CN116874944B - Preparation process of hyperbranched polymer modified polyvinyl chloride cable material - Google Patents
Preparation process of hyperbranched polymer modified polyvinyl chloride cable material Download PDFInfo
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- CN116874944B CN116874944B CN202310637308.6A CN202310637308A CN116874944B CN 116874944 B CN116874944 B CN 116874944B CN 202310637308 A CN202310637308 A CN 202310637308A CN 116874944 B CN116874944 B CN 116874944B
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- polyvinyl chloride
- hyperbranched polymer
- phosphate
- triazine
- cable material
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 51
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 51
- 229920000587 hyperbranched polymer Polymers 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 27
- 239000010452 phosphate Substances 0.000 claims abstract description 27
- -1 2-mercaptobenzothiazole sodium-4, 6-diamino-1, 3, 5-triazine Chemical compound 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 10
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 72
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 10
- FVFVNNKYKYZTJU-UHFFFAOYSA-N 6-chloro-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(Cl)=N1 FVFVNNKYKYZTJU-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 9
- VLDHWMAJBNWALQ-UHFFFAOYSA-M sodium;1,3-benzothiazol-3-ide-2-thione Chemical compound [Na+].C1=CC=C2SC([S-])=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-M 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 238000004073 vulcanization Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000010025 steaming Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 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 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 abstract description 2
- BFZUFHPKKNHSAG-UHFFFAOYSA-N [N].[P].[S] Chemical compound [N].[P].[S] BFZUFHPKKNHSAG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000035939 shock Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000155 melt Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 2
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- YACTZEZVNPAVGJ-UHFFFAOYSA-N P.C(=O)(O)C=C.C(=O)(O)C=C.C(=O)(O)C=C Chemical compound P.C(=O)(O)C=C.C(=O)(O)C=C.C(=O)(O)C=C YACTZEZVNPAVGJ-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
-
- 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
- H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention relates to the technical field of polyvinyl chloride, and discloses a preparation process of a hyperbranched polymer modified polyvinyl chloride cable material, which utilizes a spiro-phosphate di (amidodiacetic acid) intermediate and a 2-mercaptobenzothiazole sodium-4, 6-diamino-1, 3, 5-triazine intermediate to generate melt polycondensation to obtain a novel thiazole-triazine-phosphate hyperbranched polymer, and then the novel thiazole-triazine-phosphate hyperbranched polymer is mixed with auxiliaries such as polyvinyl chloride, a plasticizer, a lubricant and the like to obtain the polyvinyl chloride cable material. The three-dimensional branched structure forms a three-dimensional crosslinked network in the polyvinyl chloride matrix, so that the shock resistance of the polyvinyl chloride cable material is obviously improved; the hyperbranched polymer contains thiazole rings, triazine rings and spiro phosphate structures, so that a phosphorus-nitrogen-sulfur synergistic flame retardant effect is formed, the limiting oxygen index and the fire resistance level of the polyvinyl chloride cable material during combustion are improved, and the flame retardant property is excellent.
Description
Technical Field
The invention relates to the technical field of polyvinyl chloride, in particular to a preparation process of a hyperbranched polymer modified polyvinyl chloride cable material.
Background
The polyvinyl chloride cable material has good insulating property and good weather resistance, is widely applied to high-voltage power transmission, submarine cables, optical fiber cables and the like, and the traditional polyvinyl chloride cable material has the problem of poor flame retardance and impact resistance, so that the development of the flame-resistant and impact-resistant polyvinyl chloride cable material in recent years is a research trend.
The hyperbranched polymer has a highly branched three-dimensional structure, molecular chains are not easy to tangle, the hyperbranched polymer has unique physicochemical properties, the hyperbranched polymer has wide application prospect in high polymer materials such as cable materials, and the like, and the patent CN105733130B discloses an insulated cold-resistant flexible cable which is prepared from polyvinyl chloride resin, rosin, SBS grafted by the hyperbranched polymer, flame retardant and the like serving as raw materials, and has higher mechanical property and ageing resistance while realizing soft property and electrical insulation property. Patent CN101497630B contains phosphorus acrylate monomer and hyperbranched polymer fire retardant and its preparation method, disclosed is to adopt monohydroxy acrylate, phosphonyl dichloride, amine ethyl piperazine, etc. as raw materials, prepare hyperbranched polyphosphate ester acrylate polymer fire retardant. Can be applied to coatings of building materials, wires, cables and the like. The invention provides a hyperbranched polymer modified polyvinyl chloride cable material, which aims to improve the flame retardance and the impact resistance of the polyvinyl chloride cable material.
Disclosure of Invention
The invention provides a preparation process of a hyperbranched polymer modified polyvinyl chloride cable material, which solves the problem that the polyvinyl chloride cable material is poor in flame retardance and impact resistance.
The technical scheme provided by the invention is as follows:
A preparation process of hyperbranched polymer modified polyvinyl chloride cable material comprises the following steps: adding 100 parts by weight of polyvinyl chloride, 2-20 parts by weight of thiazole-triazine-phosphate hyperbranched polymer, 45-50 parts by weight of plasticizer, 0.5-1.5 parts by weight of lubricant and 0.1-0.4 part by weight of antioxidant into a high-speed mixer, uniformly mixing, and then carrying out melt extrusion by an extruder and granulating; and then molding in a vulcanization bed to obtain the hyperbranched polymer modified polyvinyl chloride cable material.
Further, the lubricant is stearic acid, calcium stearate, paraffin wax or polyethylene wax.
Further, the melting temperature in the extruder is 180-190 ℃, and the extrusion temperature is 175-185 ℃; then the molding temperature is 190-200 ℃ and the time is 10-20 min in the fluidized bed.
Further, the preparation method of the thiazole-triazine-phosphate hyperbranched polymer comprises the following steps:
S1, adding spiro-phosphate diacid chloride, iminodiacetic acid and potassium carbonate into an acetonitrile solvent in ice water bath, reacting for 30-60 min, then reacting for 6-24 h at the temperature of 25-45 ℃, rotationally removing acetonitrile after the reaction, adding distilled water into the product, stirring and dissolving, dropwise adding dilute hydrochloric acid to adjust the pH of the solution to 4-5, then adding ethyl acetate for extraction and separation, steaming the separated ethyl acetate solution, and recrystallizing the product in ethyl acetate to obtain a spiro-phosphate di (amidodiacetic acid) intermediate; the reaction formula is as follows:
。
s2, adding sodium mercaptobenzothiazole and 2-chloro-4, 6-diamino-1, 3, 5-triazine into an ethanol solvent, reacting at a temperature of 55-80 ℃ to obtain 4-12 h, rotating to remove acetonitrile after the reaction, washing with diethyl ether, and recrystallizing the product in dichloromethane to obtain a 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine intermediate; the reaction formula is as follows:
。
S3, uniformly mixing the 2-mercaptobenzothiazole-4, 6-diammine-1, 3, 5-triazine intermediate and the spiro-phosphate di (amidodiacetic acid) intermediate in a nitrogen atmosphere, performing melt polycondensation at 220-250 ℃, cooling, and washing with deionized water, ethanol and ethyl acetate in sequence to obtain the thiazole-triazine-phosphate hyperbranched polymer.
Further, in the step S1, the molar ratio of the spiro phosphate diacid chloride, the iminodiacetic acid and the potassium carbonate is 1:1.8-2.4:2.5-4.
Further, in the step S2, the molar ratio of the sodium mercaptobenzothiazole to the 2-chloro-4, 6-diamino-1, 3, 5-triazine is 1.1-1.6:1.
Further, in step S3, the molar ratio of the 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine intermediate and the spiro-phosphate di (amidodiacetic acid) intermediate is 1.5-2.5:1.
The invention has the technical effects that:
1. A novel spiro-phosphate di (amido diacetic acid) intermediate is prepared by utilizing the phosphorylation reaction of spiro-phosphate diacid chloride and iminodiacetic acid; the novel 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine intermediate is prepared by utilizing the substitution reaction of sodium mercaptobenzothiazole and 2-chloro-4, 6-diamino-1, 3, 5-triazine; and then carrying out melt polycondensation on the two to obtain a novel thiazole-triazine-phosphate hyperbranched polymer, and then mixing the novel thiazole-triazine-phosphate hyperbranched polymer with auxiliary agents such as polyvinyl chloride, a plasticizer, a lubricant and the like to obtain the polyvinyl chloride cable material.
2. The hyperbranched polymer has good compatibility with polyvinyl chloride, and the three-dimensional branched structure forms a three-dimensional crosslinked network in a polyvinyl chloride matrix, so that the shock resistance of the polyvinyl chloride cable material is obviously improved; the hyperbranched polymer contains thiazole rings, triazine rings and spiro phosphate structures, so that a phosphorus-nitrogen-sulfur synergistic flame retardant effect is formed, the limiting oxygen index and the fire resistance level of the polyvinyl chloride cable material during combustion are improved, and the flame retardant property is excellent.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. Preferred embodiments of the present invention are given below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
S1, adding spiro-phosphate diacid chloride, iminodiacetic acid and potassium carbonate in a molar ratio of 1:2.2:3.5 into an acetonitrile solvent under ice water bath, reacting for 60 min, then reacting for 6 h at 45 ℃, rotationally removing acetonitrile after the reaction, adding distilled water into the product, stirring for dissolving, dropwise adding dilute hydrochloric acid to adjust the pH of the solution to 4, adding ethyl acetate for extraction and separation, rotationally steaming the separated ethyl acetate solution, and recrystallizing the product in ethyl acetate to obtain the spiro-phosphate di (amidodiacetic acid) intermediate.
S2, adding sodium mercaptobenzothiazole and 2-chloro-4, 6-diamino-1, 3, 5-triazine with a molar ratio of 1.1:1 into an ethanol solvent, reacting at a temperature of 60 ℃ for 8h, removing acetonitrile by rotation after the reaction, washing by diethyl ether, and recrystallizing the product in dichloromethane to obtain the intermediate of the 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine.
S3, uniformly mixing a 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine intermediate and a spiro-phosphate di (amidodiacetic acid) intermediate in a molar ratio of 2.5:1 in a nitrogen atmosphere, performing melt polycondensation at a temperature of 240 ℃, cooling, and washing with deionized water, ethanol and ethyl acetate in sequence to obtain the thiazole-triazine-phosphate hyperbranched polymer.
S4, adding 100 parts by weight of polyvinyl chloride, 2 parts by weight of thiazole-triazine-phosphate hyperbranched polymer, 50 parts by weight of dioctyl phthalate serving as a plasticizer, 1.5 parts by weight of calcium stearate serving as a lubricant and 0.4 part by weight of antioxidant 168 into a high-speed mixer, uniformly mixing, and then carrying out melt extrusion by an extruder at a melting temperature of 180 ℃ and an extrusion temperature of 175 ℃ and granulating; and then molding 10 min in a vulcanization bed at 190 ℃ to obtain the hyperbranched polymer modified polyvinyl chloride cable material.
Example 2
S1, adding spiro-phosphate diacid chloride, iminodiacetic acid and potassium carbonate in a molar ratio of 1:2.4:4 into an acetonitrile solvent under ice water bath, reacting for 30min, then reacting for 12 h at the temperature of 45 ℃, rotationally removing acetonitrile after the reaction, adding distilled water into the product, stirring for dissolving, dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to 5, adding ethyl acetate for extraction and separation, steaming the separated ethyl acetate solution in a rotary way, and recrystallizing the product in ethyl acetate to obtain the spiro-phosphate di (amidodiacetic acid) intermediate.
S2, adding sodium mercaptobenzothiazole and 2-chloro-4, 6-diamino-1, 3, 5-triazine with the molar ratio of 1.1.6:1 into an ethanol solvent, reacting at the temperature of 60 ℃ for 12 h, removing acetonitrile by rotating after the reaction, washing by diethyl ether, and recrystallizing the product in dichloromethane to obtain the intermediate of the 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine.
S3, uniformly mixing the 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine intermediate and spiro-phosphate di (amidodiacetic acid) intermediate in a molar ratio of 1.5:1 in a nitrogen atmosphere, performing melt polycondensation at the temperature of 250 ℃, cooling, and washing with deionized water, ethanol and ethyl acetate in sequence to obtain the thiazole-triazine-phosphate hyperbranched polymer.
S4, adding 100 parts by weight of polyvinyl chloride, 6 parts by weight of thiazole-triazine-phosphate hyperbranched polymer, 45 parts by weight of plasticizer dioctyl phthalate, 1.5 parts by weight of lubricant stearic acid and 0.2 part by weight of antioxidant 168 into a high-speed mixer, uniformly mixing, then carrying out melt extrusion by an extruder, wherein the melt temperature is 180 ℃, the extrusion temperature is 185 ℃, and granulating; and then molding 20 min in a vulcanization bed at 190 ℃ to obtain the hyperbranched polymer modified polyvinyl chloride cable material.
Example 3
S1, adding spiro-phosphate diacid chloride, iminodiacetic acid and potassium carbonate in a molar ratio of 1:1.8:2.5 into an acetonitrile solvent under ice water bath, reacting for 60 min, then reacting for 6 h at a temperature of 25 ℃, rotationally removing acetonitrile after the reaction, adding distilled water into the product, stirring for dissolving, dropwise adding diluted hydrochloric acid to adjust the pH of the solution to 5, adding ethyl acetate for extraction and separation, rotationally steaming the separated ethyl acetate solution, and recrystallizing the product in ethyl acetate to obtain the spiro-phosphate di (amidodiacetic acid) intermediate.
S2, adding sodium mercaptobenzothiazole and 2-chloro-4, 6-diamino-1, 3, 5-triazine with a molar ratio of 1.4:1 into an ethanol solvent, reacting at the temperature of 80 ℃ to obtain 4h, removing acetonitrile by rotating after the reaction, washing by diethyl ether, and recrystallizing the product in dichloromethane to obtain the intermediate of the 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine.
S3, uniformly mixing a 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine intermediate and a spiro-phosphate di (amidodiacetic acid) intermediate in a molar ratio of 2:1 in a nitrogen atmosphere, performing melt polycondensation at 220 ℃, cooling, and washing with deionized water, ethanol and ethyl acetate in sequence to obtain the thiazole-triazine-phosphate hyperbranched polymer.
S4, adding 100 parts by weight of polyvinyl chloride, 13 parts by weight of thiazole-triazine-phosphate hyperbranched polymer, 50 parts by weight of plasticizer dioctyl phthalate, 1 part by weight of lubricant polyethylene wax and 0.1 part by weight of antioxidant 168 into a high-speed mixer, uniformly mixing, then carrying out melt extrusion by an extruder, wherein the melt temperature is 180 ℃, the extrusion temperature is 185 ℃, and granulating; and then molding 10 min in a vulcanization bed at 200 ℃ to obtain the hyperbranched polymer modified polyvinyl chloride cable material.
Example 4
S1, adding spiro-phosphate diacid chloride, iminodiacetic acid and potassium carbonate in a molar ratio of 1:2.4:4 into an acetonitrile solvent under ice water bath, reacting 45 min, then reacting 24 h at the temperature of 45 ℃, rotationally removing acetonitrile after the reaction, adding distilled water into the product, stirring and dissolving, dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to 4, then adding ethyl acetate for extraction and separation, steaming the separated ethyl acetate solution in a rotary way, and recrystallizing the product in ethyl acetate to obtain the spiro-phosphate di (amidodiacetic acid) intermediate.
S2, adding sodium mercaptobenzothiazole and 2-chloro-4, 6-diamino-1, 3, 5-triazine with a molar ratio of 1.1:1 into an ethanol solvent, reacting at a temperature of 60 ℃ for 10 h, removing acetonitrile by rotation after the reaction, washing by diethyl ether, and recrystallizing the product in dichloromethane to obtain the intermediate of the 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine.
S3, uniformly mixing a 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine intermediate and a spiro-phosphate di (amidodiacetic acid) intermediate in a molar ratio of 1.8:1 in a nitrogen atmosphere, performing melt polycondensation at a temperature of 240 ℃, cooling, and washing with deionized water, ethanol and ethyl acetate in sequence to obtain the thiazole-triazine-phosphate hyperbranched polymer.
S4, adding 100 parts by weight of polyvinyl chloride, 20 parts by weight of thiazole-triazine-phosphate hyperbranched polymer, 50 parts by weight of plasticizer dioctyl phthalate, 0.5 part by weight of lubricant paraffin and 0.1 part by weight of antioxidant 168 into a high-speed mixer, uniformly mixing, then carrying out melt extrusion by an extruder, wherein the melt temperature is 185 ℃, the extrusion temperature is 185 ℃, and granulating; and then molding 15 min in a vulcanization bed at 200 ℃ to obtain the hyperbranched polymer modified polyvinyl chloride cable material.
Comparative example 1
S1, adding 100 parts by weight of polyvinyl chloride, 2 parts by weight of the spiro-phosphate di (amidodiacetic acid) intermediate prepared in the embodiment 1, 50 parts by weight of dioctyl phthalate serving as a plasticizer, 1.5 parts by weight of calcium stearate serving as a lubricant and 0.4 part by weight of antioxidant 168 into a high-speed mixer, uniformly mixing, then carrying out melt extrusion by an extruder, wherein the melt temperature is 180 ℃, the extrusion temperature is 175 ℃, and granulating; and then molding 10min in a vulcanization bed at 190 ℃ to obtain the hyperbranched polymer modified polyvinyl chloride cable material.
Comparative example 2
S1, adding 100 parts by weight of polyvinyl chloride, 2 parts by weight of 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine intermediate prepared in example 1, 50 parts by weight of dioctyl phthalate serving as a plasticizer, 1.5 parts by weight of calcium stearate serving as a lubricant and 0.4 part by weight of antioxidant 168 into a high-speed mixer, uniformly mixing, and then carrying out melt extrusion by an extruder at a melting temperature of 180 ℃ and an extrusion temperature of 175 ℃ and granulating; and then molding 10 min in a vulcanization bed at 190 ℃ to obtain the hyperbranched polymer modified polyvinyl chloride cable material.
The flame retardant properties of polyvinyl chloride cable materials were tested with reference to UL94 ratings and methods of GB/T2406.1-2008.
The impact strength of the polyvinyl chloride cable material was tested with reference to the method of GB/T1843-2008.
| UL94 rating | Limiting oxygen index (%) | Impact strength (kJ/m 2) | |
| Example 1 | V-0 | 28.9 | 18.4 |
| Example 2 | V-0 | 31.3 | 28.1 |
| Example 3 | V-0 | 33.2 | 31.2 |
| Example 4 | V-0 | 34.9 | 22.0 |
| Comparative example 1 | V-0 | 27.4 | 6.9 |
| Comparative example 2 | V-1 | 25.6 | 7.3 |
The limiting oxygen index of the polyvinyl chloride cable material is larger and larger along with the gradual increase of the dosage of the thiazole-triazine-phosphate hyperbranched polymer, when the dosage is 20 parts by weight, the maximum limiting oxygen index reaches 34.9%, the UL94 grades are both V-0 grades, and the flame retardance is better and better; the impact strength increases and decreases, and when the amount is 13 parts by weight, the maximum amount reaches 31.2 kJ/m 2. Only the spiro-phosphate bis (amidodiacetic acid) intermediate was added to comparative example 1. The flame retardance is better, the limiting oxygen index is 27.4%, but the impact strength is only 6.9 kJ/m 2; in comparative example 2, only 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine intermediate was added, and its flame retardance was generally 25.6% limiting oxygen index and impact strength was 7.3 kJ/m 2.
In view of the foregoing, it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made herein without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (6)
1. A preparation method of a hyperbranched polymer modified polyvinyl chloride cable material is characterized by comprising the following steps of: the preparation method comprises the following steps: adding 100 parts by weight of polyvinyl chloride, 2-20 parts by weight of thiazole-triazine-phosphate hyperbranched polymer, 45-50 parts by weight of plasticizer, 0.5-1.5 parts by weight of lubricant and 0.1-0.4 part by weight of antioxidant into a high-speed mixer, uniformly mixing, and then carrying out melt extrusion by an extruder and granulating; then molding in a vulcanization bed to obtain a hyperbranched polymer modified polyvinyl chloride cable material;
the preparation method of the thiazole-triazine-phosphate hyperbranched polymer comprises the following steps:
S1, adding spiro-phosphate diacid chloride, iminodiacetic acid and potassium carbonate into an acetonitrile solvent in ice water bath, reacting for 30-60 min, then reacting for 6-24 h at the temperature of 25-45 ℃, rotationally removing acetonitrile after the reaction, adding distilled water into the product, stirring and dissolving, dropwise adding dilute hydrochloric acid to adjust the pH of the solution to 4-5, then adding ethyl acetate for extraction and separation, steaming the separated ethyl acetate solution, and recrystallizing the product in ethyl acetate to obtain a spiro-phosphate di (amidodiacetic acid) intermediate;
S2, adding sodium mercaptobenzothiazole and 2-chloro-4, 6-diamino-1, 3, 5-triazine into an ethanol solvent, reacting at a temperature of 55-80 ℃ to obtain 4-12 h, rotating to remove acetonitrile after the reaction, washing with diethyl ether, and recrystallizing the product in dichloromethane to obtain a 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine intermediate;
S3, uniformly mixing the 2-mercaptobenzothiazole-4, 6-diammine-1, 3, 5-triazine intermediate and the spiro-phosphate di (amidodiacetic acid) intermediate in a nitrogen atmosphere, performing melt polycondensation at 220-250 ℃, cooling, and washing with deionized water, ethanol and ethyl acetate in sequence to obtain the thiazole-triazine-phosphate hyperbranched polymer.
2. The method for preparing the hyperbranched polymer modified polyvinyl chloride cable material according to claim 1, wherein the method comprises the following steps: the lubricant is stearic acid, calcium stearate, paraffin or polyethylene wax.
3. The method for preparing the hyperbranched polymer modified polyvinyl chloride cable material according to claim 1, wherein the method comprises the following steps: the melting temperature in the extruder is 180-190 ℃ and the extrusion temperature is 175-185 ℃; then the molding temperature is 190-200 ℃ and the time is 10-20 min in the fluidized bed.
4. The method for preparing the hyperbranched polymer modified polyvinyl chloride cable material according to claim 1, wherein the method comprises the following steps: in the step S1, the mole ratio of the spiro phosphate diacyl chloride, the iminodiacetic acid and the potassium carbonate is 1:1.8-2.4:2.5-4.
5. The method for preparing the hyperbranched polymer modified polyvinyl chloride cable material according to claim 1, wherein the method comprises the following steps: the molar ratio of sodium mercaptobenzothiazole to 2-chloro-4, 6-diamino-1, 3, 5-triazine in step S2 is 1.1-1.6:1.
6. The method for preparing the hyperbranched polymer modified polyvinyl chloride cable material according to claim 1, wherein the method comprises the following steps: in the step S3, the molar ratio of the 2-mercaptobenzothiazole-4, 6-diamino-1, 3, 5-triazine intermediate and the spiro-phosphate di (amidodiacetic acid) intermediate is 1.5-2.5:1.
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