CN110423449A - The cold-resistant stress crack resistant makrolon material of height - Google Patents
The cold-resistant stress crack resistant makrolon material of height Download PDFInfo
- Publication number
- CN110423449A CN110423449A CN201910734780.5A CN201910734780A CN110423449A CN 110423449 A CN110423449 A CN 110423449A CN 201910734780 A CN201910734780 A CN 201910734780A CN 110423449 A CN110423449 A CN 110423449A
- Authority
- CN
- China
- Prior art keywords
- parts
- stress crack
- polycarbonate
- makrolon material
- crack resistant
- 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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to technical field of polycarbonate, more particularly to a kind of high durable stress crack resistant makrolon material, its quality proportioning is as follows: 20-30 parts of polycarbonate, 10-15 parts of methyl trichlorosilane, 5-10 parts of cage modle polysilsesquioxane, 2-5 parts of silane coupling agent, 1-3 parts of filler, 3-6 parts of antioxidant, 20-30 parts of distilled water, 1-2 parts of catalyst, 5-10 parts of dehydrated alcohol, containing toluene in the distilled water, the volume content of toluene is 20-30%；And provide preparation method.The present invention, as polycarbonate modified dose, is improved whole impact resistance and weatherability, solves the problems, such as that polycarbonate low-temperature impact resistance itself is not strong using cage modle polysilsesquioxane.
Description
Technical field
The invention belongs to technical field of polycarbonate, and in particular to a kind of high durable stress crack resistant polycarbonate material
Material.
Background technique
Polycarbonate (PC) is corresponding to the general name of the polyester of carbonic acid, is divided into aliphatic, aliphatic-aromatic race and fragrant adoption
Carbonic ester, wherein aromatic copolycarbonate is listed in one of five large-engineering plastics because of its excellent comprehensive performance.In aromatic series PC
In, bisphenol A-type PC is most widely used, and is widely used in preparing PC blend.Due to polycarbonate have impact strength it is high,
The excellent properties such as creep resistance, good stability of the dimension, heat-resisting, insulation, and become the outstanding person in general engineering plastic, development speed
Degree occupies first place.But many carbonate polymers be especially at low temperature it is brittle, although polycarbonate has at room temperature
There is good impact resistance, but its impact resistance quickly becomes grain at low temperature.Therefore, preparation has preferable impact resistance at low temperature
The polycarbonate of performance is of great significance.
CN1150595 discloses the preparation method of polycarbonate-polysiloxane block copolymers, with eugenol sealing end
The dimethyl silicone polymer of polycarbonate block copolymer derived from dimethyl silicone polymer-bisphenol-A, eugenol sealing end is embedding
Section copolymer is when being used to prepare polycarbonate blend as blending components, it is shown that the advantages of polycarbonate performance can be improved,
It is to be copolymerized with the polysiloxanes and polycarbonate block of eugenol sealing end, and the specific phase of cooperation turns using method
Shifting catalyst can realize that being achieved with complete weight average molecular weight under less phosgene effect increases.But its copolymer prepared
Low temperature impact performance does not protrude.
Summary of the invention
For the problems of the prior art, the present invention provides a kind of high durable stress crack resistant makrolon material, uses
Cage modle polysilsesquioxane improves whole impact resistance and weatherability, solves polycarbonate as polycarbonate modified dose
The not strong problem of low-temperature impact resistance itself.
To realize the above technical purpose, the technical scheme is that
High durable stress crack resistant makrolon material, quality proportioning are as follows:
20-30 parts of polycarbonate, 10-15 parts of methyl trichlorosilane, 5-10 parts of cage modle polysilsesquioxane, silane coupling agent
2-5 parts, 1-3 parts of filler, 3-6 parts of antioxidant, 20-30 parts of distilled water, 1-2 parts of catalyst, 5-10 parts of dehydrated alcohol, the steaming
Containing toluene in distilled water, the volume content of toluene is 20-30%.
The filler uses ABS particle, and the partial size of particle is 0.1-0.2mm.
The antioxidant uses Hinered phenols antioxidant or/and phosphite ester antioxidant.
The catalyst uses alumina silicate.
The preparation method of the makrolon material is in accordance with the following steps:
Step 1, after mixing evenly by polycarbonate, cage modle polysilsesquioxane and silane coupling agent, heated sealed stirs,
Obtain solution A；
Step 2, filler is added into dehydrated alcohol, is stirring evenly and then adding into antioxidant and obtains gum size B；
Step 3, methyl trichlorosilane is added and is stirred to react into distilled water, be then allowed to stand to obtain hydrolyzate C；
Step 4, gum size B is added and is stirred evenly into solution A, then hydrolyzate C and catalyst is added, constant temperature
Heating stirring obtains sticky mixed liquor to sticky；
Step 5, sticky mixed liquor is subjected to heating polycondensation reaction, be then fed into double screw extruder, melting extrusion is made
Grain, dry obtained product.
The mixing speed stirred evenly in the step 1 is 500-800r/min, the temperature of the heated sealed stirring
It is 30-50 DEG C, mixing speed 500-600r/min.
The temperature of heated at constant temperature stirring in the step 4 is 70-80 DEG C, mixing speed 500-1000r/min.
The temperature of heating polycondensation reaction in the step 5 is 90-100 DEG C.
The draw ratio of the double screw extruder is 40:1, screw speed 100-500r/min, and extruding pelletization temperature is
230-260 DEG C, residence time 1-2min, pressure 12-18Mpa.
Polyhedral oligomeric silsesquioxane is by internal silicon oxygen core inorganic framework (SiO1.5)xOrganic with periphery takes
For the cyclic annular nanoscale cage molecule that base is constituted, the inorganic kernel for the silicon oxygen skeleton composition that Si-O is alternately connected can inhibit polymerization
The chain movement of object molecule and assign the good thermal stability of hybrid material, mechanical property and anti-flammability.Si-O bond energy is
445.2KJ/mol, C-C bond energy is 350.7KJ/mol in contrast, and C-O bond energy is 359.1KJ/mol, therefore to destroy
Energy needed for key in POSS kernel is larger.In makrolon material and polyhedral oligomeric silsesquioxane reaction process, nothing
Machine phase and organic alternate by strong chemical bonds is asked there is no the reunion of inorganic particulate and two-phase interface binding force are weak
Topic.Si-O is converted into SiO under the action of oxygen atom2Structure simultaneously forms protective film, prevents the further oxidation of polymer, is promoted
Whole stability, while the silica (SiO that polyhedral oligomeric silsesquioxane is generated through reactions such as pyrolysis2) and other
Silicon-containing products, to environment almost without pollution；Silica itself has good stability, and expansion under the conditions of cold and hot becomes
Change it is extremely low, by silica grafting on polycarbonate, can effectively promote the stability of resin structure, not only inoxidizability
It can obtain stablizing promotion, and improve the structure weatherability of polycarbonate.Polyhedral oligomeric silsesquioxane itself is in nanometer
Grade cage molecule, can have preferable structural soundness, the development at micro-crack tip can be terminated in terms of toughening.
The molecular structural formula of silane coupling agent is general are as follows: Y-R-Si (OR)3(mono- organic functional base of Y in formula, mono- silane of SiOR
Oxygroup).Siloxy has reactivity to inorganic matter, and organic functional base has reactivity or compatibility to organic matter.In poly- carbon
Acid esters tail end can form stable structure by silane coupling agent bonding pad.Filler uses ABS particle, and the grain of particle
Diameter is 0.1-0.2mm, can make full use of the thermal stability of silica, reduces the dilatancy of material, prevents it because of expansion
Bring problem of Cracking improves the stability of polycarbonate.By nanometer two while filler and dehydrated alcohol are formed slurry
Silicon oxide surface forms hydroxyl bond, is directly fixed on polycarbonate convenient for silane coupling agent, plays the role of end-capping reagent.
Organic siliconresin is that a kind of alternately linked by silicon atom and oxygen atom forms skeleton, different organic groups again with silicon
The general designation of the polymer of atom connection.Methyl trichlorosilane reacts with water under toluene existence condition and is decomposed to form decomposition product, and
Decomposition product is the mixture of cricoid, line style and cross-linked polymer, and contains considerable hydroxyl, hydrolysate in catalyst and
Polycondensation reaction is formed under the conditions of temperature, forms highly cross-linked dimensional network structure；In the polycondensation process, in organosilicon decomposition product
It is mingled with a large amount of other materials, other materials is solidificated in structure while forming three-dimensional mesh-structured.
From the above, it can be seen that the present invention has following advantages:
1. the present invention, as polycarbonate modified dose, improves whole impact resistance and resistance to using cage modle polysilsesquioxane
Hou Xing solves the problems, such as that polycarbonate low-temperature impact resistance itself is not strong.
2. the present invention using cage modle polysilsesquioxane as modifying agent, is bonding polycondensation agent with organic siliconresin, is aided with silane
Coupling agent can carry out silicone-modified, the good molding mobility of imparting polycarbonate, demoulding on makrolon material
Anti-stress cracking after property and good hot iterative cycles.
Specific embodiment
The present invention will be described in detail in conjunction with the embodiments, but does not do any restriction to claim of the invention.
Embodiment 1
High durable stress crack resistant makrolon material, quality proportioning are as follows:
20 parts of polycarbonate, 10 parts of methyl trichlorosilane, 5 parts of cage modle polysilsesquioxane, 2 parts of silane coupling agent, filler 5
Part, 3 parts of antioxidant, 20 parts of distilled water, 1 part of catalyst, 5 parts of dehydrated alcohol.
The filler uses ABS particle, and the partial size of particle is 0.1-0.2mm.
The antioxidant uses Hinered phenols antioxidant.
The catalyst uses alumina silicate.
The preparation method of the makrolon material is in accordance with the following steps:
Step 1, after mixing evenly by polycarbonate, cage modle polysilsesquioxane and silane coupling agent, heated sealed stirs,
Obtain solution A；
Step 2, filler is added into dehydrated alcohol, is stirring evenly and then adding into antioxidant and obtains gum size B；
Step 3, methyl trichlorosilane is added and is stirred to react into distilled water, be then allowed to stand to obtain hydrolyzate C；
Step 4, gum size B is added and is stirred evenly into solution A, then hydrolyzate C and catalyst is added, constant temperature
Heating stirring obtains sticky mixed liquor to sticky；
Step 5, sticky mixed liquor is subjected to heating polycondensation reaction, be then fed into double screw extruder, melting extrusion is made
Grain, dry obtained product.
The mixing speed stirred evenly in the step 1 is 500r/min, and the temperature of the heated sealed stirring is 30
DEG C, mixing speed 500r/min.
The temperature of heated at constant temperature stirring in the step 4 is 70 DEG C, mixing speed 500r/min.
The temperature of heating polycondensation reaction in the step 5 is 90 DEG C.
The draw ratio of the double screw extruder is 40:1, and screw speed 100r/min, extruding pelletization temperature is 230
DEG C, residence time 1-2min, pressure 12Mpa.
Embodiment 2
High durable stress crack resistant makrolon material, quality proportioning are as follows:
30 parts of polycarbonate, 15 parts of methyl trichlorosilane, 10 parts of cage modle polysilsesquioxane, 5 parts of silane coupling agent, filler
8 parts, 6 parts of antioxidant, 30 parts of distilled water, 2 parts of catalyst, 10 parts of dehydrated alcohol.
The filler uses ABS particle, and the partial size of particle is 0.1-0.2mm.
The antioxidant uses phosphite ester antioxidant.
The catalyst uses alumina silicate.
The preparation method of the makrolon material is in accordance with the following steps:
Step 1, after mixing evenly by polycarbonate, cage modle polysilsesquioxane and silane coupling agent, heated sealed stirs,
Obtain solution A；
Step 2, filler is added into dehydrated alcohol, is stirring evenly and then adding into antioxidant and obtains gum size B；
Step 3, methyl trichlorosilane is added and is stirred to react into distilled water, be then allowed to stand to obtain hydrolyzate C；
Step 4, gum size B is added and is stirred evenly into solution A, then hydrolyzate C and catalyst is added, constant temperature
Heating stirring obtains sticky mixed liquor to sticky；
Step 5, sticky mixed liquor is subjected to heating polycondensation reaction, be then fed into double screw extruder, melting extrusion is made
Grain, dry obtained product.
The mixing speed stirred evenly in the step 1 is 800r/min, and the temperature of the heated sealed stirring is 50
DEG C, mixing speed 600r/min.
The temperature of heated at constant temperature stirring in the step 4 is 80 DEG C, mixing speed 1000r/min.
The temperature of heating polycondensation reaction in the step 5 is 100 DEG C.
The draw ratio of the double screw extruder is 40:1, and screw speed 500r/min, extruding pelletization temperature is 260
DEG C, residence time 2min, pressure 18Mpa.
Embodiment 3
High durable stress crack resistant makrolon material, quality proportioning are as follows:
25 parts of polycarbonate, 13 parts of methyl trichlorosilane, 7 parts of cage modle polysilsesquioxane, 4 parts of silane coupling agent, filler 7
Part, 5 parts of antioxidant, 25 parts of distilled water, 2 parts of catalyst, 8 parts of dehydrated alcohol.
The filler uses ABS particle, and the partial size of particle is 0.1-0.2mm.
The antioxidant uses Hinered phenols antioxidant.
The catalyst uses alumina silicate.
The preparation method of the makrolon material is in accordance with the following steps:
Step 1, after mixing evenly by polycarbonate, cage modle polysilsesquioxane and silane coupling agent, heated sealed stirs,
Obtain solution A；
Step 2, filler is added into dehydrated alcohol, is stirring evenly and then adding into antioxidant and obtains gum size B；
Step 3, methyl trichlorosilane is added and is stirred to react into distilled water, be then allowed to stand to obtain hydrolyzate C；
Step 4, gum size B is added and is stirred evenly into solution A, then hydrolyzate C and catalyst is added, constant temperature
Heating stirring obtains sticky mixed liquor to sticky；
Step 5, sticky mixed liquor is subjected to heating polycondensation reaction, be then fed into double screw extruder, melting extrusion is made
Grain, dry obtained product.
The mixing speed stirred evenly in the step 1 is 600r/min, and the temperature of the heated sealed stirring is 40
DEG C, mixing speed 550r/min.
The temperature of heated at constant temperature stirring in the step 4 is 75 DEG C, mixing speed 800r/min.
The temperature of heating polycondensation reaction in the step 5 is 95 DEG C.
The draw ratio of the double screw extruder is 40:1, and screw speed 300r/min, extruding pelletization temperature is 250
DEG C, residence time 2min, pressure 16Mpa.
Embodiment 4
High durable stress crack resistant makrolon material, quality proportioning are as follows:
23 parts of polycarbonate, 12 parts of methyl trichlorosilane, 8 parts of cage modle polysilsesquioxane, 3 parts of silane coupling agent, filler 6
Part, 4 parts of antioxidant, 24 parts of distilled water, 1 part of catalyst, 7 parts of dehydrated alcohol.
The filler uses ABS particle, and the partial size of particle is 0.1-0.2mm.
The antioxidant uses phosphite ester antioxidant.
The catalyst uses alumina silicate.
The preparation method of the makrolon material is in accordance with the following steps:
Step 1, after mixing evenly by polycarbonate, cage modle polysilsesquioxane and silane coupling agent, heated sealed stirs,
Obtain solution A；
Step 2, filler is added into dehydrated alcohol, is stirring evenly and then adding into antioxidant and obtains gum size B；
Step 3, methyl trichlorosilane is added and is stirred to react into distilled water, be then allowed to stand to obtain hydrolyzate C；
Step 4, gum size B is added and is stirred evenly into solution A, then hydrolyzate C and catalyst is added, constant temperature
Heating stirring obtains sticky mixed liquor to sticky；
Step 5, sticky mixed liquor is subjected to heating polycondensation reaction, be then fed into double screw extruder, melting extrusion is made
Grain, dry obtained product.
The mixing speed stirred evenly in the step 1 is 700r/min, and the temperature of the heated sealed stirring is 45
DEG C, mixing speed 550r/min.
The temperature of heated at constant temperature stirring in the step 4 is 75 DEG C, mixing speed 600r/min.
The temperature of heating polycondensation reaction in the step 5 is 95 DEG C.
The draw ratio of the double screw extruder is 40:1, and screw speed 400r/min, extruding pelletization temperature is 240
DEG C, residence time 2min, pressure 14Mpa.
Performance detection
In conclusion the invention has the following advantages that
1. the present invention, as polycarbonate modified dose, improves whole impact resistance and resistance to using cage modle polysilsesquioxane
Hou Xing solves the problems, such as that polycarbonate low-temperature impact resistance itself is not strong.
2. the present invention using cage modle polysilsesquioxane as modifying agent, is bonding polycondensation agent with organic siliconresin, is aided with silane
Coupling agent can carry out silicone-modified, the good molding mobility of imparting polycarbonate, demoulding on makrolon material
Anti-stress cracking after property and good hot iterative cycles.
It is understood that being merely to illustrate the present invention above with respect to specific descriptions of the invention and being not limited to this
Technical solution described in inventive embodiments.Those skilled in the art should understand that still can be carried out to the present invention
Modification or equivalent replacement, to reach identical technical effect；As long as meet use needs, all protection scope of the present invention it
It is interior.
Claims (9)
1. high durable stress crack resistant makrolon material, it is characterised in that: its quality proportioning is as follows:
20-30 parts of polycarbonate, 10-15 parts of methyl trichlorosilane, 5-10 parts of cage modle polysilsesquioxane, silane coupling agent 2-5
Part, 1-3 parts of filler, 3-6 parts of antioxidant, 20-30 parts of distilled water, 1-2 parts of catalyst, 5-10 parts of dehydrated alcohol, the distillation
Containing toluene in water, the volume content of toluene is 20-30%.
2. high durable stress crack resistant makrolon material according to claim 1, it is characterised in that: the filler uses
ABS particle, and the partial size of particle is 0.1-0.2mm.
3. high durable stress crack resistant makrolon material according to claim 1, it is characterised in that: the antioxidant
Using Hinered phenols antioxidant or/and phosphite ester antioxidant.
4. high durable stress crack resistant makrolon material according to claim 1, it is characterised in that: the catalyst is adopted
Use alumina silicate.
5. high durable stress crack resistant makrolon material according to claim 1, it is characterised in that: the polycarbonate
The preparation method of material is in accordance with the following steps:
Step 1, after mixing evenly by polycarbonate, cage modle polysilsesquioxane and silane coupling agent, heated sealed stirs, and obtains
Solution A；
Step 2, filler is added into dehydrated alcohol, is stirring evenly and then adding into antioxidant and obtains gum size B；
Step 3, methyl trichlorosilane is added and is stirred to react into distilled water, be then allowed to stand to obtain hydrolyzate C；
Step 4, gum size B is added and is stirred evenly into solution A, then hydrolyzate C and catalyst is added, heated at constant temperature
Stirring obtains sticky mixed liquor to sticky；
Step 5, sticky mixed liquor is subjected to heating polycondensation reaction, is then fed into double screw extruder, melting extrusion, granulation,
Dry obtained product.
6. high durable stress crack resistant makrolon material according to claim 5, it is characterised in that: in the step 1
The mixing speed stirred evenly be 500-800r/min, the temperature of heated sealed stirring is 30-50 DEG C, and mixing speed is
500-600r/min。
7. high durable stress crack resistant makrolon material according to claim 5, it is characterised in that: in the step 4
Heated at constant temperature stirring temperature be 70-80 DEG C, mixing speed 500-1000r/min.
8. high durable stress crack resistant makrolon material according to claim 5, it is characterised in that: in the step 5
Heating polycondensation reaction temperature be 90-100 DEG C.
9. high durable stress crack resistant makrolon material according to claim 5, it is characterised in that: the twin-screw squeezes
The draw ratio of machine is 40:1 out, and screw speed 100-500r/min, extruding pelletization temperature is 230-260 DEG C, residence time 1-
2min, pressure 12-18Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910734780.5A CN110423449A (en) | 2019-08-09 | 2019-08-09 | The cold-resistant stress crack resistant makrolon material of height |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910734780.5A CN110423449A (en) | 2019-08-09 | 2019-08-09 | The cold-resistant stress crack resistant makrolon material of height |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110423449A true CN110423449A (en) | 2019-11-08 |
Family
ID=68415279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910734780.5A Pending CN110423449A (en) | 2019-08-09 | 2019-08-09 | The cold-resistant stress crack resistant makrolon material of height |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110423449A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382439A (en) * | 2010-12-14 | 2012-03-21 | 重庆文理学院 | Modified polycarbonate and preparation method thereof |
| CN106700471A (en) * | 2016-12-19 | 2017-05-24 | 合肥会通新材料有限公司 | Chemical-resisting inflaming-retarding polycarbonate material and preparation method thereof |
| CN109880231A (en) * | 2019-02-28 | 2019-06-14 | 无锡市宏佳华新材料有限公司 | A kind of preparation method of polypropylene flame redardant plate |
-
2019
- 2019-08-09 CN CN201910734780.5A patent/CN110423449A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382439A (en) * | 2010-12-14 | 2012-03-21 | 重庆文理学院 | Modified polycarbonate and preparation method thereof |
| CN106700471A (en) * | 2016-12-19 | 2017-05-24 | 合肥会通新材料有限公司 | Chemical-resisting inflaming-retarding polycarbonate material and preparation method thereof |
| CN109880231A (en) * | 2019-02-28 | 2019-06-14 | 无锡市宏佳华新材料有限公司 | A kind of preparation method of polypropylene flame redardant plate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102924793B (en) | Siloxane-modified thermoplastic material and preparation method thereof | |
| CA2403839C (en) | Thermoplastic silicone polyamide elastomers | |
| US6281286B1 (en) | Toughened thermoplastic resins | |
| CN1922253B (en) | A composition having improved adherence with addition-curable material, and composite article incorporating the composition | |
| CN103881389B (en) | Addition curable self-adhesive silicone rubber composition | |
| CN104788968B (en) | Organosilicon heat conductive isolation sheet and preparation method thereof | |
| JP5763202B2 (en) | Photocrosslinkable highly transparent silicone blend | |
| CN102675884A (en) | Addition curable self-adhesive silicone rubber composition | |
| JP5201063B2 (en) | Addition-curing silicone composition and cured product thereof | |
| CN110305621A (en) | A kind of dealcoholized cold curing organosilicon sealant and preparation method thereof | |
| CN104788969B (en) | Organosilicon heat conductive insulating composition and heat-conducting insulation material | |
| CN104098914A (en) | Organosilicone heat-conduction interface material | |
| CN102977553A (en) | Epoxy/silicone polymer composite material, and preparation method and application thereof | |
| CN103013127A (en) | Addition-curable silicon rubber composition and cured product thereof | |
| CN104449552B (en) | Adhesion type Single-component addition-type silicone rubber adhesive and preparation method thereof | |
| EP1060217A1 (en) | Thermoplastic silicone elastomers | |
| CN101177530B (en) | Liquid organopolysiloxane composition for matting and cured article having a matted surface | |
| CN101724274A (en) | Fluorosilicone rubber composition and cured product thereof | |
| CN103013126A (en) | Baby rubber products and composition for forming the same | |
| CN101638481B (en) | Polyphenyl methoxylsilane and preparation method and application thereof | |
| CN106753217A (en) | A kind of preparation method of Novel hot vulcanized liquid silicon rubber | |
| CN103788660A (en) | Glass fiber/ epoxy resin hybrid modified silicone rubber mold rubber and preparation method thereof | |
| CN110423449A (en) | The cold-resistant stress crack resistant makrolon material of height | |
| CN104910634B (en) | Fluorosilicone rubber composition | |
| CN114196215B (en) | MTQ silicone resin, preparation method thereof, fluorine-containing organic silicone rubber, preparation method thereof and application 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191108 |