CN115109363B - High-toughness plastic master batch for optical cable - Google Patents
High-toughness plastic master batch for optical cable Download PDFInfo
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- CN115109363B CN115109363B CN202210963766.4A CN202210963766A CN115109363B CN 115109363 B CN115109363 B CN 115109363B CN 202210963766 A CN202210963766 A CN 202210963766A CN 115109363 B CN115109363 B CN 115109363B
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- 239000004033 plastic Substances 0.000 title claims abstract description 44
- 229920003023 plastic Polymers 0.000 title claims abstract description 44
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 41
- 230000003287 optical effect Effects 0.000 title claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- -1 polysiloxane Polymers 0.000 claims abstract description 53
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 48
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 42
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 38
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 30
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 30
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 27
- 239000004593 Epoxy Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 22
- 238000006068 polycondensation reaction Methods 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- ACECBHHKGNTVPB-UHFFFAOYSA-N silylformic acid Chemical compound OC([SiH3])=O ACECBHHKGNTVPB-UHFFFAOYSA-N 0.000 claims description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003729 cation exchange resin Substances 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- 125000003700 epoxy group Chemical group 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 239000000945 filler Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 7
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 7
- 239000001257 hydrogen Chemical group 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- LRWGOVMIZOIYFL-UHFFFAOYSA-N oxolan-2-ylidenemethanone Chemical compound O=C=C1CCCO1 LRWGOVMIZOIYFL-UHFFFAOYSA-N 0.000 description 3
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- YENOLDYITNSPMQ-UHFFFAOYSA-N carboxysilicon Chemical compound OC([Si])=O YENOLDYITNSPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2207/00—Foams characterised by their intended use
- C08J2207/06—Electrical wire insulation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use 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; Derivatives of such polymers
- C08J2427/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a high-toughness plastic master batch for an optical cable, and belongs to the technical field of cable materials. The plastic master batch consists of tetrafluoroethylene-acrylic acid copolymer, carboxyl modified polysiloxane, nano silicon dioxide, epoxy silane coupling agent and dispersing agent, wherein the epoxy silane coupling agent carries out surface modification on the nano silicon dioxide, meanwhile, epoxy groups in the epoxy silane coupling agent react with carboxyl on the tetrafluoroethylene-acrylic acid copolymer and carboxyl modified polysiloxane side chains to uniformly disperse the nano silicon dioxide between a macromolecular chain tetrafluoroethylene-acrylic acid copolymer and the carboxyl modified polysiloxane.
Description
Technical Field
The invention belongs to the technical field of cable materials, and relates to a high-toughness plastic master batch for an optical cable.
Background
The optical cable is an integrated transmission medium organically combining an optical fiber unit and a metal wire, is a cable similar to a rope and is formed by twisting a plurality of wires or groups of wires, wherein each group of wires are mutually insulated and are often twisted around a center, the whole outside of the cable is covered with a high-insulation covering layer, the cable has the characteristics of inner electrifying and outer insulating, and is made of one or more mutually insulated conductors and an outer insulating protective layer, and electric power or information is transmitted from one wire to the other wire; and along with the improvement of electric automation degree, the occasion that equipment unit needs back and forth movement is also more and more, because the inside PP material that fills of cable, PP material self mechanical properties is general, after the cable receives the exogenic action, takes place to buckle the inside PP material that fills of cable and appears breaking and produce the gap, leads to the cable core unstable, and then has reduced the life of cable. The main base material of the cable material is PVC plastic, but because the PVC plastic contains chlorine element, a large amount of toxic dense smoke and corrosive gas are easily generated in the combustion process to pollute the environment. In recent years, TPE materials have been widely used for preparing cable materials due to their weather resistance, aging resistance, heat resistance, high elasticity, environmental protection and recycling properties, but because TPE materials themselves have low toughness, fillers are required to be added to increase toughness, and generally inorganic fillers have poor dispersion properties in TPE materials, the toughness is still further improved.
Patent publication number CN114530281a discloses a flexible cable resistant to bending and a production process thereof, the cable comprises a plurality of conductors which are sequentially arranged from inside to outside, an insulating layer is wrapped outside the conductors, a wrapping tape layer is arranged outside the insulating layer, a filler is arranged between the wrapping tape layer and the insulating layer, and an outer sheath is arranged outside the wrapping tape layer; the modified PP material molecular chain contains flexible methylene chain links, the methylene chain links have good flexibility, so that the flexibility of the filler is improved, the modified PP material molecular chain contains a large number of hydroxyl groups and carbonyl groups, hydrogen bonds can be formed between the hydroxyl groups and the hydroxyl groups, the hydrogen bonds between the carbonyl groups and the hydroxyl groups can be formed, the hydrogen bonds in the modified PP material molecule can be improved, when the cable is subjected to bending acting force, the intramolecular hydrogen bonds are broken, acting force is counteracted, the toughness of the filler is improved, meanwhile, the hydrogen bonds can be recombined, and the toughness of the flexible cable is further guaranteed. The technical scheme of the invention is to increase the toughness of the cable by modifying the high-content hydrogen bond in the PP material molecule.
Patent CN113963848A discloses a preparation process of a light high-flexibility wear-resistant cable for a mobile power generation vehicle, and belongs to the technical field of cable manufacturing. And the preparation process comprises the following steps: the method comprises the following steps: step one, twisting a conductor; step two, preparing an insulated conductor; and thirdly, forming the cable. According to the invention, the modified organic silicon polyimide copolymer is added into the raw materials of the TPE cable material, so that the wear resistance of the TPE cable material is enhanced, the filler is replaced, and the increase of the specific gravity of the cable caused by the filler is avoided. And the modified organosilicon polyimide copolymer is introduced with the bisepoxy end-capped polysilsesquioxane, so that on one hand, the cage structure of the polysilsesquioxane is introduced, the wear resistance, high temperature resistance and flame retardance of the organosilicon-polyimide are further enhanced, and on the other hand, the crosslinking degree of the polymer is improved and the heat resistance and tensile strength of the polymer are improved through the introduction of epoxy groups. The technical scheme of the invention is that the wear resistance, high temperature resistance and flame retardance of the organosilicon-polyimide are enhanced through the cage structure of polysilsesquioxane, and the heat resistance and tensile strength of the polymer are further enhanced through improving the crosslinking degree of the polymer through epoxy groups.
Patent CN110862667A discloses an easily dispersible master batch with high content, and a preparation method and application thereof. The master batch comprises the following components in parts by weight: 2-20 parts of carrier, 80-98 parts of filler, 2-5 parts of dispersing agent, 0.1-2 parts of coupling agent, 0.1-2 parts of surfactant and 1-9 parts of antibacterial agent; wherein the carrier comprises polyethylene glycol and/or polyvinylpyrrolidone, and the size of the filler is micron-sized and/or below micron-sized. The technical scheme of the invention is that the prepared plastic master batch can be well fused with most polymer resins by utilizing the high viscosity and good resin affinity of polyvinylpyrrolidone.
The technical scheme that the epoxy group in the epoxy group silane coupling agent reacts with the tetrafluoroethylene-acrylic acid copolymer and carboxyl on the side chain of carboxyl modified polysiloxane to uniformly disperse the nano silicon dioxide between the macromolecular chain tetrafluoroethylene-acrylic acid copolymer and the carboxyl modified polysiloxane so that the nano silicon dioxide filled in the plastic master batch is highly dispersed in the resin carrier tetrafluoroethylene-acrylic acid copolymer and the carboxyl modified polysiloxane to enhance the toughness of the plastic master batch is not disclosed in the prior art.
Disclosure of Invention
The invention aims to provide a high-toughness plastic master batch for a photoelectric cable, which consists of tetrafluoroethylene-acrylic acid copolymer, carboxyl modified polysiloxane, nano silicon dioxide, epoxy silane coupling agent and dispersing agent, wherein the epoxy silane coupling agent is used for carrying out surface modification on the nano silicon dioxide, meanwhile, epoxy groups in the epoxy silane coupling agent are reacted with carboxyl on a tetrafluoroethylene-acrylic acid copolymer and carboxyl modified polysiloxane side chain to uniformly disperse the nano silicon dioxide between a macromolecular chain tetrafluoroethylene-acrylic acid copolymer and the carboxyl modified polysiloxane, and the filler nano silicon dioxide in the plastic master batch is highly dispersed in a resin carrier tetrafluoroethylene-acrylic acid copolymer and the carboxyl modified polysiloxane and can be used for preparing high-toughness plastic for the photoelectric cable.
The aim of the invention can be achieved by the following technical scheme:
a high-toughness plastic master batch for optical cables is composed of tetrafluoroethylene-acrylic acid copolymer, carboxyl modified polysiloxane, nano silicon dioxide, epoxy silane coupling agent and dispersing agent.
As a preferable technical scheme of the invention, the plastic master batch consists of 5-10 parts by weight of tetrafluoroethylene-acrylic acid copolymer, 5-10 parts by weight of carboxyl modified polysiloxane, 65-85 parts by weight of nano silicon dioxide, 0.5-2 parts by weight of epoxy silane coupling agent and 3-5 parts by weight of dispersing agent.
As a preferable technical scheme of the invention, the dispersing agent is any one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium stearate.
As a preferred technical scheme of the invention, the preparation method of the carboxyl modified polysiloxane comprises the following steps:
(1) Mixing and polycondensing dimethyl siloxane mixed ring, end sealing agent, carboxyl silane coupling agent and acid cation exchange resin in a container, and performing polycondensation reaction to obtain a polycondensation reaction product;
(2) And (3) carrying out reduced pressure distillation on the polycondensation reaction product, ending distillation after the quality is constant, and cooling to obtain the carboxyl modified polysiloxane.
As a preferable technical scheme of the invention, the sealing agent is hexamethyldisiloxane.
As a preferable technical scheme of the invention, the carboxyl silane coupling agent has the structure (OMe) 3 Si(CH 2 ) 2 NHCONH(CH 2 ) 2 (EO) m COOH or (OEt) 3 Si(CH 2 ) 2 NHCONH(CH 2 ) 2 (EO) m COOH, wherein m is not less than 3.
As a preferable technical scheme of the invention, the polycondensation reaction temperature is 80-150 ℃.
As a preferable technical scheme of the invention, the polycondensation reaction time is 2-4 h.
The preparation method of the high-toughness plastic master batch for the optical cable comprises the following steps of:
adding tetrafluoroethylene-acrylic acid copolymer, carboxyl modified polysiloxane and dispersing agent into organic solvent, stirring and mixing uniformly to obtain dispersion liquid, adding epoxy silane coupling agent into the dispersion liquid, heating to 90-120 ℃ for reaction for 50-80 min, cooling to 40-60 ℃, adding nano silicon dioxide, stirring uniformly to form slurry, drying the slurry to obtain paste, and carrying out single-screw cutting granulation and drying treatment on the paste to obtain the plastic master batch for the optical cable.
As a preferable technical scheme of the invention, the organic solvent is acetone or tetrahydrofuran.
The invention has the beneficial effects that:
(1) The epoxy silane coupling agent carries out surface modification on the nano silicon dioxide, so that the nano silicon dioxide filler is well dispersed in a resin carrier;
(2) The epoxy group in the epoxy group silane coupling agent reacts with the tetrafluoroethylene-acrylic acid copolymer and carboxyl on the side chain of carboxyl modified polysiloxane, nano silicon dioxide is further and evenly dispersed between the macromolecular chain tetrafluoroethylene-acrylic acid copolymer and the carboxyl modified polysiloxane, and the filler nano silicon dioxide in the plastic master batch is highly dispersed in the resin carrier tetrafluoroethylene-acrylic acid copolymer and the carboxyl modified polysiloxane, so that the epoxy group silane coupling agent can be used for preparing high-toughness plastics for optical cables.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description will refer to the specific embodiments, structures, features and effects according to the present invention in conjunction with examples.
Example 1
The high-toughness plastic master batch for the optical cable consists of 6 parts by weight of tetrafluoroethylene-acrylic acid copolymer, 9 parts by weight of carboxyl modified polysiloxane, 72 parts by weight of nano silicon dioxide, 1 part by weight of epoxy silane coupling agent and 4 parts by weight of dispersing agent sodium dodecyl benzene sulfonate.
The preparation method of the carboxyl modified polysiloxane comprises the following steps:
(1) 65 parts by weight of dimethyl siloxane mixed ring, 10 parts by weight of sealing agent hexamethyldisiloxane and 35 parts by weight of carboxyl silane coupling agent (OEt) 3 Si(CH 2 ) 2 NHCONH(CH 2 ) 2 (EO) 4 Mixing and polycondensing COOH and 18 parts by weight of acid cation exchange resin at 120 ℃ for 2 hours, and obtaining a polycondensation reaction product through polycondensation reaction;
(2) And (3) carrying out reduced pressure distillation on the polycondensation reaction product, ending distillation after the quality is constant, and cooling to obtain the carboxyl modified polysiloxane.
The preparation method of the high-toughness plastic master batch for the optical cable comprises the following steps of:
adding tetrafluoroethylene-acrylic acid copolymer, carboxyl modified polysiloxane and dispersing agent into tetrahydrofuran ketone as organic solvent, stirring and mixing uniformly to obtain dispersion liquid, adding epoxy silane coupling agent into the dispersion liquid, heating to 100 ℃ for reaction for 60min, cooling to 50 ℃, adding nano silicon dioxide, stirring uniformly to form slurry, drying the slurry to obtain paste, and carrying out single-screw cutting granulation and drying treatment on the paste to obtain the plastic master batch for the optical cable.
Example 2
The high-toughness plastic master batch for the optical cable consists of 8 parts by weight of tetrafluoroethylene-acrylic acid copolymer, 5 parts by weight of carboxyl modified polysiloxane, 70 parts by weight of nano silicon dioxide, 1.2 parts by weight of epoxy silane coupling agent and 5 parts by weight of dispersing agent sodium dodecyl benzene sulfonate.
The preparation method of the carboxyl modified polysiloxane comprises the following steps:
(1) Mixing 55 parts by weight of dimethyl siloxane mixed ring body and 8 parts by weight of end capping agent hexamethylDisiloxane, 33 parts by weight of a carboxy silane coupling agent (OMe) 3 Si(CH 2 ) 2 NHCONH(CH 2 ) 2 (EO) 3 Mixing and polycondensing COOH and 14 parts by weight of acid cation exchange resin at 90 ℃ for 3 hours, and obtaining a polycondensation reaction product through polycondensation reaction;
(2) And (3) carrying out reduced pressure distillation on the polycondensation reaction product, ending distillation after the quality is constant, and cooling to obtain the carboxyl modified polysiloxane.
The preparation method of the high-toughness plastic master batch for the optical cable comprises the following steps of:
adding tetrafluoroethylene-acrylic acid copolymer, carboxyl modified polysiloxane and dispersing agent into organic solvent acetone, stirring and mixing uniformly to obtain dispersion liquid, adding epoxy silane coupling agent into the dispersion liquid, heating to 96 ℃ for reaction for 58min, cooling to 45 ℃, adding nano silicon dioxide, stirring uniformly to form slurry, drying the slurry to obtain paste, and carrying out single-screw cutting granulation and drying treatment on the paste to obtain the plastic master batch for the optical cable.
Example 3
The high-toughness plastic master batch for the optical cable comprises 10 parts by weight of tetrafluoroethylene-acrylic acid copolymer, 7 parts by weight of carboxyl modified polysiloxane, 80 parts by weight of nano silicon dioxide, 0.9 part by weight of epoxy silane coupling agent and 5 parts by weight of dispersing agent sodium stearate.
The preparation method of the carboxyl modified polysiloxane comprises the following steps:
(1) 72 parts by weight of dimethylsiloxane hybrid ring, 8 parts by weight of sealing agent hexamethyldisiloxane, 42 parts by weight of carboxyl silane coupling agent (OMe) 3 Si(CH 2 ) 2 NHCONH(CH 2 ) 2 (EO) 5 Mixing and polycondensing COOH and 16 parts by weight of acid cation exchange resin at 100 ℃ for 2 hours, and obtaining a polycondensation reaction product through polycondensation reaction;
(2) And (3) carrying out reduced pressure distillation on the polycondensation reaction product, ending distillation after the quality is constant, and cooling to obtain the carboxyl modified polysiloxane.
The preparation method of the high-toughness plastic master batch for the optical cable comprises the following steps of:
adding tetrafluoroethylene-acrylic acid copolymer, carboxyl modified polysiloxane and dispersing agent into organic solvent acetone, stirring and mixing uniformly to obtain dispersion liquid, adding epoxy silane coupling agent into the dispersion liquid, heating to 96 ℃ for reaction for 58min, cooling to 45 ℃, adding nano silicon dioxide, stirring uniformly to form slurry, drying the slurry to obtain paste, and carrying out single-screw cutting granulation and drying treatment on the paste to obtain the plastic master batch for the optical cable.
Example 4
The high-toughness plastic master batch for the optical cable consists of 5 parts by weight of tetrafluoroethylene-acrylic copolymer, 10 parts by weight of carboxyl modified polysiloxane, 77 parts by weight of nano silicon dioxide, 0.9 part by weight of epoxy silane coupling agent and 3 parts by weight of dispersing agent sodium stearate.
The preparation method of the carboxyl modified polysiloxane comprises the following steps:
(1) Mixing 56 parts by weight of dimethyl siloxane mixed ring, 8 parts by weight of sealing agent hexamethyldisiloxane and 35 parts by weight of carboxyl silane coupling agent (OMe) 3 Si(CH 2 ) 2 NHCONH(CH 2 ) 2 (EO) 4 Mixing and polycondensing COOH and 11 parts by weight of acid cation exchange resin for 4 hours at the temperature of 120 ℃ to obtain a polycondensation reaction product;
(2) And (3) carrying out reduced pressure distillation on the polycondensation reaction product, ending distillation after the quality is constant, and cooling to obtain the carboxyl modified polysiloxane.
The preparation method of the high-toughness plastic master batch for the optical cable comprises the following steps of:
adding tetrafluoroethylene-acrylic acid copolymer, carboxyl modified polysiloxane and dispersing agent into tetrahydrofuran as organic solvent, stirring and mixing uniformly to obtain dispersion liquid, adding epoxy silane coupling agent into the dispersion liquid, heating to 110 ℃ for reaction for 60min, cooling to 55 ℃, adding nano silicon dioxide, stirring uniformly to form slurry, drying the slurry to obtain paste, and carrying out single-screw cutting granulation and drying treatment on the paste to obtain the plastic master batch for the optical cable.
Comparative example 1
A high-toughness plastic master batch for an optical cable is composed of 15 parts by weight of tetrafluoroethylene-acrylic acid copolymer, 72 parts by weight of nano silicon dioxide, 1 part by weight of epoxy silane coupling agent and 4 parts by weight of dispersing agent sodium dodecyl benzene sulfonate.
The preparation method of the high-toughness plastic master batch for the optical cable comprises the following steps of:
adding tetrafluoroethylene-acrylic acid copolymer and a dispersing agent into tetrahydrofuran ketone serving as an organic solvent, stirring and mixing uniformly to obtain a dispersion liquid, adding an epoxy silane coupling agent into the dispersion liquid, heating to 100 ℃ for reaction for 60min, cooling to 50 ℃, adding nano silicon dioxide, stirring uniformly to form slurry, drying the slurry to obtain a paste, and carrying out single-screw cutting granulation and drying treatment on the paste to obtain the plastic master batch for the optical cable.
Comparative example 2
The high-toughness plastic master batch for the optical cable consists of 15 parts by weight of carboxyl modified polysiloxane, 72 parts by weight of nano silicon dioxide, 1 part by weight of epoxy silane coupling agent and 4 parts by weight of dispersing agent sodium dodecyl benzene sulfonate.
The preparation method of the carboxyl modified polysiloxane comprises the following steps:
(1) 65 parts by weight of dimethyl siloxane mixed ring, 10 parts by weight of sealing agent hexamethyldisiloxane and 35 parts by weight of carboxyl silane coupling agent (OEt) 3 Si(CH 2 ) 2 NHCONH(CH 2 ) 2 (EO) 4 Mixing and polycondensing COOH and 18 parts by weight of acid cation exchange resin at 120 ℃ for 2 hours, and obtaining a polycondensation reaction product through polycondensation reaction;
(2) And (3) carrying out reduced pressure distillation on the polycondensation reaction product, ending distillation after the quality is constant, and cooling to obtain the carboxyl modified polysiloxane.
The preparation method of the high-toughness plastic master batch for the optical cable comprises the following steps of:
adding carboxyl modified polysiloxane and a dispersing agent into tetrahydrofuran ketone serving as an organic solvent, stirring and mixing uniformly to obtain a dispersion liquid, adding an epoxy silane coupling agent into the dispersion liquid, heating to 100 ℃ for reaction for 60min, cooling to 50 ℃, adding nano silicon dioxide, stirring uniformly to form slurry, drying the slurry to obtain a paste, and carrying out single-screw cutting granulation and drying treatment on the paste to obtain the plastic master batch for the optical cable.
Performance testing
The plastic master batches prepared in examples 1 to 4 and comparative examples 1 to 2 were molded with a matrix resin polyvinyl chloride to prepare a material for optical cables, and then the tensile yield strength and the maximum traction load test strength of the material for optical cables were tested according to GB/T8804.1-2003, with the results shown in Table 1 below:
table 1 toughness test results of materials for optical cables
From the test results in table 1, it is clear that comparative example 1, in which carboxyl-modified polysiloxane was replaced with an equivalent amount of tetrafluoroethylene-acrylic copolymer based on example 1, resulted in a material for optical cable having significantly lower tensile yield strength and maximum traction load than example 1; comparative example 2 the tetrafluoroethylene-acrylic copolymer was replaced by an equivalent amount of carboxy-modified polysiloxane based on example 1, and the resulting material for optical cable had significantly lower tensile yield strength and maximum traction load than example 1.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (5)
1. The high-toughness plastic master batch for the optical cable is characterized by comprising 5-10 parts by weight of tetrafluoroethylene-acrylic acid copolymer, 5-10 parts by weight of carboxyl modified polysiloxane, 65-85 parts by weight of nano silicon dioxide, 0.5-2 parts by weight of epoxy silane coupling agent and 3-5 parts by weight of dispersing agent;
the preparation method of the carboxyl modified polysiloxane comprises the following steps:
(1) Mixing and polycondensing dimethyl siloxane mixed ring, end sealing agent, carboxyl silane coupling agent and acid cation exchange resin in a container, and performing polycondensation reaction to obtain a polycondensation reaction product;
(2) Distilling the polycondensation reaction product under reduced pressure, ending the distillation after the quality is constant, and cooling to obtain carboxyl modified polysiloxane; the end sealing agent is hexamethyldisiloxane; the carboxyl silane coupling agent has the structure (OMe) 3 Si(CH 2 ) 2 NHCONH(CH 2 ) 2 (EO) m COOH or
(OEt) 3 Si(CH 2 ) 2 NHCONH(CH 2 ) 2 (EO) m COOH, wherein m is not less than 3;
the adding amounts of the dimethylsiloxane mixed ring body, the end enclosure agent, the carboxyl silane coupling agent and the acidic cation exchange resin in the step (1) are respectively as follows: 50-80 parts by weight of dimethyl siloxane mixed ring, 6-12 parts by weight of sealing agent, 30-50 parts by weight of carboxyl silane coupling agent and 10-20 parts by weight of acid cation exchange resin.
2. The high-toughness plastic master batch for the optical cable according to claim 1, wherein the dispersing agent is any one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium stearate.
3. The high-toughness plastic master batch for optical cables according to claim 1, wherein the polycondensation reaction temperature is 80-150 ℃, and the polycondensation reaction time is 2-4 h.
4. A method for preparing the high-toughness plastic master batch for optical cables according to any one of claims 1 to 3, wherein the preparation method comprises the following steps:
adding tetrafluoroethylene-acrylic acid copolymer, carboxyl modified polysiloxane and dispersing agent into organic solvent, stirring and mixing uniformly to obtain dispersion liquid, adding epoxy silane coupling agent into the dispersion liquid, heating to 90-120 ℃ for reaction for 50-80 min, cooling to 40-60 ℃, adding nano silicon dioxide, stirring uniformly to form slurry, drying the slurry to obtain paste, and carrying out single-screw cutting granulation and drying treatment on the paste to obtain the plastic master batch for the optical cable.
5. The method for preparing high-toughness plastic master batch for optical cables according to claim 4, wherein the organic solvent is acetone or tetrahydrofuran.
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| JP2003322776A (en) * | 2002-05-01 | 2003-11-14 | Mitsubishi Rayon Co Ltd | Optical fiber cable and optical fiber cable with plug |
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| CN113788959A (en) * | 2018-12-28 | 2021-12-14 | 浙江深蓝新材料科技有限公司 | Preparation method of organic silicon emulsion |
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|---|---|---|---|---|
| JP2003322776A (en) * | 2002-05-01 | 2003-11-14 | Mitsubishi Rayon Co Ltd | Optical fiber cable and optical fiber cable with plug |
| CN103113668A (en) * | 2013-01-07 | 2013-05-22 | 安邦电气集团有限公司 | Polymer matrix conductive composite material and method for preparing temperature self-limiting heat tracing cable from same |
| CN106987055A (en) * | 2017-05-12 | 2017-07-28 | 安徽哈雷传动机械有限公司 | The production method of speed changer sliding block material graphene modified polypropene |
| CN113788959A (en) * | 2018-12-28 | 2021-12-14 | 浙江深蓝新材料科技有限公司 | Preparation method of organic silicon emulsion |
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Denomination of invention: A high toughness plastic masterbatch for optical cables Granted publication date: 20230428 Pledgee: Ma'anshan branch of Bank of China Ltd. Pledgor: ANHUI JIUNIU PLASTIC INDUSTRY TECHNOLOGY CO.,LTD. Registration number: Y2024980006915 |