CN108299727B - Thermoplastic vulcanizate composition and method for preparing thermoplastic vulcanizate - Google Patents
Thermoplastic vulcanizate composition and method for preparing thermoplastic vulcanizate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention relates to the field of rubber, and discloses a thermoplastic vulcanized rubber composition and a preparation method of the thermoplastic vulcanized rubber, wherein the composition contains a polypropylene elastomer, and the polypropylene elastomer contains polypropylene and crosslinked ethylene propylene rubber; an inorganic filler selected from at least one of carbon black, talc, calcium carbonate, montmorillonite, kaolin, and white carbon black; and optionally a process oil. The method for preparing the thermoplastic vulcanized rubber greatly simplifies the TPV preparation process and can obtain the thermoplastic vulcanized rubber with excellent performance.
Description
Technical Field
The invention relates to the field of rubber, in particular to a thermoplastic vulcanized rubber composition and a preparation method of thermoplastic vulcanized rubber.
Background
Thermoplastic vulcanizate (TPV) belongs to thermoplastic rubber, and has the high-temperature repeatable processability of thermoplastic plastics and the elasticity of the vulcanizate at normal temperature.
The traditional TPV material is prepared by adopting a dynamic vulcanization technology. When the rubber and the plastic are melted and blended, the rubber phase is vulcanized under the action of a vulcanizing agent, shearing and heat; when the rubber phase is subjected to a crosslinking reaction, the rubber phase is reduced in size under the shearing action, and micron-sized vulcanized rubber is formed and distributed in the plastic continuous phase to form the thermoplastic elastomer with a sea-island structure. Compared with the traditional vulcanized rubber, the processing technology is simple, and the waste and defective products and the leftover materials can be recycled.
The traditional typical processing technology for preparing TPV is as described in CN1059533A, rubber, auxiliary agents, fillers, a crosslinking system and the like are mixed on an internal mixer or an open mill to obtain master batch, and then the master batch is mixed with plastic under the strong shearing of an extruder to dynamically vulcanize the rubber to form thermoplastic vulcanized rubber. Specific processing techniques are also set forth in CN 1944497A: firstly, melting plastics in a high-temperature mixer in advance, adding rubber for mixing, then adding a filler, an auxiliary agent, a softener and the like for uniform mixing, adding a vulcanizing agent and an accelerator for dynamic vulcanization, and finally obtaining the TPV. The processing procedures related to the method are more suitable for research in the laboratory stage, only a high-temperature mixer can be used, and the energy consumption, the material consumption and the operability are not beneficial to industrial production.
CN102532724A discloses a method for preparing thermoplastic dynamic vulcanized rubber by a one-step method, which comprises the steps of adding rubber, plastic, fillers and other processing aids into a mixing device (a high-speed mixer), uniformly mixing, adding into a double-stage double-screw extruder through a main feed port, adding a softening agent, an organic peroxide vulcanization system and/or a phenolic resin vulcanization system and other functional aids after the plastic is melted in the double-screw extruder, and dynamically vulcanizing to obtain the thermoplastic dynamic vulcanized rubber. The preparation method needs a dynamic vulcanization step, and is not energy-saving and environment-friendly.
Disclosure of Invention
The object of the present invention is to provide a process for producing a thermoplastic vulcanizate capable of obtaining a thermoplastic vulcanizate having good properties by blending only the composition components without having to undergo a step of dynamic vulcanization, and a thermoplastic vulcanizate composition capable of producing a thermoplastic vulcanizate having good properties.
The inventors of the present invention have found that, when a polypropylene elastomer containing polypropylene and crosslinked ethylene-propylene rubber is used in combination with an inorganic filler, a thermoplastic vulcanizate having good properties can be obtained by blending only the components of the composition without the need for a step of dynamic vulcanization.
In order to achieve the above object, the present invention provides, in a first aspect, a thermoplastic vulcanizate composition comprising:
the polypropylene elastomer contains polypropylene and crosslinked ethylene propylene rubber;
an inorganic filler selected from at least one of carbon black, talc, calcium carbonate, montmorillonite, kaolin, and white carbon black; and
optionally containing process oil.
In a second aspect, the present invention provides a process for preparing a thermoplastic vulcanizate, the process comprising: the polypropylene elastomer is blended with inorganic filler or the inorganic filler and operating oil, the polypropylene elastomer contains polypropylene and crosslinked ethylene propylene rubber, and the inorganic filler is selected from at least one of carbon black, talcum powder, calcium carbonate, montmorillonite, kaolin and white carbon black.
The method for preparing the thermoplastic vulcanized rubber greatly simplifies the TPV preparation process and can obtain the thermoplastic vulcanized rubber with excellent performance.
The method can obtain the TPV material only by blending the polypropylene elastomer with the inorganic filler or with the inorganic filler, the operating oil and the like through a common extruder, avoids dynamic vulcanization reaction in the extruder, avoids the limitation of the ethylene propylene diene monomer rubber on the preparation of the TPV, and more importantly, has the advantages of energy conservation and environmental protection when the TPV is prepared by the method.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a thermoplastic vulcanizate composition comprising:
the polypropylene elastomer contains polypropylene and crosslinked ethylene propylene rubber;
an inorganic filler selected from at least one of carbon black, talc, calcium carbonate, montmorillonite, kaolin, and white carbon black; and
optionally containing process oil.
By optionally containing a process oil, it is meant that the thermoplastic vulcanizate composition of the present invention may or may not contain a process oil.
The thermoplastic vulcanized rubber composition provided by the invention can be used for obtaining a TPV material by introducing all components in the thermoplastic vulcanized rubber composition into a common extruder for blending and extruding without adopting a dynamic vulcanization process. The thermoplastic vulcanized rubber composition provided by the invention greatly simplifies the preparation process of thermoplastic vulcanized rubber, and has the advantages of obvious energy saving and environmental protection.
Preferably, the content weight ratio of the polypropylene to the crosslinked ethylene propylene rubber in the polypropylene elastomer is 1: 0.05 to 10; more preferably 1: 0.5-1.5.
Preferably, the crosslinking degree of the crosslinked ethylene propylene rubber is not less than 80%; more preferably, the degree of crosslinking is from 82 to 92%.
The cross-linked ethylene propylene rubber can be cross-linked ethylene propylene diene monomer, and the ethylene propylene diene monomer contains an ethylene structural unit, a propylene structural unit and a third monomer.
Preferably, the third monomer in the crosslinked ethylene propylene diene monomer is at least one selected from the group consisting of 1, 4-pentadiene, 3-methyl-1, 4-pentadiene, 1, 5-hexadiene, 1, 7-octadiene, 1, 9-decadiene, and 4- (3-butenyl) styrene.
Preferably, the crosslinked ethylene-propylene-diene monomer rubber contains 15 to 45 weight percent of ethylene structural units, 55 to 80 weight percent of propylene structural units and 0.1 to 4.5 weight percent of third monomers. More preferably, the crosslinked ethylene-propylene-diene monomer rubber contains 25 to 40 wt% of an ethylene structural unit, 55 to 75 wt% of a propylene structural unit, and 1 to 3 wt% of a third monomer. The inventors of the present invention have found in their studies that when the content of the third monomer is more than 4.5% by weight, the degree of crosslinking of the vulcanized rubber thus obtained is too high, and the rubber particles are hard, which is disadvantageous for the elastic properties of the elastomer.
The polypropylene elastomer can be obtained by blending polypropylene and crosslinked ethylene propylene rubber in a reaction kettle; more preferably, the polypropylene elastomer is prepared by adopting the following method:
(1) carrying out first polymerization reaction on propylene monomers;
(2) and (2) carrying out second polymerization reaction on a third monomer, an ethylene monomer and a propylene monomer in the presence of the propylene homopolymer obtained in the step (1).
The reaction conditions of the first polymerization reaction and the second polymerization reaction are not particularly limited, and for example, the conditions of the first polymerization reaction include: the catalyst is a Ziegler-Natta catalyst, the temperature of the first polymerization reaction is 65-75 ℃, the time of the first polymerization reaction is 30-60min, and the pressure of the first polymerization reaction is 2.0-3.2 MPa; the conditions of the second polymerization reaction include: the catalyst is Ziegler-Natta catalyst, the temperature of the second polymerization reaction is 67-77 ℃, the time of the second polymerization reaction is 60-90min, and the pressure of the second polymerization reaction is 1.8-2.2 MPa.
The amount of the monomer used in the first polymerization reaction and the second polymerization reaction is not particularly limited as long as the polypropylene elastomer of the present invention can be obtained.
In the thermoplastic vulcanizate composition, the processing oil may be present in an amount of 0 to 80 parts by weight and the inorganic filler may be present in an amount of 1 to 50 parts by weight, relative to 100 parts by weight of the polypropylene elastomer; preferably, the process oil is contained in an amount of 0 to 50 parts by weight and the inorganic filler is contained in an amount of 3 to 35 parts by weight, relative to 100 parts by weight of the polypropylene elastomer. In particular, in the thermoplastic vulcanizate composition of the present invention, when containing a process oil, it is particularly preferred that the process oil is contained in an amount of 30 to 50 parts by weight relative to 100 parts by weight of the polypropylene elastomer.
More preferably, the inorganic filler of the present invention is carbon black and/or talc. In particular, the inorganic filler of the present invention is carbon black and talc or the inorganic filler is carbon black. The weight ratio of carbon black and talc, which are preferred as inorganic fillers, is 0.1 to 0.25: 1.
the thermoplastic vulcanizate composition of the present invention may further contain an antioxidant. The antioxidant may be contained in the thermoplastic vulcanizate composition in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight, relative to 100 parts by weight of the polypropylene elastomer.
Preferably, the antioxidant is selected from at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, N' -bis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) and N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
The process oil of the present invention may be one or more of paraffinic oil, engine oil and naphthenic oil. Further, the process oil may be commercially available, and for example, may be naphthenic oil KN4010 available from cramaray.
The inventors of the present invention found in their research that the thermoplastic vulcanizate prepared from the thermoplastic vulcanizate composition provided in the following embodiments has better properties, in particular, for example, the obtained TPV material has relatively stronger strength and the rubber and plastic two phases are mixed more uniformly.
Embodiment mode 1: the thermoplastic vulcanized rubber composition provided by the invention contains a polypropylene elastomer, operating oil, an inorganic filler and an antioxidant, wherein the weight ratio of the polypropylene to the crosslinked ethylene propylene rubber in the polypropylene elastomer is 1: 0.05-10 parts of crosslinked ethylene propylene rubber, wherein the crosslinking degree of the crosslinked ethylene propylene rubber is not less than 80%, the content of the operating oil is 10-80 parts by weight, the content of the inorganic filler is 1-50 parts by weight, and the content of the antioxidant is 0.1-10 parts by weight relative to 100 parts by weight of the polypropylene elastomer.
Embodiment mode 2: the thermoplastic vulcanized rubber composition provided by the invention contains a polypropylene elastomer, operating oil, an inorganic filler and an antioxidant, wherein the weight ratio of the polypropylene to the crosslinked ethylene propylene rubber in the polypropylene elastomer is 1: 0.5-1.5, wherein the crosslinking degree of the crosslinked ethylene propylene rubber is 82-92%, and relative to 100 parts by weight of the polypropylene elastomer, the content of the operating oil is 10-50 parts by weight, the content of the inorganic filler is 10-35 parts by weight, and the content of the antioxidant is 0.5-3 parts by weight; and the inorganic filler is a mixture of inorganic fillers with the weight ratio of 0.1-0.25: 1 carbon black and talc.
Embodiment mode 3: the thermoplastic vulcanized rubber composition provided by the invention contains a polypropylene elastomer, operating oil, an inorganic filler and an antioxidant, wherein the weight ratio of the polypropylene to the crosslinked ethylene propylene rubber in the polypropylene elastomer is 1: 0.5-1.5, wherein the crosslinking degree of the crosslinked ethylene propylene rubber is 82-92%, and relative to 100 parts by weight of the polypropylene elastomer, the content of the operating oil is 30-50 parts by weight, the content of the inorganic filler is 3-10 parts by weight, and the content of the antioxidant is 0.5-3 parts by weight; and the inorganic filler is carbon black.
Embodiment 4: the thermoplastic vulcanized rubber composition provided by the invention contains a polypropylene elastomer, an inorganic filler and an antioxidant, wherein the content weight ratio of polypropylene to crosslinked ethylene propylene rubber in the polypropylene elastomer is 1: 0.5-1.5, wherein the crosslinking degree of the crosslinked ethylene propylene rubber is 82-92%, and relative to 100 parts by weight of the polypropylene elastomer, the content of the inorganic filler is 10-35 parts by weight, and the content of the antioxidant is 0.5-3 parts by weight; and the inorganic filler is a mixture of inorganic fillers with the weight ratio of 0.1-0.25: 1 carbon black and talc.
In a second aspect, the present invention provides a process for preparing a thermoplastic vulcanizate, the process comprising: the polypropylene elastomer is blended with inorganic filler or the inorganic filler and operating oil, the polypropylene elastomer contains polypropylene and crosslinked ethylene propylene rubber, and the inorganic filler is selected from at least one of carbon black, talcum powder, calcium carbonate, montmorillonite, kaolin and white carbon black.
The types and amounts of the polypropylene elastomer, the processing oil and the inorganic filler in the second aspect of the present invention may be the same as those described in connection with the first aspect of the present invention, and it will be understood by those skilled in the art that the thermoplastic vulcanizate composition of the first aspect of the present invention can be prepared to give a thermoplastic vulcanizate by employing the method for preparing a thermoplastic vulcanizate provided in the second aspect.
Preferably, the conditions for blending the polypropylene elastomer with the inorganic filler or with the inorganic filler and the process oil include: the temperature is 190-.
The present invention will be described in detail below by way of specific examples. Unless otherwise specified, all of the following products are commercially available.
The polypropylene elastomers used below were prepared by the following method:
9mL of triethylaluminum with a concentration of 1.8mol/L, 1mL of diisopropyldimethoxysilane external electron donor and 20.0mg of Ziegler-Natta catalyst (the catalyst is MgCl supported) are added into a 5L high-pressure reaction kettle2-TiCl4The catalyst comprises 10 wt% of 1, 3-diether as an internal electron donor, 3 wt% of Ti and 18 wt% of Mg. The particle size of the catalyst is 20-40 μm, and the catalyst slurry with the concentration of 10 wt% is prepared by using Clarity 2# mineral white oil), then propylene gas is introduced, and a first polymerization reaction is carried out for 30min at 70 ℃ and 3.1MPa, so as to obtain polypropylene particles; then the propylene gas was vented, 10mL of 1, 9-decadiene monomer was added to the system, and then the feed was continued at a molar ratio of 1:1, the temperature of the second polymerization reaction is 67 ℃, the time is 60min, and the reaction pressure is kept at 2.0 MPa. Obtaining a polypropylene elastomer, wherein the crosslinking degree of the crosslinked ethylene propylene diene monomer rubber is 85%, the content of the ethylene structural unit is 35 wt%, the content of the propylene structural unit is 62 wt%, the content of the third monomer structural unit is 3 wt%, and the weight ratio of the polypropylene to the crosslinked ethylene propylene diene monomer rubber in the polypropylene elastomer is 1: 1.
the non-crosslinked ethylene-propylene-diene monomer rubber used in the following comparative example was a block rubber of beijing yanshan division, petrochemical, in which the content of ethylene structural units was 60% by weight, the third monomer was vinylidene norbornene (ENB) in a relative content of 5% by weight, and the mooney viscosity (125 ℃ (1+4)) was 80.
The polypropylene used in the comparative example was a homopolymeric polypropylene available from the Beijing Yanshan division, petrochemical, China, with a melt index (230 ℃, 2.16kg, g/10min) of 0.5.
The chlorinated polyethylene used in the comparative example is YZC-5505T produced by petrochemical production of the winnowing, and is mainly used as an activator of the phenolic resin.
The phenolic resin used in the comparative example was HY-2055 of Shanxi chemical research institute.
The process oil used below was naphthenic oil KN4010 available from cramaray.
The carbon black used below was N660 from cabot.
Thermoplastic vulcanizate compositions Z1-Z5 are provided below to illustrate the thermoplastic vulcanizate compositions provided by the present invention.
Examples 1 and 2 are provided below to illustrate the process of the present invention for preparing thermoplastic vulcanizates.
The particle size distribution of the following rubber phase was observed by an atomic force microscope, and the size was counted by software, and the distribution range was determined taking the particle size of 80% or more of the thermoplastic vulcanizates obtained in the following examples and comparative examples, and the rubber phase particle size distribution was obtained.
Examples 1 and 2 used a conventional twin screw extruder with a length to diameter ratio of 32, a nominal screw diameter of 35mm and a maximum screw speed of 350 rpm.
Thermoplastic vulcanizate composition Z1, consisting of:
thermoplastic vulcanizate composition Z2, consisting of:
thermoplastic vulcanizate composition Z3, consisting of:
thermoplastic vulcanizate composition Z4, consisting of:
thermoplastic vulcanizate composition Z5, consisting of:
example 1
Respectively adding the thermoplastic vulcanized rubber compositions Z1-Z5 into a common double-screw extruder for blending at the temperature of 190 ℃ for 1min to respectively obtain the thermoplastic vulcanized rubbers 1S1-1S 5.
The relevant properties of the thermoplastic vulcanizates 1S1-1S5 are listed in Table 1.
TABLE 1
The test result is shore D.
Example 2
Respectively adding the thermoplastic vulcanized rubber compositions Z1-Z5 into a common double-screw extruder for blending at the temperature of 220 ℃ for 1.2min to respectively obtain the thermoplastic vulcanized rubbers 2S1-2S 5.
The relevant properties of the thermoplastic vulcanizate 2S1-2S5 are listed in Table 2.
TABLE 2
The test result is shore D.
Comparative example 1
The comparative example adopts an internal mixer to mix rubber and resin, the length-diameter ratio of the dynamic vulcanization extruder used in the comparative example is 56, the diameter of the screw is 35, and the maximum rotating speed of the screw can reach 700 rpm.
The composition of the comparative example contained: 100g of non-crosslinked ethylene propylene diene monomer, 120g of operating oil, 100g of polypropylene, 10g of chlorinated polyethylene, 3g of carbon black, 20g of talcum powder, 2g of zinc oxide, 1g of stearic acid, 1g of antioxidant (antioxidant 1010), 3g of phenolic resin (vulcanizing agent), 0.5g of sulfur (vulcanizing agent) and 1g of rubber accelerator DM.
The method comprises the following specific steps:
1. polypropylene, non-crosslinked ethylene propylene diene monomer, an antioxidant, 80 wt% of total process oil and rubber auxiliaries (chlorinated polyethylene, carbon black, talcum powder, zinc oxide, stearic acid and an accelerator DM) are blended in an internal mixer. The method comprises the following specific steps: setting the initial temperature of an internal mixer to 120 ℃, adding non-crosslinked ethylene propylene diene monomer rubber, 40 wt% of operation oil and all rubber auxiliaries into the internal mixer for melt blending, heating the internal mixer at the speed of 20 ℃/min in the whole melt blending process, adding polypropylene, antioxidant 1010 and 40 wt% of operation oil when the temperature in the internal mixer reaches 140 ℃, continuing melt blending, and discharging when the temperature in the internal mixer reaches 150 ℃.
2. Dynamic vulcanization: and (2) under the action of a double-cone screw feeder, feeding the blending product obtained in the step (1) into a dynamic vulcanization extruder. The rest part of the operation oil, the phenolic resin and the sulfur (two vulcanizing agents) are premixed and preheated to 70 ℃, and after the vulcanizing agents are ensured to be dissolved, the mixture is added into a dynamic vulcanization extruder through a liquid metering pump. The temperature of the extruder is 200 ℃, the rotating speed of the screw is controlled at 500rpm, and the thermoplastic vulcanized rubber is obtained in the extruder through rubber-plastic blending and dynamic vulcanization of rubber.
Tests show that the thermoplastic vulcanized rubber obtained in the comparative example has the tensile strength of 13.2MPa, the 300% elongation strength of 6.45MPa, the elongation at break of 420%, the tear strength of 39KN/m, the Shore A hardness of 86.5, the 70 ℃ C. 72h permanent compression set of 67%, and the rubber phase particle size of 1-3 μm.
By comparison it can be seen that: although the TPV products prepared in the examples 1 and 2 have slightly insufficient permanent compression set, the strength of the material is relatively high, and the rubber and plastic two phases can be more uniformly mixed through atomic force microscope observation. More importantly, compared with the process of the comparative example, the process of the embodiment of the invention has simpler flow, and is more energy-saving and environment-friendly.
Compared with the method for preparing TPV by polypropylene and non-crosslinked ethylene propylene diene monomer in the comparative example, the method for preparing TPV by the polypropylene elastomer in the embodiment of the invention has the advantages that the polypropylene and the ethylene propylene monomer are blended and dispersed in the polymerization process, the rubber is subjected to in-situ crosslinking, two phases are uniformly dispersed, simultaneously, a plurality of ethylene propylene copolymers with long ethylene or long propylene sequences beneficial to the dispersion of the two phases can be generated in the polymerization process, the copolymers can play a compatible role, and the compatible effect can be achieved only by adding a compatilizer in the comparative example.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. A thermoplastic vulcanizate composition comprising:
the polypropylene elastomer contains polypropylene and crosslinked ethylene propylene rubber;
an inorganic filler selected from at least one of carbon black, talc, calcium carbonate, montmorillonite, kaolin, and white carbon black; and
optionally containing process oil;
wherein the weight ratio of the polypropylene to the crosslinked ethylene propylene rubber in the polypropylene elastomer is 1: 0.05 to 10; the crosslinking degree of the crosslinked ethylene propylene rubber is not lower than 80 percent;
the polypropylene elastomer is prepared by adopting the following method:
(1) carrying out first polymerization reaction on propylene monomers;
(2) and (2) carrying out second polymerization reaction on a third monomer, an ethylene monomer and a propylene monomer in the presence of the propylene homopolymer obtained in the step (1).
2. The composition of claim 1, wherein the polypropylene elastomer comprises polypropylene and crosslinked ethylene-propylene rubber in a weight ratio of 1: 0.5-1.5.
3. The composition of claim 1, wherein the crosslinked ethylene-propylene rubber has a degree of crosslinking of 82-92%.
4. The composition of any of claims 1-3, wherein the third monomer in the crosslinked ethylene propylene diene monomer is selected from at least one of 1, 4-pentadiene, 3-methyl-1, 4-pentadiene, 1, 5-hexadiene, 1, 7-octadiene, 1, 9-decadiene, 4- (3-butenyl) styrene.
5. The composition of claim 4, wherein the crosslinked ethylene-propylene-diene rubber has an ethylene structural unit content of 15 to 45 wt.%, a propylene structural unit content of 55 to 80 wt.%, and a third monomer content of 0.1 to 4.5 wt.%.
6. The composition according to any one of claims 1 to 3, wherein the process oil is contained in an amount of 0 to 80 parts by weight and the inorganic filler is contained in an amount of 1 to 50 parts by weight, relative to 100 parts by weight of the polypropylene elastomer.
7. The composition according to any one of claims 1 to 3, wherein the process oil is contained in an amount of 0 to 50 parts by weight and the inorganic filler is contained in an amount of 3 to 35 parts by weight, relative to 100 parts by weight of the polypropylene elastomer.
8. The composition according to any one of claims 1 to 3, further comprising an antioxidant.
9. The composition according to claim 8, wherein the antioxidant is contained in an amount of 0.1 to 10 parts by weight, relative to 100 parts by weight of the polypropylene elastomer.
10. The composition according to claim 8, wherein the antioxidant is contained in an amount of 0.5 to 3 parts by weight, relative to 100 parts by weight of the polypropylene elastomer.
11. The composition of claim 8, wherein the antioxidant is selected from at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, N' -bis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, tris (2, 4-di-tert-butylphenyl) phosphite, and N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
12. A process for preparing a thermoplastic vulcanizate using the composition of any of claims 1-11, the process comprising: the polypropylene elastomer is blended with inorganic filler or the inorganic filler and operating oil, the polypropylene elastomer contains polypropylene and crosslinked ethylene propylene rubber, and the inorganic filler is selected from at least one of carbon black, talcum powder, calcium carbonate, montmorillonite, kaolin and white carbon black.
13. The method of claim 12, wherein the conditions of the blending comprise: the temperature is 190-.
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