CN106928419A - Tungsten dioxide phenol-formaldehyde resin modified and the resin, phenolaldehyde moulding compound and a kind of preparation method of switch cover - Google Patents
Tungsten dioxide phenol-formaldehyde resin modified and the resin, phenolaldehyde moulding compound and a kind of preparation method of switch cover Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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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
- 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
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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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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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
- C08K7/00—Use of ingredients characterised by shape
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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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
- C08K2003/2258—Oxides; Hydroxides of metals of tungsten
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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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Health & Medical Sciences (AREA)
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- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to field of new, it is related to a kind of tungsten disulfide phenol-formaldehyde resin modified, it includes following component, the phenol of (1) 300 weight portion；The formalin of (2) 100~250 weight portions；The tungsten disulfide of (3) 0.1~5 weight portions；And (4) 1~10 weight portion acidic catalyst.Powdered phenolic moulding compound prepared by the present invention has the features such as good thermal conductivity, excellent in mechanical performance, simple post-processing, can be used for the preparation of switch cover.Simultaneously in the extrusion of moulding compound, injection molding process, WS2The solidification of phenolic resin can also be promoted, solidifying without ammonia for phenolic resin is realized.
Description
Technical field
The invention belongs to field of new, it is related to a kind of tungsten disulfide phenol-formaldehyde resin modified, further relates to tungsten dioxide and be modified
The preparation method of phenolic resin, the preparation method of phenolaldehyde moulding compound and a kind of preparation method of switch cover.
Background technology
In today of auto industry high speed development, the safe of continuous improvement, comfortable and environmental protection standard are to switch cover
Exploitation proposes new demand, because switch cover often works under moist, hot environment, the phenolic resin curing in switch cover
Agent (hexamethylenetetramine) can discharge the ammonia of remnants, the copper sheet on corrosion switch cover attachments, and one layer of rust is formed on copper sheet
Film, ultimately results in automobile sparking and starts failure, causes various accidents.Therefore, switch cover possesses under high temperature, wet condition
It is particularly important without ammonia release performance.Powdered phenolic resins are widely used in vehicle switch due to its excellent heat resistance
The preparation of lid, it reacts solidification, forms the product of stabilization during high-temperature molding by with curing agent (hexamethylenetetramine).
However, hexamethylenetetramine can be decomposed in high temperature cure process and discharge ammonia, cause switch cover occur during automobile starting to beat
The problems such as fire failure.Therefore, the key for solving switch cover sparking Problem of Failure is modified powdery phenolic resin, makes it can be with
Solidification is realized under conditions of existing without curing agent (hexamethylenetetramine).
Phenolic resin is an earliest class synthetic resin in macromolecular material, but pure phenolic resin is present, and fragility is big, toughness
The defects such as difference, poor thermal conductivity and heat resistance deficiency, greatly affect the performance of switch cover.In recent years, Ren Mentong
Cross different combination process, the method such as doping metals, compound and nano particle is not turned off and sends new modified phenol in resin
Urea formaldehyde, improves its mechanical performance and hot property.Currently reported use tung oil, cashew nut shell oil, boric acid, double maleic amides, oxygen
Change the phenol-formaldehyde resin modifieds such as molybdenum.In the preparation process of switch cover, in order to improve the mechanical performance of switch cover, generally from ring
The modified phenolic resin of oxygen tree fat, acrylonitrile-butadiene rubber powder is matrix resin, and preparation impact strength is high, and hardness and heat distortion temperature are moderate
Switch cover product.The addition of epoxy resin and nitrile rubber can improve phenolic resin and inorfil, the interface of filler
Bonding state, so as to be effectively improved the mechanical performance of sample, but product still suffers from poor heat resistance, the problems such as thermal deformation is big.
The content of the invention
An object of the present invention, is to provide a kind of tungsten dioxide phenol-formaldehyde resin modified, and it includes (1) 300 weight portion
Phenol；The formalin of (2) 100~250 weight portions；The tungsten disulfide of (3) 0.1~5 weight portions；And (4) 1~10 weights
Measure the acidic catalyst of part.
In above-mentioned tungsten dioxide phenol-formaldehyde resin modified, formalin mass percent concentration is 35%~40%.
In above-mentioned tungsten dioxide phenol-formaldehyde resin modified, described acidic catalyst is sulfuric acid, oxalic acid, zinc acetate, to first
At least one in benzene sulfonic acid and phosphoric acid.
It is a further object of the present invention to provide a kind of preparation method of tungsten disulfide phenol-formaldehyde resin modified, the method bag
Include following steps,
The first step：First by the phenol of 300 weight portions, the formalin of 100~250 weight portions, 1~10 weight portion
Acidic catalyst is added in four-hole bottle, and mechanical agitation is carried out to mixture, and is progressively warming up to 80 DEG C；
Second step：The tungsten disulfide of 0.1~5 weight portion is added while stirring, and makes its uniform point by ultrasonication
Dissipate in the solution, the concentration of tungsten disulfide is 0.25~10mg/ml in solution；Solution temperature is maintained between 80 DEG C -95 DEG C, is surpassed
Phonoresponse 1~3 hour, stops ultrasound；
3rd step：A certain amount of formaldehyde and oxalic acid are added, controlling reaction temperature is incubated 1.5~3 between 80 DEG C -95 DEG C
Stop heating after hour, and be neutrality with NaOH aqueous solution regulation pH, then 2~20min of strong stirring；
4th step：Dehydration is vacuumized, when solution temperature reaches 90 DEG C, rapid discharging obtains the pure solid product of color,
Broken powdering, as tungsten disulfide phenol-formaldehyde resin modified.
In above-mentioned tungsten dioxide phenol-formaldehyde resin modified preparation method, formalin mass percent concentration be 35%~
40%.
In above-mentioned tungsten dioxide phenol-formaldehyde resin modified preparation method, described acidic catalyst is sulfuric acid, oxalic acid, acetic acid
At least one in zinc, p-methyl benzenesulfonic acid and phosphoric acid.
It is another object of the present invention to provide a kind of preparation method of phenolaldehyde moulding compound, comprise the following steps successively：
The first step：First by the phenol of 300 weight portions, the formalin of 100~250 weight portions, 1~10 weight portion
Acidic catalyst is added in four-hole bottle, and mechanical agitation is carried out to mixture, and is progressively warming up to 80 DEG C；
Second step：The tungsten disulfide of 0.1~5 weight portion is added while stirring, and makes its uniform point by ultrasonication
Dissipate in the solution, the concentration of tungsten disulfide is 0.25~10mg/ml in solution；Solution temperature is maintained between 80 DEG C -95 DEG C, is surpassed
Phonoresponse 1~3 hour, stops ultrasound；
3rd step：A certain amount of formaldehyde and oxalic acid are added, controlling reaction temperature is incubated 1.5~3 between 80 DEG C -95 DEG C
Stop heating after hour, and be neutrality with NaOH aqueous solution regulation pH, then 2~20min of strong stirring；
4th step：Dehydration is vacuumized, when solution temperature reaches 90 DEG C, rapid discharging obtains the pure solid product of color,
Broken powdering, as tungsten disulfide phenol-formaldehyde resin modified；
5th step：Tungsten disulfide phenol-formaldehyde resin modified, glass fibre, releasing agent, carbon black and filler are mixed, by double spiral shells
Bar extruding pelletization, is prepared into phenolaldehyde moulding compound.
In the preparation method of above-mentioned phenolaldehyde moulding compound, formalin mass percent concentration is 35%~40%.
In the preparation method of above-mentioned phenolaldehyde moulding compound, described acidic catalyst is sulfuric acid, oxalic acid, zinc acetate, to first
At least one in benzene sulfonic acid and phosphoric acid.
It is still a further object of the present invention is to provide a kind of preparation method of switch cover, it includes above-mentioned phenolic molding compound
Each step of material, also including step F：Phenolaldehyde moulding compound is molded into switch cover by injection machine, Shooting Technique is：Mould temperature
170 DEG C~180 DEG C, 2MPa-10MPa, dwell time 30s-60s are molded, are incubated at a temperature of 160~180 DEG C after article removal
2-6h is heat-treated, and then naturally cools to room temperature, obtains the product of switch cover, wherein, the formalin matter
Amount percentage concentration is 35%~45%, and described acidic catalyst is in sulfuric acid, oxalic acid, zinc acetate, p-methyl benzenesulfonic acid and phosphoric acid
At least one.
The beneficial effects of the invention are as follows：
A：Resin synthesized by the present invention is powdery tungsten disulfide phenol-formaldehyde resin modified, and post-processing operation is simple, operation side
Just, can directly mix with filler, and solidification process need not add curing agent, it is possible to achieve without ammonia solidification.
B：Tungsten disulfide nano slices layer material is by that to the nano intercalated modified of phenolic resin, can improve phenol in the present invention
The compressive strength of urea formaldehyde, impact strength, resistance to elevated temperatures and heat conductivility.
C：Due to the addition of tungsten disulfide, switch cover product has good thermal conductivity, it is possible to make the rapid dissipation of heat,
Improve the service life of product.
D：The test of tungsten disulfide phenol-formaldehyde resin modified and moulding compound prepared by the present invention mainly has：Density, softening point, lead
Hot coefficient；The test of the switch cover of preparation mainly has：Compressive strength, impact strength, tensile strength, heat distortion temperature etc..
Specific embodiment
Embodiments of the invention are described below in detail, the embodiment is intended to be used to explain the present invention, and it is not intended that
Limitation of the present invention.
Embodiment 1:300g phenol, the formalin of 160g37%, 1.5g oxalic acid are added in four-hole bottle, oil bath adds
Heat is to 80 DEG C；1.5g WS are added while stirring2Nanoscale twins material, and make its dispersed by ultrasonication；Keep temperature
At 80 DEG C, ultrasonic reaction 1h stops ultrasound to degree；The formalin and 0.9g oxalic acid of 52g 37% are added, 92 DEG C, perseverance are warming up to
Temperature reaction 1h 20min, stop heating；PH is adjusted to neutrality with the NaOH aqueous solution, and cools the temperature to 60 DEG C, then vacuumize；
When temperature of charge reaches 90 DEG C, rapid discharging obtains brown solid product, and WS is after crushing2Mass fraction is 0.5%
Powdered phenol-formaldehyde resin.Above-mentioned resin is crushed, and is mixed with glass fibre, releasing agent, carbon black and filler, by twin-screw extrusion
Granulation, prepares phenolaldehyde moulding compound, and by injection machine injection moulding, prepare switch cover.Shooting Technique is：Mould temperature 170
DEG C, it is molded 2MPa, dwell time 30s.6h is incubated after article removal at a temperature of 160 DEG C to be heat-treated.
Embodiment 2：It is similar to Example 1, the difference is that being measured on the basis of 300g phenol, add 3.0g WS2.Other steps
It is rapid same as Example 1, obtain WS2Mass fraction is 1.0% phenolic resin, then carries out post-processing treatment, prepares vapour
Stopping switch lid sample.
Embodiment 3：It is similar to Example 1, the difference is that being measured on the basis of 300g phenol, add 4.5gWS2.Other steps
It is same as Example 1, obtain WS2Mass fraction is 1.5% phenolic resin, then carries out post-processing treatment, and prepared automobile is opened
Close lid sample.
Embodiment 4：Similar to Example 3, the difference is that being measured on the basis of 300g phenol, ultrasonic time is 30min.Other
Step is same as Example 3, obtains WS2Mass fraction is 1.5% phenolic resin, then carries out post-processing treatment, and vapour is obtained
Stopping switch lid sample.
Embodiment 5：Similar to Example 3, the difference is that being measured on the basis of 300g phenol, ultrasonic time is 1.5h.Other
Step is same as Example 3, obtains WS2Mass fraction is 1.5% phenolic resin, then carries out post-processing treatment, and vapour is obtained
Stopping switch lid sample.
Embodiment 6：Similar to Example 3, the difference is that being measured on the basis of 300g phenol, ultrasonic time is 2h.Other steps
It is rapid same as Example 3, obtain WS2Mass fraction is 1.5% phenolic resin, then carries out post-processing treatment, and automobile is obtained
Switch cover sample.
Embodiment 7：It is similar to Example 6, the difference is that with catalyst as zinc acetate, being measured on the basis of 300g phenol, vinegar
The addition of sour zinc is 1.5g.Other steps are same as Example 6, obtain WS2Mass fraction is 1.5% phenolic resin, so
After carry out post-processing treatment, switch cover sample is obtained.
Embodiment 8：Similar to Example 1, the difference is that being measured on the basis of 300g phenol, the addition of WS2 is 0g.Other
Step is same as Example 1, obtains the phenolic resin that WS2 mass fractions are 0%, then carries out post-processing treatment, and automobile is obtained
Switch cover sample.
Table 1.WS2 modified phenolic molding compound the performance test results
To sum up, WS2As a kind of resistant to elevated temperatures inorganic nano material, due to its excellent high temperature resistant and catalytic performance, quilt
It is widely used in the fields such as Aero-Space, automobile, heatproof composite modification.By WS2For the study on the modification of phenolic resin,
The heat resistance and mechanical property of phenolic resin can be not only greatly improved, but also the solidification of phenolic resin can be promoted, it is real
Show solidifying without ammonia for powdered phenol-formaldehyde resin.
The invention provides a kind of WS for preparing switch cover2Modified powdered phenol-formaldehyde resin.The resin can be in nothing
Solidifying without ammonia for phenolic resin is realized under the conditions of hexamethylenetetramine, and reduces the generation of moisture in solidification process, it is to avoid hole
Gap defect.With lamella WS2It is modifying agent, lamellar spacing is 1-10 nanometers, and powdered phenolic tree is prepared using in-situ reducing method
Fat, and the preparation of switch cover is used it for, the mechanical property of switch cover can be not only improved, can also open automobile
The service life for closing lid is greatly improved.Additionally, passing through WS2And the combination of matrix resin, greatly improves the toughness of phenolic resin, changes
It has been apt to the phenomenon of resistance to thermal decomposition, heat fading and the heat cracks of phenolaldehyde moulding compound.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member for, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, these improve and
Modification is also fallen into the protection domain of the claims in the present invention.
Claims (8)
1. a kind of tungsten disulfide phenol-formaldehyde resin modified, it is characterised in that：It is made up of the raw material of following weight part ratio：
The phenol of (1) 300 weight portion；
The formalin of (2) 100~250 weight portions；
The tungsten disulfide of (3) 0.1~5 weight portions；And
The acidic catalyst of (4) 1~10 weight portions.
2. tungsten disulfide phenol-formaldehyde resin modified according to claim 1, it is characterised in that：The formalin quality hundred
Specific concentration is divided to be 35%~40%.
3. tungsten disulfide phenol-formaldehyde resin modified according to claim 1 and 2, it is characterised in that：Described acidic catalyst
It is at least one in sulfuric acid, oxalic acid, zinc acetate, p-methyl benzenesulfonic acid and phosphoric acid.
4. the preparation method of a kind of tungsten disulfide phenol-formaldehyde resin modified as described in claim any one of 1-3, it is characterised in that：
Comprise the following steps：
The first step：First by the phenol of 300 weight portions, the formalin of 100~250 weight portions, 1~10 weight portion acidity
Catalyst is added in four-hole bottle, and mechanical agitation is carried out to mixture, and is progressively warming up to 80 DEG C；
Second step：The tungsten disulfide of 0.1~5 weight portion is added while stirring, and is dispersed in it by ultrasonication
In solution, the concentration of tungsten disulfide is 0.25~10mg/ml in solution；Solution temperature is maintained between 80 DEG C -95 DEG C, and ultrasound is anti-
Answer 1~3 hour, stop ultrasound；
3rd step：A certain amount of formaldehyde and oxalic acid are added, controlling reaction temperature is incubated 1.5~3 hours between 80 DEG C -95 DEG C
Stop heating afterwards, and be neutrality with NaOH aqueous solution regulation pH, then 2~20min of strong stirring；
4th step：Dehydration is vacuumized, when solution temperature reaches 90 DEG C, rapid discharging obtains the pure solid product of color, crushes
Powdering, as tungsten disulfide phenol-formaldehyde resin modified.
5. a kind of preparation method of phenolaldehyde moulding compound, it is characterised in that：Comprise the following steps：
The first step：First by the phenol of 300 weight portions, the formalin of 100~250 weight portions, 1~10 weight portion acidity
Catalyst is added in four-hole bottle, and mechanical agitation is carried out to mixture, and is progressively warming up to 80 DEG C；
Second step：The tungsten disulfide of 0.1~5 weight portion is added while stirring, and is dispersed in it by ultrasonication
In solution, the concentration of tungsten disulfide is 0.25~10mg/ml in solution；Solution temperature is maintained between 80 DEG C -95 DEG C, and ultrasound is anti-
Answer 1~3 hour, stop ultrasound；
3rd step：A certain amount of formaldehyde and oxalic acid are added, controlling reaction temperature is incubated 1.5~3 hours between 80 DEG C -95 DEG C
Stop heating afterwards, and be neutrality with NaOH aqueous solution regulation pH, then 2~20min of strong stirring；
4th step：Dehydration is vacuumized, when solution temperature reaches 90 DEG C, rapid discharging obtains the pure solid product of color, crushes
Powdering, as tungsten disulfide phenol-formaldehyde resin modified；
5th step：Tungsten disulfide phenol-formaldehyde resin modified, glass fibre, releasing agent, carbon black and filler are mixed, is squeezed by twin-screw
Go out granulation, be prepared into phenolaldehyde moulding compound.
6. the preparation method of a kind of phenolaldehyde moulding compound according to claim 5, it is characterised in that：The formalin matter
Amount percentage concentration is 35%~45%.
7. the preparation method of a kind of phenolaldehyde moulding compound according to claim 5 or 6, it is characterised in that：Described acidity is urged
Agent is at least one in sulfuric acid, oxalic acid, zinc acetate, p-methyl benzenesulfonic acid and phosphoric acid.
8. a kind of preparation method of switch cover, it is characterised in that：Including each step described in claim 5, also including step
Rapid six：Phenolaldehyde moulding compound is molded into switch cover by injection machine, Shooting Technique is：170 DEG C~180 DEG C of mould temperature, molding
2MPa-10MPa, dwell time 30s-60s, are incubated 2-6h and are heat-treated, so after article removal at a temperature of 160~180 DEG C
After naturally cool to room temperature, obtain the product of switch cover, wherein, the formalin mass percentage concentration be 35%~
45%, described acidic catalyst is at least one in sulfuric acid, oxalic acid, zinc acetate, p-methyl benzenesulfonic acid and phosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710144221.XA CN106928419A (en) | 2017-03-10 | 2017-03-10 | Tungsten dioxide phenol-formaldehyde resin modified and the resin, phenolaldehyde moulding compound and a kind of preparation method of switch cover |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710144221.XA CN106928419A (en) | 2017-03-10 | 2017-03-10 | Tungsten dioxide phenol-formaldehyde resin modified and the resin, phenolaldehyde moulding compound and a kind of preparation method of switch cover |
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| CN106928419A true CN106928419A (en) | 2017-07-07 |
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| CN201710144221.XA Pending CN106928419A (en) | 2017-03-10 | 2017-03-10 | Tungsten dioxide phenol-formaldehyde resin modified and the resin, phenolaldehyde moulding compound and a kind of preparation method of switch cover |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546303A (en) * | 2003-12-10 | 2004-11-17 | 玉环县苏泊尔橡塑制品有限公司 | Process for combining phenolic plastics with elastic bodies |
| CN101665612A (en) * | 2009-09-24 | 2010-03-10 | 上海欧亚合成材料有限公司 | Special type phenolic molding compound and preparation method thereof |
| CN202806404U (en) * | 2012-10-10 | 2013-03-20 | 盐城市勇驰汽车电器有限公司 | Cover plate for rocker switch of automobile instrument desk |
| CN105315418A (en) * | 2015-11-14 | 2016-02-10 | 浙江越拓新材料科技有限公司 | Tungsten disulfide modified phenolic resin and preparation method thereof |
-
2017
- 2017-03-10 CN CN201710144221.XA patent/CN106928419A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546303A (en) * | 2003-12-10 | 2004-11-17 | 玉环县苏泊尔橡塑制品有限公司 | Process for combining phenolic plastics with elastic bodies |
| CN101665612A (en) * | 2009-09-24 | 2010-03-10 | 上海欧亚合成材料有限公司 | Special type phenolic molding compound and preparation method thereof |
| CN202806404U (en) * | 2012-10-10 | 2013-03-20 | 盐城市勇驰汽车电器有限公司 | Cover plate for rocker switch of automobile instrument desk |
| CN105315418A (en) * | 2015-11-14 | 2016-02-10 | 浙江越拓新材料科技有限公司 | Tungsten disulfide modified phenolic resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄发荣等: "《酚醛树脂及其应用》", 31 January 2003 * |
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Application publication date: 20170707 |