CN115612279A - TPU (thermoplastic polyurethane) foaming composite material for communication cable/optical cable and preparation method thereof - Google Patents
TPU (thermoplastic polyurethane) foaming composite material for communication cable/optical cable and preparation method thereof Download PDFInfo
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- CN115612279A CN115612279A CN202211308394.8A CN202211308394A CN115612279A CN 115612279 A CN115612279 A CN 115612279A CN 202211308394 A CN202211308394 A CN 202211308394A CN 115612279 A CN115612279 A CN 115612279A
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 47
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000004891 communication Methods 0.000 title claims abstract description 27
- 230000003287 optical effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000005187 foaming Methods 0.000 title claims description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- -1 dimethyl siloxane Chemical class 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229920002635 polyurethane Polymers 0.000 claims description 56
- 239000004814 polyurethane Substances 0.000 claims description 56
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 239000004970 Chain extender Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000007731 hot pressing Methods 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 230000002209 hydrophobic effect Effects 0.000 abstract description 8
- 229920001971 elastomer Polymers 0.000 abstract description 4
- 229910018557 Si O Inorganic materials 0.000 abstract description 2
- 238000007385 chemical modification Methods 0.000 abstract description 2
- 239000000806 elastomer Substances 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000012948 isocyanate Substances 0.000 description 12
- 150000002513 isocyanates Chemical class 0.000 description 12
- 238000002493 microarray Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 208000005156 Dehydration Diseases 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000004927 clay Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
- C08K3/346—Clay
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/00—Use of pretreated ingredients
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention belongs to the technical field of TPU composite materials, and relates to a TPU foamed composite material for a communication cable/optical cable and a preparation method thereof. The invention uses the hydroxyl-terminated dimethyl siloxane with Si-O bond as a soft segment to ensure that the prepared thermoplastic polyurethane elastomer has certain hydrophobic property. The surface of the nanoparticle contains abundant hydroxyl groups, so that chemical modification is easy to realize, and in addition, the surface area is larger due to the nanometer and submicron scale, the hardness is high, the strength and the toughness of the blend can be ensured, and the new performance of the material can be endowed to realize multipotency.
Description
Technical Field
The invention belongs to the technical field of TPU composite materials, and relates to a TPU foamed composite material for a communication cable/optical cable and a preparation method thereof.
Background
China is the largest cable demand country and production country in the world. The wire and cable industry in China is one of the largest matching industries of national economy, and in recent years, along with the rapid growth of the national economy and the acceleration of industrialization and urbanization processes, the wire and cable industry in China generally keeps a stable growth situation, the overall development foundation of the industry is enhanced, and the comprehensive strength is further improved. The sales income of the wire and cable industry in China in 2020 is 10769 hundred million yuan, which is increased by about 5% in 2019.
The polyurethane material has the properties of higher tensile strength, excellent wear resistance, resistance to oil corrosion, resistance to electron irradiation and the like, and is widely applied to the fields of chemical engineering, light industry, construction, household appliances, transportation and the like, wherein the polyurethane has the following advantages when being used as a sheath of a communication cable and an optical cable: 1. compared with the traditional polyvinyl chloride, rubber, polyethylene and the like, the cable is easy to reduce in performance due to aging of various environmental factors, and has good weather resistance; 2. the polyurethane has the characteristics of softness, wear resistance and the like, and meanwhile, the strength of the polyurethane is higher than that of a rubber material, and meanwhile, the processing technology is simple; 3. has excellent adhesion to various other cable materials.
However, the communication cable has a very complex service environment, and is inevitably affected by various environmental factors, such as water, ultraviolet rays and the like, which shorten the service life of the polyurethane cable, so it is very important to develop a hydrophobic multifunctional TPU material.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a TPU foamed composite material with a microarray structure on the surface and good hydrophobicity for communication cables/optical cables.
The purpose of the invention can be realized by the following technical scheme:
a TPU foamed composite material for communication cables/optical cables comprises the following raw materials in parts by mass: 5-30 parts of polyurethane/reactive inorganic nanoparticle pre-dispersion, 30-50 parts of polyurethane thermoplastic elastomer and 0.01-0.05 part of antioxidant.
In the above TPU foamed composite material for communication cables/optical cables, the preparation method of the pre-dispersion of polyurethane/reactive inorganic nanoparticles specifically comprises the following steps:
s1, drying inorganic nano particles, then adding an aminosilane coupling agent and ethanol, mixing uniformly, and adding N 2 Carrying out condensation circulation in the atmosphere, and obtaining reactive inorganic nanoparticles through decompression suction filtration and centrifugal washing;
s2, uniformly dispersing the reactive inorganic nanoparticles in a THF solution containing a polyurethane thermoplastic elastomer by ultrasonic waves, and then drying to obtain a pre-dispersion of polyurethane/reactive inorganic nanoparticles.
In the TPU foamed composite material for a communication cable/optical cable described above, the inorganic nanoparticles include at least one of mesoporous silica, zinc oxide, titanium dioxide, expandable graphene, montmorillonite, and boehmite.
In the TPU foamed composite material for the communication cable/optical cable, the temperature in the condensation circulation process of the step S1 is 75-85 ℃, and the time is 10-20h.
In the TPU foamed composite material for communication cable/optical cable described above, the mass ratio of the reactive inorganic nanoparticles of step S2 to the THF solution containing the polyurethane thermoplastic elastomer is 1: (5-10).
In the above-mentioned one TPU foamed composite material for communication cable/optical cable, the THF solution in step S2 contains 20 to 25wt% of the polyurethane thermoplastic elastomer.
In the TPU foamed composite material for communication cables/optical cables, the preparation of the polyurethane thermoplastic elastomer specifically comprises the following steps: and (2) drying the hydroxyl-terminated dimethyl siloxane, the chain extender and the curing agent, then adding the chain extender, the catalyst and the curing agent (TDI), uniformly mixing, and pouring into a polytetrafluoroethylene mold for curing to obtain the polyurethane thermoplastic elastomer.
The invention also provides a preparation method of the TPU foamed composite material for the communication cable/optical cable, which comprises the following steps:
s1, preparing the raw material of claim 1;
s2, melting and blending the polyurethane thermoplastic elastomer, the polyurethane/reactive inorganic nanoparticle pre-dispersion and the antioxidant, and then carrying out hot pressing to obtain a prefabricated plate;
s3, carrying out hot pressing on the prefabricated plate and the metal net to obtain a foamed plate;
and S4, placing the foamed plate in a supercritical gas foaming kettle for pressure preservation, and finally removing the metal mesh to obtain the TPU foamed composite material.
The invention uses the hydroxyl-terminated dimethyl siloxane with Si-O bond as a soft segment to ensure that the prepared thermoplastic polyurethane elastomer has certain hydrophobic property. The surface of the nanoparticle contains abundant hydroxyl groups, so that chemical modification is easy to realize, and in addition, the surface area is larger due to the nanometer and submicron scale, the hardness is high, the strength and the toughness of the blend can be ensured, and the new performance of the material can be endowed to realize multipotency. The characteristic that amino can react with-NCO in polyurethane is utilized, the amino on the inorganic nano particles is modified and grafted by a coupling method to have reactivity, and meanwhile, the reactive inorganic nano particles can be uniformly dispersed in TPU under the condition of high filler by adopting a solution pre-dispersion method, so that the mechanical property of the TPU is enhanced, and the functionalization is realized at the same time. In addition, the inorganic nano particles can also be used as a nucleating agent, the foaming performance of the TPU is greatly improved, and the hydrophobic performance of the material is further improved by the rough surface in cooperation with a micro-array structure brought by the combination of a metal mesh and foaming.
In the preparation method of the TPU foamed composite material for the communication cable/optical cable, the melting and blending temperature of the step S2 is 110-130 ℃, and the time is 15-30min.
In the preparation method of the TPU foamed composite material for the communication cable/optical cable, the pressure in the supercritical gas foaming kettle in the step S4 is maintained for 1-2 hours at 70-85 ℃ and 10-15 MPa.
Compared with the prior art, the invention has the following beneficial effects: the composite material disclosed by the invention realizes multiple functions by changing the types of inorganic nano particles, can meet the requirements of various performances, has good long-acting hydrophobic performance due to the rough structure, and has good heat insulation performance due to the closed structure generated by foaming.
Drawings
Fig. 1 shows an SEM image of the thermoplastic elastomer cable material prepared in example 1.
Fig. 2 shows the water contact angle of the surface of the thermoplastic elastomer cable material in example 1.
Fig. 3 shows the water contact angle of the surface of the thermoplastic elastomer cable material in comparative example 1.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1:
s1, adding 100g of isocyanate into a three-neck flask, and vacuumizing for 1-2 hours in an ice-water bath; respectively weighing 10g of chain extender and 10g of hydroxyl-terminated dimethyl siloxane for dehydration treatment at 80 ℃. After moisture is fully extracted, the processed isocyanate, chain extender and hydroxyl-terminated dimethyl siloxane are placed in a vacuum oven to react for 6 hours at 80 ℃ to obtain a polyurethane thermoplastic elastomer;
s2, placing 1.5g of mesoporous silica in a vacuum oven at 85 ℃ for drying for 8 hours, after dewatering, uniformly mixing the mesoporous silica with 3ml of KH550 and 150ml of ethanol, and adding N 2 Condensing and circulating for 20h at 75 ℃ in the atmosphere, then carrying out reduced pressure suction filtration, and centrifugally washing to remove unreacted aminosilane coupling agent to obtain reactive mesoporous silica;
s3, uniformly dispersing 1.5g of reactive mesoporous silica in 10g of THF (tetrahydrofuran) solution containing 25wt% of the polyurethane thermoplastic elastomer prepared in the step S1 by ultrasonic waves, volatilizing most of solvent, and drying in a vacuum oven at 65 ℃ for 20 hours to obtain a pre-dispersion of polyurethane/reactive inorganic nanoparticles;
s4, carrying out melt blending on 36g of polyurethane prepared in the step S1 and a pre-dispersion prepared from 4g of S3 and 0.02g of antioxidant 168 at 130 ℃ for 20min, and carrying out hot pressing under the conditions of 140 ℃ and 10MPa to prepare a prefabricated plate;
s5, carrying out hot pressing on the prefabricated plate and the metal net to obtain a foamed plate;
s6, placing the foamed sheet in a supercritical gas foaming kettle, maintaining the pressure for 1h at 85 ℃ and 10.8MPa, then quickly relieving the pressure, and removing the metal net to obtain the TPU foamed material with the microarray structure on the surface.
Example 2:
s1, adding 100g of isocyanate into a three-neck flask, and then vacuumizing for 1-2 hours in an ice-water bath; respectively weighing 10g of chain extender and 10g of hydroxyl-terminated dimethyl siloxane, and dehydrating at 80 ℃. After the moisture is sufficiently pumped out, putting the processed isocyanate, the chain extender and the hydroxyl-terminated dimethyl siloxane into a vacuum oven to react for 6 hours at the temperature of 80 ℃ to obtain a polyurethane thermoplastic elastomer;
s2, placing 1.5g of montmorillonite in a vacuum oven at 85 ℃ for drying for 8 hours, after dewatering, uniformly mixing the montmorillonite with 3ml of KH550 and 150ml of ethanol, and adding the mixture in N 2 Condensing and circulating for 15h at 85 ℃ in the atmosphere, carrying out reduced pressure suction filtration, and centrifuging and washing to remove unreacted aminosilane coupling agent to obtain reactive montmorillonite;
s3, uniformly dispersing 4.5g of reactive montmorillonite in 25g of THF (tetrahydrofuran) solution containing 25wt% of polyurethane thermoplastic elastomer prepared in the step S1 by ultrasonic treatment, volatilizing most of solvent, and drying in a vacuum oven at 75 ℃ for 10 hours to obtain a pre-dispersion of polyurethane/reactive inorganic nanoparticles;
s4, carrying out melt blending on 39.25g of the polyurethane prepared in the step S1 and the pre-dispersion prepared from 10.75g of S3 and 0.01g of antioxidant 168 at 125 ℃ for 25min, and carrying out hot pressing under the conditions of 140 ℃ and 10MPa to prepare a prefabricated plate;
s5, carrying out hot pressing on the prefabricated plate and the metal net to obtain a foamed plate;
s6, placing the foamed plate in a supercritical gas foaming kettle, maintaining the pressure for 1h at 85 ℃ and 10.8MPa, then quickly relieving the pressure, and removing the metal net to obtain the TPU foamed material with the surface having the microarray structure.
Example 3:
s1, adding 100g of isocyanate into a three-neck flask, and vacuumizing for 1-2 hours in an ice-water bath; respectively weighing 10g of chain extender and 10g of hydroxyl-terminated dimethyl siloxane, and dehydrating at 80 ℃. After moisture is fully extracted, the processed isocyanate, chain extender and hydroxyl-terminated dimethyl siloxane are placed in a vacuum oven to react for 6 hours at 80 ℃ to obtain a polyurethane thermoplastic elastomer;
s2, placing 7.5g of mesoporous silica in a vacuum oven at 85 ℃ for drying for 8 hours, after dewatering, uniformly mixing the mesoporous silica with 3ml of KH550 and 150ml of ethanol, and adding N 2 Condensing and circulating for 15h at 85 ℃ in the atmosphere, then carrying out reduced pressure suction filtration, and centrifugally washing to remove unreacted aminosilane coupling agent to obtain reactive mesoporous silica;
s3, uniformly dispersing 7.5g of reactive mesoporous silica in 35g of THF (tetrahydrofuran) solution containing 20wt% of the polyurethane thermoplastic elastomer prepared in the step S1 by ultrasonic wave, volatilizing most of solvent, and drying in a vacuum oven at 75 ℃ for 10 hours to obtain a pre-dispersion of polyurethane/reactive inorganic nanoparticles;
s4, carrying out melt blending on 35.5g of polyurethane prepared in the step S1 and a pre-dispersion prepared by 14.5g of S3 and 0.01g of antioxidant 168 at 125 ℃ for 25min, and carrying out hot pressing under the conditions of 140 ℃ and 10MPa to prepare a prefabricated plate;
s5, carrying out hot pressing on the prefabricated plate and the metal net to obtain a foamed plate;
s6, placing the foamed sheet in a supercritical gas foaming kettle, maintaining the pressure for 1h at 85 ℃ and 10.8MPa, then quickly relieving the pressure, and removing the metal net to obtain the TPU foamed material with the microarray structure on the surface.
Example 4:
s1, adding 100g of isocyanate into a three-neck flask, and then vacuumizing for 1-2 hours in an ice-water bath; respectively weighing 10g of chain extender and 10g of hydroxyl-terminated dimethyl siloxane, and dehydrating at 80 ℃. After moisture is fully extracted, the processed isocyanate, chain extender and hydroxyl-terminated dimethyl siloxane are placed in a vacuum oven to react for 6 hours at 80 ℃ to obtain a polyurethane thermoplastic elastomer;
s2, placing 1.5g of expandable graphene clay in a vacuum oven at 85 ℃ for drying for 8h, after dehydration is finished, uniformly mixing the expandable graphene clay with 3ml of KH550 and 150ml of ethanol, and adding N 2 In the atmosphere, condensing and circulating for 20h at 75 ℃, then carrying out reduced pressure suction filtration, and centrifugally washing to remove unreacted aminosilane coupling agent to obtain reactive expandable graphene clay;
s3, uniformly dispersing 4.5g of reactive expandable graphene clay in 25g of THF (tetrahydrofuran) solution containing 25wt% of the polyurethane thermoplastic elastomer prepared in the step S1 by ultrasonic waves, volatilizing most of solvent, and drying in a vacuum oven at 75 ℃ for 10 hours to obtain a pre-dispersion of polyurethane/reactive inorganic nanoparticles;
s4, carrying out melt blending on 39.25g of the polyurethane prepared in the step S1 and the pre-dispersion prepared from 10.75g of S3 and 0.01g of antioxidant 168 at 125 ℃ for 25min, and carrying out hot pressing under the conditions of 140 ℃ and 10MPa to prepare a prefabricated plate;
s5, carrying out hot pressing on the prefabricated plate and the metal net to obtain a foamed plate;
s6, placing the foamed sheet in a supercritical gas foaming kettle, maintaining the pressure for 1h at 85 ℃ and 10.8MPa, then quickly relieving the pressure, and removing the metal net to obtain the TPU foamed material with the microarray structure on the surface.
Example 5:
s1, adding 100g of isocyanate into a three-neck flask, and then vacuumizing for 1-2 hours in an ice-water bath; respectively weighing 10g of chain extender and 10g of hydroxyl-terminated dimethyl siloxane for dehydration treatment at 80 ℃. After moisture is fully extracted, the processed isocyanate, chain extender and hydroxyl-terminated dimethyl siloxane are placed in a vacuum oven to react for 6 hours at 80 ℃ to obtain a polyurethane thermoplastic elastomer;
s2, drying 1.5g of titanium dioxide in a vacuum oven at 85 ℃ for 8 hours, and after dehydration is finished, uniformly mixing the titanium dioxide with 3ml of KH550 and 150ml of ethanolIn N 2 Condensing and circulating for 15h at 85 ℃ in the atmosphere, then carrying out reduced pressure suction filtration, and centrifugally washing to remove unreacted aminosilane coupling agent to obtain reactive titanium dioxide;
s3, uniformly dispersing 4.5g of reactive titanium dioxide in 25g of THF (tetrahydrofuran) solution containing 24wt% of the polyurethane thermoplastic elastomer prepared in the step S1 by ultrasonic wave, volatilizing most of solvent, and drying in a vacuum oven at 75 ℃ for 10 hours to obtain a pre-dispersion of polyurethane/reactive inorganic nanoparticles;
s4, carrying out melt blending on 39.5g of polyurethane prepared in the step S1, 10.5g of pre-dispersed substance prepared by S3 and 0.01g of antioxidant 168 at 125 ℃ for 25min, and preparing a prefabricated plate by hot pressing under the conditions of 140 ℃ and 10 MPa;
s5, carrying out hot pressing on the prefabricated plate and the metal net to obtain a foamed plate;
s6, placing the foamed plate in a supercritical gas foaming kettle, maintaining the pressure for 1h at 85 ℃ and 10.8MPa, then quickly relieving the pressure, and removing the metal net to obtain the TPU foamed material with the surface having the microarray structure.
Example 6:
s1, adding 100g of isocyanate into a three-neck flask, and then vacuumizing for 1-2 hours in an ice-water bath; respectively weighing 10g of chain extender and 10g of hydroxyl-terminated dimethyl siloxane for dehydration treatment at 80 ℃. After moisture is fully extracted, the processed isocyanate, chain extender and hydroxyl-terminated dimethyl siloxane are placed in a vacuum oven to react for 6 hours at 80 ℃ to obtain a polyurethane thermoplastic elastomer;
s2, drying 4.5g of mesoporous silica in a vacuum oven at 85 ℃ for 8 hours, after water removal is finished, uniformly mixing the mesoporous silica with 3ml of KH550 and 150ml of ethanol, and adding N 2 Condensing and circulating for 20h at 75 ℃ in the atmosphere, then carrying out reduced pressure suction filtration, and centrifugally washing to remove unreacted aminosilane coupling agent to obtain reactive mesoporous silica;
s3, uniformly dispersing 4.5g of reactive mesoporous silica in 30g of THF (tetrahydrofuran) solution containing 25wt% of the polyurethane thermoplastic elastomer prepared in the step S1 by ultrasonic wave, volatilizing most of solvent, and drying in a vacuum oven at 65 ℃ for 20 hours to obtain a pre-dispersion of polyurethane/reactive inorganic nanoparticles;
s4, carrying out melt blending on 38g of the polyurethane prepared in the step S1 and the pre-dispersed substance prepared by 12g of S3 and 0.02g of antioxidant 168 at 130 ℃ for 20min, and carrying out hot pressing under the conditions of 140 ℃ and 10MPa to prepare a prefabricated plate;
and S5, placing the prefabricated plate in a supercritical gas foaming kettle, maintaining the pressure for 1 hour at 85 ℃ and 10.8MPa, then quickly relieving the pressure, and removing the metal net to obtain the TPU foaming material with the microarray structure on the surface.
Example 7:
the only difference from example 1 is that in example 7, step S3 is: 1.5g of reactive boehmite was uniformly dispersed by sonication in 10g of a THF solution containing 25% by weight of the polyurethane thermoplastic elastomer prepared in step S1.
Example 8:
the only difference from example 1 is that the inorganic nanoparticle reactive treatment of step S2 is not performed, and step S3 directly ultrasonically and uniformly disperses the mesoporous silica in 10g of the THF solution containing 20wt% of the polyurethane thermoplastic elastomer prepared in step S1.
Comparative example 1:
the only difference from example 1 is that comparative example 1, step S4, did not add the polyurethane/reactive inorganic nanoparticle pre-dispersion.
Comparative example 2:
the only difference from example 1 is that comparative example 1, step S4, added 1g of polyurethane/reactive inorganic nanoparticle pre-dispersion.
Table 1: performance test results of the TPU foamed composite materials prepared in examples 1-8 and comparative examples 1-2
Fig. 1 shows SEM images of the thermoplastic elastomer cable material prepared in example 1. As can be seen from the figure, the modified reactive inorganic nanoparticles reach a good dispersion effect in the TPU matrix through solution pre-dispersion, and play a role in heterogeneous nucleation, thereby forming a uniform bimodal pore structure.
Fig. 2 shows the water contact angle of the surface of the thermoplastic elastomer cable material in example 1. It can be seen from the figure that the inorganic nanoparticles modified with siloxane and the foamed TPU having a coarse structure with a microarray on the surface have good hydrophobic properties.
Fig. 3 shows the water contact angle of the surface of the thermoplastic elastomer cable material in comparative example 1. It can be seen from the figure that the reactive inorganic nanoparticles are not pre-dispersed and are not distributed uniformly in the TPU, resulting in a decrease in hydrophobic properties.
From the results, the invention realizes multiple functions by changing the types of the inorganic nano particles, can meet the requirements of various properties, has good long-acting hydrophobic property due to the rough structure of the composite material, and has good heat insulation property due to the closed structure generated by foaming.
The technical scope of the invention claimed by the embodiments of the present application is not exhaustive, and new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the invention claimed by the present application; in all the embodiments of the present invention, which are listed or not listed, each parameter in the same embodiment only represents an example (i.e., a feasible embodiment) of the technical solution, and there is no strict matching and limiting relationship between the parameters, wherein the parameters may be replaced with each other without departing from the axiom and the requirements of the present invention, unless otherwise specified.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and the technical scheme also comprises the technical scheme formed by any combination of the technical characteristics. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. The TPU foamed composite material for the communication cable/optical cable is characterized by comprising the following raw materials in parts by mass: 5-30 parts of polyurethane/reactive inorganic nanoparticle pre-dispersion, 30-50 parts of polyurethane thermoplastic elastomer and 0.01-0.05 part of antioxidant.
2. The TPU foamed composite material for communication cables/optical cables according to claim 1, wherein the preparation method of the pre-dispersion of polyurethane/reactive inorganic nanoparticles comprises the following steps:
s1, drying inorganic nano particles, adding an aminosilane coupling agent and ethanol, uniformly mixing, and adding N 2 Carrying out condensation circulation in the atmosphere, and obtaining reactive inorganic nanoparticles through decompression, suction filtration and centrifugal washing;
s2, ultrasonically and uniformly dispersing the reactive inorganic nanoparticles in a THF solution containing the polyurethane thermoplastic elastomer, and then drying to obtain the pre-dispersion of the polyurethane/reactive inorganic nanoparticles.
3. The TPU foamed composite for communication/optical cables as claimed in claim 1 or 2 wherein the inorganic nanoparticles comprise at least one of mesoporous silica, zinc oxide, titanium dioxide, expandable graphene, montmorillonite and boehmite.
4. The TPU foamed composite material for communication cables/optical cables according to claim 2, wherein the temperature during the condensation cycle of step S1 is 75-85 ℃ for 10-20h.
5. The TPU foamed composite for communication cable/optical cable according to claim 2 wherein the mass ratio of the reactive inorganic nanoparticles to the THF solution containing the polyurethane thermoplastic elastomer of step S2 is 1: (5-10).
6. The TPU foamed composite material for communication cable/optical cable according to claim 2 or 5, wherein the THF solution in step S2 contains 20 to 25wt% of the polyurethane thermoplastic elastomer.
7. The TPU foamed composite material for communication cable/optical cable according to claim 1, wherein the preparation of the polyurethane thermoplastic elastomer comprises the following steps: and (2) drying the hydroxyl-terminated dimethyl siloxane, the chain extender and the curing agent, then adding the chain extender, the catalyst and the curing agent (TDI) into the mixture, uniformly mixing the mixture, and pouring the mixture into a polytetrafluoroethylene mold to cure the mixture to obtain the polyurethane thermoplastic elastomer.
8. A method of preparing the TPU foamed composite for communication cable/fiber optic cable according to claim 1, comprising the steps of:
s1, preparing the raw material of claim 1;
s2, melting and blending the polyurethane thermoplastic elastomer, the polyurethane/reactive inorganic nanoparticle pre-dispersion and the antioxidant, and then carrying out hot pressing to obtain a prefabricated plate;
s3, carrying out hot pressing on the prefabricated plate and the metal mesh to obtain a foamed plate;
and S4, placing the foamed sheet in a supercritical gas foaming kettle for medium pressure, and finally removing the metal mesh to obtain the TPU foamed composite material.
9. The method for preparing the TPU foamed composite material for the communication cable/optical cable according to claim 8, wherein the melt blending temperature of the step S2 is 110-130 ℃ and the time is 15-30min.
10. The preparation method of the TPU foamed composite material for the communication cable/optical cable according to claim 8, wherein the pressure maintaining in the supercritical gas foaming kettle of the step S4 is carried out for 1-2h at 70-85 ℃ and 10-15 MPa.
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