CN103012971A - EPDM/EVOH-MAA (ethylene-propylene-diene monomer/ethylene vinyl alcohol-methacrylic acid) dynamically vulcanizled thermoplastic elastomer for separating gas and resisting water vapor and preparation method thereof - Google Patents
EPDM/EVOH-MAA (ethylene-propylene-diene monomer/ethylene vinyl alcohol-methacrylic acid) dynamically vulcanizled thermoplastic elastomer for separating gas and resisting water vapor and preparation method thereof Download PDFInfo
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- CN103012971A CN103012971A CN2012105097042A CN201210509704A CN103012971A CN 103012971 A CN103012971 A CN 103012971A CN 2012105097042 A CN2012105097042 A CN 2012105097042A CN 201210509704 A CN201210509704 A CN 201210509704A CN 103012971 A CN103012971 A CN 103012971A
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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
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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
- B29C48/022—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
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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
- B29C48/92—Measuring, controlling or regulating
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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
- 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
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- 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
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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
- 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
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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
- 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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Abstract
The invention discloses an EPDM/EVOH-MAA (ethylene-propylene-diene monomer/ethylene vinyl alcohol-methacrylic acid) dynamically vulcanizled thermoplastic elastomer for separating gas and resisting water vapor and a preparation method thereof. The EPDM/EVOH-MAA dynamically vulcanizled thermoplastic elastomer is prepared from EPDM, EVOH-MAA, a compatilizer, a filling reinforcing agent, a vulcanizing agent, a vulcanization accelerator, an active agent, a plasticizer, a coupling agent and an antioxidant. The thermoplastic elastomer prepared by the invention not only has excellent cyclicity and gas barrier property, but also has the characteristics of resistance to water vapor, oil resistivity, abrasive resistance and the like, belongs to the domain of a high-performance engineering thermoplastic elastomer, and has wide application field. The application field comprises the fields such as an electric appliance, mechanical seal, medicine, chemical industry and the like.
Description
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to a kind of EPDM/ EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam and preparation method thereof.
Technical background
Dynamic vulcanization thermoplastic elastomer (Theremoplastic Vukcanizate) is called for short TPV, being thermoplasticity Ethylene Propylene Terpolymer dynamic vulcanization elastomerics or thermoplasticity Ethylene Propylene Terpolymer dynamic perduren, is a class blending thermoplastic elastomer material that adopts the dynamic vulcanization technology preparation.Dynamic vulcanization technology refers to when thermoplastic resin and rubber melt blending, rubber phase issues biochemical crosslinked in crosslinked action, and by strong mechanical shearing effect, be sheared into and be broken into a large amount of micron-level crosslinked rubber grains, be dispersed in the process in the thermoplastic resin external phase, terpolymer EP rubber (EPDM) microparticulate that is solid cure continuous polypropylene (PP) mutually in the macromolecular elastomer material of composition, the characteristic of rubber and plastics is well combined, obtain the high performance elastomer material of excellent combination property.Physicals and function class under the TPV normal temperature are similar to thermoset rubber, at high temperature show as the characteristic of thermoplastics, can fast, economical and easily machine-shaping, and be green material, can repeat to reclaim and use.The other similar vulcanized rubber of TPV performance has the good advantage such as heat-resisting and ageing-resistant, is able to widespread use in fields such as medical treatment, chemical industry, automobile, electrical equipment, daily and buildings.But traditional TPV material is to be composited by terpolymer EP rubber and polypropylene (PP), its barrier property of anti-infiltration the to the gases such as oxygen, nitrogen and water vapour is poor, the deficiency that also has oil resistant, organic solvent resistance, so its barrier properties for gases, resistance to air loss, solvent resistance and wear resisting property are all relatively poor, can not satisfy the TPV material in the requirement of the special dimensions such as medical treatment, chemical industry, automobile, electrical equipment, daily and building to aspects such as its barrier properties for gases, water-fast steams.
The EPDM(terpolymer EP rubber), it is the random copolymers that is formed by ethene (45% ~ 70%), propylene (30% ~ 40%) and diene the 3rd monomer (1% ~ 3%), wherein the 3rd monomer is generally dicyclopentadiene, Isosorbide-5-Nitrae-hexadiene or 2-ethylidene norbornene.It has fabulous vulcanization characteristics, minimum proportion, and it can absorb a large amount of fillers and oil and influencing characteristic is little.
The EVOH(ethylene-vinyl alcohol copolymer) be to use maximum high barrier material always, EVOH is that the iris action with polyvinyl excellent processing characteristics and vinyl alcohol polymer combines, not only show fabulous processing characteristics, and gas, smell, spices, solvent etc. are presented excellent blocking effect, also have simultaneously thermostability and reusing.
Methacrylic acid grafted ethylene-vinyl alcohol copolymer (be called for short EVOH-MAA, lower with) has not only kept the advantage of EVOH, simultaneously since the introducing of two keys can crosslinking reaction occur under the effect of vulcanizing agent make its barrier property more excellent.
Summary of the invention
The present invention is directed to problems of the prior art, a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer material that intercepts gas, water-fast steam is provided.Another object of the present invention provides the preparation method of above-mentioned EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer material.
In order to achieve the above object, the present invention realizes by following technical proposal:
A kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam, count by weight, be comprised of following component: EPDM is that 35-70 part, methacrylic acid grafted ethylene-vinyl alcohol 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, promoting agent 1-2.5 part, softening agent 0-10 part, coupling agent 0-5 part, oxidation inhibitor 0.6-1.5 part.
The preferred version of such scheme is, described EPDM, EVOH-MAA and compatilizer totally are 100 parts, packing strengthening agent 5-20 part, vulcanizing agent 0.5-5 part, vulcanization accelerator 0-1.5 part, promoting agent 1-2.5 part, softening agent 0-10 part, coupling agent 0-5 part, oxidation inhibitor 0.6-1.5 part.
The mooney viscosity of described EPDM is 20-80Pa.S.
Described methacrylic acid grafted ethylene-acetate ethylene copolymer (EVOH-MAA) melting index under 230 ℃/2.16Kg condition is 0.5-20g/10min, and the rate of vaccination of therein ethylene content 20-60%, vinyl alcohol content 40-80%, methacrylic acid is 0.5-20%.
Described compatilizer is grafting maleic anhydride with ethylene propylene terpolymer (EPDM-g-MAH), and its percentage of grafting is 0.5-1.5%.
Described vulcanizing agent is at least a in sulphur, dicumyl peroxide (DCP), the polymethylene polyphenyl isocyanate (PAPI).
Described vulcanization accelerator is tetramethylthiuram monosulfide (TMTM), 2-mercaptobenzothiazole (M), N cyclohexyl 2 benzothiazole sulfenamide (CZ), N, at least a in the N-metaphenylene maleimide (HVA-2).
Described packing strengthening agent is at least a in carbon black, the white carbon black.The preferred carbon black N330 of described carbon black, carbon black 762.
Described softening agent is paraffin oil, naphthenic oil or white mineral oil.
Described activator comprises zinc oxide (ZnO), calcium oxide (CaO), zinc carbonate (ZnCO
3), light magnesium oxide (MgO), tin protochloride (SnCl
2), at least a in the stearic acid (SA).
Described coupling agent is at least a in 3-aminopropyl triethoxysilane (KH550), γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560), γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570), sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester (NDZ-201) or aluminic acid three isopropyl esters (DL-411).
Described oxidation inhibitor comprises at least a in phenols, amine, phosphorous acid esters, monothioester class, the metal passivator.Wherein phenolic antioxidant is β-(3,5-di-tert-butyl-hydroxy phenyl) positive octadecanol ester of propionic acid (antioxidant 1076) or four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010); Amine antioxidants is octylated diphenylamine (anti-aging agent OD); Phosphite ester kind antioxidant is three ［ 2,4-di-tert-butyl-phenyl ］ phosphorous acid esters (irgasfos 168); The monothioester kind antioxidant is the two stearyl alcohol esters (oxidation inhibitor DSTDP) of thio-2 acid; Metal passivator is N, N'-two salicylidene propylene diamine (T1201), and oxidation inhibitor can be selected aforementioned at least a among the present invention.
A kind ofly prepare above-mentioned a kind of method that intercepts the EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer of gas, water-fast steam, may further comprise the steps:
(1) proportioning takes by weighing EPDM, EVOH-MAA, compatilizer, vulcanizing agent, vulcanization accelerator, promoting agent, softening agent and oxidation inhibitor and joins in the high-speed mixer and mix together by weight, and it is uniformly dispersed;
(2) proportioning takes by weighing packing strengthening agent and coupling agent by weight, and the control temperature is at 70-95 ℃ of coupling pre-treatment 4min in high-speed mixer;
(3) raw material that mixes in (1) is dropped into the loading hopper of twin screw extruder, raw material after will processing in (2) simultaneously adds in the forcing machine from the fluxing zone side feeding of forcing machine, through melt extruding, granulation gets the EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer; It is 180 ~ 220 ℃ that described twin screw extruder is respectively distinguished temperature, and extruded velocity is 120-300 rev/min.
The present invention compared with prior art has following beneficial effect:
1, the ethylene-vinyl alcohol copolymer of the barrier property the best that will generally acknowledge at present of dynamic-vulcanization thermoplastic elasticity of the present invention applies in the EPDM in the preparation thermoplastic elastomer, by grafting methacrylic acid monomer on ethylene-vinyl alcohol copolymer, at the MMA of EVOH side chain introducing with unsaturated double-bond, make it under the effect of vulcanizing agent, crosslinking reaction can occur;
2, compatilizer grafting maleic anhydride with ethylene propylene terpolymer (EPDM-g-MAH) improves the interface compatibility of EPDM and EVOH-MAA, EPDM and EVOH-MAA is disperseed under dynamic crosslinking better, crosslinkedly be the homogeneous system;
3, because packing strengthening agent improves and has improved barrier properties for gases, resistance to air loss, solvent resistance and the wear resistance of dynamic vulcanization thermoplastic elastomer;
4, product of the present invention belongs to the high-performance engineering analog thermoplastic elastomer applicable to special dimensions such as medical treatment, chemical industry, automobile, electrical equipment, daily and buildings.
Embodiment:
The below provides embodiment so that the present invention is carried out concrete description; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, content still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes to the person skilled in the art in this field according to the present invention.
All used raw materials all are commercially available prod in the embodiments of the invention, and wherein: sulphur is elected 200 order sulphur as, and carbon black is selected carbon black N330 or carbon black 762, and the particle diameter of white carbon black is the 15-500 nanometer.
In the present invention, the method that preparation intercepts the EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer of gas, water-fast steam is to adopt following steps: (1) by weight proportioning takes by weighing EPDM, EVOH-MAA, compatilizer, vulcanizing agent, vulcanization accelerator, promoting agent, softening agent and oxidation inhibitor and joins in the high-speed mixer and mix together, and it is uniformly dispersed;
(2) proportioning takes by weighing packing strengthening agent and coupling agent by weight, and the control temperature is at 70-95 ℃ of coupling pre-treatment 4min in high-speed mixer;
(3) raw material that mixes in (1) is dropped into the loading hopper of twin screw extruder, raw material after will processing in (2) simultaneously adds in the forcing machine from the fluxing zone side feeding of forcing machine, through melt extruding, granulation gets the EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer; It is 180 ~ 220 ℃ that described twin screw extruder is respectively distinguished temperature, and pressure is 10-25MP, and the footpath ratio of twin screw extruder is 30 ~ 40, and extruded velocity is 120-300 rev/min, and rate of feeding is 10 ~ 30 rev/mins.
The below is described as follows for example:
Embodiment 1
40 parts of EPDM, 55 parts of EVOH-MAA, 5 parts of EPDM-g-MAH, 2.5 parts of sulphur, 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 oxidation inhibitor DSTDP are added to high-speed mixer and mixing to be joined in the forcing machine hopper after good, simultaneously with 5 parts by NDZ-201 in advance the carbon black N330 of coupling processing join in the side feeding, through the twin screw extruder extruding pelletization.Through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, and main rate of feeding is 12 rev/mins.
Embodiment 2
With 50 parts of EPDM, 40 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 2.5 parts of sulphur, 0.5 part of CZ, 0.3 part of HAV-2,1.5 parts of MgO, 1 part of stearic acid, 3 parts of petroleum waxes, 0.2 part of antioxidant 1010,0.1 part of irgasfos 168,0.3 part of oxidation inhibitor DLSTDP through high-speed mixer mixing 3min, join after mixing in the forcing machine hopper, add simultaneously 5 parts by KH550 in advance the carbon black N330 of coupling processing join in the side feeding, through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, main rate of feeding is 12 rev/mins, and side feeding machine speed is 2.8 rev/mins.
Embodiment 3
With 60 parts of EPDM, 30 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 2.5 parts of sulphur, 0.7 part of DCP, 0.5 part of CZ, 0.3 part of 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 oxidation inhibitor T1201,0.2 part of oxidation inhibitor DLSTDP through high-speed mixer mixing 3min, join after mixing in the forcing machine hopper, add simultaneously 5 parts by KH560 in advance the carbon black N330 of coupling processing join in the side feeding, through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, main rate of feeding is 12 rev/mins, and side feeding machine speed is 2.8 rev/mins.
Embodiment 4
With 70 parts of EPDM, 20 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 5 parts of sulphur, 0.5 part of CZ, 0.3 part of HAV-2,1.5 parts of CaO, 1 part of stearic acid, 5 parts of petroleum waxes, 0.2 part of antioxidant 1010,0.2 part of T1201,0.2 part of oxidation inhibitor DLSTDP, 0.6 part of anti-aging agent OD through high-speed mixer mixing 3min, join after mixing in the forcing machine hopper, add simultaneously by KH570 in advance 2.5 parts of carbon black N330 and 2.5 parts of carbon black N762 of coupling processing join in the side feeding, through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, main rate of feeding is 12 rev/mins, and side feeding machine speed is 2.8 rev/mins.
Embodiment 5
With 35 parts of EPDM, 60 parts of EVOH-MAA, 5 parts of EPDM-g-MAH, 5 parts of sulphur, 1.0 parts of CZ, 0.3 part of HAV-2,0.5 part of MgO, 0.5 part of stearic acid, 0.5 part of antioxidant 1010,0.1 part of irgasfos 168,0.2 part of oxidation inhibitor DLSTDP, 0.6 part of anti-aging agent OD through high-speed mixer mixing 3min, join after mixing in the forcing machine hopper, add simultaneously 5 parts by NDZ-201 in advance the white carbon black of coupling processing in the side feeding, through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, main rate of feeding is 12 rev/mins, and side feeding machine speed is 2.8 rev/mins.
Embodiment 6
With 50 parts of EPDM, 40 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 2.5 parts of sulphur, 0.5 part of CZ, 0.3 part of HAV-2,1.5 parts of MgO, 1 part of stearic acid, 4 parts of petroleum waxes, 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.2 part of oxidation inhibitor DLSTDP through high-speed mixer mixing 3min, join after mixing in the forcing machine hopper, add simultaneously 5 parts by KH550 in advance the white carbon black of coupling processing in the side feeding, through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, main rate of feeding is 12 rev/mins, and side feeding machine speed is 2.8 rev/mins.
Embodiment 7
With 60 parts of EPDM, 30 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 2.5 parts of sulphur, 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 of oxidation inhibitor DLSTDP through high-speed mixer mixing 3min, join after mixing in the forcing machine hopper, add simultaneously 5 parts by KH560 in advance the white carbon black of coupling processing in the side feeding, through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, main rate of feeding is 12 rev/mins, and side feeding machine speed is 2.8 rev/mins.
Embodiment 8
With 65 parts of EPDM, 20 parts of EVOH-MAA, 15 parts of EPDM-g-MAH, 4 parts of sulphur, 0.7 part of PAPI, 0.5 part of CZ, 0.3 part of HAV-2,1.5 parts of MgO, 1 part of stearic acid, 5 parts of petroleum waxes, 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.4 part of oxidation inhibitor DLSTDP through high-speed mixer mixing 3min, join after mixing in the forcing machine hopper, add simultaneously 5 parts by KH570 in advance the white carbon black of coupling processing in the side feeding, through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, main rate of feeding is 12 rev/mins, and side feeding machine speed is 2.8 rev/mins.
Embodiment 9
With 60 parts of EPDM, 30 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 1.5 parts of sulphur, 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 petroleum waxes, 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.2 part of oxidation inhibitor DLSTDP through high-speed mixer mixing 3min, join after mixing in the forcing machine hopper, to be pre-mixed simultaneously uniformly by KH550 in advance 10 parts of carbon black N330 of coupling processing and 10 parts of carbon black N762 in the side feeding, through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, main rate of feeding is 12 rev/mins, and side feeding machine speed is 5 rev/mins.
Embodiment 10
With 60 parts of EPDM, 30 parts of EVOH-MAA, 10 parts of EPDM-g-MAH, 0.5 part of sulphur, 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 petroleum waxes, 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.2 part of oxidation inhibitor DLSTDP through high-speed mixer mixing 3min, join after mixing in the forcing machine hopper, add simultaneously 20 parts by KH550 in advance the white carbon black of coupling processing in the side feeding, through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, main rate of feeding is 12 rev/mins, and side feeding machine speed is 5 rev/mins.
Embodiment 11
With 60 parts of EPDM, 35 parts of EVOH-MAA, 5 parts of EPDM-g-MAH, 3.5 parts of sulphur, 0.7 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 petroleum waxes, 0.2 part of antioxidant 1010,0.3 part of irgasfos 168,0.3 part of anti-aging agent OD, 0.3 part of T1201 through high-speed mixer mixing 3min, join after mixing in the forcing machine hopper, to be pre-mixed simultaneously uniformly by DL-411 in advance 5 parts of carbon black N330 and 5 parts of carbon black N762 of coupling processing be added in the side feeding, through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, main rate of feeding is 12 rev/mins, and side feeding machine speed is 3.8 rev/mins.
Embodiment 12
With 60 parts of EPDM, 35 parts of EVOH-MAA, 5 parts of EPDM-g-MAH, 3.5 parts of sulphur, 0.5 part of TMTM, 0.5 part of CZ, 0.5 part of HAV-2,1.5 parts of SnCl
2, 1 part of stearic acid, 5 parts of petroleum waxes, 0.3 part of anti-aging agent OD, 0.2 part of antioxidant 1010,0.3 part of T1201,0.2 part of oxidation inhibitor DLSTDP be through high-speed mixer mixing 3min, join after mixing in the forcing machine hopper, add simultaneously 10 parts by DL-411 in advance the white carbon black of coupling processing in the side feeding, through the twin screw extruder extruding pelletization.The temperature of respectively distinguishing of forcing machine is followed successively by 180 ℃, 190 ℃, 190 ℃, 195 ℃, 205 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 215 ℃ from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 160 rev/mins, main rate of feeding is 12 rev/mins, and side feeding machine speed is 3.8 rev/mins.
In order better the correlated performances such as the obstruct gas of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer of the present invention, water-fast steam to be had direct understanding, with the elastomerics among the embodiments of the invention 1-12 according to the dependence test standard to performance tests such as its melting index, tensile strength, hardness, concrete testing standard and experimental data are as shown in the table:
Table: EPDM/EVOH-MAA elastomer performance test chart
Continued
Can find out that from upper table data EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer of the present invention not only has good gas-barrier, water-fast steam performance.Since the EVOH grafting with under the vulcanization system effect, occured behind the MAA of unsaturated double-bond the part/fully crosslinked; Reasonably select sulfuration, vulcanization accelerator, compatilizer and packing strengthening agent etc., and the control of each plant demand, so that the more traditional EPDM/PP dynamic vulcanization thermoplastic elastomer of the comprehensive mechanical property that makes the EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer of the present invention is more excellent.
Claims (13)
1. EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam, it is characterized in that: count by weight, be comprised of following component: EPDM is that 35-70 part, methacrylic acid grafted ethylene-acetate ethylene copolymer 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, promoting agent 1-2.5 part, softening agent 0-10 part, coupling agent 0-5 part, oxidation inhibitor 0.6-1.5 part.
2. a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam according to claim 1, it is characterized in that: described EPDM, methacrylic acid grafted ethylene-acetate ethylene copolymer and compatilizer totally are 100 parts, packing strengthening agent 5-20 part, vulcanizing agent 0.5-5 part, vulcanization accelerator 0-1.5 part, promoting agent 1-2.5 part, softening agent 0-10 part, coupling agent 0-5 part, oxidation inhibitor 0.6-1.5 part.
3. a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam according to claim 1, it is characterized in that: the mooney viscosity of described EPDM is 20-80Pa.S.
4. a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam according to claim 1, it is characterized in that: the melting index of described methacrylic acid grafted ethylene-acetate ethylene copolymer under 230 ℃/2.16Kg condition is 0.5-20g/10min; Ethylene content in described methacrylic acid grafted ethylene-acetate ethylene copolymer is that 20-60%, vinyl alcohol are that the percentage of grafting of content 40-80%, methacrylic acid is 0.5-20%.
5. a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam according to claim 1, it is characterized in that: described compatilizer is grafting maleic anhydride with ethylene propylene terpolymer, its percentage of grafting is 0.5-1.5%.
6. a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam according to claim 1 is characterized in that: described vulcanizing agent is at least a in sulphur, dicumyl peroxide, the polymethylene polyphenyl isocyanate.
7. a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam according to claim 1, it is characterized in that: described vulcanization accelerator comprises tetramethylthiuram monosulfide, 2-mercaptobenzothiazole, N cyclohexyl 2 benzothiazole sulfenamide, N, at least a in the N-metaphenylene maleimide.
8. a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam according to claim 1 is characterized in that: described packing strengthening agent is at least a in carbon black, the white carbon black.
9. a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam according to claim 1, it is characterized in that: described softening agent is paraffin oil, naphthenic oil or white mineral oil.
10. a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam according to claim 1 is characterized in that: described activator comprises at least a in zinc oxide, calcium oxide, zinc carbonate, light magnesium oxide, tin protochloride, the stearic acid.
11. a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam according to claim 1, it is characterized in that: described coupling agent comprises at least a in 3-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, aluminic acid three isopropyl esters.
12. a kind of EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer that intercepts gas, water-fast steam according to claim 1, it is characterized in that: described oxidation inhibitor is for comprising β-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, octylated diphenylamine, three ［ 2, the 4-di-tert-butyl-phenyl ］ the two stearyl alcohol esters (anti-DSTDP) of phosphorous acid ester, thio-2 acid, the two lauryl alcohol esters of thio-2 acid, N, at least a in the N'-two salicylidene propylene diamine.
13. one kind prepares a kind of method that intercepts the EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer of gas, water-fast steam as claimed in claim 1, it is characterized in that: may further comprise the steps:
(1) proportioning takes by weighing EPDM, methacrylic acid grafted ethylene-acetate ethylene copolymer, compatilizer, vulcanizing agent, vulcanization accelerator, promoting agent, softening agent and oxidation inhibitor and joins in the high-speed mixer and mix together by weight, and it is uniformly dispersed;
(2) proportioning takes by weighing packing strengthening agent and coupling agent by weight, and the control temperature is at 70-95 ℃ of coupling pre-treatment 4min in high-speed mixer;
(3) raw material that mixes in (1) is dropped into the loading hopper of twin screw extruder, the raw material that to process through (2) simultaneously adds in the forcing machine from the fluxing zone side feeding of forcing machine, through melt extruding, granulation gets the EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer; It is 180 ~ 220 ℃ that described twin screw extruder is respectively distinguished temperature, and extruded velocity is 120-300 rev/min.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275494A (en) * | 2013-06-04 | 2013-09-04 | 烟台泰盛精化科技有限公司 | Oil-resistant single-component room temperature vulcanized silicone rubber and preparation method thereof |
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| CN106398001A (en) * | 2016-10-09 | 2017-02-15 | 芜湖瑞德机械科技有限公司 | Tension-resistant rubber gasket and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0703279A1 (en) * | 1994-09-21 | 1996-03-27 | Buna Sow Leuna Olefinverbund GmbH | Thermoplastic molding compositions having gas barrier properties |
| CN101278007A (en) * | 2005-08-31 | 2008-10-01 | 东赛璐株式会社 | Gas barrier film, gas barrier laminate and method for production of the film or laminate |
| CN101993573A (en) * | 2009-08-03 | 2011-03-30 | 横滨橡胶株式会社 | Thermoplastic elastomer composition |
| WO2012118546A1 (en) * | 2011-03-03 | 2012-09-07 | Exxonmobil Chemical Patents Inc. | Ethylene-vinyl alcohol based thermoplastic elastomers and vulcanizates |
-
2012
- 2012-12-04 CN CN201210509704.2A patent/CN103012971B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0703279A1 (en) * | 1994-09-21 | 1996-03-27 | Buna Sow Leuna Olefinverbund GmbH | Thermoplastic molding compositions having gas barrier properties |
| CN101278007A (en) * | 2005-08-31 | 2008-10-01 | 东赛璐株式会社 | Gas barrier film, gas barrier laminate and method for production of the film or laminate |
| CN101993573A (en) * | 2009-08-03 | 2011-03-30 | 横滨橡胶株式会社 | Thermoplastic elastomer composition |
| WO2012118546A1 (en) * | 2011-03-03 | 2012-09-07 | Exxonmobil Chemical Patents Inc. | Ethylene-vinyl alcohol based thermoplastic elastomers and vulcanizates |
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|---|---|---|---|---|
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| CN105111598A (en) * | 2015-09-02 | 2015-12-02 | 苏州国泰科技发展有限公司 | Automobile rubber sealing strip and preparation method thereof |
| WO2017110568A1 (en) * | 2015-12-25 | 2017-06-29 | 株式会社クラレ | Resin composition and molded article |
| CN108473744A (en) * | 2015-12-25 | 2018-08-31 | 株式会社可乐丽 | Resin combination and formed body |
| CN108473744B (en) * | 2015-12-25 | 2020-08-04 | 株式会社可乐丽 | Resin composition and molded article |
| CN106398001A (en) * | 2016-10-09 | 2017-02-15 | 芜湖瑞德机械科技有限公司 | Tension-resistant rubber gasket and preparation method thereof |
| CN109988413A (en) * | 2017-12-29 | 2019-07-09 | 深圳光启尖端技术有限责任公司 | A kind of gas barrier material and preparation method thereof |
| CN109851973A (en) * | 2019-01-23 | 2019-06-07 | 浙江省仙居县博达异型橡塑有限公司 | A kind of ionomer ethylene propylene diene rubber and preparation method thereof |
| CN109851973B (en) * | 2019-01-23 | 2021-03-23 | 浙江省仙居县博达异型橡塑有限公司 | Ionic crosslinking ethylene propylene diene monomer rubber and preparation method thereof |
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