CN112646354A - Organic silicon-polyurethane thermoplastic elastomer and preparation method thereof - Google Patents
Organic silicon-polyurethane thermoplastic elastomer and preparation method thereof Download PDFInfo
- Publication number
- CN112646354A CN112646354A CN202011528390.1A CN202011528390A CN112646354A CN 112646354 A CN112646354 A CN 112646354A CN 202011528390 A CN202011528390 A CN 202011528390A CN 112646354 A CN112646354 A CN 112646354A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- thermoplastic elastomer
- silicone
- thermoplastic
- elastomer
- 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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
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)
Abstract
The invention relates to the technical field of elastomers, and discloses an organic silicon-polyurethane thermoplastic elastomer and a preparation method thereof, wherein the organic silicon-polyurethane thermoplastic elastomer comprises thermoplastic polyurethane, silicon rubber, a reversible cross-linking agent, a catalyst and a compatilizer; wherein the mass ratio of the thermoplastic polyurethane to the silicone rubber is 30: 70-80: 20; the reversible crosslinking agent has the structural formula of formula (1): in the formula, R1、R2、R3And R4Independently is C1-5 alkyl, C1-5 haloalkyl or phenyl; the mass ratio of the reversible cross-linking agent to the silicon rubber is 0.1-2: 100; the thermoplastic elastomer obtained by the formula has good fluidity in a molten state, is easy to process, and has excellent mechanical properties and touch feeling.
Description
Technical Field
The invention relates to the technical field of elastomers, in particular to an organic silicon-polyurethane thermoplastic elastomer and a preparation method thereof.
Background
The thermoplastic elastomer is an elastomer material which can be melted and processed, has the using characteristics of rubber and the processing performance of plastics, and has the advantages of high molding efficiency, reusability and the like. Common thermoplastic elastomers include copolymerization type, blending type and dynamic vulcanization type, and can meet the performance requirements of different applications through the matching of different polymer components.
A silicone thermoplastic elastomer is a thermoplastic elastomer based on a silicone polymer, and is generally prepared from a silicone component and a thermoplastic polymer by a specific compounding technique. The silicone component can impart softness, skin-friendliness, aging resistance, and the like. In addition, the special two-phase structure on the surface of the material often enables the material to have beautiful matte texture and fine and smooth skin touch, so that the material is particularly suitable for products in contact with human bodies, such as various wearing products, electronic communication products, household appliances, sports goods, medical appliances and the like.
Patents CN1568351A and CN107018664A disclose methods for preparing silicone thermoplastic elastomers using dynamic vulcanization techniques. The silicone rubber is crosslinked while being mixed with thermoplastic polyurethane or polyolefin, and the like, and is crushed into micron-sized small particles under the action of shearing force, and the micron-sized small particles are uniformly dispersed in the other component. By this method, a thermoplastic elastomer having excellent mechanical properties and an excellent touch can be obtained. However, a large amount of crosslinked silicone rubber particles have a filler-like effect, so that the fluidity of the product in a molten state is greatly reduced, and the product is difficult to process into a product with a complex structure or a large size. In addition, the dynamic vulcanization process is accompanied by the rapid change of the viscosity ratio of two phases, so that the requirement on the process precision is high, and the stable production is not facilitated.
Patent CN106565933A discloses a method for preparing an organic silicon thermoplastic polyurethane elastomer by copolymerizing an organic silicon component and a diisocyanate component, wherein macromolecular organic silicon containing active hydrogen, other macromolecular compounds containing active hydrogen and diisocyanate are mixed according to a certain mode and react to obtain an isocyanate group terminated prepolymer; and uniformly mixing the prepolymer with the micromolecule chain extender, pouring the mixture and curing. The organic silicon thermoplastic polyurethane prepared by the method has good mechanical property, and also has excellent hydrophobic property and low temperature resistance.
The patent CN103642048A utilizes the condensation polymerization of terminal aminopropyl polydimethylsiloxane and terminal amino polyamide to prepare the polyamide-based organic silicon thermoplastic elastomer, the elastomer has high tensile strength and low-temperature impact strength, good tear resistance, good chemical resistance and good wear resistance, and can replace common rubber and soft plastics to be widely applied to the automobile and general consumer industries.
The processing performance of the copolymerization type organic silicon thermoplastic elastomer is superior to that of a dynamic vulcanization type organic silicon thermoplastic elastomer, but the same excellent touch feeling can not be achieved, and the copolymerization type organic silicon thermoplastic elastomer has no obvious advantages in products contacting with human bodies. Therefore, in order to obtain excellent touch feeling of the thermoplastic elastomer, the dynamic vulcanization type silicone thermoplastic elastomer is still required to be adopted, and the problems of reduced fluidity and large processing difficulty in the dynamic vulcanization process are urgently required to be solved.
Disclosure of Invention
Aiming at the problem of poor flowability of the silicone thermoplastic elastomer containing silicone rubber in the prior art, the invention provides a novel formula of the silicone-polyurethane thermoplastic elastomer, and the thermoplastic elastomer obtained under the formula has good flowability in a molten state, is easy to process, has excellent mechanical property and touch feeling, and is suitable for products in contact with human bodies.
In order to achieve the purpose, the invention adopts the technical scheme that:
an organosilicon-polyurethane thermoplastic elastomer comprising thermoplastic polyurethane, silicone rubber, a reversible cross-linking agent, a catalyst, and a compatibilizer; wherein the mass ratio of the thermoplastic polyurethane to the silicone rubber is 30: 70-80: 20;
the reversible crosslinking agent has the structural formula of formula (1):
in the formula, R1、R2、R3And R4Independently is C1-5 alkyl, C1-5 haloalkyl or phenyl;
the mass ratio of the reversible cross-linking agent to the silicon rubber is 0.1-4: 100.
In the invention, the thermoplastic polyurethane and the silicon rubber are mixed, the thermoplastic polyurethane and the silicon rubber are not crosslinked in the preparation process and under the processing conditions, and the phase structure of the elastomer is greatly dependent on the proportion of two-phase substances. The higher mass fraction phase more readily becomes the continuous phase, thereby allowing phase structure and properties of the elastomer to be adjusted. When the proportion of the silicone rubber is too low, the various properties of the elastomer are closer to the properties of the thermoplastic polyurethane, which is not favorable for realizing excellent touch feeling; as the proportion of silicone rubber increases, the mechanical properties of the elastomer will decrease to some extent.
The reversible cross-linking agent developed earlier by the applicant is added in the invention, and C-ON bonds in the cross-linking agent can be homocleaved into carbon free radicals and nitroxide free radicals at high temperature and can be recombined into covalent bonds at low temperature, so that the reversible cross-linking of the silicone rubber is realized. The inventor tries to use the cross-linking agent in a thermoplastic polyurethane-silicon rubber composite system, and finds that the preparation simplicity of the thermoplastic polyurethane-silicon rubber composite material can be effectively improved, and the problem of poor flowability of the product in the reprocessing process is solved. Conventional dynamic vulcanization processes require the silicone rubber to be sheared and broken while being uniformly and fully crosslinked. In actual production, the crosslinking of silicone rubber can cause the melt viscosity of the system to rise sharply, the mass transfer to be poor, and the strong shearing heat generation is accompanied, so that great difficulty is brought to the process control. In the using process of the product, the fluidity of the product is obviously reduced due to a large amount of vulcanized silicone rubber particles, and the forming efficiency and the yield of the product are influenced. The silicon rubber component of the elastomer of the invention forms a crosslinking structure only after cooling, the good fluidity is always kept in the processing process, the reversible crosslinking agent can uniformly react with the vinyl, the strict process control is not needed, and even the charging sequence can be flexibly adjusted. In the using process of the product, the silicon rubber is subjected to secondary crosslinking at high temperature, so that the elastomer shows good fluidity, and the problem that similar products are difficult to process is solved.
The thermoplastic polyurethane refers to a thermoplastic elastomer containing a urethane functional group, and includes any one of polyether type thermoplastic polyurethane, polyester type thermoplastic polyurethane, polycarbonate type thermoplastic polyurethane, and fatty type thermoplastic polyurethane. Generally, such thermoplastic polyurethanes are obtained by reacting an organic diisocyanate, a polyether polyol or polyester polyol, and a chain extender, etc. In the formula system, polyurethane is used as a continuous phase component, so that the advantages of high strength, good wear resistance, low temperature resistance and the like can be fully utilized.
The silicone rubber is high-temperature vulcanized silicone rubber and comprises a siloxane polymer and a reinforcing filler; wherein the mass portion of the reinforcing filler is 10-50%; the Shore A hardness of the vulcanized silicone rubber is 30-70A.
Silicone rubber is the safest and nontoxic elastomeric material, and has a soft touch and excellent high and low temperature resistance. Silicone rubbers reinforced with fillers typically have Shore A hardness of 10-90A. In the formula system of the invention, the silicone rubber with Shore A hardness lower than 30A has too large difference with polyurethane components in modulus and strength, and the prepared elastomer has lower mechanical property; the flexibility of the silicone rubber with the Shore A hardness higher than 70A is not enough, and the hardness of the elastomer cannot be effectively reduced.
The moles of ethylene units in the siloxane polymer constitute 0.02-2% of the total moles; the reinforcing filler comprises mineral fillers such as white carbon black, calcium carbonate, wollastonite, diatomite and the like, and metal oxides and hydroxides such as alumina, magnesium oxide and the like.
The catalyst comprises a complex of platinum or rhodium; the mass ratio of the effective component in the catalyst to the silicon rubber is 5 multiplied by 10-5～5×10-3:100. The effective component in the catalyst refers to the mass content of platinum or rhodium in the catalyst.
Preferably, the catalyst comprises a complex of platinum with tetramethyldivinyldisiloxane (Karstedt's catalyst) or an alcoholic solution of chloroplatinic acid; further preferably, the catalysisThe mass ratio of the agent to the silicone rubber is 2X 10-5～2×10-3:100. In the usual hydrosilylation cross-linking silicone rubber reactions, the amount of catalyst must be strictly optimized to achieve the optimum cross-linking rate. In the invention, the silicon rubber is always in a de-crosslinking state in the hydrosilylation reaction process, and the viscosity of the system is not increased rapidly along with the addition of the catalyst, so that higher catalyst dosage can be adopted within an acceptable cost range.
The compatilizer is selected from silane coupling agent or polymer containing siloxane component, wherein the molecule of the silane coupling agent contains one or more of epoxy group, amino group, isocyanate group, carboxyl group, acid anhydride, silanol or amido group, and the polymer comprises KH550, KH560, KH570, isocyanate propyl triethoxysilane, hydroxyl silicone oil, amino silicone oil, epoxy modified silicone oil and the like.
The mass fraction of the compatilizer in the organic silicon-polyurethane thermoplastic elastomer is 0.05-5%.
The invention also provides a preparation method of the organic silicon-polyurethane thermoplastic elastomer, which is obtained by melting and blending thermoplastic polyurethane, silicon rubber, a reversible cross-linking agent, a catalyst and a compatilizer.
The blending temperature is 160-210 ℃ in the preparation process.
In the conventional preparation process of the polyurethane thermal elastomer, the adding sequence of the main material, the auxiliary agent or the cross-linking agent has strict requirements, and the reduction of the processing performance of the product caused by the advance cross-linking of the silicon rubber is avoided, but the preparation method of the organic silicon-polyurethane thermoplastic elastomer is insensitive to the adding sequence of the raw materials, can adopt various adding sequences, and the optional adding modes can be exemplified as follows:
(1) adding the thermoplastic polyurethane into a mixing device at a processing temperature, sequentially adding the silicon rubber, the compatilizer, the reversible crosslinking agent and the catalyst after the thermoplastic polyurethane is melted, or mixing the reversible crosslinking agent and the silicon rubber on a kneader or a double-roll open mill or the like at normal temperature in advance, and adding the mixture into a reaction system. The method is similar to the dynamic vulcanization technology in the feeding sequence, and is different in that the cross-linking agent is in a dissociation state in the mixing process, and practically no or few cross-linking occurs, so that strong shearing is not needed to realize the crushing of the silicon rubber, and only proper shearing and mixing are needed to ensure that a two-phase structure reaches a stable state. The requirements of the process on the process control precision and the equipment power are far lower than those of the dynamic vulcanization method;
(2) adding the silicon rubber, the reversible cross-linking agent and the catalyst into mixing equipment at a processing temperature, fully reacting, and then pelletizing. The obtained silicone rubber particles are processed with thermoplastic polyurethane and a compatilizer in a mixing device according to a conventional blending method. The method divides the preparation process into two steps, can make the hydrosilylation reaction of the silicon rubber more complete, and simplifies the second mixing process, for example, a double screw extruder with shorter length-diameter ratio can be adopted.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the molten state of the organic silicon-polyurethane thermoplastic elastomer, the silicon rubber component can automatically remove crosslinking, so that the elastomer has better fluidity; after the molding and cooling, the silicone rubber components recover the cross-linking state, the internal phase structure can be flexibly adjusted, and the elastomer is endowed with excellent mechanical properties and touch feeling.
(2) The organic silicon-polyurethane thermoplastic elastomer can be prepared by the traditional banburying or extrusion technology, has no requirement on the charging sequence of raw materials, has simple and convenient process, and is beneficial to realizing stable and efficient production.
(3) The organosilicon-polyurethane thermoplastic elastomer does not have crosslinking and crushing of the elastomer in the preparation process, and the reaction and mixing speed do not need to be accurately controlled, so that a simpler and more flexible preparation process can be adopted.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The raw materials used in the examples and comparative examples are as follows:
thermoplastic Polyurethane (TPU)
TPU 1: commercial Covestro Desmopan 9370;
TPU 2: commercially available Covestro Desmopan 85085 a.
Silicone Rubber (SR)
SR 1: the material is commercially available Wacker Elastosil R401/30, and the reinforcing filler is fumed silica with the mass fraction of about 25 percent and the Shore hardness of 30A;
SR 2: the reinforcing filler of the commercial Wacker Elastosil R401/70 is fumed silica with the mass fraction of about 35 percent and the Shore hardness of 70A.
Self-making of a reversible cross-linking agent: adding 73g of alkoxylamine diol and 0.73g of 4-dimethylaminopyridine into a glass reaction kettle, adding 5L of tetrahydrofuran and 100g of triethylamine under the protection of nitrogen, cooling in an ice-water bath for 30min, then slowly adding 71g of dimethylchlorosilane, and after reacting for 0.5h, continuing to react for 12h at room temperature. Centrifuging the solution, taking supernatant, and evaporating the solvent to obtain a dark red product, wherein the structural formula is as follows:
hydrogen-containing silicone oil crosslinking agent: commercially available, H content (mass fraction) 1.5%, viscosity 100 cst.
Compatilizer
COM 1: commercially available gamma-glycidoxypropyltrimethoxysilane (KH 560);
COM 2: commercially available isocyanatopropyltriethoxysilane.
Catalyst: commercial Heraeus Karstedt catalyst with a platinum content (mass fraction) of 3000 ppm.
The test methods for the experimental results in examples and comparative examples are as follows:
shore (Shore A) hardness: ASTM D2240;
tensile strength: ASTM D412;
elongation at break: ASTM D412;
tear strength: ASTM D624(Die C);
melt Flow Rate (MFR): ASTM D1238, 10kg, 190 ℃;
test specimens were prepared in a press vulcanizer at a mold temperature of 190 ℃.
Examples 1 to 2
Weighing the raw materials according to the proportion in the table 1, adding TPU into a torque rheometer, adding SR after torque is stable, mixing for 2min, adding a reversible cross-linking agent and a compatilizer, adding a catalyst after torque is stable, and mixing for 3 min. The mixing temperature of the torque rheometer was 180 ℃ and the rotational speed was 80 rpm.
Example 3
The raw materials are weighed according to the proportion in the table 1, SR and the reversible cross-linking agent are added into a torque rheometer and mixed for 2min, the catalyst is added, after the torque is stable, TPU and the compatilizer are added, and the mixture is continuously mixed for 2 min. The mixing temperature of the torque rheometer was 180 ℃ and the rotational speed was 80 rpm.
Comparative examples 1 to 2
Weighing the raw materials according to the proportion in the table 1, adding TPU into a torque rheometer, adding SR after torque is stable, mixing for 2.5min, adding hydrogen-containing silicone oil, adding a catalyst after torque is stable, and mixing for 3 min. The mixing temperature of the torque rheometer was 180 ℃ and the rotational speed was 80 rpm.
Comparative example 3
Weighing the raw materials according to the proportion in the table 1, adding the TPU into a torque rheometer, adding the SR after the torque is stable, and mixing for 2.5 min. The mixing temperature of the torque rheometer was 180 ℃ and the rotational speed was 80 rpm.
The elastomers prepared in the examples and comparative examples were subjected to formation tests, and the raw material ratios and the properties of the products are shown in table 1.
TABLE 1 raw material proportions and product Properties
As can be seen from Table 1, in example 1, compared with example 2, by adjusting the ratio of the two phases of silicone rubber and polyurethane, elastomers with different hardness can be prepared. Because the mechanical strength of the polyurethane is generally higher than that of silicon rubber, the higher the addition proportion of the silicon rubber is, the lower the hardness of the elastomer is, and the mechanical strength is reduced along with the hardness;
example 1 the use of different grades of polyurethane and silicone rubber had a significant impact on the physical properties of the elastomer as compared to example 3. By adopting the silicone rubber and the polyurethane with higher hardness, the mechanical strength of the elastomer can be greatly improved, but the hardness of the elastomer is increased and the elongation at break is reduced. In the formula development, the types and proportions of the raw materials can be flexibly adjusted according to specific use requirements;
compared with the comparative example 1, the elastomer prepared by the reversible crosslinking agent is closer to the elastomer prepared by the conventional hydrogen-containing silicone oil crosslinking agent in mechanical property, but the melt flow rate is obviously higher than that of the elastomer prepared by the conventional hydrogen-containing silicone oil crosslinking agent, namely, the elastomer shows obviously better processing flowability;
compared with the comparative example 2, the silicone rubber-polyurethane elastomer prepared by adopting the simple blending mode has very poor mechanical property and limited use value although the silicone rubber-polyurethane elastomer has very good fluidity.
In summary, the technology disclosed in the invention can be used for conveniently preparing the organic silicon-polyurethane thermoplastic elastomer with different hardness. Compared with the traditional dynamic vulcanization technology, the elastomer prepared by the technology has better fluidity (higher melt flow rate) and close mechanical properties. Compared with simple blending, the elastomer prepared by the technology has better mechanical property.
Claims (9)
1. An organic silicon-polyurethane thermoplastic elastomer is characterized by comprising thermoplastic polyurethane, silicon rubber, a reversible cross-linking agent, a catalyst and a compatilizer; wherein the mass ratio of the thermoplastic polyurethane to the silicone rubber is 30: 70-80: 20;
the reversible crosslinking agent has the structural formula of formula (1):
in the formula, R1、R2、R3And R4Independently is C1-5 alkyl, C1-5 haloalkyl or phenyl;
the mass ratio of the reversible cross-linking agent to the silicon rubber is 0.1-4: 100.
2. The silicone-polyurethane thermoplastic elastomer according to claim 1, wherein the thermoplastic polyurethane refers to a thermoplastic elastomer containing a urethane functional group, and includes any one of polyether type thermoplastic polyurethane, polyester type thermoplastic polyurethane, polycarbonate type thermoplastic polyurethane, and fatty type thermoplastic polyurethane.
3. The silicone-polyurethane thermoplastic elastomer of claim 1, wherein the silicone rubber is a high temperature vulcanized silicone rubber comprising a silicone polymer and a reinforcing filler; wherein the mass portion of the reinforcing filler is 10-50%; the Shore A hardness of the vulcanized silicone rubber is 30-70A.
4. The silicone-polyurethane thermoplastic elastomer of claim 3, wherein the moles of ethylene units in the siloxane polymer comprise 0.02-2% of the total moles; the reinforcing filler comprises one or more of white carbon black, calcium carbonate, wollastonite, diatomite, alumina and magnesium oxide.
5. The silicone-polyurethane thermoplastic elastomer of claim 1, wherein the catalyst comprises a complex of platinum or rhodium; the mass ratio of the effective component in the catalyst to the silicon rubber is 5 multiplied by 10-5～5×10-3:100。
6. The silicone-polyurethane thermoplastic elastomer of claim 1 or 5, wherein the catalyst comprises a complex of platinum with tetramethyldivinyldisiloxane or an alcohol solution of chloroplatinic acid.
7. The silicone-polyurethane thermoplastic elastomer of claim 1, wherein the compatibilizer comprises a polymer of a silane coupling agent having a siloxane component; the mass fraction of the compatilizer in the organic silicon-polyurethane thermoplastic elastomer is 0.05-5%.
8. A method for preparing the organosilicon-polyurethane thermoplastic elastomer as claimed in any one of claims 1 to 7, wherein the thermoplastic polyurethane, the silicone rubber, the reversible crosslinking agent, the catalyst and the compatibilizer are melt blended to obtain the silicone-polyurethane thermoplastic elastomer.
9. The method for preparing the silicone-polyurethane thermoplastic elastomer as claimed in claim 8, wherein the blending temperature is 160-210 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011528390.1A CN112646354A (en) | 2020-12-22 | 2020-12-22 | Organic silicon-polyurethane thermoplastic elastomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011528390.1A CN112646354A (en) | 2020-12-22 | 2020-12-22 | Organic silicon-polyurethane thermoplastic elastomer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112646354A true CN112646354A (en) | 2021-04-13 |
Family
ID=75359124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011528390.1A Pending CN112646354A (en) | 2020-12-22 | 2020-12-22 | Organic silicon-polyurethane thermoplastic elastomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112646354A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114058187A (en) * | 2021-12-03 | 2022-02-18 | 东莞市蔚美硅材料科技有限公司 | Silicone rubber with low permanent deformation at break and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010047684A (en) * | 2008-08-21 | 2010-03-04 | Olympus Corp | Thermoplastic silicone rubber composition and molded article |
| CN102153853A (en) * | 2011-03-16 | 2011-08-17 | 广东工业大学 | Polyurethane/silicon rubber thermoplastic elastomer and preparation method thereof |
| WO2013127989A1 (en) * | 2012-03-02 | 2013-09-06 | Fundación Cidetec | Self-healing elastomeric material |
| CN106751736A (en) * | 2017-01-20 | 2017-05-31 | 成都康普斯科技有限公司 | A kind of silicon rubber/polyurethane termoplastic elastomer and preparation method thereof |
| CN107057361A (en) * | 2017-05-17 | 2017-08-18 | 安徽万朗磁塑股份有限公司 | A kind of thermoplastic vulcanizates silicon rubber refrigerator sealing strip material |
| CN109135293A (en) * | 2017-06-28 | 2019-01-04 | 万华化学集团股份有限公司 | A kind of dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer and preparation method thereof |
| CN109608866A (en) * | 2018-11-30 | 2019-04-12 | 广东省石油与精细化工研究院 | Thermally conductive thermoplastic dynamic vulcanized silicon rubber of one kind and preparation method thereof |
| CN110591051A (en) * | 2019-09-30 | 2019-12-20 | 常州大学 | Preparation method and application of silicone rubber film with underwater self-healing capability and adhesiveness |
| CN110606986A (en) * | 2019-09-20 | 2019-12-24 | 杭州聚丰新材料有限公司 | Silicone rubber cross-linking agent, and preparation method and application thereof |
-
2020
- 2020-12-22 CN CN202011528390.1A patent/CN112646354A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010047684A (en) * | 2008-08-21 | 2010-03-04 | Olympus Corp | Thermoplastic silicone rubber composition and molded article |
| CN102153853A (en) * | 2011-03-16 | 2011-08-17 | 广东工业大学 | Polyurethane/silicon rubber thermoplastic elastomer and preparation method thereof |
| WO2013127989A1 (en) * | 2012-03-02 | 2013-09-06 | Fundación Cidetec | Self-healing elastomeric material |
| CN106751736A (en) * | 2017-01-20 | 2017-05-31 | 成都康普斯科技有限公司 | A kind of silicon rubber/polyurethane termoplastic elastomer and preparation method thereof |
| CN107057361A (en) * | 2017-05-17 | 2017-08-18 | 安徽万朗磁塑股份有限公司 | A kind of thermoplastic vulcanizates silicon rubber refrigerator sealing strip material |
| CN109135293A (en) * | 2017-06-28 | 2019-01-04 | 万华化学集团股份有限公司 | A kind of dynamic vulcanization silicon rubber/thermoplastic polyurethane elastomer and preparation method thereof |
| CN109608866A (en) * | 2018-11-30 | 2019-04-12 | 广东省石油与精细化工研究院 | Thermally conductive thermoplastic dynamic vulcanized silicon rubber of one kind and preparation method thereof |
| CN110606986A (en) * | 2019-09-20 | 2019-12-24 | 杭州聚丰新材料有限公司 | Silicone rubber cross-linking agent, and preparation method and application thereof |
| CN110591051A (en) * | 2019-09-30 | 2019-12-20 | 常州大学 | Preparation method and application of silicone rubber film with underwater self-healing capability and adhesiveness |
Non-Patent Citations (2)
| Title |
|---|
| 师文博，等: "热塑性动态硫化硅橡胶的制备及其性能研究", 《广东化工》 * |
| 段辉平，等编: "《材料科学与工程实验教程》", 30 April 2019, 北京航空航天大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114058187A (en) * | 2021-12-03 | 2022-02-18 | 东莞市蔚美硅材料科技有限公司 | Silicone rubber with low permanent deformation at break and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2464455C (en) | Thermoplastic polyurethane-silicone elastomers | |
| JP2668534B2 (en) | Thermoplastic polyurethane resin composition for extrusion molding and injection molding | |
| CN1307218C (en) | Diene rubber, process for production thereof, rubber compositions, process for producing the same, and crosslinked rubbers | |
| CN108587123B (en) | Dynamically vulcanized thermoplastic polyurethane/polysiloxane elastomer and preparation method thereof | |
| CN109694581B (en) | Dynamic vulcanized silicone rubber/thermoplastic polyurethane elastomer material and preparation method thereof | |
| EP3033367B1 (en) | Compatibilized tire tread compositions | |
| CN109265967B (en) | Matte TPU material and preparation method thereof | |
| CN110467713A (en) | Thermoplastic silicone polyurethane elastomer material and preparation method thereof | |
| CN109181278B (en) | Polyurethane/fluorosilicone rubber thermoplastic elastomer and preparation method thereof | |
| EP3775048B1 (en) | Thermoplastic composition | |
| CN1989179A (en) | Cross-linkable siloxane urea copolymers | |
| CN111808430A (en) | Fluorosilicone rubber compound and preparation method thereof | |
| CN100480332C (en) | Heat cured silicon rubber nano composite material and preparation process thereof | |
| KR101740339B1 (en) | Thermoplastic Silicone Elastomer, Method for the Preparation Thereof and Thermoplastic Silicone Elastomer Composition | |
| CN112646354A (en) | Organic silicon-polyurethane thermoplastic elastomer and preparation method thereof | |
| CN113088090A (en) | High-resilience low-pressure-change silicone rubber material and preparation method thereof | |
| CN105367985A (en) | TPE composition and high toughness EVA product prepared from TPE composition | |
| CA1188838A (en) | Oil extended silicone elastomer composition | |
| Zhang et al. | Polyurethane-polysiloxane copolymer compatibilized SiR/TPU TPV with comfortable human touch toward wearable devices | |
| JPH07149987A (en) | Rubber composition | |
| CN109943025A (en) | A kind of thermoplastic polyester elastomer alloy and preparation method thereof | |
| CN107541004A (en) | A kind of anti-load endurance type TPE thermoplastic elastomer (TPE)s and preparation method thereof | |
| CN111154265B (en) | Silicone rubber/polybutylene succinate non-petroleum-based thermoplastic vulcanized rubber and preparation method thereof | |
| RU2622384C2 (en) | Filled elastomer containing polyurethane | |
| CN114058187A (en) | Silicone rubber with low permanent deformation at break 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210413 |