CN107778563A - A kind of toughness reinforcing nitrile rubber and preparation method thereof - Google Patents
A kind of toughness reinforcing nitrile rubber and preparation method thereof Download PDFInfo
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- CN107778563A CN107778563A CN201711269671.8A CN201711269671A CN107778563A CN 107778563 A CN107778563 A CN 107778563A CN 201711269671 A CN201711269671 A CN 201711269671A CN 107778563 A CN107778563 A CN 107778563A
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- C—CHEMISTRY; METALLURGY
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- 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
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/02—Copolymers with acrylonitrile
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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
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- C08K2201/003—Additives being defined by their diameter
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- C08K2201/011—Nanostructured additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention discloses a kind of toughness reinforcing nitrile rubber and preparation method thereof, including following parts by weight raw material to be prepared：10 20 parts of nanometer glass fiber, 5 10 parts of modifying agent, 15 20 parts of EP rubbers, 10 15 parts of polystyrene, 60 70 parts of nitrile rubber, 13 parts of coupling agent, 0.3 0.5 parts of crosslinking agent；The present invention carries out the nanometer glass fiber Jing Guo specific aim modification with nitrile rubber compound, and nanometer glass fiber is set to be dispersed in nitrile rubber system, obtained nitrile rubber tensile strength performance is excellent, is advantageous to application of the nitrile rubber in more areas.
Description
Technical field
The present invention relates to material modified field, and in particular to a kind of toughness reinforcing nitrile rubber and preparation method thereof.
Background technology
Nitrile rubber is the polymer being polymerized using methyl methacrylate as monomer, is a kind of thermoplastic.By
In with that resistance to ag(e)ing is good, translucency is good, good insulating, high mechanical strength, good weatherability, good flame resistance etc. are excellent is comprehensive
Can, so being widely used for a long time in fields such as electronics, electrical equipment, machinery, automobile, medical apparatus, food processings.
With the continuous improvement that people are required material tensile property, the modified nitrile rubber of unstretched enhancing has been difficult to
Meet demand, thus, stretching enhancing modification is carried out to nitrile rubber and is necessitated.The stretching enhancing to nitrile rubber is modified now
Processing method species is various, and modified effect is also fine, especially with the appearance and application of nano material, the stretching of nitrile rubber
Intensity increases significant effect, nitrile rubber is largely used in more areas, but there is also deficiency.Although nano material has
The advantages of tensile strength enhancing effect is good, and addition is small, but there is also difficulties in dispersion, the defects of cost is high.Stretch by force
To spend in modifying process, nano material, which disperses inequality, can influence its stretching enhancing effect, and obtained material modified tensile strength is relatively low,
Material modified production and application are adversely affected.
The content of the invention
A kind of the defects of it is an object of the invention to overcome existing nitrile rubber tensile strength poor, there is provided toughness reinforcing fourth
Nitrile rubber material and preparation method thereof；The present invention carries out the nanometer glass fiber Jing Guo specific aim modification and nitrile rubber
It is compound, and nanometer glass fiber is dispersed in nitrile rubber system, obtained nitrile rubber tensile strength performance
It is excellent, be advantageous to application of the nitrile rubber in more areas.
In order to realize foregoing invention purpose, the invention provides a kind of toughness reinforcing nitrile rubber, including following parts by weight
Raw material are prepared：The nanometer glass fiber of 10-20 parts, the modifying agent of 5-10 parts, the EP rubbers of 15-20 parts, 10-15 parts
Polystyrene, the nitrile rubber of 60-70 parts, the coupling agent of 1-3 parts, the crosslinking agent of 0.3-0.5 parts.
A kind of above-mentioned toughness reinforcing nitrile rubber, resin material tensile strength can be increased according to nanometer glass fiber and crosslinking
General principle, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve nanometer glass fiber
Compatibility between nitrile rubber, and make nanometer glass fiber disperse evenly, to make nanometer glass fiber in nitrile rubber
It is more preferable to the tensile strength humidification of nitrile rubber, modified butyronitrile rubber is also made by controlling the degree of polymerization of nitrile rubber
Glue material reaches optimum balance relation between tensile strength and processability, so as to which the nitrile rubber that makes to obtain is with excellent
Under conditions of different tensile strength, it may have excellent processability, it is applied in more areas.
A kind of above-mentioned toughness reinforcing nitrile rubber, wherein, a diameter of 1-10nm of described nanometer glass fiber, draw ratio is
2-10 ︰ 1；Nanometer glass fiber draw ratio is bigger, and dispersiveness is poorer, and nanometer glass fiber draw ratio is smaller, to nitrile rubber
Tensile strength humidification is poorer；Preferably, a diameter of 3-5nm of described nanometer glass fiber, draw ratio are 3-6 ︰ 1.
A kind of above-mentioned toughness reinforcing nitrile rubber, wherein, described modifying agent is phenyl phosphorus diamides and acetyl tributyl citrate
The mixture of tributyl composition；Described modifying agent can improve the compatibility of nanometer glass fiber and nitrile rubber, and and can exists
Nanometer glass fiber surface forms polar group, beneficial to scattered；Preferably, phenyl phosphorus diamides and acetyl in described modifying agent
The ratio between amount of material of ATBC is 1 ︰ 1.
A kind of above-mentioned toughness reinforcing nitrile rubber, wherein, the degree of polymerization of polystyrene is bigger, then nitrile rubber material after being crosslinked
The tensile strength of material is poorer, and processability is better, and the polymer of polystyrene is smaller, then the stretching of nitrile rubber is strong after being crosslinked
Degree is better, and processability is poorer, therefore, selects the rational polystyrene degree of polymerization, is balanced stretch intensive properties and the weight of processability
Want means.The degree of polymerization of described polystyrene is 220-340；Preferably, the degree of polymerization of described polystyrene is 260-
300；Optimal, the degree of polymerization of described polystyrene is 280；By preferred, obtained nitrile rubber had both had excellent
Tensile strength, it may have preferable processability, be adapted to the application in more areas.
Wherein, the described nitrile rubber degree of polymerization is 1000-1600；Preferably, the degree of polymerization of the nitrile rubber is
1200-1400；Most preferably, the degree of polymerization of described nitrile rubber is 1300；By preferred, obtained nitrile rubber was both
With excellent tensile strength, it may have preferable processability.
A kind of above-mentioned toughness reinforcing nitrile rubber, wherein, described coupling agent is mercapto hydroxypropyl methyl dimethoxysilane；Mercapto
Hydroxypropyl methyl dimethoxysilane can increase the compatibility between nanometer glass fiber and nitrile rubber and modifying agent, improve fourth
The performance of nitrile rubber material.
Wherein, described crosslinking agent is aziridine, and the crosslinking agent can be by the polymer raw materials of two kinds of different polymerization degrees
Appropriate crosslinking, improve the tensile strength of nitrile rubber.
A kind of above-mentioned toughness reinforcing nitrile rubber, wherein, its raw material also includes dispersant, plasticizer, antistatic additive, dye
One or more auxiliary agents in toner, brightener；Above-mentioned auxiliary agent can improve the processability of nitrile rubber, increase its function
Property etc. effect, so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of system of toughness reinforcing nitrile rubber
Preparation Method, comprise the following steps：
（1）Nanometer glass fiber is handled with coupling agent；
（2）Nanometer glass fiber Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）Combined Processing is carried out after nanometer glass fiber after cladding is well mixed with nitrile rubber in the electric field, is mixed
Close material；
（4）Combined Processing is being carried out after compound is well mixed with polystyrene, crosslinking agent, EP rubbers, zinc stearate, is being obtained
To toughness reinforcing nitrile rubber.
A kind of preparation method of toughness reinforcing nitrile rubber, first carries out coupling processing with coupling agent to nanometer glass fiber,
Increase nanometer glass fiber and modifying agent, the compatibility of nitrile rubber；Place is modified to nanometer glass fiber with modifying agent again
Reason, and form polar group on its surface；Finally make the pole in nanometer glass fiber surface and nitrile rubber chain using external electric field
Property group polarization, it is powered, by repelling each other between electric charge or attracting principle, while making nanometer glass fiber dispersed,
Can be bonded with the polar group on nitrile rubber chain, so that the tensile strength enhancing effect of nanometer glass fiber obtains maximum journey
The embodiment of degree, so as to get modified butadiene acrylonitrile rubber tensile strength significantly improve；The preparation method is simple and reliable, is suitable for toughness reinforcing
Extensive, the industrialized production of nitrile rubber.
A kind of preparation method of above-mentioned toughness reinforcing nitrile rubber, wherein, it is preferred that step 1 carries out coupling processing process
In can use ultrasonic assistant；Shaken by the high speed of ultrasonic wave, make nanometer glass fiber dispersiveness more preferable, and to coupling processing
With facilitation.
A kind of preparation method of above-mentioned toughness reinforcing nitrile rubber, wherein, the electric field energy described in step 3 produces to group
Polarization, make group powered, so as to promote the scattered and bonded effect of nanometer glass fiber, improve modified butadiene acrylonitrile rubber
Tensile strength.
Preferably, described electric-field intensity is 1.5-3.2kv/m；Electric-field intensity is too small, and polarization effect is weak, to nano-glass
The dispersion effect of fiber is poor；Electric-field intensity is excessive, and polarization effect is too strong, and intermolecular force is too big, and strand produces orientation and moved
It is dynamic, arrangement and the bonded performance for having an impact, nitrile rubber may being reduced to strand；Most preferably, described electricity
Field intensity is 2.0-2.5kv/m.
Wherein, it is preferred that described electric field is the constant parallel electric field of direction of an electric field；The constant parallel electric field of direction of an electric field
Best to the polarization effect of polar group, group intermolecular forces are stable, and the scattered and bonded promotion to nanometer glass fiber is made
Use best results.
Compared with prior art, beneficial effects of the present invention：
1st, nitrile rubber of the present invention targetedly screens the species of modifying agent, coupling agent and crosslinking agent, makes nano-glass fine
Compatibility between dimension and nitrile rubber is more preferable, and the dispersiveness in nitrile rubber is more preferable, and nanometer glass fiber is to nitrile rubber
Tensile strength humidification it is more preferable.
2nd, nitrile rubber of the present invention passes through the fourth that controls the degree of polymerization of nitrile rubber and polystyrene to make modified
Nitrile rubber material reaches optimum balance relation between tensile strength and processability, so as to get nitrile rubber with excellent
Under conditions of different tensile strength, it may have excellent processability.
3rd, the preparation method of nitrile rubber of the present invention, using the polarization of external electric field, nano-glass can be promoted fine
Dimension is scattered and bonded in nitrile rubber system, and the tensile strength enhancing effect of nanometer glass fiber is more preferable, obtained butyronitrile
The tensile strength of elastomeric material is higher.
4th, the preparation method of nitrile rubber of the present invention is simple, reliable, be adapted to toughness reinforcing nitrile rubber it is extensive,
Industrialized production.
Embodiment
With reference to test example and embodiment, the present invention is described in further detail.But this should not be understood
Following embodiment is only limitted to for the scope of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that present invention is realized
The scope of invention.
Embodiment 1
（1）15 parts of nanometer glass fiber is handled with 2 parts of mercapto hydroxypropyl methyl dimethoxysilane；
（2）By the nanometer glass fiber Jing Guo coupling agent treatment 4 parts of phenyl phosphorus diamides and 4 parts of the fourth of acetyl tributyl citrate three
Ester carries out cladding processing；
（3）In electric-field strength after nanometer glass fiber after cladding is well mixed with the nitrile rubber that 65 parts of the degree of polymerization is 1300
Spend to be extruded in the constant parallel electric field of 2.5kv/m direction of an electric field, obtain compound；
（4）Polystyrene that the compound that step 3 is obtained and 12 parts of the degree of polymerization are 280,18 parts of EP rubbers, 0.4 part
Extruded after aziridine is well mixed, obtain toughness reinforcing nitrile rubber.
Embodiment 2
（1）10 parts of nanometer glass fiber is handled with 1 part of mercapto hydroxypropyl methyl dimethoxysilane；
（2）By the nanometer glass fiber Jing Guo coupling agent treatment 2.5 parts of phenyl phosphorus diamides and 2.5 parts of acetyl tributyl citrate
Tributyl carries out cladding processing；
（3）In electric field after nanometer glass fiber after cladding is well mixed with the nitrile rubber that 60 parts of the degree of polymerization is 1600
Intensity is to be extruded in 3.2kv/m electric field, obtains compound；
（4）Polystyrene that the compound that step 3 is obtained and 10 parts of the degree of polymerization are 220,15 parts of EP rubbers, 0.3 part
Extruded after aziridine is well mixed, obtain toughness reinforcing nitrile rubber.
Embodiment 3
（1）20 parts of nanometer glass fiber is handled with 3 parts of mercapto hydroxypropyl methyl dimethoxysilane；
（2）By the nanometer glass fiber Jing Guo coupling agent treatment 5 parts of phenyl phosphorus diamides and 5 parts of the fourth of acetyl tributyl citrate three
Ester carries out cladding processing；
（3）In electric field after nanometer glass fiber after cladding is well mixed with the nitrile rubber that 70 parts of the degree of polymerization is 1000
Intensity is to be extruded in the constant parallel electric field of 1.5kv/m direction of an electric field, obtains compound；
（4）Polystyrene that the compound that step 3 is obtained and 15 parts of the degree of polymerization are 340,20 parts of EP rubbers, 0.5 part
Extruded after aziridine is well mixed, obtain toughness reinforcing nitrile rubber.
Comparative example 1
（1）15 parts of nanometer glass fiber is handled with 2 parts of mercapto hydroxypropyl methyl dimethoxysilane；
（2）By the nanometer glass fiber Jing Guo coupling agent treatment and 5 parts of dispersant, the butyronitrile rubber that 65 parts of the degree of polymerization is 1300
Extruded after glue is well mixed in the constant parallel electric field of the direction of an electric field that electric-field intensity is 2.5kv/m, obtain compound；
（3）Polystyrene that the compound that step 2 is obtained and 12 parts of the degree of polymerization are 280,18 parts of EP rubbers, 0.4 part
Extruded after aziridine is well mixed, obtain nitrile rubber.
Comparative example 2
（1）15 parts of nanometer glass fiber is handled with 2 parts of mercapto hydroxypropyl methyl dimethoxysilane；
（2）By the nanometer glass fiber Jing Guo coupling agent treatment 4 parts of phenyl phosphorus diamides and 4 parts of the fourth of acetyl tributyl citrate three
Ester carries out cladding processing；
（3）It is 280 by nitrile rubber that the nanometer glass fiber after cladding and 65 parts of the degree of polymerization are 1300,12 parts of the degree of polymerization
Polystyrene, 18 parts of EP rubbers, 0.4 part of aziridine it is well mixed after extruded, obtain nitrile rubber.
Comparative example 3
（1）15 parts of nanometer glass fiber is handled with 2 parts of mercapto hydroxypropyl methyl dimethoxysilane；
（2）Nanometer glass fiber Jing Guo coupling agent treatment is entered with 4 parts of polystyrene and 4 parts of tributyl 2-acetylcitrate
The processing of row cladding；
（3）In electric-field strength after nanometer glass fiber after cladding is well mixed with the nitrile rubber that 65 parts of the degree of polymerization is 1300
Spend to be extruded in the constant parallel electric field of 2.5kv/m direction of an electric field, obtain compound；
（4）Polystyrene that the compound that step 3 is obtained and 12 parts of the degree of polymerization are 280,18 parts of EP rubbers, 0.4 part
Extruded after aziridine is well mixed, obtain nitrile rubber.
Comparative example 4
（1）15 parts of nanometer glass fiber is handled with 2 parts of mercapto hydroxypropyl methyl dimethoxysilane；
（2）By the nanometer glass fiber Jing Guo coupling agent treatment 4 parts of phenyl phosphorus diamides and 4 parts of the fourth of acetyl tributyl citrate three
Ester carries out cladding processing；
（3）It is 280 polystyrene, 18 parts of EP rubbers, 0.4 by the nanometer glass fiber after cladding and 12 parts of the degree of polymerization
In the electric field side that electric-field intensity is 2.5kv/m after nitrile rubber that part aziridine, 65 parts of the degree of polymerization are 2000 is well mixed
Extruded into constant parallel electric field, obtain nitrile rubber.
Comparative example 5
（1）15 parts of nanometer glass fiber is handled with 2 parts of mercapto hydroxypropyl methyl dimethoxysilane；
（2）By the nanometer glass fiber Jing Guo coupling agent treatment 4 parts of phenyl phosphorus diamides and 4 parts of the fourth of acetyl tributyl citrate three
Ester carries out cladding processing；
（3）In electric-field strength after nanometer glass fiber after cladding is well mixed with the nitrile rubber that 65 parts of the degree of polymerization is 900
Spend to be extruded in the constant parallel electric field of 2.5kv/m direction of an electric field, obtain compound；
（4）Polystyrene that the compound that step 3 is obtained and 12 parts of the degree of polymerization are 200,18 parts of EP rubbers, 0.4 part
Extruded after aziridine is well mixed, obtain nitrile rubber.
By the nitrile rubber in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, record data is as follows：
| Performance | Tensile strength（MPa） | Elongation at break（%） | Processability |
| Embodiment 1 | 49 | 26 | ++++ |
| Embodiment 2 | 48 | 29 | ++++ |
| Embodiment 3 | 48 | 33 | ++++ |
| Comparative example 1 | 38 | 18 | ++++ |
| Comparative example 2 | 41 | 12 | ++++ |
| Comparative example 3 | 41 | 15 | ++++ |
| Comparative example 4 | 43 | 18 | ++++ |
| Comparative example 5 | 50 | 9.1 | ++ |
| Nitrile rubber | 26 | 7.8 | +++ |
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the toughness reinforcing nitrile rubber of the present invention being prepared in embodiment 1-3, received
Rice glass fibre is uniformly dispersed, and good with the compatibility of nitrile rubber, nitrile rubber tensile strength is good, and elongation at break is high,
Processability is good；And in comparative example 1, modifying agent is not used processing is modified to nanometer glass fiber, although adding dispersant,
But nanometer glass fiber dispersion effect is poor, the poor compatibility with nitrile rubber, the tensile strength of nitrile rubber and fracture are stretched
Long rate significantly reduces；Do not carry out Combined Processing in comparative example 2 in the electric field, nanometer glass fiber dispersion effect is poor, nitrile rubber
The tensile strength and elongation at break of material significantly reduce；Modifying agent is not the application defined in comparative example 3, nano-glass
Fiber dispersion effect is poor, and the tensile strength and elongation at break of nitrile rubber significantly reduce；Cross-linking reaction is same in comparative example 4
Sample is carried out in the electric field, and electric field has a negative impact to cross-linking reaction, so as to get the tensile strength of nitrile rubber and disconnected
Split elongation reduction；The nitrile rubber and the polystyrene degree of polymerization used in comparative example 5 is too small, although there is tensile strength after compound
Increased, but its elongation at break and processability significantly reduce, and are unfavorable for the application of nitrile rubber.
Claims (10)
1. a kind of toughness reinforcing nitrile rubber, it is characterised in that be prepared including following parts by weight raw material：10-20 parts
Nanometer glass fiber, the modifying agent of 5-10 parts, the EP rubbers of 15-20 parts, the polystyrene of 10-15 parts, the butyronitrile of 60-70 parts
Rubber, the coupling agent of 1-3 parts, the crosslinking agent of 0.3-0.5 parts；The modifying agent is phenyl phosphorus diamides and the fourth of acetyl tributyl citrate three
The mixture of ester composition；The coupling agent is mercapto hydroxypropyl methyl dimethoxysilane, and the crosslinking agent is aziridine；It is described poly-
The degree of polymerization of styrene is 220-340；The nitrile rubber degree of polymerization is 1000-1600.
2. nitrile rubber according to claim 1, it is characterised in that phenyl phosphorus diamides and second in the modifying agent
The ratio between amount of material of acyl ATBC is 1 ︰ 1.
3. nitrile rubber according to claim 1, it is characterised in that the degree of polymerization of the polystyrene is 260-
300。
4. nitrile rubber according to claim 3, it is characterised in that the degree of polymerization of the polystyrene is 280.
5. nitrile rubber according to claim 1, it is characterised in that the nitrile rubber degree of polymerization is 1200-
1400。
6. nitrile rubber according to claim 5, it is characterised in that the nitrile rubber degree of polymerization is 1300.
7. a kind of preparation method of the nitrile rubber as described in claim any one of 1-6, it is characterised in that including following step
Suddenly：
（1）Nanometer glass fiber is handled with coupling agent；
（2）Nanometer glass fiber Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）Combined Processing is carried out after nanometer glass fiber after cladding is well mixed with nitrile rubber in the electric field, is mixed
Close material；
（4）Combined Processing is being carried out after compound is well mixed with polystyrene, EP rubbers, crosslinking agent, is obtaining toughness reinforcing fourth
Nitrile rubber material.
8. preparation method according to claim 7, it is characterised in that step（3）Middle electric-field intensity is 1.5-3.2kv/m.
9. preparation method according to claim 8, it is characterised in that step（3）Middle electric-field intensity is 2.0-2.5kv/m.
10. preparation method according to claim 7, it is characterised in that step（3）Middle electric field, which is that direction of an electric field is constant, puts down
Row electric field.
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| CN201711269671.8A CN107778563A (en) | 2017-12-05 | 2017-12-05 | A kind of toughness reinforcing nitrile rubber and preparation method thereof |
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| CN201711269671.8A CN107778563A (en) | 2017-12-05 | 2017-12-05 | A kind of toughness reinforcing nitrile rubber and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194854A (en) * | 2020-09-22 | 2021-01-08 | 江苏金陵奥普特高分子材料有限公司 | Low-dielectric-property composite thermoplastic elastomer and preparation method thereof |
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2017
- 2017-12-05 CN CN201711269671.8A patent/CN107778563A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194854A (en) * | 2020-09-22 | 2021-01-08 | 江苏金陵奥普特高分子材料有限公司 | Low-dielectric-property composite thermoplastic elastomer and preparation method thereof |
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