CN114573977B - High-temperature-radiation-resistant crosslinked TPU sheath material, preparation method thereof and cable - Google Patents
High-temperature-radiation-resistant crosslinked TPU sheath material, preparation method thereof and cable Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 62
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 229920002635 polyurethane Polymers 0.000 claims abstract description 44
- 239000004814 polyurethane Substances 0.000 claims abstract description 44
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 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 22
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003063 flame retardant Substances 0.000 claims abstract description 22
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 21
- 239000000314 lubricant Substances 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- 238000004513 sizing Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 10
- 239000005060 rubber Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 4
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 4
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000010408 sweeping Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 27
- 239000005038 ethylene vinyl acetate Substances 0.000 description 26
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 25
- 230000032683 aging Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000009472 formulation Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
-
- 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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
-
- 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
Abstract
The invention relates to the technical field of sheath sizing materials, in particular to a high-temperature irradiation-resistant crosslinked TPU sheath material, a preparation method thereof and a cable, and the high-temperature irradiation-resistant crosslinked TPU sheath material comprises the following components in parts by weight: 90-100 parts of polyurethane IPN polymer, 5-10 parts of compatilizer, 20-40 parts of flame retardant, 0.1-0.2 part of antioxidant and 0.5-1 part of lubricant, wherein the components of the polyurethane IPN polymer comprise tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and at least one of vinyl acetate EVA and styrene butadiene rubber SBS, and the components are as follows: TDI: EPDM: (EVA and/or SBS) = (1-2): (2-3): (2-4). The high-temperature irradiation-resistant crosslinked TPU sheath material obtained by the formula and the process has the characteristics of high tensile strength and high elongation at break, has a temperature resistance grade of-40-105 ℃ and a VW-1 combustion grade, and simultaneously meets the oil resistance requirement of UL 60 ℃.
Description
Technical Field
The invention relates to the technical field of sheath sizing materials, in particular to a high-temperature irradiation-resistant crosslinked TPU sheath material, a preparation method thereof and a cable.
Background
The industrial drag chain wire is a composite cable, which can prevent the electric wires from entanglement, abrasion, pull-off, hanging and scattering when the equipment unit moves back and forth, and protect the electric wires, and the cable can also move back and forth along with the drag chain. To accommodate the back and forth movement of the drag chain, such wires typically require a wire jacket with high flexibility and good wear resistance.
Along with the wider and wider application range of cables, the application environment is more and more extreme, the requirements on tensile strength and elongation at break of the conventional irradiation crosslinking TPU sheath rubber compound are higher and higher, and the rubber compound on the market is difficult to simultaneously meet the high temperature resistance at 105 ℃ and the low temperature resistance at minus 40 ℃ and the oil resistance at UL 60 ℃, so that the sheath rubber compound meeting the performance conditions is required to be developed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-temperature irradiation-resistant crosslinked TPU sheath material, which comprises the following components in parts by weight: 90-100 parts of polyurethane IPN polymer, 5-10 parts of compatilizer, 20-40 parts of flame retardant, 0.1-0.2 part of antioxidant and 0.5-1 part of lubricant, wherein the components of the polyurethane IPN polymer comprise tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and at least one of vinyl acetate EVA and styrene butadiene rubber SBS, and the components are as follows: TDI: EPDM: (EVA and/or SBS) = (1-2): (2-3): (2-4).
Preferably, the composition of the compatibilizer is Evaloy HP4051.
Preferably, the component of the flame retardant is diethyl aluminum hypophosphite or melamine cyanurate.
Preferably, the antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Preferably, the lubricant component is erucamide.
In another aspect, the present application provides a method for preparing a high temperature irradiation-resistant crosslinked TPU sheathing compound, comprising the steps of:
s100, preparing a polyurethane IPN polymer, which comprises the following steps:
a. tetrahydrofuran THF, toluene diisocyanate TDI, vinyl acetate EVA, (ethylene propylene diene monomer (EPDM) and/or styrene butadiene rubber (SBS)) are mixed according to the following ratio of (1-2) (1-2-3): dissolving the components (2-4) in an acetone solvent, and fully stirring for 40-50 min at a rotating speed of 300-500 r/min to obtain a prepolymerization solution;
b. adding a catalyst, heating to 50 ℃, and stirring at a low speed of 100-200 r/min for reaction for 6H;
c. adding deionized water and a blocking agent, stirring for 5-10 min at the rotating speed of 600-900r/min, stopping the reaction, and decompressing and evaporating acetone and water to obtain a polyurethane IPN polymer;
s200, weighing and mixing the polyurethane IPN polymer, the compatilizer, the antioxidant and the lubricant according to the mass parts of the component proportions, and putting the mixture into an internal mixer for banburying;
s300, when the banburying temperature reaches 110 ℃, sweeping the internal mixer for one time, and simultaneously adding a flame retardant;
s400, when the banburying temperature reaches 140 ℃, conveying the mixture obtained by blending to a double-screw extruder for extrusion granulation to obtain TPU sheath sizing material;
s500, after the sizing material is extruded and molded, crosslinking is carried out by using an irradiation dose of 10Mrad, and the crosslinked TPU sheath material is obtained.
On the other hand, the application provides a cable, which is manufactured by the high-temperature-resistant irradiation crosslinking TPU sheath material prepared by the preparation method.
From the above, the following beneficial effects can be obtained by applying the invention: the high-temperature irradiation-resistant crosslinked TPU sheath material obtained by the formula and the process not only meets the high-temperature resistance of the grade of minus 40-105 ℃, but also meets the oil resistance of UL 60 ℃. The type, the dosage and the proportion of the polyurethane IPN polymer are properly selected to meet the oil resistance requirement at 60 ℃ and the temperature resistance grade at-40 ℃ and meet the VW-1 combustion grade requirement.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the drawings that are used in the description of the embodiments of the present application or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained from these drawings without inventive faculty for a person skilled in the art.
Fig. 1 is a flow chart of a preparation method of a high-temperature irradiation-resistant crosslinked TPU jacket material according to an embodiment of the application.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
In order to solve the technical problems, the embodiment provides a high-temperature irradiation-resistant crosslinked TPU sheath material, which comprises the following components in parts by weight: 90-100 parts of polyurethane IPN polymer, 5-10 parts of compatilizer, 20-40 parts of flame retardant, 0.1-0.2 part of antioxidant and 0.5-1 part of lubricant, wherein the components of the polyurethane IPN polymer comprise tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and vinyl acetate EVA, and the components are as follows: TDI: EPDM: EVA= (1-2): (2-3): (2-4).
Wherein the compatible resin is Evaloy HP4051, the flame retardant is diethyl aluminum hypophosphite or melamine cyanurate, the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the lubricant is erucamide.
In order to meet the requirement of-40 ℃, the formula selects a low-temperature compatilizer Evaloy HP4051 in raw materials, and the embrittlement temperature is lower than-50 ℃, so that the low-temperature performance is improved.
In order to meet the oil resistance at 60 ℃, an interpenetrating network polymer technology is adopted, and the cohesion of a sizing material system is improved.
To meet VW-1 burn grade, diethyl aluminum hypophosphite or melamine cyanurate was added. In addition, the lubricant is a low molecular organic substance, which reduces flame retardant performance and should be added in a controlled amount.
In order to meet the ageing resistance and tensile strength, the components of the polyurethane IPN polymer comprise tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and vinyl acetate EVA or styrene butadiene rubber SBS, the Ethylene Propylene Diene Monomer (EPDM) and the vinyl acetate EVA or styrene butadiene rubber SBS are mixed to enable the material to meet the ageing resistance and tensile strength, and simultaneously, the tetrahydrofuran THF and the toluene diisocyanate TDI are mixed to prepare the finally obtained rubber material to have the characteristics of wear resistance, oil resistance, good low temperature performance and high strength, so that the produced cable has excellent performance, has the characteristics of high tensile strength and high elongation at break, and also has the temperature resistance grade of-40-105 ℃ and the VW-1 combustion grade, and simultaneously meets the oil resistance requirement of UL 60 ℃.
Specifically, the high temperature irradiation resistant crosslinked TPU sheath material in this embodiment comprises the following components in parts by weight: 100 parts of polyurethane IPN polymer, 5 parts of compatilizer, 30 parts of flame retardant, 0.2 part of antioxidant and 1 part of lubricant. The polyurethane IPN polymer comprises tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and vinyl acetate EVA, and comprises the following components in percentage by weight: TDI: EPDM: eva=1: 1:2:2.
the application provides a preparation method of a high-temperature irradiation-resistant crosslinked TPU sheath material, which is shown in figure 1 and comprises the following steps:
s100, preparing a polyurethane IPN polymer, wherein the steps are as follows:
a. tetrahydrofuran THF, toluene diisocyanate TDI, vinyl acetate EVA and ethylene propylene ternary rubber EPDM are dissolved in an acetone solvent according to the proportion of 1:1:2:2, and fully stirred for 40-50 min at the rotating speed of 300-500 r/min to obtain a prepolymerization solution;
in this step, the mixture was sufficiently stirred at 500r/min for 50min so that the mixture was uniformly mixed in preparation for the subsequent reaction.
b. Adding a catalyst, heating to 50 ℃, and stirring at a low speed of 100-200 r/min for reaction for 6H;
the mixture was allowed to react well in this step by heating the catalyst and heating, and further by stirring at a low speed of 200r/min for 6H, the mixture was allowed to react well.
c. Adding deionized water and a blocking agent, stirring for 5-10 min at the rotating speed of 600-900r/min, stopping the reaction, and decompressing and evaporating acetone and water to obtain a polyurethane IPN polymer; preferably, the rotation speed in the step is 600r/min, and the reaction is stopped after stirring for 10 min. In the polycondensation reaction, the active functional groups are usually present at both ends of the polymer, and when the appropriate functional groups are present, the chain ends of the polymer molecules can still continue to participate in the reaction to increase the chain length, and in order to eliminate the activity of the end groups, the end group functional groups can be disappeared by adding an end capping agent, so that the reaction is stopped.
S200, weighing and mixing the polyurethane IPN polymer, the compatilizer and the lubricant according to the mass parts of the component proportions, and putting the mixture into an internal mixer for banburying;
s300, when the banburying temperature reaches 110 ℃, sweeping the internal mixer for one time, and simultaneously adding a flame retardant; the polyurethane IPN polymer and the compatilizer are uniformly mixed, and the flame retardant is better dispersed when the flame retardant is added, so that the excellent flame retardant property is ensured.
S400, when the banburying temperature reaches 140 ℃, conveying the mixture obtained by blending to a double-screw extruder for extrusion granulation to obtain TPU sheath sizing material;
s500, after the sizing material is extruded and molded, crosslinking is carried out by using an irradiation dose of 10Mrad, and the crosslinked TPU sheath material is obtained.
Extruding the obtained high-temperature-resistant irradiation crosslinking TPU sheath material into a cable wire through an extruder.
Example 2
100 parts of polyurethane IPN polymer, 5 parts of compatilizer, 30 parts of flame retardant, 0.2 part of antioxidant and 1 part of lubricant. The polyurethane IPN polymer comprises tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and styrene butadiene rubber SBS, and comprises the following components in percentage by weight: TDI: EPDM: sbs=1: 1:2:2.
in the step a of preparing the polyurethane IPN polymer, tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and styrene butadiene rubber (SBS) are dissolved in an acetone solvent according to the proportion of 1:1:2:2, and other steps are the same as in example 1, and the obtained high-temperature-resistant irradiation crosslinking TPU sheath material is extruded into a cable wire through an extruder.
Example 3
100 parts of polyurethane IPN polymer, 5 parts of compatilizer, 30 parts of flame retardant, 0.2 part of antioxidant and 1 part of lubricant. The polyurethane IPN polymer comprises tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and styrene butadiene rubber SBS, and comprises the following components in percentage by weight: TDI: EPDM: sbs=3: 3:2:2.
in the step a of preparing the polyurethane IPN polymer, tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and styrene butadiene rubber (SBS) are dissolved in an acetone solvent according to the ratio of 3:3:2:2, and the other steps are the same as in example 1, and the obtained high-temperature-resistant irradiation crosslinking TPU sheath material is extruded into a cable wire through an extruder.
Example 4
100 parts of polyurethane IPN polymer, 5 parts of compatilizer, 30 parts of flame retardant, 0.2 part of antioxidant and 1 part of lubricant. The polyurethane IPN polymer comprises tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and vinyl acetate EVA, and comprises the following components in percentage by weight: TDI: EPDM: eva=3: 3:2:2.
in the step a of preparing the polyurethane IPN polymer, tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and vinyl acetate EVA are dissolved in an acetone solvent according to the ratio of 3:3:2:2, and the other steps are the same as in example 1, and the obtained high-temperature-radiation-resistant crosslinked TPU sheath material is extruded into a cable wire through an extruder.
Example 5
100 parts of polyurethane IPN polymer, 5 parts of compatilizer, 30 parts of flame retardant, 0.2 part of antioxidant and 1 part of lubricant. The polyurethane IPN polymer comprises tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM), vinyl acetate EVA and styrene butadiene rubber SBS, and comprises the following components in percentage by weight: TDI: EPDM: EVA: sbs=1: 1:2:2:2.
in step a of preparing the polyurethane IPN polymer tetrahydrofuran THF, toluene diisocyanate TDI, ethylene propylene diene monomer EPDM, vinyl acetate EVA and styrene butadiene rubber SBS were mixed according to 1:1:2:2:2 in an acetone solvent, and the other steps are the same as in example 1, and the obtained high-temperature irradiation-resistant crosslinked TPU sheath material is extruded into a cable wire through an extruder.
Example 6
100 parts of polyurethane IPN polymer, 5 parts of compatilizer, 30 parts of flame retardant, 0.2 part of antioxidant and 1 part of lubricant. The polyurethane IPN polymer comprises tetrahydrofuran THF, toluene diisocyanate TDI and ethylene propylene diene monomer rubber EPDM, and comprises the following components in proportion: TDI: epdm=1: 1:2.
in step a of preparing the polyurethane IPN polymer tetrahydrofuran THF, toluene diisocyanate TDI, ethylene propylene diene rubber EPDM were prepared according to 1:1:2 in an acetone solvent, and the other steps are the same as in example 1, and the obtained high-temperature irradiation-resistant crosslinked TPU sheath material is extruded into a cable wire through an extruder.
Example 7
100 parts of polyurethane IPN polymer, 5 parts of compatilizer, 30 parts of flame retardant, 0.2 part of antioxidant and 1 part of lubricant. The polyurethane IPN polymer comprises tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and styrene butadiene rubber SBS, and comprises the following components in percentage by weight: TDI: sbs=1: 1:2:4.
in step a of preparing the polyurethane IPN polymer, tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and styrene butadiene rubber SBS are mixed according to the following ratio of 1:1:2:4 in an acetone solvent, and the other steps are the same as in example 1, and the obtained high-temperature irradiation-resistant crosslinked TPU sheath material is extruded into a cable wire through an extruder.
Example 8
100 parts of polyurethane IPN polymer, 5 parts of compatilizer, 30 parts of flame retardant, 0.2 part of antioxidant and 1 part of lubricant. The polyurethane IPN polymer comprises tetrahydrofuran THF, toluene diisocyanate TDI, ethylene propylene diene monomer EPDM and vinyl acetate EVA, and comprises the following components in percentage by weight: TDI: EPDM: eva=1: 1:2:4.
in step a of preparing the polyurethane IPN polymer tetrahydrofuran THF, toluene diisocyanate TDI, ethylene propylene diene rubber EPDM and vinyl acetate EVA were mixed according to 1:1:2:4 in an acetone solvent, and the other steps are the same as in example 1, and the obtained high-temperature irradiation-resistant crosslinked TPU sheath material is extruded into a cable wire through an extruder.
Table 1 below shows the proportions of the IPN polymer components of the high temperature radiation resistant crosslinked TPU sheathing compounds of examples 1 to 8:
| proportion of the mixture | THF | TDI | EVA | EPDM | SBS |
| Example 1 | 1 | 1 | 2 | 2 | - |
| Example 2 | 1 | 1 | - | 2 | 2 |
| Example 3 | 3 | 3 | - | 2 | 2 |
| Example 4 | 3 | 3 | 2 | 2 | - |
| Example 5 | 1 | 1 | 2 | 2 | 2 |
| Example 6 | 1 | 1 | - | 2 | - |
| Example 7 | 1 | 1 | - | 2 | 4 |
| Example 8 | 1 | 1 | 4 | 2 | - |
TABLE 1
The cable performance test results of examples 1 to 8 are shown in table 2 below.
TABLE 2
The cable performance test results of examples 1 to 8 and comparative examples are shown in Table 2.
As can be seen from comparison of the test results of examples 1, 2, 3 and 4, the higher the ratio of tetrahydrofuran THF to toluene diisocyanate TDI has an effect on polymerization, the poorer the ageing resistance of the cable, so the ratio of tetrahydrofuran THF to toluene diisocyanate TDI needs to be moderate;
from comparison of the test results of examples 1, 6, 7 and 8, it can be seen that the higher the proportion of the vinyl acetate EVA, the higher the tensile strength of the obtained rubber compound, and the ageing resistance is good, but the elongation is not qualified and the cold bending performance at-40 ℃ is not qualified, because the crosslinking degree of the vinyl acetate EVA and the styrene butadiene rubber SBS under irradiation is higher, the excessive content of the vinyl acetate EVA and the styrene butadiene rubber SBS can harden the rubber compound, and therefore, the elongation and the cold bending performance at-40 ℃ are not qualified. In example 6, the performances of the Ethylene Vinyl Acetate (EVA) and styrene butadiene rubber (SBS) are poor in all aspects when the EVA and SBS are not added, so that the advantages of high tensile strength and good ageing resistance of the EVA and SBS can be seen.
As can be seen from comparison of the test results of example 1, example 2, example 6, the ageing resistance of the cable is poor if at least two of the ethylene propylene diene monomer EPDM, the vinyl acetate EVA and the styrene butadiene rubber SBS are not mixed among the components of the polyurethane IPN polymer. According to the test results of example 1 and example 2, the use of one of ethylene-propylene-diene rubber EPDM mixed with vinyl acetate EVA and styrene-butadiene rubber SBS can satisfy tensile strength, elongation, low temperature resistance and high temperature aging resistance, while satisfying VW-1 combustion rating and oil resistance requirements at UL 60 ℃.
As can be seen from the comparison of the test results of the embodiment 1, the embodiment 2 and the embodiment 5, the ethylene-propylene ternary rubber EPDM, the vinyl acetate EVA and the styrene-butadiene rubber SBS are matched and mixed for use, so that the mechanical strength of the rubber material can be enhanced, and the ageing resistance can be improved. Thus, the formulations of example 1, example 2 and example 5 are all formulations meeting the product requirements. From the test results, it can be seen that the formulation of example 5 performs best, but for cost reasons, the most preferred formulations are those of example 1 and example 2, which can reduce cost while meeting the respective performance requirements.
The high-temperature irradiation-resistant crosslinked TPU sheath material obtained by the formula and the process has the characteristics of high tensile strength and high elongation at break, has a temperature resistance grade of-40-105 ℃ and a VW-1 combustion grade, and simultaneously meets the oil resistance requirement of UL 60 ℃.
The above-described embodiments do not limit the scope of the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the above embodiments should be included in the scope of the present invention.
Claims (6)
1. A preparation method of a high-temperature irradiation-resistant crosslinked TPU sheath material is characterized by comprising the following steps: comprises the following components in parts by weight: 90-100 parts of polyurethane IPN polymer, 5-10 parts of compatilizer, 20-40 parts of flame retardant, 0.1-0.2 part of antioxidant and 0.5-1 part of lubricant, wherein the components of the polyurethane IPN polymer comprise tetrahydrofuran THF, toluene diisocyanate TDI, ethylene Propylene Diene Monomer (EPDM) and at least one of vinyl acetate EVA and styrene butadiene rubber SBS, and the components are as follows: TDI: EPDM: (EVA and/or SBS) = (1-2): (2-3): 2;
the preparation method comprises the following steps:
s100, preparing a polyurethane IPN polymer, which comprises the following steps:
a. tetrahydrofuran THF, toluene diisocyanate TDI, ethylene propylene ternary rubber EPDM, (vinyl acetate EVA and/or styrene butadiene rubber SBS) are mixed according to the following ratio of (1-2) to (2-3): 2 are dissolved in an acetone solvent and fully stirred for 40 to 50 minutes at the rotating speed of 300 to 500r/min to obtain a prepolymerization solution;
b. adding a catalyst, heating to 50 ℃, and stirring at a low speed of 100-200 r/min for reaction for 6H;
c. adding deionized water and a blocking agent, stirring for 5-10 min at the rotating speed of 600-900r/min, stopping the reaction, and decompressing and evaporating acetone and water to obtain a polyurethane IPN polymer;
s200, weighing and mixing the polyurethane IPN polymer, the compatilizer, the antioxidant and the lubricant according to the mass parts of the component proportions, and putting the mixture into an internal mixer for banburying;
s300, when the banburying temperature reaches 110 ℃, sweeping the internal mixer for one time, and simultaneously adding a flame retardant;
s400, when the banburying temperature reaches 140 ℃, conveying the mixture obtained by blending to a double-screw extruder for extrusion granulation to obtain TPU sheath sizing material;
s500, after the sizing material is extruded and molded, crosslinking by using an irradiation dose of 10Mrad to obtain the high-temperature irradiation-resistant crosslinked TPU sheath material.
2. The method for preparing the high-temperature irradiation-resistant crosslinked TPU sheath material according to claim 1, which is characterized in that: the component of the compatilizer is Evaloy HP4051.
3. The method for preparing the high-temperature irradiation-resistant crosslinked TPU sheath material according to claim 1, which is characterized in that: the components of the flame retardant are diethyl aluminum hypophosphite or melamine cyanurate.
4. The method for preparing the high-temperature irradiation-resistant crosslinked TPU sheath material according to claim 1, which is characterized in that: the antioxidant comprises pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
5. The method for preparing the high-temperature irradiation-resistant crosslinked TPU sheath material according to claim 1, which is characterized in that: the lubricant component is erucamide.
6. A cable, characterized in that: the high-temperature-resistant irradiation crosslinking TPU sheath material prepared by the preparation method of claim 1.
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