CN111454534A - Preparation method and application of graphene/styrene thermoplastic elastomer - Google Patents
Preparation method and application of graphene/styrene thermoplastic elastomer Download PDFInfo
- Publication number
- CN111454534A CN111454534A CN202010417813.6A CN202010417813A CN111454534A CN 111454534 A CN111454534 A CN 111454534A CN 202010417813 A CN202010417813 A CN 202010417813A CN 111454534 A CN111454534 A CN 111454534A
- Authority
- CN
- China
- Prior art keywords
- graphene
- styrene
- thermoplastic elastomer
- coupling agent
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of styrene thermoplastic elastomer materials, in particular to a preparation method and application of a graphene/styrene thermoplastic elastomer. The styrene-butadiene-styrene block copolymer elastomer (SBS) is treated by a specific solvent to reach a swelling and dissolving adhesion state with a proper degree, the graphene is added and mixed uniformly, and the mixture is decompressed and evaporated to dryness under the stirring state, so that a very uniform composite effect can be realized. The graphene/styrene-butadiene-styrene segmented copolymer elastomer prepared by the method has excellent aging resistance, melt fluidity, solubility and mechanical properties, and the prepared adult product has antibacterial and far infrared functions, the antibacterial rate is up to 93%, and the far infrared emissivity is up to 0.95.
Description
Technical Field
The invention relates to the field of styrene thermoplastic elastomer materials, in particular to a preparation method and application of a graphene/styrene thermoplastic elastomer.
Background
SBS styrene thermoplastic elastomer is styrene-butadiene-styrene three-segment copolymer, also known as thermoplastic styrene-butadiene block copolymer or thermoplastic styrene-butadiene rubber, abbreviated as SBS. The material can flow after being heated, and is easy to process and mold. After cooling to room temperature, the polystyrene chain segments are gathered into glassy micro-regions, which play a role of physical cross-linking points for the polybutadiene chain segments, thereby enabling the material to show the characteristics of rubber. And are therefore referred to as "thermoplastic elastomers". However, the SBS has poor aging resistance due to the double bond contained in the main chain, and the butadiene block is crosslinked under the oxidation condition of high temperature air, thereby increasing the hardness and viscosity.
The graphene has excellent optical, electrical and mechanical properties, is almost completely transparent, only absorbs 2.3 percent of light, has the heat conductivity coefficient as high as 5300W/m.k, is a novel material with a single-layer sheet structure and is made of carbon atoms, and has the characteristics of high chemical reaction activity and high filling property, unique physical antibacterial property and function of emitting far infrared rays.
Therefore, the SBS composite material which has good mechanical property, aging resistance, physical antibiosis and far infrared ray emission and wider application range is prepared, and an important direction for the development of the adult product industry is provided.
Disclosure of Invention
The invention aims to provide a preparation method and application of a graphene/styrene thermoplastic elastomer, and the prepared thermoplastic elastomer has excellent mechanical property, aging resistance, high temperature resistance, antibacterial property and far infrared emission property, prolongs the service life and expands the application field.
In order to achieve the above effects, the technical scheme of the invention is as follows:
a preparation method of a graphene/styrene thermoplastic elastomer comprises the following steps:
step 1: carrying out coupling agent pretreatment modification on graphene, mixing the graphene and the coupling agent in a mass ratio of 1: 100-200, carrying out stirring reaction for 1-3 hours at 50-80 ℃, and carrying out filter pressing to remove redundant coupling agent;
step 2: treating the styrene thermoplastic elastomer with a specific solvent, partially dissolving the styrene thermoplastic elastomer with a component A solvent with equal mass, and adding a component B solvent with equal mass for continuous swelling to achieve a swelling and dissolving adhesion state; then, gradually adding the pretreated and modified graphene at a stirring speed of 200-400 r/min, wherein the mass ratio of the pretreated and modified graphene to the styrene thermoplastic elastomer is 1: 100-500; after being uniformly compounded, the mixture is placed in a closed container, the solvent is distilled out under reduced pressure, and the mixture is continuously stirred for 1 to 3 hours;
wherein the component A solvent is one or more than two solvent mixed solutions of cyclohexane, dimethylbenzene, methylbenzene and butyl acetate; the component B solvent is one or more than two solvent mixed solution of tetrahydrofuran, carbon tetrachloride, chloroform, ethanol, isobutanol and acetone;
and step 3: adding a composite coupling agent, wherein the mass ratio of the composite coupling agent to the elastomer is 1: 10-40; and reacting for 2-4 h, discharging to form a glue solution, and carrying out gel drying on the glue solution to obtain the graphene/styrene-butadiene-styrene segmented copolymer thermoplastic elastomer product.
In the preparation method of the graphene/styrene thermoplastic elastomer, in the step 1, a coupling agent is prepared by mixing bisamino type official functional group silane and methacryloxypropyltrimethoxysilane according to a mass ratio of 1: 0.2-0.8.
In the preparation method of the graphene/styrene thermoplastic elastomer, in the step 2, the thermoplastic elastomer is in a sticky state after swelling and dissolving, and the viscosity of a glue solution is kept at 1-10 Pa.s.
In the preparation method of the graphene/styrene thermoplastic elastomer, in the step 2, the styrene thermoplastic elastomer is styrene-butadiene-styrene three-stage copolymer.
The preparation method of the graphene/styrene thermoplastic elastomer comprises the step 3 of using a four-arm coupling agent and a two-arm coupling agent as a composite coupling agentThe coupling agent is compounded, and the molar ratio n of the four-arm coupling agent to the two-arm coupling agent(four-arm coupling agent)：n(two-arm coupling agent)0.05-20 percent; wherein, the two-arm coupling agent is one or more than two of dichlorodiphenylmethylsilane, 1, 2-dichloroethane or 1, 2-dibromoethane, and the four-arm coupling agent is one or two of silicon tetrachloride or tin tetrachloride.
The application of the graphene/styrene thermoplastic elastomer is characterized in that the graphene/styrene thermoplastic elastomer is applied to the field of adult products.
The application of the graphene/styrene thermoplastic elastomer comprises the steps of performing oil-filling blending on 60-100 parts by weight of the graphene/styrene-butadiene-styrene block copolymer thermoplastic elastomer and 0-40 parts by weight of naphthenic oil or paraffin oil, and directly performing injection molding to obtain adult products, or performing extrusion granulation in a screw extruder and performing injection molding to obtain adult product parts.
The design idea of the invention is as follows:
the graphene has excellent antibacterial performance and can emit far infrared rays at normal temperature. The graphene has a large specific surface area, is easy to absorb water, has poor hydrophilicity, can be directly added into the latex, can easily form extremely tiny particles in the latex or can be dispersed unevenly, and has a certain influence on the film forming property of the latex. The graphene can generate far infrared light waves with the wavelength of 8-14 microns when being heated, but at normal temperature, the far infrared emissivity of the graphene is low, and the emitted far infrared rays cannot be completely absorbed by a human body.
In order to better disperse and compound the graphene and/or styrene thermoplastic elastomer, the dispersion and the compound are carried out in a glue solution state under a high-viscosity state. The styrene thermoplastic elastomer high polymer material has low heat conductivity coefficient and slow heat dissipation. The heat preservation effect is better than that of metal or other inorganic non-metal materials, so that the far infrared radiation effect of the graphene is better. Meanwhile, the high compression ratio of the graphene and the styrene thermoplastic elastomer is compounded, so that the tensile strength, the bending strength and the impact strength of the styrene thermoplastic elastomer are obviously improved.
The invention has the advantages and beneficial effects that:
1. the invention leads SBS thermoplastic elastomer to form adhesion state after swelling and dissolving in specific solvent combination, then carries out coupling agent pretreatment modification on graphene, and finally compounds the two. The method has the advantages of simple process, simple equipment, recyclable solvent and high compounding efficiency.
2. In the state of completely dissolved solution, graphene is easy to agglomerate and precipitate. In a completely insoluble state, graphene is difficult to disperse in SBS. The invention creates a solvent system capable of keeping the limited dissolved swelling state of SBS, so that SBS has proper viscosity under the condition of keeping a certain viscosity, graphene is conveniently and uniformly distributed in the system, no coagulation occurs, and uniform compounding can be realized by a simple process.
3. The graphene/styrene-butadiene-styrene segmented copolymer elastomer is prepared into the adult product, so that the adult product has unique functions of resisting bacteria and emitting far infrared rays.
Detailed Description
In the specific implementation process, the styrene-butadiene-styrene block copolymer elastomer (SBS) is treated by a specific solvent to reach a bonding state of swelling and dissolution at a proper degree, the graphene is added and mixed uniformly, and the mixture is decompressed and evaporated to dryness under the stirring state, so that a very uniform composite effect can be realized.
The present invention is illustrated by the following examples, which should be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. Any modification, equivalent replacement or improvement made within the spirit and principle of the present invention should be included within the protection scope of the present invention without departing from the principle of the present invention.
Example 1
In this embodiment, the graphene/SBS thermoplastic elastomer composite adult toy and the preparation method thereof are as follows:
(1) mixing 1g of graphene and 100g of coupling agent (diamine type official energy group silane and methacryloxypropyltrimethoxysilane are mixed according to the mass ratio of 1: 0.5) in a beaker, stirring and reacting for 2 hours at the temperature of 60 ℃, and then carrying out filter pressing on redundant coupling agent to obtain the pretreated and modified graphene.
(2) 100g of styrene thermoplastic elastomer (SBS) is dissolved by 100g of mixed solvent of xylene, cyclohexane and butyl acetate (the mass ratio of the xylene, the cyclohexane and the butyl acetate is 1:1:1), then 100g of mixed solvent of isobutanol and acetone (the mass ratio of the isobutanol and the acetone is 1:1) is added for continuous swelling, the swelling and dissolving state is reached, and the viscosity of glue solution is kept at 2Pa s. The pre-treated modified graphene will then be added gradually at a stirring speed of 300 rpm. The vessel was then closed and the solvent was distilled off under reduced pressure with continued stirring for 2 h.
(3) Then adding four-arm coupling agent silicon tetrachloride and two-arm coupling agent dichlorodiphenylmethylsilane to compound the mixture (the molar ratio n is(four-arm coupling agent)：n(two-arm coupling agent)2), the mass of the composite coupling agent is 10 g. And reacting for 3 hours, discharging to form glue solution, and carrying out gel drying on the glue solution to obtain the graphene/styrene-butadiene-styrene block copolymer thermoplastic elastomer product.
(4) The composite graphene/styrene-butadiene-styrene segmented copolymer thermoplastic elastomer is added with 20g of paraffin oil, oil-filled and blended, and directly injected into adult products, or extruded and granulated in a screw extruder and then injected into the adult product parts (such as airplane cups, false sun gears and the like).
The electric conductivity of the graphene/SBS composite material prepared by the method is 4.5S/m, which is higher than that of a common composite method, and the composite uniformity of the method is very high. The far infrared emissivity of the adult product is tested to be 0.935, and the antibacterial rate of the escherichia coli reaches 90.2%.
Example 2
In this embodiment, the graphene/SBS thermoplastic elastomer composite adult toy and the preparation method thereof are as follows:
(1) mixing 1g of graphene and 150g of coupling agent (diamine type official energy group silane and methacryloxypropyltrimethoxysilane are mixed according to the mass ratio of 1: 0.6) in a beaker, stirring and reacting for 2 hours at 80 ℃, and then carrying out filter pressing on redundant coupling agent to obtain the pretreated and modified graphene.
(2) 120g of styrene thermoplastic elastomer (SBS) is partially dissolved by 120g of mixed solvent of xylene, cyclohexane and butyl acetate (the mass ratio of the xylene, the cyclohexane and the butyl acetate is 1:1:1), then 120g of mixed solvent of isobutanol and acetone (the mass ratio of the isobutanol to the acetone is 1:1) is added for continuous swelling, the swelling and dissolving state is reached, and the viscosity of glue solution is kept at 1.2 Pa.s. The pre-treated modified graphene will then be added gradually at a stirring speed of 300 rpm. The vessel was then closed and the solvent was distilled off under reduced pressure with continued stirring for 3 h.
(3) Then the four-arm coupling agent stannic chloride and the two-arm coupling agent 1, 2-dibromoethane are added to be compounded (the molar ratio n is(four-arm coupling agent)：n(two-arm coupling agent)3) the mass of the composite coupling agent is 12 g. And reacting for 3 hours, discharging to form glue solution, and carrying out gel drying on the glue solution to obtain the graphene/styrene-butadiene-styrene block copolymer thermoplastic elastomer product.
(4) The composite graphene/styrene-butadiene-styrene segmented copolymer thermoplastic elastomer is added with 30g of paraffin oil, oil-filled and blended, and directly injected into adult products, or extruded and granulated in a screw extruder and then injected into the adult product parts (such as airplane cups, false sun gears and the like).
The electric conductivity of the graphene/SBS composite material prepared by the method is 2.8S/m, which is higher than that of a common composite method, and the composite uniformity of the method is very high. The far infrared emissivity of the adult product is tested to be 0.94, and the antibacterial rate of escherichia coli reaches 91.2%.
Example 3
In this embodiment, the graphene/SBS thermoplastic elastomer composite adult toy and the preparation method thereof are as follows:
(1) mixing 1g of graphene and 200g of coupling agent (diamine type official energy group silane and methacryloxypropyltrimethoxysilane are mixed according to the mass ratio of 1: 0.8) in a beaker, stirring and reacting for 2 hours at 80 ℃, and then carrying out filter pressing on redundant coupling agent to obtain the pretreated and modified graphene.
(2) 150g of styrene thermoplastic elastomer (SBS) is partially dissolved by 150g of mixed solvent of xylene, cyclohexane and butyl acetate (the mass ratio of the xylene, the cyclohexane and the butyl acetate is 1:1:1), then 150g of mixed solvent of isobutanol and acetone (the mass ratio of the isobutanol and the acetone is 1:1) is added for continuous swelling, the swelling and dissolving state is reached, and the viscosity of glue solution is kept at 1Pa s. The pre-treated modified graphene will then be added gradually at a stirring speed of 300 rpm. The vessel was then closed and the solvent was distilled off under reduced pressure with continued stirring for 2 h.
(3) Then adding silicon tetrachloride which is a four-arm coupling agent and 1, 2-dichloroethane which is a two-arm coupling agent into the mixture to compound the mixture (the molar ratio n is(four-arm coupling agent)：n(two-arm coupling agent)2), the mass of the composite coupling agent is 15 g. And reacting for 2 hours, discharging to form glue solution, and carrying out gel drying on the glue solution to obtain the graphene/styrene-butadiene-styrene block copolymer thermoplastic elastomer product.
(4) The composite graphene/styrene-butadiene-styrene segmented copolymer thermoplastic elastomer is added with 35g of paraffin oil, oil-filled and blended, and directly injected into adult products, or extruded and granulated in a screw extruder and then injected into the adult product parts (such as airplane cups, false sun gears and the like).
The electric conductivity of the graphene/SBS composite material prepared by the method is 3.2S/m, which is higher than that of a common composite method, and the composite uniformity of the method is very high. The far infrared emissivity of the adult product is tested to be 0.92, and the antibacterial rate of the escherichia coli reaches 91.4%.
The embodiment result shows that the graphene/styrene-butadiene-styrene segmented copolymer elastomer prepared by the invention has excellent aging resistance, melt flowability, solubility and mechanical properties, and the prepared adult product has antibacterial and far infrared functions, the antibacterial rate is up to 93%, and the far infrared emissivity is up to 0.95.
Claims (7)
1. A preparation method of a graphene/styrene thermoplastic elastomer is characterized by comprising the following steps:
step 1: carrying out coupling agent pretreatment modification on graphene, mixing the graphene and the coupling agent in a mass ratio of 1: 100-200, carrying out stirring reaction for 1-3 hours at 50-80 ℃, and carrying out filter pressing to remove redundant coupling agent;
step 2: treating the styrene thermoplastic elastomer with a specific solvent, partially dissolving the styrene thermoplastic elastomer with a component A solvent with equal mass, and adding a component B solvent with equal mass for continuous swelling to achieve a swelling and dissolving adhesion state; then, gradually adding the pretreated and modified graphene at a stirring speed of 200-400 r/min, wherein the mass ratio of the pretreated and modified graphene to the styrene thermoplastic elastomer is 1: 100-500; after being uniformly compounded, the mixture is placed in a closed container, the solvent is distilled out under reduced pressure, and the mixture is continuously stirred for 1 to 3 hours;
wherein the component A solvent is one or more than two solvent mixed solutions of cyclohexane, dimethylbenzene, methylbenzene and butyl acetate; the component B solvent is one or more than two solvent mixed solution of tetrahydrofuran, carbon tetrachloride, chloroform, ethanol, isobutanol and acetone;
and step 3: adding a composite coupling agent, wherein the mass ratio of the composite coupling agent to the elastomer is 1: 10-40; and reacting for 2-4 h, discharging to form a glue solution, and carrying out gel drying on the glue solution to obtain the graphene/styrene-butadiene-styrene segmented copolymer thermoplastic elastomer product.
2. The method for preparing a graphene/styrene thermoplastic elastomer according to claim 1, wherein in the step 1, the coupling agent is a mixture of bisamino type official functional group silane and methacryloxypropyltrimethoxysilane in a mass ratio of 1: 0.2-0.8.
3. The method for preparing a graphene/styrene thermoplastic elastomer according to claim 1, wherein in the step 2, the viscosity of the solution of the thermoplastic elastomer in a sticky state after swelling and dissolution is maintained at 1 to 10 Pa-s.
4. The method of claim 1, wherein in step 2, the styrenic thermoplastic elastomer is a styrene-butadiene-styrene terpolymer.
5. The method for preparing the graphene/styrene thermoplastic elastomer according to claim 1, wherein in the step 3, the composite coupling agent is formed by compounding a four-arm coupling agent and a two-arm coupling agent, and the molar ratio n of the four-arm coupling agent to the two-arm coupling agent is(four-arm coupling agent)：n(two-arm coupling agent)0.05-20 percent; wherein, the two-arm coupling agent is one or more than two of dichlorodiphenylmethylsilane, 1, 2-dichloroethane or 1, 2-dibromoethane, and the four-arm coupling agent is one or two of silicon tetrachloride or tin tetrachloride.
6. Use of the graphene/styrenic thermoplastic elastomer according to any of claims 1 to 5, wherein the graphene/styrenic thermoplastic elastomer is used in the field of adult products.
7. The application of the graphene/styrene thermoplastic elastomer as claimed in claim 6, wherein the graphene/styrene-butadiene-styrene block copolymer thermoplastic elastomer 60-100 parts by weight and the naphthenic oil or the paraffin oil 0-40 parts by weight are subjected to oil-extended blending, and the mixture is directly injected into adult products or extruded and granulated in a screw extruder and then injected into the adult products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010417813.6A CN111454534A (en) | 2020-05-18 | 2020-05-18 | Preparation method and application of graphene/styrene thermoplastic elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010417813.6A CN111454534A (en) | 2020-05-18 | 2020-05-18 | Preparation method and application of graphene/styrene thermoplastic elastomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111454534A true CN111454534A (en) | 2020-07-28 |
Family
ID=71675713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010417813.6A Pending CN111454534A (en) | 2020-05-18 | 2020-05-18 | Preparation method and application of graphene/styrene thermoplastic elastomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111454534A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247785A (en) * | 2000-03-07 | 2001-09-11 | Polymatech Co Ltd | Composite thermoplastic elastomer composition and molding therefrom |
| CN106243742A (en) * | 2016-08-04 | 2016-12-21 | 深圳市炫丽塑胶科技有限公司 | A kind of aqueous self-lubricating thermoplastic elastomer and its production and use |
| CN109851975A (en) * | 2019-01-10 | 2019-06-07 | 四川长虹电器股份有限公司 | A kind of graphene composite material and preparation method thereof |
-
2020
- 2020-05-18 CN CN202010417813.6A patent/CN111454534A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247785A (en) * | 2000-03-07 | 2001-09-11 | Polymatech Co Ltd | Composite thermoplastic elastomer composition and molding therefrom |
| CN106243742A (en) * | 2016-08-04 | 2016-12-21 | 深圳市炫丽塑胶科技有限公司 | A kind of aqueous self-lubricating thermoplastic elastomer and its production and use |
| CN109851975A (en) * | 2019-01-10 | 2019-06-07 | 四川长虹电器股份有限公司 | A kind of graphene composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102924847B (en) | Heat reversible crosslinking polyvinyl chloride (PVC) cable material and preparation method thereof | |
| CN105482266A (en) | Thermoplastic vulcanized rubber material for automobile steering device dust-proof cover and preparation method of thermoplastic vulcanized rubber material | |
| CN112480613B (en) | Damping halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof | |
| CN111040296B (en) | Polyolefin composition with high mechanical property and preparation method thereof | |
| CN103289164A (en) | Flame-retardant polymer antistatic plastic | |
| CN115584109B (en) | Composite material, preparation method and application thereof, and degradable mulching film | |
| CN114957979B (en) | Barrier nylon composite material and preparation method and application thereof | |
| CN110283415B (en) | Thermoplastic elastomer with both conductivity and flame retardance and preparation method thereof | |
| WO2020011006A1 (en) | Ageing-resistant rubber composition and processing method therefor and use thereof | |
| CN112266565A (en) | Antibacterial environment-friendly flame-retardant elastomer and preparation method and application thereof | |
| CN113622045B (en) | Glass-like polymer fiber and preparation method thereof | |
| CN111454534A (en) | Preparation method and application of graphene/styrene thermoplastic elastomer | |
| CN113121949B (en) | Master batch for polyester extrusion foaming and application thereof | |
| JP6903130B2 (en) | Sacrificial microsphere | |
| CN106009124A (en) | Difficult-to-oxidize color-changing rubber cable material | |
| CN106751095A (en) | Isomerism containing L POSS crosslinking agents is modified to reclaim PS and preparation method thereof | |
| CN101402711A (en) | Method for grafting maleic anhydride with ethylene propylene terpolymer | |
| KR100816411B1 (en) | Polymer composite material and process for producing the same | |
| CN111484666A (en) | Modified powdered rubber toughened polypropylene composite material and preparation method thereof | |
| CN114933878A (en) | Strong plastic-lined metal pipe rapid bonding adhesive and preparation method thereof | |
| CN112297566A (en) | High-temperature-resistant high-barrier polyethylene film and preparation method thereof | |
| CN112795064A (en) | Foaming material with silica gel synthetic rubber Interpenetrating Polymer Network (IPN) structure and preparation method thereof | |
| CN105985549A (en) | Heat-resistant rubber cable sheath material | |
| CN112430367A (en) | Irradiation crosslinking silicone rubber substrate energy storage cable material and preparation method thereof | |
| CN107488342B (en) | Whisker filled polycarbonate and polyethylene glycol terephthalate composite material with high thermal stability and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200728 |
|
| RJ01 | Rejection of invention patent application after publication |