CN106617402A - Fluoroether/fluorosilicone composite rubber glove and preparing method thereof - Google Patents
Fluoroether/fluorosilicone composite rubber glove and preparing method thereof Download PDFInfo
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- CN106617402A CN106617402A CN201710012665.8A CN201710012665A CN106617402A CN 106617402 A CN106617402 A CN 106617402A CN 201710012665 A CN201710012665 A CN 201710012665A CN 106617402 A CN106617402 A CN 106617402A
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- rubber
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- fluorosioloxane
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0006—Gloves made of several layers of material
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
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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
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Gloves (AREA)
Abstract
The invention provides a fluoroether/fluorosilicone composite rubber glove. The fluoroether/fluorosilicone composite rubber glove comprises a fiber glove lining. The surface of the fiber glove lining is coated with a fluorosilicone rubber layer. The surface of the fluorosilicone rubber layer is coated with a fluoroether rubber layer. The fluorosilicone rubber layer is formed by applying fluorosilicone rubber cement to the surface of the fiber glove lining through sizing immersion. The fluoroether rubber layer is formed by applying fluoroether rubber cement to the surface of fluorosilicone rubber through spraying. The fluoroether rubber and the fluorosilicone rubber are both rubber filled with hydroxyethyl methacrylate modified graphene. The composite rubber glove has both the characteristics of the fluorosilicone rubber layer of being resistant to heat, cold, solvents and chemicals, and the properties of the fluoroether rubber layer of being resistant to high temperature and highly corrosive media and super stable, and can be applied to the special industry field.
Description
Technical field
The invention belongs to rubber gloves field, more particularly to a kind of fluorine ether/fluorine silicon compounded rubber gloves and its preparation side
Method.
Background technology
Rubber gloves is widely used in the social every field such as hospital, family, electron trade, food service industry, gardening plantation,
Primarily serve isolation pollution, the effect of protection both hands.If traditional rubber gloves is divided into the different of raw materials used-sizing material
Dry kind, such as：Emgloves, with Heveatex as primary raw material；Butyronitrile gloves, with by butadiene and acrylonitrile Jing emulsion polymerization
Into artificial synthesized latex be primary raw material；Butylbenzene gloves, with by the artificial synthesized of butadiene and styrene emulsion polymerization
Latex is primary raw material.
Fluorosioloxane rubber is to apply most common fluorine silicon systems row new material so far.Because fluorine is the most strong element of electronegativity, its
The C-F key quite stables connected into carbon atom, heat resistance is also higher.Fluorine element is introduced into siloxanes, not only with silica
The superior heat resistance of alkane, weatherability, hydrophobicity and demoulding, and the waterproof with fluorochemical, oil resistant and solvent resistance
Etc. performance.Therefore, fluorosioloxane rubber can be used in -60-200 DEG C of temperature province and excellent with oil resistant, solvent resistance etc.
Good performance.The own Jing of fluorosioloxane rubber is applied to the essential industry such as aerospace, aircraft, automobile, petrochemical industry, machinery, artificial organs portion
The field such as door and national defence, communications and transportation, medical science, electronic apparatus.
Fluoroether rubber is a kind of high molecular polymer containing a large amount of carbon fluorine and fluoroalkyl ether molecular structure.It is excellent because having
High-low temperature resistant, powerful oxidation corrosion resistance agent and resistant to many chemical mediator performance, by as the materials'use under extreme condition.With China
The industrial products reliability such as economic development, particularly Aero-Space, the promotion of high-end automobile industry and chemical industry instrument and meter will
Increase, fluoroether rubber is asked to be increasingly becoming irreplaceable encapsulant.
Although fluorine silicon and fluoroether rubber all have very excellent performance, with better than General Purpose Rubber comprehensive
Can, but with present industrial expansion, the requirement to rubber performance also thus develop with excellent properties by more and more higher
Blended rubber product increasingly receives publicity.CN 200810219534.8 discloses a kind of fluorubber and Silicone Rubber Blends
And preparation method thereof, prepared by mechanical blending method using materials such as fluorubber, silicon rubber, bulking agent, acid-acceptor and reinforcing agents
Fluorubber and Silicone Rubber Blends, in embodiment the oil resistant mass change of blend more than 28%, even up to
38.3%.CN 201210087884.X disclose a kind of fluorubber, silicon rubber and fluorosioloxane rubber tertiary blending high-low temperature resistant oil resistant
Material and preparation method, also due to the presence of silicon rubber, its blend oil resistant volume change is in 20%-24%.
However, at this stage with regard to fluorosioloxane rubber and fluoroether rubber jointly come prepare rubber gloves research and report also very
It is few, therefore, it is an object of the invention to study the fluorine silicon/fluoroether rubber gloves with very outstanding properties.
The content of the invention
The invention aims to solve the deficiencies in the prior art, there is provided one kind can be suitably used for various stringent environmental conditions
Such as：The very excellent fluorine silicon/fluoroether rubber gloves of combination property under the harsh conditions such as high temperature, low temperature, high intensity, high corrosion and
Its preparation method.
To solve the above problems, the technical solution used in the present invention is：
A kind of fluorine ether/fluorine silicon compounded rubber gloves, including fiber glove lining, in fiber glove liner surface fluorine is coated with
Silastic-layer, in fluorosioloxane rubber layer surface fluoroether rubber layer is coated with, and the fluorosioloxane rubber layer is by fluorosioloxane rubber rubber cement using leaching
The mode of slurry is coated in fiber glove liner surface, and the fluoroether rubber layer is applied by fluoroether rubber rubber cement by the way of spraying
On fluorosioloxane rubber surface；Wherein described fluorine ether, fluorosioloxane rubber are the rubber of the grapheme modified filling of hydroxyethyl methacrylate.
Wherein, the fluorine ether of the grapheme modified filling of the hydroxyethyl methacrylate or the preparation method of fluorosioloxane rubber include
Following steps：
(1) the hydroxyethyl methacrylate latex by graphite oxide, solids content for 25-35% mixes with isopropanol, right
Mixture carries out water bath sonicator and processes dispersed to graphite oxide, and mixture is carried out into 50-70 DEG C instead under constantly stirring
Should, obtain the graphite oxide product of hydroxyethyl methacrylate-modified；
(2) reduction treatment is carried out to product in (1), obtains the graphite ene product of hydroxyethyl methacrylate-modified；
(3) fluorine ether or crude rubber of fluorinated silicone rubber are taken, DMF is added, is stirred to fluorine ether or fluorosioloxane rubber and is dissolved, while taking step
(2) product for obtaining, adds DMF, ultrasound to obtain uniform graphene dispersing solution, pour the graphene dispersing solution into fluoroether rubber
Organic solution in, the process of mixed liquor water bath sonicator is fallen back, after removing organic solvent, vacuumize at 120-150 DEG C
3-6h is dried, Graphene/fluoroether rubber or Graphene/fluorosioloxane rubber mixture is obtained；
(4) it is rubber composition in (3) and acid-acceptor zinc oxide, vulcanizing agent dibenzoyl peroxide is uniform on rubber mixing machine
Mixing, carries out respectively hot-press vulcanization and two sections of constant-pressure and high-temperature sulfurations, obtains rubber product.
Graphite oxide and the mass ratio of hydroxyethyl methacrylate latex are 6-1 in the step (1):1.
The graphite ene product of hydroxyethyl methacrylate-modified and fluorine ether or the matter of crude rubber of fluorinated silicone rubber in the step (3)
Measuring ratio is:0.5-8:80.
Described fluoroether rubber rubber cement is composed of the following components in parts by weight：60～80 parts of fluoroether rubber, tetrahydrofuran 20
～70 parts.
Described fluorosioloxane rubber rubber cement is composed of the following components in parts by weight：60～80 parts of fluorosioloxane rubber, tetrahydrofuran 20
～70 parts.
In addition, present invention also offers the preparation method of fluorine ether/fluorine silicon compounded rubber gloves, it is characterised in that bag
Include following steps：
(1) dispensing：According to 60～80 parts of weight portion fluoroether rubber, 20～70 parts of preparation fluoroether rubber rubber cements of tetrahydrofuran；
According to 60～80 parts of fluorosioloxane rubber, 20～70 parts of preparation fluorosioloxane rubber rubber cements of tetrahydrofuran；
(2) soaking paste：Fiber glove lining is placed on streamline mould after surface treatment, above-mentioned configuration is immersed good
In fluorosioloxane rubber rubber cement, then 30-60 minutes are dried under the conditions of temperature is for 80-120 DEG C；
(3) spray：Gloves crude product after drying in step (2) is sprayed into the good fluoroether rubber rubber cement of above-mentioned configuration, in 60
First solidification 10-15 minutes at a temperature of DEG C -80 DEG C, abundant solidification 20-40 minutes minute at a temperature of 90 DEG C -110 DEG C, it is cooled to
30-60 DEG C, so it is repeated twice cooling and demolding and obtains final product the compounded rubber gloves.
The present invention technique effect be：
(1) main inventive concept of the invention is to be improved using fluorosioloxane rubber layer and fluoroether rubber layer two-layer composite bed
Individual layer pulp layer prepares rubber gloves；It is heat-resisting, cold-resistant and resistance to molten that prepared compounded rubber gloves combine fluorosioloxane rubber layer
The characteristics of agent, chemicals-resistant, but also with fluoroether rubber layer high temperature resistant and strong corrosive medium, overstable characteristic, can be applied to
Special industry field.
(2) by the present invention in that being changed to Graphene with the hydroxyethyl methacrylate latex containing active hydroxyl groups group
Property, essentially consist in the mutual of carbon fluosilicic strand in carbon fluorine molecule chain, the fluorosioloxane rubber strengthened in Graphene and fluoroether rubber
Effect, increases dispersiveness of the Graphene in rubber, so as to further function as the mechanical property for lifting rubber, heat-resisting quantity and resistance to
Friction and wear property.
(3) preparation method of the present invention is in process of production using pipelining production, and simple production process, cost is relatively low,
Suitable large-scale industrial production.
Specific embodiment
Technical scheme is further elaborated with reference to embodiment：
Embodiment 1
A kind of preparation method of fluorine ether/fluorine silicon compounded rubber gloves, comprises the steps：
(1) dispensing：According to 60 parts of the fluoroether rubber of the grapheme modified filling of weight parts of methacrylic acid hydroxyl ethyl ester, tetrahydrochysene furan
Mutter 30 parts and prepare fluoroether rubber rubber cement；According to 60 parts of the fluorosioloxane rubber of the grapheme modified filling of hydroxyethyl methacrylate, tetrahydrochysene
30 parts of preparation fluorosioloxane rubber rubber cements of furans；
(2) soaking paste：Fiber glove lining is placed on streamline mould after surface treatment, above-mentioned configuration is immersed good
In fluorosioloxane rubber rubber cement, then dry 60 minutes under the conditions of temperature is for 80 DEG C；
(3) spray：Gloves crude product after drying in step (2) is sprayed into the good fluoroether rubber rubber cement of above-mentioned configuration, in 60
Just solidify 15 minutes at a temperature of DEG C, 20 minute minute is fully solidified at a temperature of 110 DEG C, be cooled to 30 DEG C, be so repeated twice
Cooling and demolding obtains final product the compounded rubber gloves.
Wherein, the preparation method of the fluorine ether of the grapheme modified filling of hydroxyethyl methacrylate or fluorosioloxane rubber includes as follows
Step：
(1) the hydroxyethyl methacrylate latex that graphite oxide, solids content are 30% is mixed with isopropanol, to mixing
Thing carries out water bath sonicator and processes dispersed to graphite oxide, and mixture is carried out into 60 DEG C of reactions under constantly stirring, obtains
The graphite oxide product of hydroxyethyl methacrylate-modified；Graphite oxide is 3 with the mass ratio of hydroxyethyl methacrylate latex:
1；
(2) reduction treatment is carried out to product in (1), obtains the graphite ene product of hydroxyethyl methacrylate-modified；
(3) fluorine ether or crude rubber of fluorinated silicone rubber are taken, DMF is added, is stirred to fluorine ether or fluorosioloxane rubber and is dissolved, while taking step
(2) product for obtaining, adds DMF, ultrasound to obtain uniform graphene dispersing solution, pour the graphene dispersing solution into fluoroether rubber
Organic solution in, the process of mixed liquor water bath sonicator is fallen back, after removing organic solvent, at 130 DEG C vacuumize drying
5h, obtains Graphene/fluoroether rubber or Graphene/fluorosioloxane rubber mixture；The Graphene of hydroxyethyl methacrylate-modified is produced
Thing is with the mass ratio of fluorine ether or crude rubber of fluorinated silicone rubber:5:80；
(4) it is rubber composition in (3) and acid-acceptor zinc oxide, vulcanizing agent dibenzoyl peroxide is uniform on rubber mixing machine
Mixing, carries out respectively hot-press vulcanization and two sections of constant-pressure and high-temperature sulfurations, obtains rubber product.
Embodiment 2
A kind of preparation method of fluorine ether/fluorine silicon compounded rubber gloves, comprises the steps：
(1) dispensing：According to 80 parts of the fluoroether rubber of the grapheme modified filling of weight parts of methacrylic acid hydroxyl ethyl ester, tetrahydrochysene furan
Mutter 50 parts and prepare fluoroether rubber rubber cement；According to 80 parts of the fluorosioloxane rubber of the grapheme modified filling of hydroxyethyl methacrylate, tetrahydrochysene
50 parts of preparation fluorosioloxane rubber rubber cements of furans；
(2) soaking paste：Fiber glove lining is placed on streamline mould after surface treatment, above-mentioned configuration is immersed good
In fluorosioloxane rubber rubber cement, then dry 30 minutes under the conditions of temperature is for 120 DEG C；
(3) spray：Gloves crude product after drying in step (2) is sprayed into the good fluoroether rubber rubber cement of above-mentioned configuration, in 80
Just solidify 10 minutes at a temperature of DEG C, 20 minute minute is fully solidified at a temperature of 110 DEG C, be cooled to 40 DEG C, be so repeated twice
Cooling and demolding obtains final product the compounded rubber gloves.
Wherein, the same embodiment of the preparation method of fluorine ether or fluorosioloxane rubber of the grapheme modified filling of hydroxyethyl methacrylate
1。
Embodiment 3
A kind of preparation method of fluorine ether/fluorine silicon compounded rubber gloves, comprises the steps：
(1) dispensing：According to 70 parts of the fluoroether rubber of the grapheme modified filling of weight parts of methacrylic acid hydroxyl ethyl ester, tetrahydrochysene furan
Mutter 50 parts and prepare fluoroether rubber rubber cement；According to 70 parts of the fluorosioloxane rubber of the grapheme modified filling of hydroxyethyl methacrylate, tetrahydrochysene
50 parts of preparation fluorosioloxane rubber rubber cements of furans；
(2) soaking paste：Fiber glove lining is placed on streamline mould after surface treatment, above-mentioned configuration is immersed good
In fluorosioloxane rubber rubber cement, then dry 45 minutes under the conditions of temperature is for 100 DEG C；
(3) spray：Gloves crude product after drying in step (2) is sprayed into the good fluoroether rubber rubber cement of above-mentioned configuration, in 70
Just solidify 12 minutes at a temperature of DEG C, 30 minute minute is fully solidified at a temperature of 100 DEG C, be cooled to 40 DEG C, be so repeated twice
Cooling and demolding obtains final product the compounded rubber gloves.
Wherein, the same embodiment of the preparation method of fluorine ether or fluorosioloxane rubber of the grapheme modified filling of hydroxyethyl methacrylate
1。
Embodiment 4
A kind of preparation method of fluorine ether/fluorine silicon compounded rubber gloves, comprises the steps：
(1) dispensing：According to 75 parts of the fluoroether rubber of the grapheme modified filling of weight parts of methacrylic acid hydroxyl ethyl ester, tetrahydrochysene furan
Mutter 60 parts and prepare fluoroether rubber rubber cement；According to 75 parts of the fluorosioloxane rubber of the grapheme modified filling of hydroxyethyl methacrylate, tetrahydrochysene
60 parts of preparation fluorosioloxane rubber rubber cements of furans；
(2) soaking paste：Fiber glove lining is placed on streamline mould after surface treatment, above-mentioned configuration is immersed good
In fluorosioloxane rubber rubber cement, then dry 50 minutes under the conditions of temperature is for 110 DEG C；
(3) spray：Gloves crude product after drying in step (2) is sprayed into the good fluoroether rubber rubber cement of above-mentioned configuration, in 75
Just solidify 13 minutes at a temperature of DEG C, 30 minute minute is fully solidified at a temperature of 100 DEG C, be cooled to 40 DEG C, be so repeated twice
Cooling and demolding obtains final product the compounded rubber gloves.
Wherein, the same embodiment of the preparation method of fluorine ether or fluorosioloxane rubber of the grapheme modified filling of hydroxyethyl methacrylate
1。
Comparative example 1
With the method for embodiment 3, but fiber glove liner surface is only coated with fluorosioloxane rubber glue-line.
Comparative example 2
With the method for embodiment 3, but fiber glove liner surface is only coated with fluoroether rubber glue-line.
Performance test
The performance of embodiment of the present invention 1-4 products obtained therefrom products obtained therefrom is tested, test result see the table below 1.
As can be known from the above table, the compounded rubber gloves of embodiment 1-4 have very excellent combination property.
Embodiment 3 see the table below 2 with the contrast of comparative example 1-2 results of property：
As can be known from the above table, performance test ratio 1-2 of the rubber gloves of embodiment 3 is excellent.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to,
Although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it still may be used
To modify to the technical scheme described in foregoing embodiments, or equivalent is carried out to which part technical characteristic.
All any modification, equivalent substitution and improvements within the spirit and principles in the present invention, made etc., should be included in the present invention's
Within protection domain.
Claims (7)
1. a kind of fluorine ether/fluorine silicon compounded rubber gloves, it is characterised in that including fiber glove lining, in fiber glove lining table
Face is coated with fluorosioloxane rubber layer, and in fluorosioloxane rubber layer surface fluoroether rubber layer is coated with, and the fluorosioloxane rubber layer is by fluorosioloxane rubber
Rubber cement is coated in fiber glove liner surface by the way of soaking paste, and the fluoroether rubber layer is by fluoroether rubber rubber cement using spraying
Mode be coated in fluorosioloxane rubber surface；Wherein described fluorine ether, that fluorosioloxane rubber is hydroxyethyl methacrylate is grapheme modified
The rubber of filling.
2. fluorine ether according to claim 1/fluorine silicon compounded rubber gloves, it is characterised in that the hydroxyethyl methacrylate second
The fluorine ether of the grapheme modified filling of ester or the preparation method of fluorosioloxane rubber comprise the steps：
(1) the hydroxyethyl methacrylate latex by graphite oxide, solids content for 25-35% mixes with isopropanol, to mixing
Thing carries out water bath sonicator and processes dispersed to graphite oxide, and mixture is carried out into 50-70 DEG C of reaction under constantly stirring, obtains
To the graphite oxide product of hydroxyethyl methacrylate-modified；
(2) reduction treatment is carried out to product in (1), obtains the graphite ene product of hydroxyethyl methacrylate-modified；
(3) fluorine ether or crude rubber of fluorinated silicone rubber are taken, DMF is added, is stirred to fluorine ether or fluorosioloxane rubber and is dissolved, while take step (2) obtaining
The product for arriving, adds DMF, ultrasound to obtain uniform graphene dispersing solution, pour the graphene dispersing solution into fluoroether rubber have
In machine solution, during the process of mixed liquor water bath sonicator is fallen back, after removing organic solvent, at 120-150 DEG C drying is vacuumized
3-6h, obtains Graphene/fluoroether rubber or Graphene/fluorosioloxane rubber mixture；
(4) rubber composition in (3) and acid-acceptor zinc oxide, vulcanizing agent dibenzoyl peroxide are uniformly mixed on rubber mixing machine
Close, hot-press vulcanization and two sections of constant-pressure and high-temperature sulfurations are carried out respectively, obtain rubber product.
3. fluorine ether according to claim 2/fluorine silicon compounded rubber gloves, it is characterised in that oxidation stone in the step (1)
Ink is 6-1 with the mass ratio of hydroxyethyl methacrylate latex:1.
4. the fluorine ether according to Claims 2 or 3/fluorine silicon compounded rubber gloves, it is characterised in that first in the step (3)
The modified graphite ene product of base hydroxy-ethyl acrylate is with the mass ratio of fluorine ether or crude rubber of fluorinated silicone rubber:0.5-8:80.
5. fluorine ether according to claim 4/fluorine silicon compounded rubber gloves, it is characterised in that described fluoroether rubber rubber cement
It is composed of the following components in parts by weight：60～80 parts of fluoroether rubber, 20～70 parts of tetrahydrofuran.
6. fluorine ether according to claim 5/fluorine silicon compounded rubber gloves, it is characterised in that described fluorosioloxane rubber rubber cement
It is composed of the following components in parts by weight：60～80 parts of fluorosioloxane rubber, 20～70 parts of tetrahydrofuran.
7. the preparation method of fluorine ether described in a kind of claim 6/fluorine silicon compounded rubber gloves, it is characterised in that including following step
Suddenly：
(1) dispensing：According to 60～80 parts of weight portion fluoroether rubber, 20～70 parts of preparation fluoroether rubber rubber cements of tetrahydrofuran；According to
60～80 parts of fluorosioloxane rubber, 20～70 parts of preparation fluorosioloxane rubber rubber cements of tetrahydrofuran；
(2) soaking paste：Fiber glove lining is placed on streamline mould after surface treatment, the good fluorine silicon of above-mentioned configuration is immersed
In rubber slurry, then 30-60 minutes are dried under the conditions of temperature is for 80-120 DEG C；
(3) spray：Gloves crude product after drying in step (2) is sprayed into the good fluoroether rubber rubber cement of above-mentioned configuration, in 60 DEG C -80
Just solidify 10-15 minutes at a temperature of DEG C, 20-40 minutes minute are fully solidified at a temperature of 90 DEG C -110 DEG C, be cooled to 30-60
DEG C, so it is repeated twice cooling and demolding and obtains final product the compounded rubber gloves.
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| CN201710012665.8A CN106617402B (en) | 2017-01-06 | 2017-01-06 | A kind of fluorine ether/fluorine silicon compounded rubber gloves and preparation method thereof |
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| CN107828165A (en) * | 2017-11-21 | 2018-03-23 | 张文平 | A kind of silicon/fluorine ether/fluorine silicon composite rubber material and preparation method thereof |
| CN107964143A (en) * | 2017-12-07 | 2018-04-27 | 单动力 | A kind of isoamyl/fluorine silicon/fluorine ether compounded rubber and preparation method thereof |
| CN113529431A (en) * | 2021-07-14 | 2021-10-22 | 山东星宇手套有限公司 | High-performance silica gel gloves and preparation method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN106617402B (en) | 2018-01-30 |
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