CN103012971B - A kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer intercepting gas, resistance to steam and preparation method thereof - Google Patents

A kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer intercepting gas, resistance to steam and preparation method thereof Download PDF

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CN103012971B
CN103012971B CN201210509704.2A CN201210509704A CN103012971B CN 103012971 B CN103012971 B CN 103012971B CN 201210509704 A CN201210509704 A CN 201210509704A CN 103012971 B CN103012971 B CN 103012971B
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epdm
evoh
maa
steam
resistance
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CN103012971A (en
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杨桂生
杨军明
孙利明
石允慧
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Hefei Genius New Materials Co Ltd
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Hefei Genius New Materials 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
    • B29C48/03—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
    • B29C48/022—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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device
    • 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
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • 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
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention discloses EPDM/ EVOH MAA dynamic vulcanization thermoplastic elastomer of a kind of obstruct, resistance to steam and preparation method thereof.EPDM/ EVOH MAA dynamic vulcanization thermoplastic elastomer is made up of EPDM, EVOH MAA, compatilizer, packing strengthening agent, vulcanizing agent, vulcanization accelerator, activating agent, plasticizer, coupling agent, antioxidant, thermoplastic elastomer (TPE) prepared by the present invention not only has the cyclicity of excellence, gas barrier property, also there is resistance to steam, oil resistant, the characteristic such as wear-resisting, belong to high-performance engineering analog thermoplastic elastomer category, application is wide, the field such as including electrical equipment, mechanical seal, medicine and chemical industry.

Description

A kind of EPDM/EVOH-MAA dynamic-vulcanization thermoplastic bullet intercepting gas, resistance to steam Gonosome and preparation method thereof
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to a kind of intercept gas, the EPDM/ of resistance to steam EVOH-MAA dynamic vulcanization thermoplastic elastomer and preparation method thereof.
Technical background
Dynamic vulcanization thermoplastic elastomer (Theremoplastic Vukcanizate) is called for short TPV, for thermoplasticity ternary Second the third dynamic vulcanization elastomer or thermoplasticity EPDM dynamic perduren, be that the class using dynamic vulcanization technology to prepare is total to Mixed type thermoplastic elastic material.Dynamic vulcanization technology refers to that, when thermoplastic resin is with rubber melt blending, rubber is being handed over Connection effect issues biochemical crosslinking, and by strong mechanical shearing effect, is cut into and is broken into a large amount of micron-level crosslinked rubber Glue granule, is dispersed in the process in thermoplastic resin continuous phase, and ethylene propylene diene rubber (EPDM) microgranule being solid cure divides It is dispersed in the macromolecular elastomer material of continuous polypropylene (PP) middle composition mutually, the characteristic of rubber Yu plastics is well combined in one Rise, obtain the high performance elastomer material of excellent combination property.Physical property under TPV room temperature and be functionally similar to thermosetting rubber Glue, at high temperature shows as the characteristic of thermoplastic, can with fast, economical and machine-shaping easily, and be environmental protection Material, can repeat to reclaim use.Additionally TPV performance is similar to vulcanite, has the excellent advantage such as heat-resisting and ageing-resistant, doctor The fields such as treatment, chemical industry, automobile, electrical equipment, daily and building are extensively applied.But traditional TPV material is to pass through EPDM Rubber is composited with polypropylene (PP), and it, to the gas such as oxygen, nitrogen and the resistance to permeation barrier poor performance of steam, there is also Oil resistant, the deficiency of organic solvent resistance, so its barrier properties for gases, air-tightness, solvent resistance and anti-wear performance are the most poor, no TPV material can be met at special dimensions such as medical treatment, chemical industry, automobile, electrical equipment, daily and buildings to its barrier properties for gases, water-fast steaming The requirement of the aspects such as gas.
EPDM(ethylene propylene diene rubber), be by ethylene (45% ~ 70%), propylene (30% ~ 40%) and diene Third monomer (1% ~ 3%) random copolymer formed, wherein Third monomer is usually dicyclopentadiene, Isosorbide-5-Nitrae-hexadiene or 2-ethylidene norbornene Alkene.It has fabulous vulcanization characteristics, minimum proportion, and it can absorb substantial amounts of filler and oil and influencing characterisitic is little.
EVOH(ethylene-vinyl alcohol copolymer) always apply most high barrier material, EVOH is by vinyl polymerization The excellent processing characteristics of thing and the iris action of vinyl alcohol polymer combine, and not only show fabulous processing characteristics, and Also gas, abnormal smells from the patient, spice, solvent etc. are presented the blocking effect of excellence, the most also there is heat stability and reusing.
Metering system acid grafted ethylene-ethenol copolymer (being called for short EVOH-MAA, lower same) not only maintains the excellent of EVOH Point, simultaneously because the introducing of double bond, it is possible to occur cross-linking reaction to make its barrier property more excellent under the effect of vulcanizing agent.
Summary of the invention
The present invention is directed to problems of the prior art, it is provided that a kind of intercept gas, the EPDM/EVOH-of resistance to steam MAA dynamic vulcanization thermoplastic elastomer material.It is a further object to provide above-mentioned EPDM/EVOH-MAA dynamic vulcanization The preparation method of thermoplastic elastic material.
In order to achieve the above object, the present invention is realized by following technical proposal:
A kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer intercepting gas, resistance to steam, by weight Meter, is made up of following component: EPDM is that 35-70 part, metering system acid grafted ethylene-ethenol copolymer (EVOH-MAA) are 20-60 part, compatilizer 5-15 part, packing strengthening agent 5-20 part, vulcanizing agent 0.5-5 part, vulcanization accelerator 0-1.5 part, activity Agent 1-2.5 part, plasticizer 0-10 part, coupling agent 0-5 part, antioxidant 0.6-1.5 part.
The preferred version of such scheme is, described EPDM, EVOH-MAA and compatilizer are generally 100 parts, packing strengthening agent 5-20 part, vulcanizing agent 0.5-5 part, vulcanization accelerator 0-1.5 part, activating agent 1-2.5 part, plasticizer 0-10 part, coupling agent 0-5 part, antioxidant 0.6-1.5 part.
The Mooney viscosity of described EPDM is 20-80Pa.S.
Described metering system acid grafted ethylene-acetate ethylene copolymer (EVOH-MAA) is in 230 DEG C/2.16Kg condition Lower melt index is 0.5-20g/10min, wherein ethylene contents 20-60%, vinyl alcohol content 40-80%, the connecing of methacrylic acid The rate of kind is 0.5-20%.
Described compatilizer is grafting maleic anhydride with ethylene propylene terpolymer (EPDM-g-MAH), and its percent grafting is 0.5-1.5%.
Described vulcanizing agent is in sulfur, cumyl peroxide (DCP), polymethylene polyphenyl isocyanate (PAPI) At least one.
Described vulcanization accelerator be tetramethylthiuram monosulfide (TMTM), 2-mercaptobenzothiazole (M), N-cyclohexyl- At least one in 2-[4-morpholinodithio sulfenamide (CZ), N, N-metaphenylene maleimide (HVA-2).
Described packing strengthening agent is at least one in white carbon black, white carbon.Described white carbon black preferred white carbon black N330, white carbon black 762。
Described plasticizer is paraffin oil, naphthenic oil or white mineral oil.
Described activator includes zinc oxide (ZnO), calcium oxide (CaO), zinc carbonate (ZnCO3), light magnesium oxide (MgO), Stannous chloride (SnCl2), at least one in stearic acid (SA).
Described coupling agent is 3-aminopropyl triethoxysilane (KH550), γ-(2,3-epoxy the third oxygen) propyl group trimethoxy Base silane (KH560), γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570), isopropyl three (dioctylphyrophosphoric acid Acyloxy) in titanate esters (NDZ-201) or aluminic acid three isopropyl ester (DL-411) at least one.
Described antioxidant includes at least one in phenols, amine, phosphorous acid esters, monothioester class, matal deactivator.Its Middle phenolic antioxidant be β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester (antioxidant 1076) or four [β- (3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (antioxidant 1010)；Amine antioxidants is octylated diphenylamine (age resistor OD)；Phosphite ester kind antioxidant is three ［ 2,4-di-tert-butyl-phenyl ］ phosphite ester (irgasfos 168)；Monothioester class Antioxidant is the double octadecyl (antioxidant DSTDP) of thio-2 acid；Matal deactivator is N, N'-bis-salicylidene propane diamine (T1201), in the present invention antioxidant can be selected for aforementioned at least one.
A kind of prepare above-mentioned a kind of intercept gas, resistance to steam EPDM/EVOH-MAA dynamic-vulcanization thermoplastic elastic The method of body, comprises the following steps:
(1) proportioning weighs EPDM, EVOH-MAA, compatilizer, vulcanizing agent, vulcanization accelerator, activating agent, increasing by weight Mould agent and antioxidant joins in high-speed mixer and mixes together so that it is be uniformly dispersed；
(2) proportioning weighs packing strengthening agent and coupling agent by weight, controls temperature at 70-95 DEG C at high-speed mixer Middle coupling pretreatment 4min；
(3) raw material mixed in (1) is put into the loading hopper of double screw extruder, simultaneously will be after (2) process Raw material side feeding at the fluxing zone of extruder adds in extruder, through melt extruding, and pelletize, obtain EPDM/EVOH-MAA dynamic Sulfuration thermoplastic elastomer；Described double screw extruder each district temperature is 180 ~ 220 DEG C, and extruded velocity is 120-300 rev/min Clock.
The present invention compared with prior art, has the advantages that
1, dynamic-vulcanization thermoplastic of the present invention is elastic by ethylene-vinyl alcohol copolymer optimal for the barrier property generally acknowledged at present Apply to prepared by EPDM in thermoplastic elastomer (TPE), by being grafted metering system on ethylene-vinyl alcohol copolymer Acid monomers, introduces the MMA of band unsaturated double-bond so that it is can crosslink reaction under the effect of vulcanizing agent on EVOH side chain；
2, compatilizer grafting maleic anhydride with ethylene propylene terpolymer (EPDM-g-MAH) improves the interface of EPDM Yu EVOH-MAA The compatibility, makes EPDM Yu EVOH-MAA preferably disperse under dynamic crosslinking, cross-links as homogeneous system；
3, improve due to packing strengthening agent and improve the barrier properties for gases of dynamic vulcanization thermoplastic elastomer, air-tightness, Solvent resistance and wearability；
4, the product of the present invention is applicable to the special dimensions such as medical treatment, chemical industry, automobile, electrical equipment, daily and building, belongs to high Performance engineering analog thermoplastic elastomer.
Detailed description of the invention:
Embodiment is given below so that the present invention to be specifically described, it is necessary to it is pointed out here that be following example only It is used to further illustrate the present invention, it is impossible to be interpreted as limiting the scope of the invention, being skilled in technique of this field Some nonessential improvement and adjustment that the present invention is made by personnel according to present invention still fall within protection scope of the present invention.
All raw materials used in embodiments of the invention are all commercially available prod, wherein: sulfur elects 200 mesh sulfur, charcoal as Black selection white carbon black N330 or white carbon black 762, the particle diameter of white carbon is 15-500 nanometer.
In the present invention, preparation intercepts the EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer of gas, resistance to steam Method is to use following steps: (1) proportioning by weight weighs EPDM, EVOH-MAA, compatilizer, vulcanizing agent, sulfuration promotion Agent, activating agent, plasticizer and antioxidant join in high-speed mixer and mix together so that it is be uniformly dispersed；
(2) proportioning weighs packing strengthening agent and coupling agent by weight, controls temperature at 70-95 DEG C at high-speed mixer Middle coupling pretreatment 4min；
(3) raw material mixed in (1) is put into the loading hopper of double screw extruder, simultaneously will be after (2) process Raw material side feeding at the fluxing zone of extruder adds in extruder, through melt extruding, and pelletize, obtain EPDM/EVOH-MAA dynamic Sulfuration thermoplastic elastomer；Described double screw extruder each district temperature is 180 ~ 220 DEG C, and pressure is 10-25MP, twin-screw extrusion The footpath ratio of machine is 30 ~ 40, and extruded velocity is 120-300 rev/min, and rate of feeding is 10 ~ 30 revs/min.
Citing below is described as follows:
Embodiment 1
By 40 parts of EPDM, 55 parts of EVOH-MAA, 5 parts of EPDM-g-MAH, 2.5 parts of sulfur, 0.5 part of CZ, 0.3 part of HAV-2, 0.5 part of ZnO, 0.5 part of stearic acid, 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.2 part of antioxidant DSTDP are added to high mixed Join in extruder hopper after machine mixes, be pre-conjugated the white carbon black N330 of process by 5 parts by NDZ-201 simultaneously and join In the feeding of side, through double screw extruder extruding pelletization.Through double screw extruder extruding pelletization.Each district temperature of extruder is from feeding Section to head temperature be followed successively by 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min, and main rate of feeding is 12 revs/min.
Embodiment 2
By 50 parts of EPDM, 40 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 2.5 parts of sulfur, 0.5 part of CZ, 0.3 part of HAV-2, 1.5 parts of MgO, 1 part of stearic acid, 3 parts of pertroleum waxes, 0.2 part of antioxidant 1010,0.1 part of irgasfos 168,0.3 part of antioxidant DLSTDP Through high-speed mixer mixing 3min, join after mix homogeneously in extruder hopper, be simultaneously introduced 5 parts and be pre-conjugated by KH550 The white carbon black N330 processed joins in the feeding of side, through double screw extruder extruding pelletization.Each district temperature of extruder is from feeding section It is followed successively by 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C to head temperature, Extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min, and main rate of feeding is 12 revs/min, side feeding machine speed Degree is 2.8 revs/min.
Embodiment 3
By 60 parts of EPDM, 30 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 2.5 parts of sulfur, 0.7 part of DCP, 0.5 part of CZ, 0.3 Part HAV-2,1.5 parts of MgO, 1 part of stearic acid, 10 parts of naphthenic oils, 0.2 part of antioxidant 1010,0.2 part of antioxidant T1201,0.2 part Antioxidant DLSTDP, through high-speed mixer mixing 3min, joins after mix homogeneously in extruder hopper, be simultaneously introduced 5 parts by KH560 is pre-conjugated the white carbon black N330 of process and joins in the feeding of side, through double screw extruder extruding pelletization.Each district of extruder Temperature be followed successively by from feeding section to head temperature 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min, and main rate of feeding is 12 revs/min Clock, side feeding machine speed is 2.8 revs/min.
Embodiment 4
By 70 parts of EPDM, 20 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 5 parts of sulfur, 0.5 part of CZ, 0.3 part of HAV-2,1.5 Part CaO, 1 part of stearic acid, 5 parts of pertroleum waxes, 0.2 part of antioxidant 1010,0.2 part of T1201,0.2 part of antioxidant DLSTDP, 0.6 part Age resistor OD, through high-speed mixer mixing 3min, joins after mix homogeneously in extruder hopper, is simultaneously introduced by KH570 in advance 2.5 parts of white carbon black N330 and 2.5 parts of white carbon black N762 of coupling processing join in the feeding of side, through double screw extruder extruding pelletization. Each district temperature of extruder be followed successively by from feeding section to head temperature 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min, main feeding speed Degree is 12 revs/min, and side feeding machine speed is 2.8 revs/min.
Embodiment 5
By 35 parts of EPDM, 60 parts of EVOH-MAA, 5 parts of EPDM-g-MAH, 5 parts of sulfur, 1.0 parts of CZ, 0.3 part of HAV-2,0.5 Part MgO, 0.5 part of stearic acid, 0.5 part of antioxidant 1010,0.1 part of irgasfos 168,0.2 part of antioxidant DLSTDP, 0.6 part anti-old Agent OD, through high-speed mixer mixing 3min, joins after mix homogeneously in extruder hopper, be simultaneously introduced 5 parts pre-by NDZ-201 The white carbon of first coupling processing is in the feeding of side, through double screw extruder extruding pelletization.Each district temperature of extruder is from feeding section It is followed successively by 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C to head temperature, Extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min, and main rate of feeding is 12 revs/min, side feeding machine speed Degree is 2.8 revs/min.
Embodiment 6
By 50 parts of EPDM, 40 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 2.5 parts of sulfur, 0.5 part of CZ, 0.3 part of HAV-2, 1.5 parts of MgO, 1 part of stearic acid, 4 parts of pertroleum waxes, 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.2 part of antioxidant DLSTDP, through high-speed mixer mixing 3min, joins after mix homogeneously in extruder hopper, be simultaneously introduced 5 parts pre-by KH550 The white carbon of first coupling processing is in the feeding of side, through double screw extruder extruding pelletization.Each district temperature of extruder is from feeding section It is followed successively by 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C to head temperature, Extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min, and main rate of feeding is 12 revs/min, side feeding machine speed Degree is 2.8 revs/min.
Embodiment 7
By 60 parts of EPDM, 30 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 2.5 parts of sulfur, 0.7 part of PAPI, 0.5 part of CZ, 0.3 part of HAV-2,1.5 parts of CaO, 1 part of stearic acid, 10 parts of white mineral oils, 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.4 part Antioxidant DLSTDP, through high-speed mixer mixing 3min, joins after mix homogeneously in extruder hopper, be simultaneously introduced 5 parts by KH560 is pre-conjugated the white carbon of process in the feeding of side, through double screw extruder extruding pelletization.Each district temperature of extruder from Feeding section to head temperature be followed successively by 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min, and main rate of feeding is 12 revs/min, and side is fed Material motor speed is 2.8 revs/min.
Embodiment 8
By 65 parts of EPDM, 20 parts of EVOH-MAA, 15 parts of EPDM-g-MAH, 4 parts of sulfur, 0.7 part of PAPI, 0.5 part of CZ, 0.3 Part HAV-2,1.5 parts of MgO, 1 part of stearic acid, 5 parts of pertroleum waxes, 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.4 part resist Oxygen agent DLSTDP, through high-speed mixer mixing 3min, joins after mix homogeneously in extruder hopper, be simultaneously introduced 5 parts by KH570 is pre-conjugated the white carbon of process in the feeding of side, through double screw extruder extruding pelletization.Each district temperature of extruder from Feeding section to head temperature be followed successively by 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min, and main rate of feeding is 12 revs/min, and side is fed Material motor speed is 2.8 revs/min.
Embodiment 9
By 60 parts of EPDM, 30 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 1.5 parts of sulfur, 1.5 parts of DCP, 0.3 part of PAPI, 0.5 part of CZ, 0.3 part of HAV-2,1.5 parts of MgO, 1 part of stearic acid, 10 parts of pertroleum waxes, 0.2 part of antioxidant 1010,0.2 part of antioxidant 168,0.2 part of antioxidant DLSTDP is through high-speed mixer mixing 3min, joins in extruder hopper after mix homogeneously, will simultaneously Be pre-mixed uniformly by KH550 be pre-conjugated 10 parts of white carbon black N330 of process with in 10 parts of white carbon black N762 to side feeding, through pair Screw extruder extruding pelletization.Each district temperature of extruder be followed successively by from feeding section to head temperature 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min, main rate of feeding is 12 revs/min, and side feeding machine speed is 5 revs/min.
Embodiment 10
By 60 parts of EPDM, 30 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 0.5 part of sulfur, 0.5 part of TMTM, 0.5 part of CZ, 0.5 part of HAV-2,1.5 parts of MgO, 1 part of stearic acid, 5 parts of pertroleum waxes, 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.2 part Antioxidant DLSTDP, through high-speed mixer mixing 3min, joins after mix homogeneously in extruder hopper, be simultaneously introduced 20 parts by KH550 is pre-conjugated the white carbon of process in the feeding of side, through double screw extruder extruding pelletization.Each district temperature of extruder from Feeding section to head temperature be followed successively by 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min, and main rate of feeding is 12 revs/min, and side is fed Material motor speed is 5 revs/min.
Embodiment 11
By 60 parts of EPDM, 35 parts of EVOH-MAA, 5 parts of EPDM-g-MAH, 3.5 parts of sulfur, 0.7 part of TMTM, 0.5 part of CZ, 0.5 Part HAV-2,1.5 parts of MgO, 1 part of stearic acid, 5 parts of pertroleum waxes, 0.2 part of antioxidant 1010,0.3 part of irgasfos 168,0.3 part anti-old Agent OD, 0.3 part of T1201, through high-speed mixer mixing 3min, join in extruder hopper, will mix in advance simultaneously after mix homogeneously 5 parts of white carbon black N330 and 5 parts of white carbon black N762 that conjunction is pre-conjugated process by DL-411 uniformly are added in the feeding of side, squeeze through twin screw Go out machine extruding pelletization.Each district temperature of extruder be followed successively by from feeding section to head temperature 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min Clock, main rate of feeding is 12 revs/min, and side feeding machine speed is 3.8 revs/min.
Embodiment 12
By 60 parts of EPDM, 35 parts of EVOH-MAA, 5 parts of EPDM-g-MAH, 3.5 parts of sulfur, 0.5 part of TMTM, 0.5 part of CZ, 0.5 Part HAV-2,1.5 parts of SnCl2, 1 part of stearic acid, 5 parts of pertroleum waxes, 0.3 part of age resistor OD, 0.2 part of antioxidant 1010,0.3 part T1201,0.2 part of antioxidant DLSTDP, through high-speed mixer mixing 3min, join in extruder hopper, simultaneously after mix homogeneously Add 10 parts and be pre-conjugated the white carbon of process in the feeding of side by DL-411, through double screw extruder extruding pelletization.Extruder Each district temperature be followed successively by from feeding section to head temperature 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, 205 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 160 revs/min, and main rate of feeding is 12 Rev/min, side feeding machine speed is 3.8 revs/min.
For preferably obstruct gas, water-fast steaming to EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer of the present invention The correlated performances such as gas have directly understanding, are melted it according to associated test standards by the elastomer in embodiments of the invention 1-12 Melting the performance tests such as index, hot strength, hardness, concrete testing standard is as shown in the table with experimental data:
Table: EPDM/EVOH-MAA elastomer performance test table
Continued
Can be seen that from upper table data, the EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer of the present invention not only has excellent Good gas barrier, water-fast steam performance.Issue in vulcanizing system effect after being grafted the MAA of band unsaturated double-bond due to EVOH Give birth to and partially completely cross-linked；Reasonably select sulfuration, vulcanization accelerator, compatilizer and packing strengthening agent etc., and each plant demand Control so that the present invention makes the comprehensive mechanical property of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer more traditional EPDM/PP dynamic vulcanization thermoplastic elastomer is more excellent.

Claims (12)

1. the EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer intercepting gas, resistance to steam, it is characterised in that: press Parts by weight meter, is made up of following component: EPDM be 35-70 part, metering system acid grafted ethylene-ethenol copolymer be 20- 60 parts, compatilizer 5-15 part, packing strengthening agent 5-20 part, vulcanizing agent 0.5-5 part, vulcanization accelerator 0-1.5 part, activating agent 1-2.5 part, plasticizer 0-10 part, coupling agent 0-5 part, antioxidant 0.6-1.5 part；Described metering system acid grafted ethylene-second Enol copolymer melt index under the conditions of 230 DEG C/2.16kg is 0.5-20g/10min；Described methacrylic acid grafting second Ethylene contents in alkene-ethenol copolymer is 20-60%, vinyl alcohol is content 40-80%, the percent grafting of methacrylic acid is 0.5-20%。
A kind of EPDM/EVOH-MAA dynamic-vulcanization thermoplastic bullet intercepting gas, resistance to steam the most according to claim 1 Gonosome, it is characterised in that: described EPDM, metering system acid grafted ethylene-ethenol copolymer and compatilizer are generally 100 parts, Packing strengthening agent 5-20 part, vulcanizing agent 0.5-5 part, vulcanization accelerator 0-1.5 part, activating agent 1-2.5 part, plasticizer 0-10 Part, coupling agent 0-5 part, antioxidant 0.6-1.5 part.
A kind of EPDM/EVOH-MAA dynamic-vulcanization thermoplastic bullet intercepting gas, resistance to steam the most according to claim 1 Gonosome, it is characterised in that: the Mooney viscosity of described EPDM is 20-80Pa.s.
A kind of EPDM/EVOH-MAA dynamic-vulcanization thermoplastic bullet intercepting gas, resistance to steam the most according to claim 1 Gonosome, it is characterised in that: described compatilizer is grafting maleic anhydride with ethylene propylene terpolymer, and its percent grafting is 0.5-1.5%.
A kind of EPDM/EVOH-MAA dynamic-vulcanization thermoplastic bullet intercepting gas, resistance to steam the most according to claim 1 Gonosome, it is characterised in that: described vulcanizing agent be in sulfur, cumyl peroxide, polymethylene polyphenyl isocyanate extremely Few one.
A kind of EPDM/EVOH-MAA dynamic-vulcanization thermoplastic bullet intercepting gas, resistance to steam the most according to claim 1 Gonosome, it is characterised in that: described vulcanization accelerator include tetramethylthiuram monosulfide, 2-mercaptobenzothiazole, N-cyclohexyl- 2-[4-morpholinodithio sulfenamide, N, at least one in N-metaphenylene maleimide.
A kind of EPDM/EVOH-MAA dynamic-vulcanization thermoplastic bullet intercepting gas, resistance to steam the most according to claim 1 Gonosome, it is characterised in that: described packing strengthening agent is at least one in white carbon black, white carbon.
A kind of EPDM/EVOH-MAA dynamic-vulcanization thermoplastic bullet intercepting gas, resistance to steam the most according to claim 1 Gonosome, it is characterised in that: described plasticizer is paraffin oil, naphthenic oil or white mineral oil.
A kind of EPDM/EVOH-MAA dynamic-vulcanization thermoplastic bullet intercepting gas, resistance to steam the most according to claim 1 Gonosome, it is characterised in that: described activating agent includes zinc oxide, calcium oxide, zinc carbonate, light magnesium oxide, stannous chloride, stearic acid In at least one.
A kind of EPDM/EVOH-MAA dynamic-vulcanization thermoplastic intercepting gas, resistance to steam the most according to claim 1 Elastomer, it is characterised in that: described coupling agent includes 3-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl group three Methoxy silane, γ-(methacryloxypropyl) propyl trimethoxy silicane, isopropyl three (dioctylphyrophosphoric acid acyloxy) metatitanic acid At least one in ester, aluminic acid three isopropyl ester.
11. a kind of EPDM/EVOH-MAA dynamic-vulcanization thermoplastics intercepting gas, resistance to steam according to claim 1 Elastomer, it is characterised in that: described antioxidant is for including β-(3,5-di-tert-butyl-hydroxy phenyl) positive octadecanol of propanoic acid Ester, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, octylated diphenylamine, three ［ 2,4-di-t-butyls Phenyl ］ phosphite ester, the double octadecyl (anti-DSTDP) of thio-2 acid, thio-2 acid double lauryl alcohol ester, N, the sub-water of N'-bis- At least one in Yankee propane diamine.
Prepare a kind of EPDM/EVOH-MAA dynamic vulcanization intercepting gas, resistance to steam as claimed in claim 1 for 12. 1 kinds The method of thermoplastic elastomer (TPE), it is characterised in that: comprise the following steps:
(1) by weight proportioning weigh EPDM, metering system acid grafted ethylene-ethenol copolymer, compatilizer, vulcanizing agent, Vulcanization accelerator, activating agent, plasticizer and antioxidant join in high-speed mixer and mix together so that it is be uniformly dispersed；
(2) proportioning weighs packing strengthening agent and coupling agent by weight, controls temperature 70-95 DEG C of idol in high-speed mixer Connection pretreatment 4min；
(3) raw material that mixes in (1) is put into the loading hopper of double screw extruder, simultaneously will be through raw material that (2) process from squeezing Going out at the fluxing zone of machine in side feeding addition extruder, through melt extruding, pelletize obtains EPDM/EVOH-MAA dynamic-vulcanization thermoplastic Elastomer；Described double screw extruder each district temperature is 180 ~ 220 DEG C, and extruded velocity is 120-300 rev/min, rate of feeding It it is 10～30 revs/min.
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