compatilizer (6 Kg) with the mass ratio of 22:72:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 11
Prepolymer 11 (20 Kg), EVA/LLDPE (74 Kg) and a compatilizer (6 Kg) with the mass ratio of 20:74:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 12
Prepolymer 12 (19 Kg), EVA/LLDPE (75 Kg) and a compatilizer (6 Kg) with the mass ratio of 19:75:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 13
Prepolymer 13 (25 Kg), EVA/LLDPE (69 Kg) and a compatilizer (6 Kg) with the mass ratio of 25:69:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 14
Prepolymer 14 (21 Kg), EVA/LLDPE (72 Kg), a compatilizer (5 Kg) and organosilicon (2 Kg) in a mass ratio of 21:72:5:2 are weighed, stirred for 30min at the condition of 60r/min and 200 ℃ in rotation speed, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 15
Prepolymer 15 (19 Kg), EVA/LLDPE (75 Kg) and a compatilizer (6 Kg) with the mass ratio of 19:75:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 16
Prepolymer 16 (26 Kg), EVA/LLDPE (68 Kg) and a compatilizer (6 Kg) with the mass ratio of 26:68:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Example 17
Prepolymer 17 (6 Kg), EVA/LLDPE (74 Kg) and a compatilizer (6 Kg) with the mass ratio of 20:74:6 are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
Comparative example 1
91 parts of EVA/LLDPE (94 Kg), 6 parts of compatilizer (maleic anhydride grafted ethylene vinyl acetate copolymer) (6 Kg) and organic silicon (3 Kg) are weighed, stirred for 30min under the conditions of 50r/min of rotating speed and 200 ℃ of temperature, extruded, melted, blended and granulated by a double-screw extruder, and the flame-retardant cable material is obtained. The twin screw extruder used was as described in example 1.
The flame retardant cable materials obtained in examples 1 to 17 and comparative example 1 were injection molded into standard vertical combustion (UL-94) bars, limiting Oxygen Index (LOI) bars, wherein the injection molding temperature was 190 to 210 ℃ and the injection pressure was 70 to 90MPa. The combustion performance and oxygen index were measured according to ASTM D3801, ASTM D2863-97, the results of which are shown in Table one, NC indicating no rating.
Figure BDA0004119078480000211
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Figure BDA0004119078480000221
Table 1 shows the UL-94 and LOI test results of all examples and comparative examples. When the content of the prepolymer is about 20, the flame-retardant cable material has better flame retardant property, can generally pass through V-0 grade, and the oxygen index is obviously improved to 28.8%, which proves that the prepared prepolymer reduces the addition amount of the traditional inorganic flame retardant to a certain extent, and achieves obvious effect in flame-retardant materials.
Finally, it is to be understood that the embodiments of the application disclosed herein are illustrative of the principles of the embodiments of the present application. Other modified embodiments are also within the scope of the present application. Accordingly, the embodiments disclosed herein are by way of example only and not limitation. Those skilled in the art can adopt alternative configurations to implement the applications herein according to embodiments herein. Accordingly, embodiments of the present application are not limited to those precisely described in the application.

Claims (15)

1. A flame retardant cable material, comprising:
a cable material matrix comprising an ethylene-vinyl acetate copolymer and a linear low density polyethylene;
the prepolymer is a reaction product of an acid source and an oxygen-surrounding source under the action of a catalyst, wherein the reaction product comprises a cross-linked structure formed by transesterification of an epoxy group and a carboxyl group, and at least one of the acid source or the oxygen-surrounding source contains a P element;
and a product of a partial reaction of the prepolymer with the ethylene-vinyl acetate copolymer, wherein the product is a polymer containing an ester group and a phosphaphenanthrene compound or a polymer containing an ester group and a phosphonate group.
2. The flame retardant cable material of claim 1, wherein the cable material matrix is 65 to 76% by mass, the prepolymer is 1 to 10% by mass, and the prepolymer is 10 to 25% by mass of the product of the partial reaction with the ethylene-vinyl acetate copolymer.
3. The flame-retardant cable material according to claim 1, further comprising a compatibilizer and a catalytic carbonizing agent, wherein the compatibilizer is maleic anhydride grafted ethylene vinyl acetate copolymer, the catalytic carbonizing agent is organic silicon, the mass percent of the compatibilizer is 4-6%, and the mass percent of the catalytic carbonizing agent is 0-3%.
4. The flame-retardant cable material of claim 1, wherein the reaction product of the acid source and the cyclic oxygen source under the action of a catalyst is
Figure FDA0004119078470000021
Wherein X and Y are natural numbers, the range of X is between 40 and 60, and the range of Y is between 3 and 10.
5. The flame retardant cable material of claim 5, wherein the prepolymer is formed with a mole percent of cyclic oxygen source, acid source and catalyst in the range of 1 (1-1.05): (0.05-0.15).
6. The flame retardant cable material of claim 5, wherein said acid source comprises a compound of formula (i):
Figure FDA0004119078470000022
wherein R of formula (I) is selected from C 2 -C 10 A group or a furan ring-containing or DOPO structure-containing group, the C 2 -C 10 The group comprises linear alkane, cycloalkane and aromatic ring; the DOPO structural group is a group containing one or two DOPO structures.
7. The flame retardant cable material of claim 6, wherein the acid source comprises any one or more of succinic acid, 1, 4-cyclohexanedicarboxylic acid, furandicarboxylic acid, 5-norbornene-2, 3 dicarboxylic acid, DOPO-ITA, terephthalic acid, TPNA, and DMZH, wherein the structural formulas of DOPO-ITA, TPNA, and DMZH are each:
Figure FDA0004119078470000031
8. the flame retardant cable material of claim 5, wherein the epoxy source comprises a compound having the structural formula (II):
Figure FDA0004119078470000032
wherein R1 of formula (II) is selected from C10-C30 ether epoxy groups or phosphonate structure-containing groups; the ether group of C10-C30 is glycidyl ether group containing at least two aromatic rings; the phosphonate structural group refers to a group containing at least one benzene ring structure and containing only one phosphonate structure and having carbon atoms within 25.
9. The flame retardant cable material of claim 8, wherein the epoxy source comprises any one or more of EDPDO, soy epoxy, and DGEBA, wherein the EDPDO, soy epoxy, and DGEBA have the structural formula:
Figure FDA0004119078470000041
10. the preparation method of the flame-retardant cable material is characterized by comprising the following steps:
melting an epoxy source, adding an acid source into the molten epoxy source, uniformly mixing, adding a catalyst, and pre-reacting for a specific time in a specific temperature range to form a prepolymer, wherein the prepolymer comprises a cross-linked structure formed by transesterification of epoxy groups and carboxyl groups, and at least one of the acid source or the epoxy source contains P element;
and fully mixing the prepolymer with a cable material matrix, and then carrying out melt blending granulation to form the flame-retardant cable material, wherein the cable material matrix is a mixture of an ethylene-vinyl acetate copolymer and linear low-density polyethylene, and in the process of melt blending granulation, the prepolymer and the ethylene-vinyl acetate copolymer partially react to form a product which is a polymer containing ester groups and phosphaphenanthrene compounds or a polymer containing ester groups and phosphonate groups.
11. The method for preparing a flame retardant cable material according to claim 10, wherein the pre-reaction temperature is 140-170 ℃; the process conditions for mixing the prepolymer and the mixture of ethylene-vinyl acetate copolymer and linear low density polyethylene are: stirring for 15-30 min by a double-screw extruder at the rotating speed of 40-60 r/min and the temperature of 170-200 ℃.
12. The method of producing a flame retardant cable material according to claim 10, wherein in the step of thoroughly mixing the prepolymer and the cable material matrix plus auxiliary materials, the mass percentage of the cable material matrix is 68% to 76%, and the mass percentage of the prepolymer is 17% to 26%; during melt blending granulation, the prepolymer is partially reacted with the ethylene-vinyl acetate copolymer to give a product of 10 to 25 mass%.
13. The method for preparing a flame retardant cable material according to claim 10, further comprising a compatibilizer and a catalytic carbonizing agent which are fully mixed with the prepolymer and the cable material matrix flame retardant cable material, wherein the compatibilizer is maleic anhydride grafted ethylene vinyl acetate copolymer, the catalytic carbonizing agent is organic silicon, the mass percent of the compatibilizer is 4-6%, and the mass percent of the catalytic carbonizing agent is 0-3%.
14. The method of preparing a flame retardant cable material according to claim 10, wherein the prepolymer is formed with a cyclic oxygen source, an acid source and a catalyst in a mole percent range of 1 (1-1.05): (0.05-0.15).
15. The method of preparing a flame retardant cable material of claim 14, wherein said acid source comprises a compound having the structural formula (i):
Figure FDA0004119078470000061
wherein R of formula (I) is selected from C 2 -C 10 A group or a furan ring-containing or DOPO structure-containing group, the C 2 -C 10 The group comprises linear alkane, cycloalkane and aromatic ring; the DOPO structural group is a group containing one or two DOPO structures;
the epoxy source includes a compound having the structural formula (II):
Figure FDA0004119078470000062
wherein R1 of formula (II) is selected from C10-C30 ether epoxy groups or phosphonate structure-containing groups; the ether group of C10-C30 is glycidyl ether group containing at least two aromatic rings; the phosphonate structural group refers to a group containing at least one benzene ring structure and only one phosphonate structure and having carbon atoms within 25;
the catalyst comprises 1,5, 7-triazabicyclo [4, 0] dec-5-ene (TBD) or zinc acetate.
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