CN117964964A - Preparation method of thermoplastic low-density elastomer for hydrolysis-resistant low-smoke halogen-free cable material - Google Patents
Preparation method of thermoplastic low-density elastomer for hydrolysis-resistant low-smoke halogen-free cable material Download PDFInfo
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- CN117964964A CN117964964A CN202311813790.0A CN202311813790A CN117964964A CN 117964964 A CN117964964 A CN 117964964A CN 202311813790 A CN202311813790 A CN 202311813790A CN 117964964 A CN117964964 A CN 117964964A
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- low
- hydrolysis
- cable material
- smoke halogen
- free cable
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- 239000000463 material Substances 0.000 title claims abstract description 109
- 229920001971 elastomer Polymers 0.000 title claims abstract description 59
- 239000000779 smoke Substances 0.000 title claims abstract description 49
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 39
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 39
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 31
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 31
- 239000000806 elastomer Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 239000005060 rubber Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 230000002209 hydrophobic effect Effects 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- -1 peroxy compound Chemical class 0.000 claims description 13
- 230000003712 anti-aging effect Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 9
- 239000005662 Paraffin oil Substances 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- 229920005672 polyolefin resin Polymers 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 6
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 6
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 4
- 239000004702 low-density polyethylene Substances 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 claims description 3
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- SKWZHINXPDOQDF-UHFFFAOYSA-N disilanyl(ethenyl)silane Chemical compound [SiH3][SiH2][SiH2]C=C SKWZHINXPDOQDF-UHFFFAOYSA-N 0.000 claims 1
- 239000012257 stirred material Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 12
- 229910052736 halogen Inorganic materials 0.000 abstract description 9
- 150000002367 halogens Chemical class 0.000 abstract description 9
- 230000035939 shock Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 19
- 239000003921 oil Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000009472 formulation Methods 0.000 description 9
- 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 description 7
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- FYAMXEPQQLNQDM-UHFFFAOYSA-N Tris(1-aziridinyl)phosphine oxide Chemical compound C1CN1P(N1CC1)(=O)N1CC1 FYAMXEPQQLNQDM-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- 239000013536 elastomeric material Substances 0.000 description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 2
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 description 2
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RINWGRJHXCCLOV-UHFFFAOYSA-N BPO Chemical compound BPO RINWGRJHXCCLOV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a thermoplastic low-density elastomer for a hydrolysis-resistant low-smoke halogen-free cable material, which belongs to the technical field of cable material preparation, and the prepared thermoplastic low-density elastomer composite material for the hydrolysis-resistant low-smoke halogen-free cable material can be applied to various cable materials, and the cable material prepared from the composite material has more excellent tensile mechanical properties (high mechanical strength and high elongation): tensile strength and elongation at break are carried out according to GB/T1040.3 standard; the thermal shock resistance effect is better. The cable material prepared by the invention has better performance than index value in GB/T32129, and has more excellent tensile mechanical property, thermal shock resistance and hydrolysis resistance than low smoke halogen-free material of EVA+POE resin system. Compared with PVC cable material (halogen-containing), the PVC cable material has the advantage of more environmental protection and low temperature resistance.
Description
Technical Field
The invention belongs to the technical field of cable material preparation, and particularly relates to a preparation method of a thermoplastic low-density elastomer for a hydrolysis-resistant low-smoke halogen-free cable material.
Background
The plastic for wire and cable insulation and sheath is commonly called as cable material, which comprises rubber, polyolefin, polyurethane and other varieties, however, the materials are all high polymer materials, and have the defects of inflammability and a large amount of smoke generated during combustion, and the common practice in the industry is to add flame retardant or inorganic powder (calcium carbonate, magnesium hydroxide, aluminum hydroxide and the like) into the base materials to obtain the smokeless flame retardant property of the cable material. However, with the increase of the filling amount of the flame retardant and the inorganic powder, the strength and the elongation of the composite material are gradually reduced, and when the composite material is used in a special environment, the severe requirements on the maintenance of mechanical properties are met, such as the cable line under water or in a mine is often contacted with water, so that the requirements on a hot water soaking test (70 ℃/7 d) are put on the cable material in GB/T32129.
The invention discloses a smokeless flame-retardant waterproof cable material as disclosed in a patent with publication number CN 113896988A, and belongs to the technical field of cable material manufacturing. And the waterproof cable material comprises the following raw materials in parts by weight: 55 to 95 parts of PP resin, 15 to 30 parts of low-density polyethylene resin, 6.5 to 12.5 parts of auxiliary agent, 2.5 to 6.5 parts of glass fiber, 0.3 to 1.5 parts of silane coupling agent, 3.5 to 9.5 parts of modified hydrotalcite, 1.5 to 5.5 parts of anti-aging agent and 1.5 to 3 parts of lubricant. According to the invention, the flame retardant property and the waterproof property of the cable material are improved by introducing the auxiliary agent and the modified hydrotalcite into the cable material system, wherein the modified hydrotalcite has excellent flame retardant property and smoke suppression property, can be stably dispersed in the cable material system, and has small migration; and the auxiliary agent molecular chain contains a large amount of silicon-oxygen bonds, so that the migration of the modified hydrotalcite is further reduced, and the stability of the flame retardant property of the cable material is improved.
However, the auxiliary agent of the invention needs the steps of nitrogen introduction, stirring, dropwise adding, reduced pressure distillation and the like, the production steps are complex, the time is long, the production efficiency is not realized, meanwhile, the water resistance is evaluated by adopting the sample volume expansion rate after the distilled water at 35 ℃ is treated for 7 days, and the test standard requirement of GB/T32129 is not met.
Disclosure of Invention
The invention aims at: in order to solve the problems, a preparation method of a thermoplastic low-density elastomer for hydrolysis-resistant low-smoke halogen-free cable material is provided.
The technical scheme adopted by the invention is as follows: a method for preparing a thermoplastic low-density elastomer for hydrolysis-resistant low-smoke halogen-free cable material, which comprises the following steps:
S1: firstly preparing a modified hydrophobic oligomer, weighing industrial white oil (preferably high-bridge petrochemical 32# paraffin oil and Jincheng 32# paraffin oil) according to a proportion, and controlling the temperature of the reaction kettle in a stirring temperature-controlled reaction kettle at 90-120 ℃ and the stirring rotating speed at 500-3000 rpm;
S2: uniformly stirring unsaturated siloxane (preferably vinyl tri (methoxyethoxy) silane, vinyl trimethoxy silane and vinyl triethoxy silane), hydroxyl-terminated liquid rubber (preferably HFHTPB-I type, HFHTPB-II type and HFHTPB-III type), an initiator B (preferably BPO, TAPO, TBPO, TAPA) and a catalyst (preferably dibutyl tin dilaurate and stannous octoate) in a mixing tank at room temperature at a stirring speed of 500-3000 rpm for 1-3 h;
S3: and then uniformly stirring materials in the mixing tank, and uniformly feeding the materials into a temperature-controlled reaction kettle, wherein the feeding time is controlled to be 1-2 h. After the material in the mixing tank is put in, the reaction kettle needs to be kept for 0.5-1 h, after the heat preservation is finished, the reaction kettle is cooled to room temperature and discharged to a feeding bin, and the material prepared in the feeding bin is the modified hydrophobic oligomer;
S4: firstly, weighing rubber resin (preferably powdery SEBS and SBS) and isocyanate-terminated liquid rubber (preferably isocyanate-terminated butadiene rubber TY-IR I type and TY-IR II type) according to the proportion, and stirring, dispersing and premixing in a high-speed stirring and dispersing machine, wherein the stirring rotation speed is 2000-4000 rpm;
S5: after the liquid rubber and the powder rubber resin are uniformly dispersed, adding polyolefin resin (preferably LLDPE, mLLDPE, EPPE), anti-aging auxiliary agent (preferably antioxidant 1010, antioxidant 1076 and antioxidant DLTDP) and initiator A (preferably DTBP, TAHP and double-five initiator) according to the proportion, and continuously stirring for 10-30 min
S6: feeding the materials prepared in the step S3 and the step S5 to a double-screw extruder through a weightless feeder, wherein the process temperature is controlled at 170-220 ℃, and the prepared materials are as follows: a thermoplastic low-density elastomer material for hydrolysis-resistant low-smoke halogen-free cable materials.
In a preferred embodiment, in the step S1, the technical white oil is one of paraffinic oil and naphthenic oil, and the component ratio is: 95-98 parts.
In a preferred embodiment, in the step S2, the unsaturated group siloxane is one of vinyltris (methoxyethoxy) silane, vinyltrimethoxysilane, and vinyltriethoxysilane.
In a preferred embodiment, in the step S1, the hydroxyl-terminated liquid rubber is preferably hydroxyl-terminated polybutadiene, and the component ratio is: 0.2-2 parts.
In a preferred embodiment, in the step S1, the initiator B is one or two of an azodinitrile compound and an organic peroxy compound, and the component ratio is: 0.01 to 0.1 part.
In a preferred embodiment, in the step S1, the catalyst is one or more of organotin, organozinc and organobismuth catalysts, and the component ratio is: 0.1 to 1 part.
In a preferred embodiment, in the step S4, the rubber resin is: SEBS, SBS, SEPS, SIS, wherein the isocyanate-terminated liquid rubber is: and an isocyanate-terminated butadiene rubber.
In a preferred embodiment, in the step S5, the polyolefin resin is: LDPE, LLDPE, mLLDPE, EPPE, ULDPE, HDPE, PP, one or more than one kind of materials.
In a preferred embodiment, in the step S5, the anti-aging auxiliary agent is: one or three of hindered phenols, phosphites and thioesters.
In a preferred embodiment, in the step S5, the initiator a is: one or two of azodinitrile compound and organic peroxy compound.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
In the invention, the prepared thermoplastic low-density elastomer composite material for the hydrolysis-resistant low-smoke halogen-free cable material can be applied to various cable materials, and the cable material prepared by the composite material has more excellent tensile mechanical properties (high mechanical strength and high elongation): tensile strength and elongation at break are carried out according to GB/T1040.3 standard; the heat shock resistance effect is better: executing according to GB/T32129 standard; excellent hydrolysis resistance (70 ℃/7d water bath): sample preparation is carried out according to the GB/T1040.3 standard, and a sample water bath treatment method is carried out according to the GB/T32129 standard; excellent insulating properties (high volume resistivity): executing according to the GB/T1410 standard; low temperature resistance (impact embrittlement temperature lower): performed according to the GB/T5470 standard. The cable material prepared by the invention has better performance than index value in GB/T32129, and has more excellent tensile mechanical property, thermal shock resistance and hydrolysis resistance than low smoke halogen-free material of EVA+POE resin system. Compared with PVC cable material (halogen-containing), the PVC cable material has the advantage of more environmental protection and low temperature resistance.
Drawings
FIG. 1 is a schematic diagram of the flow principle of the present invention;
FIG. 2 is a schematic representation of the reaction scheme for synthesizing hydroxyl-terminated siloxane oligomers of the present invention;
FIG. 3 is a diagram of the general formula of a carbamate reaction performed in accordance with the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
With reference to figures 1 to 3 of the drawings,
A thermoplastic low-density elastomer for hydrolysis-resistant low-smoke halogen-free cable material is mainly prepared from rubber resin, polyolefin resin, anti-aging auxiliary agent, initiator A, isocyanate-terminated liquid rubber and modified hydrophobic oligomer. The weight portion ratio of the raw materials is as follows: 15 to 40 parts of rubber resin, 30 to 60 parts of polyolefin resin, 0.1 to 0.5 part of anti-aging auxiliary agent, 0.001 to 0.01 part of initiator A, 0.1 to 1 part of isocyanate-terminated liquid rubber and 15 to 40 parts of modified hydrophobic oligomer.
Wherein the rubber resin is: SEBS, SBS, SEPS, SIS, one or more than one kind of materials.
The polyolefin resin is: LDPE, LLDPE, mLLDPE, EPPE, ULDPE, HDPE, PP, one or more than one kind of materials.
The anti-aging auxiliary agent is as follows: one or three of hindered phenols, phosphites and thioesters.
The initiator A is: one or two of azodinitrile compound and organic peroxy compound.
The isocyanate-terminated liquid rubber comprises: and an isocyanate-terminated butadiene rubber.
The modified hydrophobic oligomer is prepared from industrial white oil, unsaturated siloxane monomer, hydroxyl-terminated liquid rubber, an initiator B and a catalyst, wherein the industrial white oil is one of paraffin oil and naphthenic oil, and the components are as follows: 95-98 parts; the unsaturated siloxane monomer is preferably vinyl siloxane monomer, and the composition ratio is as follows: 1-4 parts; the hydroxyl-terminated liquid rubber is preferably hydroxyl-terminated polybutadiene, and comprises the following components in percentage by weight: 0.2-2 parts; the initiator B is one or two of azodinitrile compound and organic peroxy compound, and the component ratio is as follows: 0.01 to 0.1 part; the catalyst is one or more of organotin, organozinc and organobismuth catalysts, and the component ratio is as follows: 0.1 to 1 part.
The invention prepares the modified hydrophobic oligomer containing hydroxyl groups through the free radical polymerization of functional monomers (vinyl siloxane monomers and hydroxyl-terminated butadiene rubber), and then carries out carbamate reaction on the modified hydrophobic oligomer containing hydroxyl groups and a grafted polymer main chain containing isocyanate groups, thereby preparing the polymer composite material with hydrophobic effect, so that the polymer composite material has excellent hydrolysis resistance in preparing inorganic powder filled low smoke halogen-free cable materials, and meets the test standard method and index requirements of GB/T32129.
The preparation method of the thermoplastic low-density elastomer for the hydrolysis-resistant low-smoke halogen-free cable material comprises the following specific implementation steps:
step one: preparing a modified hydrophobic oligomer, weighing industrial white oil (preferably high-bridge petrochemical 32# paraffin oil and Jincheng 32# paraffin oil) according to a proportion, uniformly stirring the industrial white oil (preferably high-bridge petrochemical 32# paraffin oil and Jincheng 32# paraffin oil) in a stirring temperature-control reaction kettle, controlling the temperature of the reaction kettle to be 90-120 ℃, stirring the industrial white oil at a rotation speed of 500-3000 rpm, firstly adding vinyl siloxane (preferably vinyl tri (methoxyethoxy) silane, vinyl trimethoxysilane and vinyl triethoxysilane), hydroxyl-terminated polybutadiene (preferably HFHTPB-I, HFHTPB-II and HFHTPB-III), an initiator B (preferably BPO, TAPO, TBPO, TAPA) and a catalyst (preferably dibutyl tin dilaurate and stannous octoate) into the mixing tank according to the proportion, uniformly stirring the materials in the mixing tank for 1-3 hours at a stirring speed of 1-2 hours. After the material in the mixing tank is put in, the reaction kettle needs to be kept for 0.5-1 h, and after the heat preservation is finished, the reaction kettle is cooled to room temperature and discharged to a feeding bin, and the material prepared in the feeding bin is the modified hydrophobic oligomer.
Step two: firstly weighing rubber resin (preferably powdery SEBS and SBS) and isocyanate-terminated liquid rubber (preferably isocyanate-terminated butadiene rubber TY-IR I type and TY-IR II type) according to the proportion, stirring, dispersing and premixing in a high-speed stirring and dispersing machine, stirring at a speed of 20004000rpm, adding polyolefin resin (preferably LLDPE, mLLDPE, EPPE), anti-aging auxiliary agent (preferably antioxidant 1010, antioxidant 1076 and antioxidant DLTDP) and initiator A (preferably DTBP, TAHP and double-five initiator) according to the proportion after the liquid rubber and the powder rubber resin are uniformly dispersed, and continuously stirring for 10-30 min.
Step three: feeding the materials prepared in the first step and the second step to a double-screw extruder through a weightless feeder, wherein the process temperature is controlled to be 170-220 ℃, and the prepared materials are as follows: a thermoplastic low-density elastomer material for hydrolysis-resistant low-smoke halogen-free cable materials.
The mechanism for the present invention is as follows:
In the first step, the initiator B is used for carrying out free radical initiation reaction, the mass ratio of vinyl siloxane (preferably 3-4 parts) to hydroxyl-terminated polybutadiene (preferably 0.5-1 part) is controlled, and industrial white oil (preferably 32# white oil) is used as a solvent carrier for carrying out free radical polymerization to synthesize the hydroxyl-terminated siloxane oligomer.
In the second step, the unsaturated bond is contained in the isocyanate-terminated butadiene rubber through the mechanism of initiating free radicals of the initiator A, and the isocyanate-terminated butadiene rubber molecules can be initiated to be grafted on a polyolefin molecular main chain (preferably LLDPE, mLLDPE, EPPE) and a styrene-butadiene rubber molecular main chain (preferably SEBS and SBS), and the rate of the free radical grafting reaction is obviously faster than that of carbamate, so that after the grafting reaction is rapidly completed, the isocyanate-terminated groups grafted on the polyolefin molecular main chain and the styrene-butadiene rubber molecular main chain can react with the hydroxyl-terminated siloxane oligomer prepared in the first step under the action of a catalyst (preferably dibutyl tin dilaurate and stannous octoate) so that the composite material prepared from the whole polyolefin molecular main chain and the styrene-butadiene rubber molecular main chain has hydrophobic property.
Example 1:
Preparation of modified hydrophobic oligomer: the preparation process conditions and the material ratios were as shown in Table 1 below.
Table 1 modified hydrophobic oligomer dosage table
| Material name | Composition ratio |
| 32# White oil | 95.75 Parts |
| Vinyl triethoxysilane | 3.5 Parts |
| Hydroxyl-terminated polybutadiene HFHTPB-III | 0.5 Part |
| Initiator B: TAPO (TAPO) | 0.05 Part |
| Catalyst dibutyl tin dilaurate | 0.2 Part |
| Process conditions | Preparation of modified hydrophobic oligomer according to the Process conditions of step one |
The hydrolysis-resistant low-smoke halogen-free cable material is prepared from a thermoplastic low-density elastomer material: the preparation process conditions and the material ratios were as shown in Table 2 below.
Table 2 thermoplastic low density elastomer material formulation table for hydrolysis resistant low smoke zero halogen cable material
Preparation of hydrolysis-resistant low-smoke halogen-free cable material: the material ratios of the cable materials were as shown in table 3 below.
Table 3 hydrolysis resistant low smoke zero halogen cable material dosing table and performance test
Remarks: performance test: the low-smoke halogen-free cable material is used for respectively testing tensile mechanical properties, mechanical properties after water bath treatment, volume resistivity, impact embrittlement resistance temperature and thermal shock resistance by using a flat vulcanizing instrument, a sheet punching machine, a volume surface resistivity tester, an electronic universal testing machine, a high-low temperature circulation testing box, an impact testing machine and other devices.
Comparative example 1:
Comparative example 1 was compared with example 1, except that the thermoplastic low-density elastomer composite material was prepared by directly blending and granulating the component materials according to the proportions, and then the low-smoke halogen-free cable material was prepared, and the preparation process conditions and the material proportions were carried out according to the following tables 4 and 5.
Table 4 comparative example 1 thermoplastic low density elastomeric material formulation table
Table 5 comparative example 1 low smoke zero halogen cable material dosing table and performance test
Comparative example 2:
comparative example 2 is different from example 1 in that the formulation of the modified oligomer contains vinyltriethoxysilane, but the preparation process conditions and the material ratios are as shown in tables 6, 7 and 8 below.
Table 6 comparative example 2 modified oligomer dosage table
Table 7 comparative example 2 thermoplastic low density elastomeric material formulation table
Table 8 comparative example 2 Low smoke zero halogen Cable Material formulation Table and Performance test results Table
Comparative example 3:
comparative example 3 is different from example 1 in that the formulation of the modified oligomer does not contain vinyltriethoxysilane but contains hydroxyl terminated polybutadiene, and the preparation process conditions and the material ratios are as shown in tables 9, 10 and 11 below.
Table 9 comparative example 3 modified oligomer formulation table
| Material name | Composition ratio |
| 32# White oil | 95.75 Parts |
| Vinyl triethoxysilane | 0 Part of |
| Hydroxyl-terminated polybutadiene HFHTPB-III | 4.0 Parts of |
| Initiator B: TAPO (TAPO) | 0.05 Part |
| Catalyst dibutyl tin dilaurate | 0.2 Part |
| Process conditions | Preparing the modified oligomer according to the process conditions of the first step |
Table 10 comparative example 3 thermoplastic low density elastomeric material formulation table
Table 11 comparative example 3 low smoke zero halogen cable material dosing table
Comparative example 4
Comparative example 4 is a low smoke halogen-free cable material formulation prepared by using conventional EVA+POE on the market, and compared with the two low smoke halogen-free systems in the example, the different low smoke halogen-free systems are compared, and the preparation process conditions and the material proportion are carried out according to the following table 12.
Table 12 comparative example 4eva+poe low smoke zero halogen cable material dosing table
Technical advanced description: the performance summary of example 1 and comparative examples 1, 2, 3, 4 is shown in table 13: (1) The hydrolysis-resistant low-smoke halogen-free cable material prepared in the embodiment 1 is optimal in initial strength and elongation; (2) The hydrolysis-resistant low-smoke halogen-free cable material prepared in example 1 has the minimum strength and elongation attenuation after water bath aging; (3) The hydrolysis-resistant low-smoke halogen-free cable material prepared in the embodiment 1 has high volume resistivity (insulativity) and good low-temperature impact embrittlement performance at minus 40 ℃; (4) The thermal shock cracking resistance of the hydrolysis-resistant low-smoke halogen-free cable material prepared in the example 1 is superior to that of an EVA+POE system. Because the formula of the low-smoke halogen-free cable material is consistent with other components, the preparation method of the thermoplastic low-density elastomer for the hydrolysis-resistant low-smoke halogen-free cable material has innovation and practical economic benefit.
Table 13 summary of examples and comparative examples performance tables
From the above experimental parameters, it can be known that: in the invention, the prepared thermoplastic low-density elastomer composite material for the hydrolysis-resistant low-smoke halogen-free cable material can be applied to various cable materials, and the cable material prepared by the composite material has more excellent tensile mechanical properties (high mechanical strength and high elongation): tensile strength and elongation at break are carried out according to GB/T1040.3 standard; the heat shock resistance effect is better: executing according to GB/T32129 standard; excellent hydrolysis resistance (70 ℃/7d water bath): sample preparation is carried out according to the GB/T1040.3 standard, and a sample water bath treatment method is carried out according to the GB/T32129 standard; excellent insulating properties (high volume resistivity): executing according to the GB/T1410 standard; low temperature resistance (impact embrittlement temperature lower): performed according to the GB/T5470 standard. The cable material prepared by the invention has better performance than index value in GB/T32129, and has more excellent tensile mechanical property, thermal shock resistance and hydrolysis resistance than low smoke halogen-free material of EVA+POE resin system. Compared with PVC cable material (halogen-containing), the PVC cable material has the advantage of more environmental protection and low temperature resistance.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The previous description is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a thermoplastic low-density elastomer for hydrolysis-resistant low-smoke halogen-free cable material is characterized by comprising the following steps: the method comprises the following steps:
s1: firstly preparing a modified hydrophobic oligomer, weighing industrial white oil according to a proportion, and placing the industrial white oil in a stirring temperature-control reaction kettle, wherein the temperature of the reaction kettle is controlled to be 90-120 ℃, and the stirring rotating speed is 500-3000 rpm;
S2: uniformly stirring unsaturated siloxane, hydroxyl-terminated liquid rubber, an initiator B and a catalyst in a mixing tank at room temperature according to the proportion, wherein the stirring speed is 500-3000 rpm, and the stirring time is 1-3 h;
S3: then uniformly feeding the uniformly stirred materials in the mixing tank into a temperature-controlled reaction kettle, wherein the feeding time is controlled to be 1-2 h, after the feeding of the materials in the mixing tank is completed, the reaction kettle needs to be insulated for 0.5-1 h, after the insulation is completed, the materials are cooled to room temperature and discharged to a feeding bin, and the materials prepared in the feeding bin are modified hydrophobic oligomers;
S4: firstly, weighing rubber resin and isocyanate-terminated liquid rubber according to the proportion, stirring, dispersing and premixing in a high-speed stirring and dispersing machine, wherein the stirring rotation speed is 2000-4000 rpm;
S5: after the liquid rubber and the powder rubber resin are uniformly dispersed, adding the polyolefin resin, the anti-aging auxiliary agent and the initiator A according to the proportion, and continuously stirring for 10-30 min;
S6: feeding the modified hydrophobic oligomer prepared in the step S3 and the material prepared in the step S5 to a double-screw extruder through a weightless feeder, wherein the process temperature is controlled at 170-220 ℃, and the prepared material is: a thermoplastic low-density elastomer material for hydrolysis-resistant low-smoke halogen-free cable materials.
2. The method for preparing the thermoplastic low-density elastomer for the hydrolysis-resistant low-smoke halogen-free cable material, which is characterized in that: in the step S1, the industrial white oil is one of paraffin oil and naphthenic oil, and the components are as follows: 95-98 parts.
3. The method for preparing the thermoplastic low-density elastomer for the hydrolysis-resistant low-smoke halogen-free cable material, which is characterized in that: in the step S2, the unsaturated siloxane is one of vinyltrisilane, vinyltrimethoxysilane and vinyltriethoxysilane, and the component ratio is: 1-4 parts.
4. The method for preparing the thermoplastic low-density elastomer for the hydrolysis-resistant low-smoke halogen-free cable material, which is characterized in that: in the step S2, the component ratio of the hydroxyl-terminated liquid rubber is as follows: 0.2-2 parts.
5. The method for preparing the thermoplastic low-density elastomer for the hydrolysis-resistant low-smoke halogen-free cable material, which is characterized in that: in the step S2, the initiator B is one or two of azodinitrile compound and organic peroxy compound, and the component ratio is as follows: 0.01 to 0.1 part.
6. The method for preparing the thermoplastic low-density elastomer for the hydrolysis-resistant low-smoke halogen-free cable material, which is characterized in that: in the step S2, the catalyst is one or more of organotin, organozinc and organobismuth catalysts, and the component ratio is: 0.1 to 1 part.
7. The method for preparing the thermoplastic low-density elastomer for the hydrolysis-resistant low-smoke halogen-free cable material, which is characterized in that: in step S4, the rubber resin is: SEBS, SBS, SEPS, SIS, wherein the isocyanate-terminated liquid rubber is: an isocyanate-terminated butadiene rubber; 15-40 parts of rubber resin; 0.1 to 1 part of isocyanate-terminated liquid rubber component.
8. The method for preparing the thermoplastic low-density elastomer for the hydrolysis-resistant low-smoke halogen-free cable material, which is characterized in that: in step S5, the polyolefin resin is: LDPE, LLDPE, mLLDPE, EPPE, ULDPE, HDPE, PP, the component ratio is 30-60 parts.
9. The method for preparing the thermoplastic low-density elastomer for the hydrolysis-resistant low-smoke halogen-free cable material, which is characterized in that: in step S5, the anti-aging auxiliary agent is: one or more of hindered phenols, phosphites and thioesters, and the anti-aging auxiliary agent comprises 0.1-0.5 part by weight;
The initiator A is as follows: one or two of azodinitrile compound and organic peroxy compound, and the component ratio of the initiator A is 0.001-0.01 part.
10. The method for preparing the thermoplastic low-density elastomer for the hydrolysis-resistant low-smoke halogen-free cable material, which is characterized in that: in the step S6, the dosage component ratio of the modified hydrophobic oligomer is 15-40 parts.
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