CN103980621A - High-performance dynamic vulcanization thermoplastic elastomer and preparation method thereof - Google Patents

High-performance dynamic vulcanization thermoplastic elastomer and preparation method thereof Download PDF

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Publication number
CN103980621A
CN103980621A CN201410220053.4A CN201410220053A CN103980621A CN 103980621 A CN103980621 A CN 103980621A CN 201410220053 A CN201410220053 A CN 201410220053A CN 103980621 A CN103980621 A CN 103980621A
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rubber
thermoplastic elastomer
dynamic vulcanization
epdm
parts
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徐红岩
孙晓斌
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TOTAL POLYMER VISION (SUZHOU) CO Ltd
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TOTAL POLYMER VISION (SUZHOU) CO Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • 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
    • C08L23/14—Copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • 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

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention relates to a high-performance dynamic vulcanization thermoplastic elastomer and a preparation method thereof. The high-performance dynamic vulcanization thermoplastic elastomer is characterized by being prepared from the following main raw material in parts by weight: 30-50 parts of ethylene-propylene-diene-monomer rubber, 20-60 parts of polypropylene, 5-15 parts of filler, 10-60 parts of rubber oil, 0.2-2.0 parts of crosslinking agent and a certain weight fraction of auxiliaries. The preparation method comprises the following steps: preparing the raw materials in the formula in respective parts by weight, and firstly feeding the raw materials into an internal mixer to be internally mixed, so that a mixture is obtained, wherein technological parameters of the internal mixer comprise that speed ratio of a rotor is 1:(1.1-1.18) and temperature is 150-200 DEG C; then feeding the mixture into a double-screw extruder and carrying out dynamic vulcanization pelletizing processing, wherein technological parameters of the double-screw extruder comprise that length-diameter ratio of a screw is 38-58, rotating speed of the screw is 200-500r/min and temperature of the screw is 140-200 DEG C. The prepared high-performance dynamic vulcanization thermoplastic elastomer has excellent oil resistance and low permanent compression set.

Description

A kind of high-performance dynamic vulcanization thermoplastic elastomer and preparation method thereof
Technical field
The present invention relates to dynamic vulcanization thermoplastic elastomer field, be specifically related to a kind of high-performance dynamic vulcanization thermoplastic elastomer and preparation method thereof.Dynamic vulcanization thermoplastic elastomer of the present invention is the high-performance thermoplastic elastomerics that a kind of compression set is low, oil-proofness is excellent, can be applicable to the fields such as cushioning material, automotive trim and oil-resistant seal material.
Background technology
Thermoplastic Vulcanizate (English name Thermoplastic Vulcanizate), claims again polyolefin alloy thermoplastic elastomer, is called for short TPV.EPT rubber/thermoplastic elastomer is as a kind of Thermoplastic Vulcanizate, it is fast-developing a kind of environmental friendly material, have the thermoplastic processability of snappiness and the acrylic resin of traditional rubber concurrently, have the advantages such as environment-protecting asepsis safety, tint permanence that durometer level is wide, good, weathering resistance, antifatigue and temperature tolerance are better.As a kind of rubber novel material of energy-conserving and environment-protective, the development prospect of thermoplastic elastic material is very good.
But the phenomenon that oil-proofness is poor, permanent compression set is higher that existing thermoplastic elastomer exists is also undisputable fact, general elastomerics oil-proofness is all at 100% left and right (volumetric expansion per-cent, 120 DEG C of ASTM 3# oil, 70h), be difficult to reach the performance requriements of high-quality product, limit its commercial applications, for example possess good oil-proofness and low permanent compression set for the sheath elasticity of demand body of automobile aspect, otherwise soak through long-time high temperature, gasoline, performance just can significantly reduce, reduction of service life.Therefore, prepare a kind of high performance dynamic vulcanization thermoplastic elastomer material, for the scope of application that expands this material, it is very necessary promoting to promote.
Summary of the invention
The invention provides a kind of high-performance dynamic vulcanization thermoplastic elastomer and preparation method thereof, object is to solve the problem that oil-proofness is poor, permanent compression set is higher that existing thermoplastic elastomer exists.
For achieving the above object, the technical scheme that a kind of high-performance dynamic vulcanization thermoplastic elastomer of the present invention adopts is: this high-performance dynamic vulcanization thermoplastic elastomer is to carry out banburying through Banbury mixer, then processes and prepare through twin screw extruder; Wherein, the parameter of described Banbury mixer is: the speed ratio of rotor is 1: 1.1 ~ 1: 1.18, and temperature is 150 DEG C～200 DEG C; The parameter of twin screw extruder is: length-to-diameter ratio is 38～58, and rotating speed is 200 revs/min～500 revs/min, and temperature is 140 DEG C～200 DEG C;
Composition of raw materials is mainly made up of the material of following weight part:
30 ~ 50 parts of terpolymer EP rubbers;
20 ~ 60 parts of polypropylene;
5 ~ 15 parts of fillers;
10 ~ 60 parts of rubber oils;
0.2 ~ 2.0 part of linking agent;
0.2 ~ 2.0 part of crosslinking coagent;
Wherein:
(1) in described terpolymer EP rubber, the content of ethene is 50% ~ 75% of terpolymer EP rubber gross weight, the content of propylene is 20% ~ 35% of terpolymer EP rubber gross weight, the 3rd monomer ethylidene norbornene (being called for short ENB) content is 5% ~ 15% of terpolymer EP rubber gross weight, the Mooney viscosity (ML 1+4,125 DEG C) of described terpolymer EP rubber is between 20 to 100;
(2) homopolymer that described polypropylene is propylene, or the multipolymer of ethene and propylene, melting index is 0.2 to 30.0 gram/10 minutes;
(3) described filler is selected from any one in talcum powder, wilkinite, calcium carbonate superfine powder and kaolin;
(4) described rubber oil is white oil, paraffin oil or naphthenic oil, and the kinematic viscosity under its 40 DEG C of conditions is at 40mm 2/ s～400 mm 2between/s;
(5) described linking agent is organo-peroxide, and this organo-peroxide is selected from two (the tertiary butyl peroxidation)-2 of the one in following compounds: 2,5-, 5-dimethyl-3-hexin; Two (the tertiary butyl peroxidation)-2 of 2,5-, 5-dimethylhexane; Dicumyl peroxide; Tert-butyl hydroperoxide sec.-propyl carbonic ether; Tertiary butyl cumene peroxide; Two-(t-butyl peroxy sec.-propyl) benzene;
(6) described crosslinking coagent is selected from the one in following compounds: diphenyl methane dimaleimide; 1,6-hexylene glycol double methacrylate; N,N '-penylene bismaleimides; Trimethoxy propane trimethyl acrylic ester.
Related content in technique scheme is explained as follows:
1, in such scheme, preferably scheme is that described terpolymer EP rubber is block glue, for any one in following rubber: the EPDM 4045 of Mitsui chemistry, EPDM 8120E, EPDM 8075E, the EPDM 6861 of German bright Sheng, EPDM 4969, the EPDM S505 of Korea S SK, EPDM S5206F, the EPDM 9500 of american exxon, EPDM 8800, EPDM 8600.
2, in such scheme, preferably scheme is the oxidation inhibitor that also comprises 0.1～1.5 weight part in described composition of raw materials, and described oxidation inhibitor is selected the one in following material, or at least two kinds of combinations in any proportion:
Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010);
β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester (antioxidant 1076);
2,6 ditertiary butyl p cresol (antioxidant 264);
1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (antioxidant CA);
2,2-methylene-bis (4-methyl-6-tert-butylphenol) (antioxidant 2246).
3, in such scheme, preferably scheme is the anti UV agent that also comprises 0.1～1.5 weight part in described composition of raw materials, and described anti UV agent is selected the one in following material, or at least two kinds of combinations in any proportion:
2-(2 '-hydroxyl-3 ' 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole (trade(brand)name: UV light absorber UV-327);
2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole (trade(brand)name: ultraviolet absorbent uv-326);
Octabenzone (trade(brand)name: ultraviolet absorbent UV-531);
ESCALOL 567 (trade(brand)name: UV light absorber UV-9).
4, in such scheme, Mooney viscosity is to weigh rubber molecular-weight average and a plastic index, and mooney viscosity is measured with mooney's viscosimeter.Mooney's viscosimeter is the rotor of a standard, with constant rotating speed (general 2 revs/min), in sample, rotates.Rotor rotate suffered shearing resistance size with sample the variation of the viscosity in sulfidation relevant, can be presented on the scale card taking Mooney as unit by device for measuring force, reading numerical values can be made Mooney vulcanization curve in the same time interval.The unit of mooney viscosity is (Z 1+4,125 DEG C), and according to GB 1232 standard regulations, Mooney (rotation) viscosity represents with 125 DEG C of 1+4 of symbols Z.Wherein Z represents to rotate viscosity number; 1 represents that be 1min warm up time; 4 represent that rotation time is 4min; 125 DEG C represent that test temperature is 125 DEG C, often represent mooney viscosity (GB/T 1233-2008 " the mensuration disk of unvulcanized rubber incipient cure characteristic is sheared viscosmeter and measured ") with ML125 DEG C of 1+4 traditionally.
5, in such scheme, melting index (Melting Index, MI): thermoplastics is under certain temperature and pressure, and melt by the gravimetric value of standard capillary, represented with (g/10min) in ten minutes.
6,, in such scheme, in International System of Units, kinematic viscosity unit is this, i.e. per second square metre of (m 2/ S), conventional centistoke (cst) in practical measurement, the unit that represents centistoke is that square millimeter per second (is 1cst=1mm 2/ S).Lubricating oil after kinematic viscosity is widely used in and measures jet fuel, diesel oil, lubricated wet goods liquid petroleum product deep color petroleum product, uses, the viscosity of former wet goods, the mensuration of kinematic viscosity adopts counter-current.
For achieving the above object, the technical scheme that a kind of high-performance method for preparing thermoplastic elastomer through dynamic vulcanization of the present invention adopts is: after the material in described composition of raw materials is prepared according to parts by weight separately, first send into and in Banbury mixer, carry out banburying and obtain mixture, wherein, the processing parameter of described Banbury mixer is: the speed ratio of rotor is 1: 1.1 ~ 1: 1.18, and temperature is 150 DEG C～200 DEG C; Then, described mixture is sent in twin screw extruder and carried out dynamic vulcanization granulation processing, and wherein, the processing parameter of described twin screw extruder is: screw slenderness ratio is 38～58, screw speed is 200 revs/min～500 revs/min, and extruder temperature is 140 DEG C～200 DEG C.
Principle of design of the present invention: first, the present invention introduces the rubber of high the 3rd monomer ethylidene norbornene (ENB) in formula; Common without not oil resistant of the crosslinked terpolymer EP rubber of over cure (EPDM), easily distortion.And had crossbinding node between the molecular chain of terpolymer EP rubber after crosslinked, and make the intermolecular fixing link that had, not yielding, between the molecule of getting into terpolymer EP rubber that oil molecule also just can not be a large amount of, this has just improved oil-proofness.In rubber, the 3rd monomer ethylidene norbornene (ENB) can be opened two keys under the existence of free radical, and the two keys on adjacent molecular chain can aggregate into the structure that carbon-to-carbon connects.In molecule, the 3rd monomer ethylidene norbornene (ENB) content is more, and intermolecular carbon-to-carbon point of connection just may be more, and molecular structure just may be more stable.Therefore the distortion of crosslinked rear product is just little, and oil-proofness is just high.
Then, the present invention adds rubber internal mixing technique in Production Flow Chart.The technique of producing at present dynamic vulcanization thermoplastic elastomer is generally the terpolymer EP rubber that uses particle shape, and the rubber of this particle shape can directly drop into twin-screw extrusion apparatus processing.And the form of the rubber of high the 3rd monomer ethylidene norbornene (ENB) is block, can not directly drop into twin-screw extrusion apparatus processing, the present invention adopts banburying process first to make niggerhead and other starting material fully knead in Banbury mixer, and then drops into twin-screw extrusion equipment and carry out dynamic vulcanization production thermoplastic elastomer.Such process combination had both solved the processing problems of niggerhead, due to the mixing property of the abundant kneading of banburying equipment, the performance of product was improved again.
Because technique scheme is used, the present invention compared with prior art has following advantages and effect: the oil-proofness of the high-performance dynamic vulcanization thermoplastic elastomer that the present invention makes significantly improves, its percent volume swell is below 55%, quality percent swell is (test conditions: oil resistant test oil is ASTM3# oil maintains 70 hours at 120 DEG C) below 45%.And permanent compression set improves a lot equally, elastomerics hardness is in the time of 65A, and its pressure becomes 30% left and right; When 75A, press and become 35% left and right; When 85A, press and become 40% left and right; When 40D, press and become below 50%.In sum, this thermoplastic elastomer performance has obtained remarkable lifting, thereby has expanded the range of application of EPT rubber/thermoplastic elastomer.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment mono-～embodiment tetra-: a kind of high-performance dynamic vulcanization thermoplastic elastomer and preparation method thereof
Preparation method: according to the composition of raw materials in table 1 by polypropylene, terpolymer EP rubber, the banburying 20 ~ 30 minutes in Banbury mixer of filler and oxidation inhibitor, the speed ratio of closed-smelting machine rotor is 1: 1.1 ~ 1: 1.18, temperature is 150 DEG C～200 DEG C.Then miscellany and linking agent, crosslinking coagent etc. are added from the main spout of twin screw extruder, 50 kgs/hour of feed rate, rubber oil adds adjusting product hardness to set(ting)value from the intermediate zone of twin screw.The diameter of twin screw extruder is 65 millimeters, and length-to-diameter ratio is 48, and temperature controlling range is 140 DEG C ~ 220 DEG C, and screw speed is controlled at 250rpm ~ 350rpm.The performance of test material, the results are shown in Table 2.
Prepare again the thermoplastic elastomer of comparative example one and comparative example two by similar composition of raw materials and preparation method, difference is the 3092PM granulated rubber that in comparative example one and comparative example two, terpolymer EP rubber used is Mitsui Chemicals, and directly raw mixture is stirred and joined in double-screw feeder, without Banbury mixer banburying.
The composition of raw materials (unit: parts by weight) of the thermoplastic elastomer of table 1 embodiment mono-~ tetra-and comparative example one ~ bis-preparation
Project Embodiment mono- Embodiment bis- Embodiment tri- Embodiment tetra- Comparative example one Comparative example two
Polypropylene 25 30 45 55 25 45
Terpolymer EP rubber 50 45 50 50 50 50
Filler 10 15 15 10 15 15
Linking agent 1.1 1.2 1.0 1.2 1.1 1.0
Crosslinking coagent 1.0 1.1 1.0 1.0 1.0 1.0
Oxidation inhibitor 0.1 0.1 0.2 0.2 0.1 0.1
Calcium stearate 0.15 0.15 0.15 0.15 0.15 0.15
Anti UV agent 0.10 0.10 0.2 0.2 0.10 0.10
The description of contents of table 1 is as follows:
1, terpolymer EP rubber: embodiment mono-is the EPDM 4045 of Mitsui chemistry, the 6861 block glue that embodiment bis-and three is German bright Sheng, the EPDM 9500 that embodiment tetra-is american exxon.In above terpolymer EP rubber, the content of ethene is 50% ~ 75% of terpolymer EP rubber gross weight, the content of propylene is 20% ~ 35% of terpolymer EP rubber gross weight, the 3rd monomer ethylidene norbornene content is 5% ~ 15% of terpolymer EP rubber gross weight, the Mooney viscosity (ML 1+4,125 DEG C) of described terpolymer EP rubber is between 20 to 100.
2, in above embodiment and comparative example, the homopolymer that described polypropylene is propylene, or the multipolymer of ethene and propylene, melting index is 0.2 to 30.0 gram/10 minutes.
3, filler: embodiment mono-is talcum powder, and embodiment bis-and three is kaolin, and embodiment tetra-is calcium carbonate superfine powder, and comparative example one and two is kaolin.
4, linking agent: embodiment mono-is 2, two (the tertiary butyl peroxidation)-2 of 5-, 5-dimethyl-3-hexin, embodiment bis-is dicumyl peroxide, embodiment tri-is tert-butyl hydroperoxide sec.-propyl carbonic ether, embodiment tetra-is 2, two (the tertiary butyl peroxidation)-2 of 5-, 5-dimethylhexane, comparative example one and two is 2, two (the tertiary butyl peroxidation)-2 of 5-, 5-dimethyl-3-hexin.
5, crosslinking coagent: embodiment mono-is diphenyl methane dimaleimide, and embodiment bis-and three is 1,6-hexylene glycol double methacrylate, and embodiment tetra-is trimethoxy propane trimethyl acrylic ester, and comparative example one and two is 1,6-hexylene glycol double methacrylate.
6, oxidation inhibitor: embodiment mono-is antioxidant 264, and embodiment bis-and three is antioxidant 1010, and embodiment tetra-is antioxidant 1076, and comparative example one and two is antioxidant 1010.
7, anti UV agent: embodiment mono-is UV light absorber UV-327, and embodiment bis-and three is ultraviolet absorbent uv-326, and embodiment tetra-is ultraviolet absorbent UV-531, and comparative example one and two is ultraviolet absorbent uv-326.
8, in above embodiment and comparative example, rubber oil used is white oil, paraffin oil or naphthenic oil, and the kinematic viscosity under its 40 DEG C of conditions is at 40mm 2/ s～400 mm 2between/s.
The performance index of table 2 embodiment mono-~ tetra-and comparative example one ~ bis-
Performance Embodiment mono- Embodiment bis- Embodiment tri- Embodiment tetra- Comparative example one Comparative example two
Hardness, Shao A, Shao D 65A 75A 85A 40D 65A 85A
Tear strength, MPa 25.9 34.6 46.6 70.8 31.6 45.1
Tensile strength, MPa 6.4 7.2 8.5 15.9 4.8 7.3
Elongation, % 460 508 510 568 600 650
Permanent compression set, % 30 35 40 50 48 56
Oil-proofness (percent volume swell) 69 62 56 50 110 98
Above-described embodiment is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.

Claims (5)

1. a high-performance dynamic vulcanization thermoplastic elastomer, is characterized in that: this high-performance dynamic vulcanization thermoplastic elastomer is to carry out banburying through Banbury mixer, then processes and prepare through twin screw extruder; Wherein, the parameter of described Banbury mixer is: the speed ratio of rotor is 1: 1.1 ~ 1: 1.18, and temperature is 150 DEG C～200 DEG C; The parameter of twin screw extruder is: length-to-diameter ratio is 38～58, and rotating speed is 200 revs/min～500 revs/min, and temperature is 140 DEG C～200 DEG C;
Composition of raw materials is mainly made up of the material of following weight part:
30 ~ 50 parts of terpolymer EP rubbers;
20 ~ 60 parts of polypropylene;
5 ~ 15 parts of fillers;
10 ~ 60 parts of rubber oils;
0.2 ~ 2.0 part of linking agent;
0.2 ~ 2.0 part of crosslinking coagent;
Wherein:
(1) in described terpolymer EP rubber, the content of ethene is 50% ~ 75% of terpolymer EP rubber gross weight, the content of propylene is 20% ~ 35% of terpolymer EP rubber gross weight, the 3rd monomer ethylidene norbornene content is 5% ~ 15% of terpolymer EP rubber gross weight, the Mooney viscosity (ML 1+4,125 DEG C) of described terpolymer EP rubber is between 20 to 100;
(2) homopolymer that described polypropylene is propylene, or the multipolymer of ethene and propylene, melting index is 0.2 to 30.0 gram/10 minutes;
(3) described filler is selected from any one in talcum powder, wilkinite, calcium carbonate superfine powder and kaolin;
(4) described rubber oil is white oil, paraffin oil or naphthenic oil, and the kinematic viscosity under its 40 DEG C of conditions is at 40mm 2/ s～400 mm 2between/s;
(5) described linking agent is organo-peroxide, and this organo-peroxide is selected from two (the tertiary butyl peroxidation)-2 of the one in following compounds: 2,5-, 5-dimethyl-3-hexin; Two (the tertiary butyl peroxidation)-2 of 2,5-, 5-dimethylhexane; Dicumyl peroxide; Tert-butyl hydroperoxide sec.-propyl carbonic ether; Tertiary butyl cumene peroxide; Two-(t-butyl peroxy sec.-propyl) benzene;
(6) described crosslinking coagent is selected from the one in following compounds: diphenyl methane dimaleimide; 1,6-hexylene glycol double methacrylate; N,N '-penylene bismaleimides; Trimethoxy propane trimethyl acrylic ester.
2. high-performance dynamic vulcanization thermoplastic elastomer according to claim 1, it is characterized in that: described terpolymer EP rubber is block glue, for any one in following rubber: the EPDM 4045 of Mitsui chemistry, EPDM 8120E, EPDM 8075E, the EPDM 6861 of German bright Sheng, EPDM 4969, the EPDM S505 of Korea S SK, EPDM S5206F, the EPDM 9500 of american exxon, EPDM 8800, EPDM 8600.
3. high-performance dynamic vulcanization thermoplastic elastomer according to claim 1, it is characterized in that: the oxidation inhibitor that also comprises 0.1～1.5 weight part in described composition of raw materials, described oxidation inhibitor is selected the one in following material, or at least two kinds of combinations in any proportion:
Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester;
2,6 ditertiary butyl p cresol;
1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane;
2,2-methylene-bis (4-methyl-6-tert-butylphenol).
4. high-performance dynamic vulcanization thermoplastic elastomer according to claim 1, it is characterized in that: the anti UV agent that also comprises 0.1～1.5 weight part in described composition of raw materials, described anti UV agent is selected the one in following material, or at least two kinds of combinations in any proportion:
2-(2 '-hydroxyl-3 ' 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole;
2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole;
2-hydroxyl-4-octyloxy benzophenone;
ESCALOL 567.
5. according to the high-performance method for preparing thermoplastic elastomer through dynamic vulcanization one of claim 1 ~ 4 Suo Shu, it is characterized in that: after the material in described composition of raw materials is prepared according to parts by weight separately, first send into and in Banbury mixer, carry out banburying and obtain mixture, wherein, the processing parameter of described Banbury mixer is: the speed ratio of rotor is 1: 1.1 ~ 1: 1.18, and temperature is 150 DEG C～200 DEG C; Then, described mixture is sent in twin screw extruder and carried out dynamic vulcanization granulation processing, and wherein, the processing parameter of described twin screw extruder is: screw slenderness ratio is 38～58, screw speed is 200 revs/min～500 revs/min, and extruder temperature is 140 DEG C～200 DEG C.
CN201410220053.4A 2014-05-23 2014-05-23 High-performance dynamic vulcanization thermoplastic elastomer and preparation method thereof Pending CN103980621A (en)

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