Butyl rubber type thermoplastic vulcanized rubber as well as preparation method and application thereof

Abstract

The invention provides butyl rubber type thermoplastic vulcanized rubber as well as a preparation method and application thereof. The thermoplastic vulcanized rubber comprises the following components: butyl rubber, polypropylene, a phenolic resin vulcanization system, an anti-aging agent, a softening agent and filler, the phenolic resin vulcanization system comprises a phenolic resin main vulcanizing agent and an auxiliary vulcanizing agent; the phenolic resin main vulcanizing agent is selected from at least one of octyl phenolic resin and tert-butyl phenolic resin; the auxiliary vulcanizing agent is selected from at least one of stannous chloride and tetrabromobisphenol A. The butyl rubber type thermoplastic vulcanized rubber provided by the invention is prepared from butyl rubber, polypropylene and a composite phenolic resin vulcanization system through a dynamic vulcanization method, tetrabromobisphenol A and stannous chloride are adopted as co-vulcanizing agents to form the phenolic resin vulcanization system containing chlorine and bromine halogens, and a proper amount of white carbon black is contained in filler. The composition is simple, sulfur and an accelerant thereof are not contained, and the obtained butyl rubber type thermoplastic vulcanized rubber is excellent in mechanical property and can be processed and formed by adopting extrusion, injection molding and mold pressing methods.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a butyl rubber type thermoplastic vulcanizate and a preparation method and application thereof. Background Art

[0002] Thermoplastic vulcanizate (TPV) is an elastomeric material with the reproducible processing performance of the plastic phase, prepared by a dynamic vulcanization process in which a vulcanized rubber phase is dispersed in a plastic continuous phase under the action of strong shear force. Compared with traditional vulcanized rubber, TPV can be recycled, has a cleaner production process, and consumes less energy. It is a new type of elastomeric material that is greener, more environmentally friendly, and safer.

[0003] At present, polypropylene EPDM rubber TPV has been commercialized. The EPDM used in EPDM rubber TPV has odor pollution due to the presence of the third monomer residue, and because peroxide vulcanizers are usually used, it is easy to decompose ketones and aldehydes with pungent odors during high-temperature dynamic vulcanization. Compared with butyl rubber, EPDM has a lower loss factor and a narrower damping temperature range. Therefore, butyl rubber TPV, which combines the excellent air tightness, shock absorption and damping performance of butyl rubber, and low odor, has become an important development direction of TPV. However, the vulcanization reaction activity of butyl rubber is low, the vulcanization time is long, and the amount of vulcanizer used is high. To this end, the use of brominated butyl rubber (BIIR) instead of IIR to prepare TPV materials (invention patents CN 110791031 A, CN 104725732 B) can improve this phenomenon. BIIR is a modified product of IIR, and active allyl bromide is introduced into the molecular chain. Since the bond energy of the Br-C bond is small, the cross-linking reaction activity of IIR is enhanced, making it have a faster vulcanization speed and stronger vulcanization adaptability. However, due to the complex production process and the high price of brominated butyl rubber, the production cost of TPV is too high.

[0004] The invention innovatively adopts stannous chloride and tetrabromobisphenol A as co-vulcanizing agents, introduces two halogen elements, chlorine and bromine, and adds an appropriate amount of white carbon black to form a vulcanization system with octyl phenolic resin or tert-butyl phenolic resin to prepare butyl rubber type TPV. Compared with the butyl rubber type thermoplastic vulcanizate in the prior art, the vulcanization activity is improved and the safety is high. Compared with the brominated butyl rubber type TPV, the production cost is low. Summary of the invention

[0005] In order to solve the above problems in the prior art, the present invention provides a butyl rubber type thermoplastic vulcanizate and a preparation method and application thereof.

[0006] In a first aspect, the present invention provides a butyl rubber type thermoplastic vulcanizate, wherein the components of the thermoplastic vulcanizate include: butyl rubber, polypropylene, a phenolic resin vulcanization system, an antioxidant, a softener and a filler;

[0007] The phenolic resin vulcanization system comprises a phenolic resin main vulcanizer and an auxiliary vulcanizer; the phenolic resin main vulcanizer is selected from at least one of octylphenolic resin and tert-butylphenolic resin; the auxiliary vulcanizer is selected from at least one of stannous chloride and tetrabromobisphenol A.

[0008] As a specific embodiment of the present invention, the mass ratio of the butyl rubber, polypropylene, phenolic resin vulcanization system, antioxidant, softener and filler is 100: (40-100): (1-10): (0.5-2): (5-40): (5-40).

[0009] As a specific embodiment of the present invention, the weight ratio of the phenolic resin main vulcanizing agent to the auxiliary vulcanizing agent in the phenolic resin vulcanization system is (5-15):1, preferably (6-8):1.

[0010] As a specific embodiment of the present invention, the co-vulcanizing agent is a co-vulcanizing agent composed of stannous chloride and tetrabromobisphenol A, and the molar ratio of bromine to chlorine in the co-vulcanizing agent is (0.05-5):1, preferably (0.1-3):1.

[0011] As a specific embodiment of the present invention, the antioxidant includes at least one of the antioxidant 1010 and the antioxidant 168; and / or the softener includes at least one of paraffin oil and rubber oil 6030.

[0012] As a specific embodiment of the present invention, the filler includes filler A and filler B, the filler A is white carbon black, and the filler B is at least one of talcum powder, titanium dioxide, and light calcium; the mass ratio of the filler A to the filler B is (5-20): (0-20).

[0013] As a specific embodiment of the present invention, the butyl rubber unsaturation degree (mole fraction %) is 1.7±0.20, and the Mooney viscosity ML (1+8) 125℃ 50±5.

[0014] As a specific embodiment of the present invention, the polypropylene has a melt index of 0.3-3.8 g / 10 min at 230° C. and 2.16 kg, and a heat deformation temperature of 90-105° C.

[0015] The above raw materials in the present invention can be prepared in-house or commercially available, and the present invention is not particularly limited thereto.

[0016] In a second aspect, the present invention provides a method for preparing the butyl rubber type thermoplastic vulcanizate, comprising the following steps:

[0017] S1: Evenly mix polypropylene and butyl rubber, antioxidant, softener, white carbon black and other fillers to obtain a rubber-plastic blend;

[0018] S2: adding a vulcanizing agent to the rubber-plastic blend obtained in step S1 and mixing the mixture evenly to obtain a rubber-plastic vulcanization premix;

[0019] S3: Granulate the rubber-plastic vulcanization premix obtained in step S2 to obtain granules of butyl rubber type thermoplastic vulcanizate.

[0020] As a specific embodiment of the present invention, in step S1 and step S2, the mixing conditions independently include: mixing temperature of 175-220° C., rotation speed of 100-300 r / min, and mixing time of 5-10 min.

[0021] As a specific embodiment of the present invention, in step S3, the granulation method includes dynamic vulcanization granulation, the granulation equipment is preferably a twin-screw extruder, and the process conditions include: the twin-screw temperature is 165-220°C, and the rotation speed is 100-300r / min.

[0022] In a third aspect, the present invention provides applications of the butyl rubber-type thermoplastic vulcanizate in the fields of seals, shock absorbers, plastic floors, water pipes, and cables.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The invention adopts a vulcanization system containing both chlorine and bromine elements, takes stannous chloride and tetrabromobisphenol A as auxiliary vulcanizing agents, and prepares a butyl rubber type thermoplastic vulcanizer. Compared with the butyl rubber type thermoplastic vulcanizer in the prior art, the invention can achieve high vulcanization activity and less vulcanizer dosage of brominated butyl rubber type thermoplastic vulcanizate without changing the preparation process, and has higher safety. Meanwhile, compared with the brominated butyl rubber type thermoplastic vulcanizate, butyl rubber is used as the rubber phase, and the production cost is lower. DETAILED DESCRIPTION

[0025] The present invention will be further described below in conjunction with specific embodiments, but they do not constitute any limitation to the present invention.

[0026] The specific information of the test method used in each embodiment of the present invention is as follows:

[0027] The GT-AT-7000M electronic tensile testing machine of Taiwan High Speed ​​Rail Technology Co., Ltd. was used to test the tensile strength and elongation at break. The test standard was based on GB / T 528-2009.

[0028] The hardness test was carried out using the LX-A Shore hardness tester produced by Shanghai Testing Machinery Co., Ltd., and the test standard was based on GB / T531-1999.

[0029] Example 1

[0030] This embodiment provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, the specific details of which are as follows:

[0031] S1: Using an internal mixer at a temperature of 190° C., 65 parts by mass of polypropylene (PP 4220, produced by Yanshan Petrochemical) were added and mixed for 2 min, and 100 parts by mass of butyl rubber (IIR 301, produced by LANXESS, Germany), 1 part by mass of antioxidant (1010, Shanghai Shanpu Chemical), 20 parts by mass of rubber oil (6030, produced by Karamay Petrochemical), 15 parts by mass of light calcium (1250, produced by Shanghai Botong Chemical) and 5 parts by mass of white carbon black (produced by Jilin Shuanglong Chemical) were added and mixed for 7 min to obtain a rubber-plastic melt blend;

[0032] S2: placing the rubber-plastic melt blend in step S1 on a cold roll mill, adding 8 parts by mass of octylphenol-formaldehyde resin (RT4201, produced by Jinan Shengquan), 0.35 parts by mass of tetrabromobisphenol A (Aladdin) and 0.45 parts by mass of stannous chloride (produced by Tianjin Beilian) as a vulcanizing agent after rolling, and mixing evenly to obtain a premix;

[0033] S3: The rubber-plastic premix prepared in S2 is dynamically vulcanized and extruded into pellets using a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0034] Example 2

[0035] This embodiment provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, the specific details of which are as follows:

[0036] S1: Using an internal mixer at a temperature of 190°C, 55 parts by mass of polypropylene (PP 4220, Yanshan Petrochemical) was added and mixed for 2 min, and 100 parts by mass of butyl rubber (IIR 301, Lanxess, Germany), 1 part by mass of antioxidant (1010, Shanghai Shanpu Chemical), 20 parts by mass of rubber oil (6030, Karamay Petrochemical), 12 parts by mass of light calcium (1250, Shanghai Botong Chemical) and 8 parts by mass of white carbon black (produced by Jilin Shuanglong Chemical) were added and mixed for 7 min to obtain a rubber-plastic melt blend;

[0037] S2: placing the rubber-plastic melt blend in step S1 on a cold roll mill, adding 6 parts by mass of tert-butylphenol-formaldehyde resin (RT4201, Jinan Shengquan), 0.45 parts by mass of tetrabromobisphenol A (Aladdin) and 0.45 parts by mass of stannous chloride (Tianjin Beilian) vulcanizing agent after rolling to obtain a premix;

[0038] S3: The rubber-plastic premix prepared in S2 is subjected to dynamic vulcanization extrusion pelletizing by a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0039] Example 3

[0040] This embodiment provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, the specific details of which are as follows:

[0041] S1: Using an internal mixer at a temperature of 190°C, 45 parts by mass of polypropylene (PP 4220, Yanshan Petrochemical) was added and mixed for 2 min, and 100 parts by mass of butyl rubber (IIR 301, LANXESS, Germany), 1 part by mass of antioxidant (168, BASF), 20 parts by mass of paraffin oil (P-500, Shandong Taichang Petrochemical), 10 parts by mass of light calcium (1250, Shanghai Botong Chemical) and 10 parts by mass of white carbon black (produced by Jilin Shuanglong Chemical) were added, mixed for 7 min to obtain a rubber-plastic melt blend, which was cooled for standby use;

[0042] S2: placing the rubber-plastic molten blend in step S1 on a cold roll mill, adding 8 parts by mass of tert-butylphenol-formaldehyde resin (RT4201, Jinan Shengquan), 0.35 parts by mass of tetrabromobisphenol A (Aladdin) and 0.45 parts by mass of stannous chloride (Tianjin Beilian) vulcanizing agent after rolling, and mixing evenly to obtain a premix;

[0043] S3: The rubber-plastic premix prepared in S2 is subjected to dynamic vulcanization extrusion pelletizing by a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0044] Example 4

[0045] This embodiment provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, the specific details of which are as follows:

[0046] S1: Using an internal mixer at a temperature of 190°C, 65 parts by mass of polypropylene (PP 4220, Yanshan Petrochemical) were added and mixed for 2 min, and 100 parts by mass of butyl rubber (IIR 301, Lanxess, Germany), 1 part by mass of antioxidant (1010, Shanghai Shanpu Chemical), 20 parts by mass of rubber oil (6030, Karamay Petrochemical), 5 parts by mass of talc (K brand, Guilin Guiguang) and 15 parts by mass of white carbon black (produced by Jilin Shuanglong Chemical) were added and mixed for 7 min to obtain a rubber-plastic melt blend;

[0047] S2: placing the rubber-plastic melt blend in step S1 on a cold roll mill, adding 8 parts by mass of octylphenol-formaldehyde resin (RT4201, Jinan Shengquan), 0.25 parts by mass of tetrabromobisphenol A (Aladdin) and 0.35 parts by mass of stannous chloride (Tianjin Beilian) vulcanizing agent after rolling, and mixing evenly to obtain a premix;

[0048] S3: The rubber-plastic premix prepared in S2 is subjected to dynamic vulcanization extrusion pelletizing by a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0049] Example 5

[0050] This embodiment provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, the specific details of which are as follows:

[0051] S1: Using an internal mixer at a temperature of 190°C, 67 parts by mass of polypropylene (PP 4220, Yanshan Petrochemical) was added and mixed for 2 min, and 100 parts by mass of butyl rubber (IIR 301, LANXESS, Germany), 1 part by mass of antioxidant (1010, Shanghai Shanpu Chemical), 20 parts by mass of rubber oil (6030, Karamay Petrochemical) and 20 parts by mass of white carbon black (produced by Jilin Shuanglong Chemical) were added and mixed for 7 min to obtain a rubber-plastic melt blend;

[0052] S2: placing the rubber-plastic melt blend in step S1 on a cold roll mill, adding 8 parts by mass of octylphenol-formaldehyde resin (RT4201, Jinan Shengquan), 0.75 parts by mass of tetrabromobisphenol A (Aladdin) and 0.65 parts by mass of stannous chloride (Tianjin Beilian) vulcanizing agent after rolling to obtain a premix;

[0053] S3: The rubber-plastic premix prepared in S2 is dynamically vulcanized by a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0054] Example 6

[0055] This embodiment provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, the specific details of which are as follows:

[0056] S1: Using an internal mixer at a temperature of 200° C., 67 parts by mass of polypropylene (PP 4220, Yanshan Petrochemical) were added and mixed for 2 min, and 100 parts by mass of butyl rubber (IIR 301, LANXESS, Germany), 1 part by mass of antioxidant (1010, Shanghai Shanpu Chemical), 20 parts by mass of rubber oil (6030, Karamay Petrochemical), 11 parts by mass of light calcium (1250, Shanghai Botong Chemical) and 9 parts by mass of white carbon black (produced by Jilin Shuanglong Chemical) were added and mixed for 7 min to obtain a rubber-plastic melt blend, which was cooled for standby use;

[0057] S2: placing the rubber-plastic melt blend in step S1 on a cold roll mill, adding 8 parts by mass of octylphenol-formaldehyde resin (RT4201, Jinan Shengquan), 0.25 parts by mass of tetrabromobisphenol A (Aladdin) and 0.95 parts by mass of stannous chloride (Tianjin Beilian) vulcanizing agent after rolling to obtain a premix;

[0058] S3: The rubber-plastic premix prepared in S2 is dynamically vulcanized by a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0059] Example 7

[0060] This embodiment provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, the specific details of which are as follows:

[0061] S1: Using an internal mixer at a temperature of 200° C., 67 parts by mass of polypropylene (PP 4220, Yanshan Petrochemical) were added and mixed for 2 min, and 100 parts by mass of butyl rubber (IIR 301, LANXESS, Germany), 1 part by mass of antioxidant (1010, Shanghai Shanpu Chemical), 20 parts by mass of rubber oil (6030, Karamay Petrochemical), 5 parts by mass of light calcium (1250, Shanghai Botong Chemical) and 15 parts by mass of white carbon black (produced by Jilin Shuanglong Chemical) were added and mixed for 7 min to obtain a rubber-plastic melt blend, which was cooled for standby use;

[0062] S2: placing the rubber-plastic melt blend in step S1 on a cold roll mill, adding 8 parts by mass of octylphenol-formaldehyde resin (RT4201, Jinan Shengquan), 0.75 parts by mass of tetrabromobisphenol A (Aladdin) and 0.1 parts by mass of stannous chloride (Tianjin Beilian) vulcanizing agent after rolling to obtain a premix;

[0063] S3: The rubber-plastic premix prepared in S2 is dynamically vulcanized by a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0064] Comparative Example 1

[0065] This comparative example provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, and the specific details are as follows:

[0066] S1: Using an internal mixer at a temperature of 190° C., 65 parts by mass of polypropylene (PP 4220, produced by Yanshan Petrochemical) were added and mixed for 2 min, and 100 parts by mass of butyl rubber (IIR 301, produced by LANXESS, Germany), 1 part by mass of antioxidant (1010, Shanghai Shanpu Chemical), 20 parts by mass of rubber oil (6030, produced by Karamay Petrochemical), 15 parts by mass of light calcium (1250, produced by Shanghai Botong Chemical) and 5 parts by mass of white carbon black (produced by Jilin Shuanglong Chemical) were added and mixed for 7 min to obtain a rubber-plastic melt blend;

[0067] S2: placing the rubber-plastic melt blend in step S1 on a cold roll mill, adding 8 parts by mass of octylphenol-formaldehyde resin (RT4201, produced by Jinan Shengquan) and 0.45 parts by mass of stannous chloride (produced by Tianjin Beilian) as a vulcanizing agent after rolling, and mixing evenly to obtain a premix;

[0068] S3: The rubber-plastic premix prepared in S2 is dynamically vulcanized and extruded into pellets using a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0069] Comparative Example 2

[0070] This comparative example provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, and the specific details are as follows:

[0071] S1: Using an internal mixer at a temperature of 190°C, 45 parts by mass of polypropylene (PP 4220, Yanshan Petrochemical) was added and mixed for 2 min, and 100 parts by mass of butyl rubber (IIR 301, Lanxess, Germany), 1 part by mass of antioxidant (1010, Shanghai Shanpu Chemical), 20 parts by mass of paraffin oil (P-500, Shandong Taichang Petrochemical), 10 parts by mass of light calcium (1250, Shanghai Botong Chemical) and 10 parts by mass of white carbon black (produced by Jilin Shuanglong Chemical) were added and mixed for 7 min to obtain a rubber-plastic melt blend, which was cooled for standby use;

[0072] S2: placing the rubber-plastic molten blend in step S1 on a cold roll mill, adding 8 parts by mass of tert-butylphenol-formaldehyde resin (RT4201, Jinan Shengquan) and 0.45 parts by mass of stannous chloride (Tianjin Beilian) vulcanizing agent after rolling, and mixing evenly to obtain a premix;

[0073] S3: The rubber-plastic premix prepared in S2 is subjected to dynamic vulcanization extrusion pelletizing by a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0074] Comparative Example 3

[0075] This comparative example provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, and the specific details are as follows:

[0076] S1: Using an internal mixer at a temperature of 190° C., 67 parts by mass of polypropylene (PP 4220, Yanshan Petrochemical) was added and mixed for 2 min, and 100 parts by mass of butyl rubber (IIR 301, LANXESS, Germany), 1 part by mass of antioxidant (1010, Shanghai Shanpu Chemical), 20 parts by mass of rubber oil (6030, Karamay Petrochemical) and 20 parts by mass of white carbon black (produced by Jilin Shuanglong Chemical) were added and mixed for 7 min to obtain a rubber-plastic melt blend; 8

[0077] S2: placing the rubber-plastic melt blend in step S1 on a cold roll mill, adding 8 parts by mass of octylphenol-formaldehyde resin (RT4201, Jinan Shengquan) and 0.65 parts by mass of stannous chloride (Tianjin Beilian) vulcanizing agent after rolling to obtain a premix;

[0078] S3: The rubber-plastic premix prepared in S2 is dynamically vulcanized by a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0079] Comparative Example 4

[0080] This comparative example provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, and the specific details are as follows:

[0081] S1: Using an internal mixer at a temperature of 190° C., 67 parts by mass of polypropylene (PP 4220, Yanshan Petrochemical) was added and mixed for 2 min, and 100 parts by mass of bromobutyl rubber (2255, Exxon), 1 part by mass of antioxidant (1010, Shanghai Shanpu Chemical), 20 parts by mass of rubber oil (6030, Karamay Petrochemical) and 20 parts by mass of white carbon black (produced by Jilin Shuanglong Chemical) were added and mixed for 7 min to obtain a rubber-plastic melt blend;

[0082] S2: placing the rubber-plastic melt blend in step S1 on a cold roll mill, adding 8 parts by mass of octylphenol-formaldehyde resin (RT4201, Jinan Shengquan) and 0.45 parts by mass of stannous chloride (Tianjin Beilian) vulcanizing agent after rolling to obtain a premix;

[0083] S3: The rubber-plastic premix prepared in S2 is dynamically vulcanized by a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0084] Comparative Example 5

[0085] This comparative example provides a butyl rubber type thermoplastic vulcanizate and a preparation method thereof, and the specific details are as follows:

[0086] S1: Using an internal mixer at a temperature of 190°C, 67 parts by mass of polypropylene (PP 4220, Yanshan Petrochemical) was added and mixed for 2 min, and 100 parts by mass of butyl rubber (IIR 301, LANXESS, Germany), 1 part by mass of antioxidant (1010, Shanghai Shanpu Chemical), 20 parts by mass of rubber oil (6030, Karamay Petrochemical) and 20 parts by mass of light calcium (1250, Shanghai Botong Chemical) were added and mixed for 7 min to obtain a rubber-plastic melt blend;

[0087] S2: placing the rubber-plastic melt blend in step S1 on a cold roll mill, adding 8 parts by mass of octylphenol-formaldehyde resin (RT4201, Jinan Shengquan), 0.75 parts by mass of tetrabromobisphenol A (Aladdin) and 0.65 parts by mass of stannous chloride (Tianjin Beilian) vulcanizing agent after rolling to obtain a premix;

[0088] S3: The rubber-plastic premix prepared in S2 is dynamically vulcanized by a twin-screw extruder at an extrusion temperature of 200° C. and a screw speed of 200 r / min to obtain pellets of butyl rubber-type thermoplastic vulcanizate.

[0089] The butyl rubber type thermoplastic vulcanizates prepared in Examples 1-7 and Comparative Examples 1-5 were subjected to performance tests, and the obtained performance parameters are shown in Table 1.

[0090] Table 1 Ratios and properties of raw material components in Examples 1-7 and Comparative Examples 1-5

[0091]

[0092]

[0093] As can be seen from Table 1, when the co-vulcanizing agent tetrabromobisphenol A and stannous chloride in the present invention are used and the amount of the vulcanizing agent is 8 parts by mass, the prepared butyl rubber type thermoplastic vulcanizate has a Shore hardness of 75A, a tensile strength of up to 12.59 MPa, and an elongation at break of 405%, and has good physical properties. The butyl rubber type thermoplastic vulcanizate of the present invention has moderate hardness at room temperature, high physical properties, and high elongation at break.

[0094] Any numerical value mentioned in the present invention includes all values ​​that increase by one unit each time from the lowest value to the highest value if there is only an interval of two units between any minimum value and any maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, time, etc. is declared to be 50-90, in this specification it means that 51-89, 52-88... and 69-71 and 70-71 are specifically listed. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 can be appropriately considered as a unit. These are just some specially specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed lowest and highest values ​​are considered to have been disclosed.

[0095] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A butyl rubber type thermoplastic vulcanizate, characterized in that: The components of the thermoplastic vulcanizate include: butyl rubber, polypropylene, phenolic resin vulcanization system, antioxidant, softener and filler; The phenolic resin vulcanization system comprises a phenolic resin main vulcanizer and an auxiliary vulcanizer; the phenolic resin main vulcanizer is selected from at least one of octylphenolic resin and tert-butylphenolic resin; the auxiliary vulcanizer is selected from at least one of stannous chloride and tetrabromobisphenol A.

2. The butyl rubber type thermoplastic vulcanizate according to claim 1, characterized in that: The mass ratio of the butyl rubber, polypropylene, phenolic resin vulcanization system, antioxidant, softener and filler is 100: (40-100): (1-10): (0.5-2): (5-40): (5-40); And / or, the weight ratio of the phenolic resin main vulcanizing agent to the auxiliary vulcanizing agent in the phenolic resin vulcanization system is (5-15):1, preferably (6-8):1; And / or, the co-vulcanizing agent is a co-vulcanizing agent composed of stannous chloride and tetrabromobisphenol A, and the molar ratio of bromine to chlorine in the co-vulcanizing agent is (0.05-5):1, preferably (0.1-3):

1.

3. The butyl rubber type thermoplastic vulcanizate according to claim 1 or 2, characterized in that: The antioxidant includes at least one of the antioxidant 1010 and the antioxidant 168 ; and / or the softener includes at least one of paraffin oil and rubber oil 6030 .

4. The butyl rubber type thermoplastic vulcanizate according to any one of claims 1 to 3, characterized in that: The filler includes filler A and filler B, wherein filler A is white carbon black, and filler B is at least one of talcum powder, titanium dioxide, and light calcium; the mass ratio of filler A to filler B is (5-20): (0-20).

5. The butyl rubber type thermoplastic vulcanizate according to any one of claims 1 to 4, characterized in that: The butyl rubber unsaturation degree (mole fraction%) is 1.7±0.20, and the Mooney viscosity is ML (1+8) 125℃ 50±5.

6. The butyl rubber type thermoplastic vulcanizate according to any one of claims 1 to 5, characterized in that: The polypropylene has a melting index of 0.3-3.8 g / 10 min at 230° C. and 2.16 kg, and a heat deformation temperature of 90-105° C.

7. A method for preparing a butyl rubber type thermoplastic vulcanizate according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1: Evenly mix polypropylene and butyl rubber, antioxidant, softener, white carbon black and other fillers to obtain a rubber-plastic blend; S2: adding a vulcanizing agent to the rubber-plastic blend obtained in step S1 and mixing the mixture evenly to obtain a rubber-plastic vulcanization premix; S3: Granulate the rubber-plastic vulcanization premix obtained in step S2 to obtain granules of butyl rubber type thermoplastic vulcanizate.

8. The preparation method according to claim 6 or 7, characterized in that: In step S1 and step S2, the mixing conditions independently include: mixing temperature of 175-220° C., rotation speed of 100-300 r / min, and mixing time of 5-10 min.

9. The preparation method according to any one of claims 6 to 8, characterized in that: In step S3, the granulation method includes dynamic vulcanization granulation, and the granulation equipment is preferably a twin-screw extruder. The process conditions include: the twin-screw temperature is 165-220° C., and the rotation speed is 100-300 r / min.

10. Use of the butyl rubber type thermoplastic vulcanizate according to any one of claims 1 to 6 or the butyl rubber type thermoplastic vulcanizate prepared by the preparation method according to any one of claims 7 to 9 in the fields of seals, shock absorbers, plastic floors, water pipes, and cables.

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