CN109593349B - Flame-retardant thermoplastic dynamic vulcanized silicone rubber and preparation method thereof - Google Patents
Flame-retardant thermoplastic dynamic vulcanized silicone rubber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses flame-retardant thermoplastic dynamic vulcanized silicone rubber and a preparation method thereof. The flame-retardant thermoplastic dynamic vulcanized silicone rubber is prepared from the following raw materials: thermoplastic polyurethane elastomer, silicon rubber compound, flame retardant, crosslinking agent, compatilizer and catalyst. Also discloses a method for preparing the flame-retardant thermoplastic dynamic vulcanized silicone rubber by dynamic vulcanization. The flame-retardant thermoplastic dynamic vulcanized silicone rubber prepared by the invention has the characteristics of good flame retardance, comfortable hand feeling, recoverability, excellent mechanical property and the like, and can be widely applied to the fields of electronics, electrics, automobiles, war industry, communication and the like.
Description
Technical Field
The invention relates to flame-retardant thermoplastic dynamic vulcanized silicone rubber and a preparation method thereof.
Background
Dynamic vulcanization is a new rubber vulcanization technology, and is a process of melting and blending unvulcanized rubber and a thermoplastic material under the action of high shear, and simultaneously adding a vulcanizing agent to vulcanize the unvulcanized rubber and the thermoplastic material. In this process, the thermoset rubber phase (dispersed phase) is uniformly dispersed in the thermoplastic material (continuous phase) in a certain particle size range, and the rubber phase particles are crosslinked, finally obtaining thermoplastic dynamic vulcanizate (TPV). The main characteristic of dynamic vulcanization is that the rubber phase which is thermosetting is loaded in the thermoplastic material, so that the characteristics of the thermosetting rubber and the thermoplastic plastic are combined, and the processing and recycling of the material are facilitated.
Thermoplastic polyurethane elastomers (TPU) are thermoplastic elastomers with excellent properties, are divided into two main types of polyethers and polyesters, are polymerized from isocyanate and polyol, have excellent mechanical properties, oil resistance and wear resistance, but have poor weather resistance and processability. Among them, polyether TPU has excellent mechanical properties, and also has higher hydrolysis resistance and weather resistance, and is widely favored by the market. However, the flame retardancy of polyether TPU is poor, which greatly limits the application of the polyether TPU in various industries.
The silicon rubber is rubber with a main chain formed by alternating silicon and oxygen atoms, and two organic groups are connected to the silicon atoms, so that the silicon rubber has excellent hand feeling and good weather resistance, can keep stable mechanical property at the temperature of between 40 ℃ below zero and 200 ℃, and keeps certain toughness, rebound resilience and hardness. Meanwhile, the silicon rubber has excellent flame retardant property, and a carbonized layer is formed on the surface of the silicon rubber during combustion to isolate air so as to prevent the continuous combustion of flame.
Therefore, the problems can be effectively solved by combining the characteristics of TPU and silicone rubber. In the prior art, US4500688 and CN106751736A both prepare TPU/silicone rubber thermoplastic elastomers through different dynamic vulcanization systems, but flame retardant thermoplastic dynamic vulcanized silicone rubber is not further studied. CN108485011A prepares flame-retardant thermoplastic vulcanized rubber with styrene-isoprene-butadiene/polypropylene as a base material by a dynamic vulcanization method, but the base material and the flame-retardant mechanism of the flame-retardant thermoplastic dynamic vulcanized rubber are essentially different from those of the flame-retardant thermoplastic dynamic vulcanized rubber of the invention. CN106349685A prepares a flame-retardant polyurethane cable material by a simple blending method, and the flame-retardant polyurethane cable material is essentially different from the flame-retardant thermoplastic dynamic vulcanized silicone rubber of the invention.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the flame-retardant thermoplastic dynamic vulcanized silicone rubber with good flame retardance, recoverability and excellent mechanical property by using a dynamic vulcanization method and the preparation method thereof. According to the invention, the thermoplastic dynamic vulcanized silicone rubber with flame retardant property is prepared in one step through dynamic vulcanization, and simultaneously, the great damage of the addition of a flame retardant to the material performance during simple blending is avoided, and the obtained product has silky handfeel and excellent mechanical property and flame retardance.
The technical scheme adopted by the invention is as follows:
the flame-retardant thermoplastic dynamic vulcanized silicone rubber is prepared from the following raw materials in parts by mass: 30-70 parts of thermoplastic polyurethane elastomer, 30-70 parts of silicone rubber compound, 10-30 parts of flame retardant, 1-5 parts of cross-linking agent, 5-20 parts of compatilizer and 0.01-0.5 part of catalyst.
Preferably, in the flame-retardant thermoplastic dynamic vulcanized silicone rubber, the thermoplastic polyurethane elastomer is at least one of polyether type TPU and polyester type TPU.
Preferably, in the flame-retardant thermoplastic dynamic vulcanized silicone rubber, the Shore hardness of the thermoplastic polyurethane elastomer is 60A-95A.
Preferably, in the flame-retardant thermoplastic dynamic vulcanized silicone rubber, the silicone rubber compound is white carbon black reinforced methyl vinyl silicone rubber (or called methyl vinyl raw rubber); more preferably, the method for reinforcing the methyl vinyl silicone rubber crude rubber by the white carbon black is a gas phase method or a precipitation method.
Preferably, the flame-retardant thermoplastic dynamic vulcanized silicone rubber has a vinyl group molar content of 0.04-0.5% in the silicone rubber compound.
Preferably, in the flame-retardant thermoplastic dynamic vulcanized silicone rubber, the flame retardant is an aryl phosphate ester flame retardant; further preferably, the flame retardant is at least one of bisphenol a-bis (diphenyl phosphate) (BDP), triphenyl phosphate (TPP), resorcinol bis (diphenyl phosphate) (RDP); still more preferably, the flame retardant is bisphenol a-bis (diphenyl phosphate).
Preferably, in the flame-retardant thermoplastic dynamic vulcanized silicone rubber, the cross-linking agent is siloxane containing Si-H bonds; more preferably, the cross-linking agent is hydrogen-containing silicone oil, and the molar content of Si-H bonds in the cross-linking agent is 0.4-2%.
Preferably, in the flame-retardant thermoplastic dynamic vulcanized silicone rubber, the compatilizer is at least one of ethylene acrylic acid copolymer (EAA), ethylene methyl acrylate copolymer (EMA) and ethylene vinyl acetate copolymer (EVA).
Preferably, in the flame-retardant thermoplastic dynamic vulcanized silicone rubber, the catalyst is a platinum catalyst; further, the platinum-based catalyst is selected from metallic platinum, platinum black, a platinum-supported catalyst, or a platinum-containing alloy.
The preparation method of the flame-retardant thermoplastic dynamic vulcanized silicone rubber comprises the following steps:
1) in an internal mixer or an extruder, melting and blending the thermoplastic polyurethane elastomer, the silicone rubber compound, the flame retardant, the crosslinking agent and the compatilizer, extruding and granulating to obtain a premix;
2) and mixing the premix with a catalyst, adding the mixture into a double-screw extruder to perform dynamic vulcanization reaction, extruding and granulating to obtain the flame-retardant thermoplastic dynamic vulcanized silicone rubber.
Preferably, in step 1) of the preparation method of the flame-retardant thermoplastic dynamic vulcanized silicone rubber, the melt blending process parameters are as follows: the temperature is 160-200 ℃, the time is 3-10 min, and the rotating speed is 30-100 r/min.
Preferably, in step 2) of the preparation method of the flame-retardant thermoplastic dynamic vulcanized silicone rubber, the process parameters of the twin-screw extruder are as follows: the processing temperature is 170-210 ℃, the screw rotating speed is 200-320 r/min, and the dynamic vulcanization reaction time is 1-4 min.
The invention has the beneficial effects that:
the flame-retardant thermoplastic dynamic vulcanized silicone rubber prepared by the invention has the characteristics of good flame retardance, comfortable hand feeling, recoverability, excellent mechanical property and the like, and can be widely applied to the fields of electronics, electrics, automobiles, war industry, communication and the like.
Compared with the prior art, the invention has the following advantages:
1) according to the invention, by virtue of a dynamic vulcanization technology, dynamic crosslinking of the silicon rubber in a thermoplastic polyurethane elastomer melt is realized under the action of high-temperature shearing in the extrusion process, and meanwhile, uniform dispersion of a flame retardant in a polymer is realized, so that the flame retardance of the material is improved, and meanwhile, the performance loss caused by repeated processing of the dynamic vulcanized silicon rubber for realizing functionalization is avoided.
2) The invention realizes the thermodynamic compatibility of thermoplastic polyurethane elastomer (TPU) with larger polarity difference and silicon rubber by adding the compatilizer, and simultaneously realizes the thermodynamic compatibility of an organic high polymer material phase and an inorganic flame-retardant material phase, so that the prepared flame-retardant thermoplastic dynamic vulcanized silicon rubber has excellent mechanical property (the tensile strength can reach 13MPa) and flame-retardant property (UL-94: v-0).
3) The raw materials and processing equipment used in the invention are common industrial raw materials and equipment, are convenient to use and low in cost, can realize large-scale industrial production, have no solvent or toxic volatile gas pollution, meet the requirements of environmental protection, and have practical significance.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention. The starting materials/equipment used in the examples were all available from conventional commercial sources unless otherwise specified. The methods for detecting the performance parameters of the silicone rubber are standard test methods known in the art unless otherwise specified.
Examples 1 to 3 and comparative example 1
The compositions of the silicone rubbers of examples 1 to 3 and comparative example 1 are shown in table 1, and the compositions described in table 1 are all parts by mass.
TABLE 1 Silicone rubber compositions of examples 1-3 and comparative example 1
| Name (R) | TPU | Silicone rubber compound | Compatilizer | Crosslinking agent | Catalyst and process for preparing same | Flame retardant |
| Example 1 | 70 | 30 | 5 | 2.5 | 0.05 | 10 |
| Example 2 | 50 | 50 | 5 | 2.5 | 0.05 | 10 |
| Example 3 | 30 | 70 | 5 | 2.5 | 0.05 | 10 |
| Comparative example 1 | 70 | 30 | 5 | 0 | 0 | 10 |
The preparation method of the flame-retardant thermoplastic dynamic vulcanized silicone rubber of the embodiment 1-3 comprises the following steps:
step one), adding a thermoplastic polyurethane elastomer (TPU), a silicone rubber compound, a compatilizer, a crosslinking agent and a flame retardant in a formula shown in Table 1 into an internal mixer, setting the temperature at 160 ℃, the rotating speed at 100rpm, and the internal mixing time for 10min, and extruding and granulating to obtain a premix. The thermoplastic polyurethane elastomer used in examples 1 to 3 was WHT-8285 (polyether) available from Wanhua chemical company, the silicone rubber compound was EN-5150A available from Token organosilicon company, the compatibilizer was EVA, the crosslinking agent was hydrogen-containing silicone oil available from Dow Corning company, the type was JHF-901, the platinum catalyst was RD7 platinum catalyst available from Dow Corning company, and the flame retardant was bisphenol A-bis (diphenyl phosphate) (BDP).
And step two), adding the premix obtained in the step one into a catalyst platinum in a formula shown in Table 1, uniformly mixing, adding into a double-screw extruder, setting the temperature at 190 ℃ and the rotating speed of screws at 250rpm, carrying out dynamic vulcanization reaction for 2min, and extruding and granulating to obtain the flame-retardant thermoplastic dynamic vulcanized silicone rubber. The prepared flame-retardant thermoplastic dynamic vulcanized silicone rubber has uniform appearance and comfortable hand feeling.
The silicone rubber of comparative example 1 was prepared as follows:
the formulations in Table 1 were prepared according to the process parameters of examples 1-3, but without the addition of a crosslinking agent and catalyst (i.e., using a non-dynamic vulcanization process), to obtain samples.
The performance parameters of examples 1-3 and comparative example 1 are shown in Table 2.
TABLE 2 Silicone rubber Performance parameters for examples 1-3 and comparative example 1
As can be seen by comparison, the performances of examples 1-3 prepared by dynamic vulcanization are obviously superior to those of comparative example 1. Examples 4 to 6 and comparative example 2
The compositions of the silicone rubbers of examples 4 to 6 and comparative example 2 are shown in table 3, and the compositions described in table 3 are all parts by mass.
TABLE 3 Silicone rubber compositions for examples 4-6 and comparative example 2
| Name (R) | TPU | Silicone rubber compound | Compatilizer | Crosslinking agent | Catalyst and process for preparing same | Flame retardant |
| Example 4 | 60 | 40 | 5 | 2 | 0.1 | 10 |
| Example 5 | 60 | 40 | 10 | 2 | 0.1 | 10 |
| Example 6 | 60 | 40 | 20 | 2 | 0.1 | 10 |
| Comparative example 2 | 60 | 40 | 0 | 2 | 0.1 | 10 |
The preparation method of the flame-retardant thermoplastic dynamic vulcanized silicone rubber of the embodiment 4-6 comprises the following steps:
step one), adding a thermoplastic polyurethane elastomer (TPU), a silicone rubber compound, a compatilizer, a crosslinking agent and a flame retardant in a formula shown in Table 3 into an internal mixer, setting the temperature at 200 ℃, the rotating speed at 30rpm, and the internal mixing time for 3min, and extruding and granulating to obtain a premix. The thermoplastic polyurethane elastomer used in examples 4 to 6 was S-185ALL (polyester) from Taiwan Queen corporation, the silicone rubber compound was EN-8151 from Dongjue Silicone corporation, the compatibilizer was ethylene acrylic acid copolymer (EAA), the crosslinking agent was hydrogen-containing silicone oil from Dow Corning corporation, the model was JHF-901, the platinum catalyst was RD7 platinum catalyst from Dow Corning corporation, and the flame retardant was RDP.
And step two), adding the premix obtained in the step one into a catalyst platinum in a formula shown in Table 3, uniformly mixing, adding into a double-screw extruder, setting the temperature at 200 ℃, setting the rotating speed of the screws at 300rpm, carrying out dynamic vulcanization reaction for 3min, and extruding and granulating to obtain the flame-retardant thermoplastic dynamic vulcanized silicone rubber. The prepared flame-retardant thermoplastic dynamic vulcanized silicone rubber has uniform appearance and comfortable hand feeling.
The silicone rubber of comparative example 2 was prepared as follows:
the formulations in Table 3 were prepared according to the process parameters of examples 4-6, but without the addition of a compatibilizer to obtain samples.
The performance parameters of examples 4-6 and comparative example 2 are shown in Table 4.
TABLE 4 Silicone rubber Performance parameters for examples 4-6 and comparative example 2
As can be seen by comparison, the performance of examples 4-6 prepared by dynamic vulcanization after the addition of the compatibilizer is significantly better than that of comparative example 2.
Examples 7 to 10 and comparative example 3
The compositions of the silicone rubbers of examples 7 to 10 and comparative example 3 are shown in table 5, and the compositions described in table 5 are all parts by mass.
TABLE 5 Silicone rubber compositions of examples 7-10 and comparative example 3
The preparation method of the flame-retardant thermoplastic dynamic vulcanized silicone rubber of the embodiment 7-10 comprises the following steps:
step one), adding a thermoplastic polyurethane elastomer (TPU), a silicone rubber compound, a compatilizer, a crosslinking agent and a flame retardant in a formula shown in Table 5 into an internal mixer, setting the temperature at 190 ℃, the rotating speed at 80rpm, and the internal mixing time for 4min, and extruding and granulating to obtain a premix. The thermoplastic polyurethane elastomer used in examples 7 to 10 was WHT-8285 of Wanhua chemical company, the silicone rubber compound was EN-5150A of Dongjue organosilicon company, the compatibilizer was EMA, the crosslinking agent was hydrogen-containing silicone oil of Dow Corning company, the model was JHF-901, the platinum catalyst was RD7 platinum catalyst of Dow Corning company, and the flame retardant was TPP.
And step two), adding the premix obtained in the step one into a catalyst platinum in a formula shown in Table 5, uniformly mixing, adding into a double-screw extruder, setting the temperature at 210 ℃ and the rotating speed of screws at 320rpm, carrying out dynamic vulcanization reaction for 1min, and extruding and granulating to obtain the flame-retardant thermoplastic dynamic vulcanized silicone rubber. The prepared flame-retardant thermoplastic dynamic vulcanized silicone rubber has uniform appearance and comfortable hand feeling.
The silicone rubber of comparative example 3 was prepared as follows:
step one) the formulations in table 5 were prepared (without crosslinker and catalyst in the formulation, i.e. using a non-dynamic vulcanization process) according to the process parameters of examples 7-10, but without adding flame retardant, to obtain a premix.
And step two), adding the premix obtained in the step one into a flame retardant in a formula shown in Table 5, simply blending in a double-screw extruder, setting the temperature at 210 ℃ and the rotating speed of screws at 320rpm, and extruding and granulating to obtain a sample.
The performance parameters of examples 7-10 and comparative example 3 are shown in Table 6.
TABLE 6 Silicone rubber Performance parameters for examples 7-10 and comparative example 3
As can be seen by comparison, the performances of examples 7-10 prepared by dynamic vulcanization are obviously superior to those of comparative example 3. Examples 11 to 13 and comparative example 4
The compositions of the silicone rubbers of examples 11 to 13 and comparative example 4 are shown in table 7, and the compositions described in table 7 are all parts by mass.
TABLE 7 Silicone rubber compositions of examples 11-13 and comparative example 4
| Name (R) | TPU | Silicone rubber compound | Compatilizer | Crosslinking agent | Catalyst and process for preparing same | Flame retardant |
| Example 11 | 60 | 40 | 5 | 1 | 0.5 | 10 |
| Example 12 | 60 | 40 | 5 | 3 | 0.3 | 10 |
| Example 13 | 60 | 40 | 5 | 5 | 0.05 | 10 |
| Comparative example 4 | 60 | 40 | 5 | 0 | 0 | 10 |
The preparation method of the flame-retardant thermoplastic dynamic vulcanized silicone rubber of the embodiment 11-13 comprises the following steps:
step one), adding a thermoplastic polyurethane elastomer (TPU), a silicone rubber compound, a compatilizer, a crosslinking agent and a flame retardant in a formula shown in Table 7 into an internal mixer, setting the temperature at 160 ℃, the rotating speed at 80rpm, and the internal mixing time for 3min, and extruding and granulating to obtain a premix. The thermoplastic polyurethane elastomer used in examples 11 to 13 was WHT-8285 available from Wanhua chemical company, the silicone rubber compound was EN-5150A available from Token organosilicon company, the compatibilizer was EMA, the crosslinking agent was hydrogen-containing silicone oil available from Dow Corning company, the type was JHF-901, the platinum catalyst was RD7 platinum catalyst available from Dow Corning company, and the flame retardant was BDP.
And step two), adding the premix obtained in the step one into a catalyst platinum in a formula shown in Table 7, uniformly mixing, adding into a double-screw extruder, setting the temperature at 170 ℃, setting the rotating speed of screws at 200rpm, carrying out dynamic vulcanization reaction for 4min, and extruding and granulating to obtain the flame-retardant thermoplastic dynamic vulcanized silicone rubber. The prepared flame-retardant thermoplastic dynamic vulcanized silicone rubber has uniform appearance and comfortable hand feeling.
The silicone rubber of comparative example 4 was prepared as follows:
step one) the formulations in table 7 were prepared according to the process parameters of examples 11-13, but without the addition of cross-linking agents and catalysts (i.e., using a non-dynamic vulcanization process) to obtain a premix.
And step two), blending and extruding the premix in the step one in a double-screw extruder, setting the temperature at 170 ℃ and the rotating speed of the screw at 200rpm, and extruding and granulating to obtain a sample.
The performance parameters of examples 11-13 and comparative example 4 are shown in Table 8.
TABLE 8 Silicone rubber Performance parameters for examples 11-13 and comparative example 4
As can be seen by comparison, the performances of examples 11-13 prepared by dynamic vulcanization with different cross-linking agents and catalyst ratios are significantly better than those of comparative example 4.
Claims (3)
1. A flame-retardant thermoplastic dynamic vulcanized silicone rubber is characterized in that: the composite material is prepared from the following raw materials in parts by mass: 60 parts of thermoplastic polyurethane elastomer, 40 parts of silicone rubber compound, 10 parts of flame retardant, 2 parts of cross-linking agent, 20 parts of compatilizer and 0.1 part of catalyst;
the Shore hardness of the thermoplastic polyurethane elastomer is 60-95A;
the silicone rubber compound is methyl vinyl silicone rubber reinforced by white carbon black; the molar content of vinyl in the silicon rubber compound is 0.04-0.5%;
the flame retardant is resorcinol bis (diphenyl phosphate);
the cross-linking agent is hydrogen-containing silicone oil, and the molar content of Si-H bonds in the cross-linking agent is 0.4-2%;
the compatilizer is ethylene acrylic acid copolymer;
the preparation method of the flame-retardant thermoplastic dynamic vulcanized silicone rubber comprises the following steps:
1) in an internal mixer or an extruder, melting and blending the thermoplastic polyurethane elastomer, the silicone rubber compound, the flame retardant, the crosslinking agent and the compatilizer, extruding and granulating to obtain a premix;
2) mixing the premix with a catalyst, adding the mixture into a double-screw extruder to perform dynamic vulcanization reaction, extruding and granulating to obtain the flame-retardant thermoplastic dynamic vulcanized silicone rubber;
in the step 1), the melt blending process parameters are as follows: the temperature is 160-200 ℃, the time is 3-10 min, and the rotating speed is 30-100 r/min;
in the step 2), the technological parameters of the double-screw extruder are as follows: the processing temperature is 170-210 ℃, the screw rotating speed is 200-320 r/min, and the dynamic vulcanization reaction time is 1-4 min.
2. A flame retardant thermoplastic dynamic silicone sulfide rubber according to claim 1, wherein: the catalyst is a platinum catalyst.
3. The method for preparing a flame-retardant thermoplastic dynamic vulcanized silicone rubber according to any one of claims 1 to 2, characterized by comprising: the method comprises the following steps:
1) in an internal mixer or an extruder, melting and blending the thermoplastic polyurethane elastomer, the silicone rubber compound, the flame retardant, the crosslinking agent and the compatilizer, extruding and granulating to obtain a premix;
2) mixing the premix with a catalyst, adding the mixture into a double-screw extruder to perform dynamic vulcanization reaction, extruding and granulating to obtain the flame-retardant thermoplastic dynamic vulcanized silicone rubber;
in the step 1), the melt blending process parameters are as follows: the temperature is 160-200 ℃, the time is 3-10 min, and the rotating speed is 30-100 r/min;
in the step 2), the technological parameters of the double-screw extruder are as follows: the processing temperature is 170-210 ℃, the screw rotating speed is 200-320 r/min, and the dynamic vulcanization reaction time is 1-4 min.
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| CN112143231B (en) * | 2020-08-21 | 2022-03-29 | 北京化工大学 | Silicone rubber/polyurethane thermoplastic vulcanized rubber and preparation method and application thereof |
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| CN114316606B (en) * | 2021-12-31 | 2023-02-10 | 东莞市正安有机硅科技有限公司 | Polyolefin base material thermoplastic dynamic vulcanized silicone rubber particles and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2149719A5 (en) * | 1971-08-12 | 1973-03-30 | Uniroyal Inc | |
| WO2009017868A1 (en) * | 2007-07-27 | 2009-02-05 | Dow Global Technologies Inc. | Compositions of thermoplastic polyurethane (tpu), polybutadiene and polydiene-based tpu |
| CN102153853A (en) * | 2011-03-16 | 2011-08-17 | 广东工业大学 | Polyurethane/silicon rubber thermoplastic elastomer and preparation method thereof |
| CN105924972A (en) * | 2016-05-24 | 2016-09-07 | 北京化工大学 | Silicone rubber/polyurethane thermoplastic vulcanized rubber and preparing method thereof |
| CN105949773A (en) * | 2016-05-05 | 2016-09-21 | 成都硅宝科技股份有限公司 | Organosilicon thermoplastic film and preparation method thereof |
| CN106795369A (en) * | 2014-08-12 | 2017-05-31 | 玛尔提贝斯股份有限公司 | Thermoplastic polyurethane elastomer silicone |
| 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 |
-
2018
- 2018-11-30 CN CN201811458023.1A patent/CN109593349B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2149719A5 (en) * | 1971-08-12 | 1973-03-30 | Uniroyal Inc | |
| WO2009017868A1 (en) * | 2007-07-27 | 2009-02-05 | Dow Global Technologies Inc. | Compositions of thermoplastic polyurethane (tpu), polybutadiene and polydiene-based tpu |
| CN102153853A (en) * | 2011-03-16 | 2011-08-17 | 广东工业大学 | Polyurethane/silicon rubber thermoplastic elastomer and preparation method thereof |
| CN106795369A (en) * | 2014-08-12 | 2017-05-31 | 玛尔提贝斯股份有限公司 | Thermoplastic polyurethane elastomer silicone |
| CN105949773A (en) * | 2016-05-05 | 2016-09-21 | 成都硅宝科技股份有限公司 | Organosilicon thermoplastic film and preparation method thereof |
| CN105924972A (en) * | 2016-05-24 | 2016-09-07 | 北京化工大学 | Silicone rubber/polyurethane thermoplastic vulcanized rubber and preparing method thereof |
| 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 |
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