CN116656078A - Composite multilayer thermoplastic winding core pipe and preparation method thereof - Google Patents
Composite multilayer thermoplastic winding core pipe and preparation method thereof Download PDFInfo
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- CN116656078A CN116656078A CN202310651350.3A CN202310651350A CN116656078A CN 116656078 A CN116656078 A CN 116656078A CN 202310651350 A CN202310651350 A CN 202310651350A CN 116656078 A CN116656078 A CN 116656078A
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- 238000004804 winding Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 93
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003063 flame retardant Substances 0.000 claims abstract description 59
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 31
- 239000005011 phenolic resin Substances 0.000 claims abstract description 31
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 24
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 239000012745 toughening agent Substances 0.000 claims abstract description 21
- 239000004088 foaming agent Substances 0.000 claims abstract description 20
- 239000008187 granular material Substances 0.000 claims abstract description 18
- 238000007493 shaping process Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 10
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 9
- 239000004156 Azodicarbonamide Substances 0.000 claims description 8
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 8
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- GEXXRGPMFWDDHM-UHFFFAOYSA-N 1-butylperoxy-3-(2-butylperoxypropan-2-yl)benzene Chemical compound C(CCC)OOC(C)(C)C1=CC(=CC=C1)OOCCCC GEXXRGPMFWDDHM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- FCZCIXQGZOUIDN-UHFFFAOYSA-N ethyl 2-diethoxyphosphinothioyloxyacetate Chemical compound CCOC(=O)COP(=S)(OCC)OCC FCZCIXQGZOUIDN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J9/06—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 chemical blowing agent
- C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- 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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
-
- 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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- 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
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K5/14—Peroxides
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The application relates to the technical field of high polymer materials, and particularly discloses a composite multilayer thermoplastic winding core tube and a preparation method thereof. The composite multilayer thermoplastic winding core pipe comprises the following raw materials in parts by weight: 40-60 parts of acrylonitrile-butadiene-styrene copolymer, 0.1-1 part of cross-linking agent, 1-5 parts of modified powder, 1-3 parts of foaming agent, 5-15 parts of toughening agent and 0.5-1.5 parts of dispersing agent; the raw materials of the modified powder comprise phenolic resin, an organic solvent and flame-retardant powder. The preparation method of the composite multilayer thermoplastic winding core pipe comprises the following steps: firstly, melting, blending and granulating an acrylonitrile-butadiene-styrene copolymer, a cross-linking agent, modified powder, a foaming agent, a toughening agent and a dispersing agent to obtain granules, then melting and extruding the granules, and extruding the products into a die for shaping to obtain the winding core pipe.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a composite multilayer thermoplastic winding core tube and a preparation method thereof.
Background
The winding core tube refers to a member for winding various kinds of band-shaped products such as films, tapes or papers, etc., to facilitate storage or transportation of the products. The existing winding core pipe is made of different materials and is generally formulated according to the product to be curled and is divided into a paper winding core pipe, a plastic winding core pipe, a metal winding core pipe and the like. The plastic winding core tube is usually an ABS plastic tube, the ABS resin is an important general synthetic resin, mainly a blend or terpolymer of acrylonitrile, butadiene and styrene, is a tough and rigid thermoplastic plastic, has very wide application, but has poor flame retardant property due to the performance characteristic of the molecular structure of the ABS itself.
Disclosure of Invention
In order to improve the flame retardant property of the prepared plastic pipe, the application provides a composite multilayer thermoplastic winding core pipe and a preparation method thereof.
In a first aspect, the present application provides a composite multilayer thermoplastic winding core pipe, which adopts the following technical scheme:
the composite multilayer thermoplastic winding core pipe comprises the following raw materials in parts by weight: 40 to 60 parts of acrylonitrile-butadiene-styrene copolymer, 0.1 to 1 part of cross-linking agent, 1 to 5 parts of modified powder, 1 to 3 parts of foaming agent, 5 to 15 parts of toughening agent and 0.5 to 1.5 parts of dispersing agent; the raw materials of the modified powder comprise phenolic resin, an organic solvent and flame-retardant powder.
By adopting the technical scheme, the organic solvent enables the phenolic resin to be uniformly loaded on the flame-retardant powder, and the acrylonitrile-butadiene-styrene copolymer and the phenolic resin have better compatibility, so that the modified powder is uniformly dispersed in the acrylonitrile-butadiene-styrene copolymer; the cross-linking agent enables the phenolic resin to be cross-linked with the acrylonitrile-butadiene-styrene copolymer, when exposed fire is encountered, a barrier layer is formed, and the flame-retardant powder can conduct heat rapidly, so that the flame retardant property of the plastic pipe is improved.
In a specific embodiment, the flame retardant powder comprises a mixture of nano titanium dioxide and alumina powder, and the weight ratio of nano titanium dioxide to alumina powder is 1: (2-3).
By adopting the technical scheme, the nano titanium dioxide and the alumina powder are matched with each other while the nano titanium dioxide and the alumina powder conduct heat rapidly, and the forming of the barrier layer can be promoted, so that the flame retardant property of the coiled pipe is further improved; in addition, the alumina powder has higher hardness and can also improve the wear resistance of the coiled pipe.
In a specific embodiment, the method of preparing the modified powder comprises the steps of; sequentially adding phenolic resin and flame-retardant powder into an organic solvent, uniformly stirring to obtain a mixture, and then carrying out negative pressure suction on the mixture and drying to obtain modified powder; and the weight ratio of the phenolic resin to the organic solvent to the flame retardant powder is 1: (2-3): (1.5-2.5).
By adopting the technical scheme, firstly adding phenolic resin into an organic solvent, uniformly stirring to enable the phenolic resin to be dissolved in the organic solvent, then adding flame-retardant powder, uniformly stirring to enable the flame-retardant powder to be uniformly dispersed in the phenolic resin to obtain a mixture, and then carrying out negative pressure suction and drying on the mixture to enable the phenolic resin to be uniformly loaded on the flame-retardant powder to obtain modified powder; and the proportion of the phenolic resin, the organic solvent and the flame-retardant powder is further limited, so that the modification effect of the flame-retardant powder is improved.
In a specific embodiment, the organic solvent comprises ethanol.
By adopting the technical scheme, the ethanol is used as a solvent and has a certain defoaming effect, so that the phenolic resin is uniformly loaded on the flame-retardant powder. In addition, the ethanol is volatile, so that the ethanol is convenient to remove, no impurities remain, and the quality of the prepared winding core pipe is improved.
In a specific embodiment, the crosslinking agent comprises one or a mixture of two of 1, 3-bis-butylperoxyisopropyl benzene and dicumyl oxide.
In a specific embodiment, the blowing agent comprises azodicarbonamide.
In a specific embodiment, the toughening agent comprises one or a mixture of two of a styrene-butadiene block copolymer, a methyl methacrylate-butadiene styrene copolymer.
By adopting the technical scheme, the toughening effect of the styrene-butadiene block copolymer and the methyl methacrylate-butadiene styrene copolymer is good, and the toughness and the bearing strength of the winding core pipe can be improved.
In a specific embodiment, the dispersant comprises one or a mixture of two of ethylene bis stearamide, ethylene acrylic acid copolymer.
By adopting the technical scheme, the ethylene bis-stearamide and the ethylene-acrylic acid copolymer have good dispersing effect, so that the raw materials can be uniformly mixed, and the performance of the prepared winding core pipe is improved.
In a second aspect, the present application provides a method for preparing a composite multilayer thermoplastic winding core pipe, which adopts the following technical scheme:
the preparation method of the composite multilayer thermoplastic winding core pipe comprises the following steps:
firstly, melting, blending and granulating an acrylonitrile-butadiene-styrene copolymer, a cross-linking agent, modified powder, a foaming agent, a toughening agent and a dispersing agent to obtain granules, then melting and extruding the granules, and extruding the products into a die for shaping to obtain the winding core pipe.
By adopting the technical scheme, the winding core pipe with higher flame retardant property is prepared by using the method.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the application, the organic solvent enables the phenolic resin to be uniformly loaded on the flame-retardant powder, and the acrylonitrile-butadiene-styrene copolymer and the phenolic resin have good compatibility, so that the modified powder is uniformly dispersed in the acrylonitrile-butadiene-styrene copolymer; the cross-linking agent enables the phenolic resin to be cross-linked with the acrylonitrile-butadiene-styrene copolymer, when encountering open fire, a barrier layer is formed, and the flame-retardant powder can conduct heat rapidly, so that the flame-retardant performance of the plastic pipe is improved;
2. according to the application, the nano titanium dioxide and the alumina powder are matched with each other while fast heat conduction is achieved, and the forming of the barrier layer can be promoted, so that the flame retardant property of the coiled pipe is further improved; in addition, the alumina powder has higher hardness, and can also improve the wear resistance of the coiled pipe;
3. according to the method, firstly, an acrylonitrile-butadiene-styrene copolymer, a cross-linking agent, modified powder, a foaming agent, a toughening agent and a dispersing agent are subjected to melt blending granulation, then melt extrusion is carried out, and a product is extruded into a die for shaping, so that the winding core pipe with higher flame retardant property is obtained.
Detailed Description
The present application will be described in further detail with reference to examples.
All the starting materials in the examples are commercially available. Wherein phenolic resin CAS number: 9003-35-4; alumina powder CAS number: 1344-28-1; styrene-butadiene block copolymer CAS number: 71342-87-5;
preparation example
Preparation example 1
Preparation example 1 provides a preparation method of modified powder, comprising the following steps:
adding phenolic resin into an organic solvent, stirring uniformly, adding flame-retardant powder, stirring uniformly to obtain a mixture, carrying out negative pressure suction on the mixture by using a negative pressure suction machine, and then adding the mixture into a drying box for drying at a drying temperature of 60 ℃ to obtain modified powder; wherein the organic solvent is ethanol, the flame-retardant powder is a mixture of nano titanium dioxide and alumina powder, and the weight ratio of the nano titanium dioxide to the alumina powder is 1:1.5; the weight ratio of the phenolic resin to the organic solvent to the flame-retardant powder is 1:1.5:1.
preparation example 2
Preparation example 2 differs from preparation example 1 in that the flame retardant powder is nano titanium dioxide; the remaining steps are identical to those of preparation 1.
Preparation example 3
Preparation example 3 differs from preparation example 1 in that the flame-retardant powder is alumina powder; the remaining steps are identical to those of preparation 1.
Preparation example 4
Preparation example 4 differs from preparation example 1 in that the weight ratio of nano titanium dioxide to alumina powder in the flame-retardant powder is 1:2; the remaining steps are identical to those of preparation 1.
Preparation example 5
The preparation example 5 is different from the preparation example 1 in that the weight ratio of nano titanium dioxide to alumina powder in the flame retardant powder is 1:2.5; the remaining steps are identical to those of preparation 1.
Preparation example 6
Preparation example 6 differs from preparation example 1 in that the weight ratio of nano titanium dioxide to alumina powder in the flame-retardant powder is 1:3, a step of; the remaining steps are identical to those of preparation 1.
Preparation example 7
Preparation example 7 differs from preparation example 1 in that the weight ratio of nano titanium dioxide to alumina powder in the flame-retardant powder is 1:3.5; the remaining steps are identical to those of preparation 1.
Preparation example 8
Preparation example 8 differs from preparation example 5 in that the weight ratio of phenolic resin, organic solvent, flame retardant powder is 1:2:1.5; the remaining steps are identical to those of preparation 5.
Preparation example 9
Preparation example 9 differs from preparation example 5 in that the weight ratio of phenolic resin, organic solvent, flame retardant powder is 1:2.5:2; the remaining steps are identical to those of preparation 5.
Preparation example 10
The difference between the preparation example 10 and the preparation example 5 is that the weight ratio of the phenolic resin, the organic solvent and the flame retardant powder is 1:3:2.5; the remaining steps are identical to those of preparation 5.
PREPARATION EXAMPLE 11
Preparation 11 differs from preparation 5 in that the weight ratio of phenolic resin, organic solvent, flame retardant powder is 1:3.5:3, a step of; the remaining steps are identical to those of preparation 5.
Examples
Example 1
Example 1 provides a method for preparing a composite multilayer thermoplastic winding core tube, comprising the following steps:
firstly, 40kg of acrylonitrile-butadiene-styrene copolymer, 0.1kg of cross-linking agent, 1kg of modified powder in preparation example 1, 1kg of foaming agent, 5kg of toughening agent and 0.5kg of dispersing agent are melted, blended and granulated to obtain granules, and then the granules are melted and extruded, and the products are extruded into a die for shaping to obtain a winding core pipe; wherein the cross-linking agent is 1, 3-bis-butyl peroxyisopropyl benzene; the foaming agent is azodicarbonamide; the toughening agent is a styrene-butadiene block copolymer; the dispersing agent is ethylene-acrylic acid copolymer.
Examples 2 to 11
Examples 2 to 11 differ from example 1 in the selection of modified powders, as detailed in Table 1.
Table 1 selection of modified powders in examples 1 to 11
Example 12
Example 12 provides a method for preparing a composite multilayer thermoplastic winding core tube, comprising the following steps:
firstly, 50kg of acrylonitrile-butadiene-styrene copolymer, 0.5kg of cross-linking agent, 3kg of modified powder in preparation example 9, 2kg of foaming agent, 10kg of toughening agent and 1kg of dispersing agent are melted, blended and granulated to obtain granules, and then the granules are melted and extruded, and the products are extruded into a die for shaping to obtain a winding core pipe; wherein the cross-linking agent is 1, 3-bis-butyl peroxyisopropyl benzene; the foaming agent is azodicarbonamide; the toughening agent is a styrene-butadiene block copolymer; the dispersing agent is ethylene-acrylic acid copolymer.
Example 13
Example 13 provides a method for preparing a composite multilayer thermoplastic winding core tube, comprising the following steps:
firstly, 60kg of acrylonitrile-butadiene-styrene copolymer, 1kg of cross-linking agent, 5kg of modified powder in preparation example 9, 3kg of foaming agent, 15kg of toughening agent and 1.5kg of dispersing agent are melted, blended and granulated to obtain granules, and then the granules are melted and extruded, and the products are extruded into a die for shaping to obtain a winding core pipe; wherein the cross-linking agent is 1, 3-bis-butyl peroxyisopropyl benzene; the foaming agent is azodicarbonamide; the toughening agent is a styrene-butadiene block copolymer; the dispersing agent is ethylene-acrylic acid copolymer.
Comparative example
Comparative example 1
Comparative example 1 provides a method for preparing a composite multilayer thermoplastic winding core tube, comprising the following steps:
firstly, 41.1kg of acrylonitrile-butadiene-styrene copolymer, 1kg of foaming agent, 5kg of toughening agent and 0.5kg of dispersing agent are melted, blended and granulated to obtain granules, and then the granules are melted and extruded, and the products are extruded into a die for shaping to obtain a winding core pipe; wherein the cross-linking agent is 1, 3-bis-butyl peroxyisopropyl benzene; the foaming agent is azodicarbonamide; the toughening agent is a styrene-butadiene block copolymer; the dispersing agent is ethylene-acrylic acid copolymer.
Comparative example 2
Comparative example 2 provides a method for preparing a composite multilayer thermoplastic winding core tube, comprising the following steps:
firstly, carrying out melt blending granulation on 40kg of acrylonitrile-butadiene-styrene copolymer, 1.1kg of modified powder in preparation example 1, 1kg of foaming agent, 5kg of toughening agent and 0.5kg of dispersing agent to obtain granules, and then carrying out melt extrusion on the granules, extruding the products into a die for shaping to obtain a winding core pipe; wherein the cross-linking agent is 1, 3-bis-butyl peroxyisopropyl benzene; the foaming agent is azodicarbonamide; the toughening agent is a styrene-butadiene block copolymer; the dispersing agent is ethylene-acrylic acid copolymer.
Comparative example 3
Comparative example 3 provides a method for preparing a composite multilayer thermoplastic winding core tube, comprising the following steps:
firstly, 40kg of acrylonitrile-butadiene-styrene copolymer, 1.1kg of flame retardant powder, 1kg of foaming agent, 5kg of toughening agent and 0.5kg of dispersing agent are melted, blended and granulated to obtain granules, and then the granules are melted and extruded, and the products are extruded into a die for shaping to obtain a winding core pipe; wherein the flame-retardant powder is a mixture of nano titanium dioxide and alumina powder, and the weight ratio of the nano titanium dioxide to the alumina powder is 1:1.5; the cross-linking agent is 1, 3-bis-butyl peroxyisopropyl benzene; the foaming agent is azodicarbonamide; the toughening agent is a styrene-butadiene block copolymer; the dispersing agent is ethylene-acrylic acid copolymer.
Performance test flame retardant performance: the prepared winding core tube is detected according to GB-T2406.2-2009 "combustion behavior measured by oxygen index method for plastics", so as to obtain an oxygen index A, and the higher the oxygen index A is, the better the flame retardant property of the winding core tube is.
TABLE 2 results of performance measurements on winding core tubes
By combining example 1 with comparative examples 1 to 3, the oxygen index in example 1 is the highest, so that the flame retardant performance of the winding core tube in example 1 is the best, and it can be seen that when the winding core tube is prepared, the modified powder and the cross-linking agent are added, the surface of the modified powder is loaded with phenolic resin, so that the phenolic resin is uniformly dispersed in the acrylonitrile-butadiene-styrene copolymer, the cross-linking agent cross-links the phenolic resin and the acrylonitrile-butadiene-styrene copolymer, a barrier layer is formed when exposed fire is encountered, and the flame retardant powder in the modified powder is rapidly thermally conductive, so that the flame retardant performance of the winding core tube is improved.
By combining examples 1-3, the oxygen index in example 1 is the highest, so that the flame retardant performance of the winding core tube in example 1 is the best, and it can be seen that when preparing the modified powder, the flame retardant powder is a mixture of nano titanium dioxide and alumina powder, and the combination of the nano titanium dioxide and alumina powder is beneficial to the formation of the barrier layer, so that the flame retardant performance of the winding core tube can be further improved.
In combination with examples 1 and 4-7 and in combination with examples 4-6, the winding core tube has better flame retardant performance, and it can be seen that when preparing the modified powder, the ratio of nano titanium dioxide to alumina powder in the flame retardant powder is preferably 1: (2-3), and the flame retardant effect of the prepared modified powder is better.
In combination with examples 5 and examples 8 to 11, and in combination with examples 8 to 10, the winding core tube has a good flame retardant property, and it can be seen that when the flame retardant powder is modified with a phenolic resin, the ratio of the phenolic resin, the organic solvent, and the flame retardant powder is preferably 1: (2-3): (1.5-2.5), the modification effect of the flame-retardant powder is optimal, thereby improving the flame-retardant property of the winding core pipe.
In combination with examples 9, 12 and 13, there was no significant change in oxygen index in examples 9, 12 and 13, and it was found that increasing the amount of each raw material used in the preparation of the winding core tube had little effect on the flame retardant properties of the prepared winding core tube.
The above embodiments are not intended to limit the scope of the present application, so: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.
Claims (9)
1. A composite multilayer thermoplastic winding core pipe is characterized in that: the raw materials of the winding core pipe comprise the following components in parts by weight: 40-60 parts of acrylonitrile-butadiene-styrene copolymer, 0.1-1 part of cross-linking agent, 1-5 parts of modified powder, 1-3 parts of foaming agent, 5-15 parts of toughening agent and 0.5-1.5 parts of dispersing agent; the raw materials of the modified powder comprise phenolic resin, an organic solvent and flame-retardant powder.
2. The composite multi-layer thermoplastic winding core tube of claim 1, wherein: the flame-retardant powder comprises a mixture of nano titanium dioxide and alumina powder, and the weight ratio of the nano titanium dioxide to the alumina powder is 1: (2-3).
3. The composite multilayer thermoplastic winding core tube of claim 2, wherein: the preparation method of the modified powder comprises the following steps of; sequentially adding phenolic resin and flame-retardant powder into an organic solvent, uniformly stirring to obtain a mixture, and then carrying out negative pressure suction on the mixture and drying to obtain modified powder; and the weight ratio of the phenolic resin to the organic solvent to the flame retardant powder is 1: (2-3): (1.5-2.5).
4. The composite multilayer thermoplastic winding core tube of claim 3, wherein: the organic solvent comprises ethanol.
5. The composite multi-layer thermoplastic winding core tube of claim 1, wherein: the cross-linking agent comprises one or a mixture of two of 1, 3-bis-butyl peroxyisopropyl benzene and dicumyl oxide.
6. The composite multi-layer thermoplastic winding core tube of claim 1, wherein: the foaming agent comprises azodicarbonamide.
7. The composite multi-layer thermoplastic winding core tube of claim 1, wherein: the toughening agent comprises one or a mixture of two of a styrene-butadiene block copolymer and a methyl methacrylate-butadiene styrene copolymer.
8. The composite multi-layer thermoplastic winding core tube of claim 1, wherein: the dispersing agent comprises one or a mixture of two of ethylene bis stearamide and ethylene-acrylic acid copolymer.
9. A method for preparing the composite multilayer thermoplastic winding core tube as claimed in any one of claims 1 to 8, characterized in that: the method comprises the following steps:
firstly, melting, blending and granulating an acrylonitrile-butadiene-styrene copolymer, a cross-linking agent, modified powder, a foaming agent, a toughening agent and a dispersing agent to obtain granules, then melting and extruding the granules, and extruding the products into a die for shaping to obtain the winding core pipe.
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| JPS61291644A (en) * | 1985-06-19 | 1986-12-22 | Sekisui Chem Co Ltd | Flame-retardant abs resin composition |
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| CN106674865A (en) * | 2016-12-02 | 2017-05-17 | 长兴天晟能源科技有限公司 | Flame-retardant master batch for ABS (acrylonitrile-butadiene-styrene) |
| CN114672095A (en) * | 2022-05-11 | 2022-06-28 | 南京中超新材料股份有限公司 | High-flame-retardancy low-smoke halogen-free cable sheath material and preparation method thereof |
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| JPS61291644A (en) * | 1985-06-19 | 1986-12-22 | Sekisui Chem Co Ltd | Flame-retardant abs resin composition |
| CN102250444A (en) * | 2011-07-01 | 2011-11-23 | 江苏技术师范学院 | Halogen-free flame-resistance acrylonitrile butadiene styrene (ABS) composite material and preparation method thereof |
| CN103602028A (en) * | 2013-10-24 | 2014-02-26 | 合肥会通新材料有限公司 | Injection-molding-grade foaming ABS material and preparation method thereof |
| CN106674865A (en) * | 2016-12-02 | 2017-05-17 | 长兴天晟能源科技有限公司 | Flame-retardant master batch for ABS (acrylonitrile-butadiene-styrene) |
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