CN104245822B - Comprise the compositions of EPDM and polyolefin elastomer, its preparation and purposes - Google Patents

Comprise the compositions of EPDM and polyolefin elastomer, its preparation and purposes Download PDF

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Publication number
CN104245822B
CN104245822B CN201280071176.5A CN201280071176A CN104245822B CN 104245822 B CN104245822 B CN 104245822B CN 201280071176 A CN201280071176 A CN 201280071176A CN 104245822 B CN104245822 B CN 104245822B
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propylene
compositions
ethylene
elastomer
diene terpolymer
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CN104245822A (en
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励亮
M·B·乔希
J·沈
E·P·茹尔丹
V·K·逖瓦利
童军
P·P·帕特奇
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Abstract

The compositions provided comprises: the ethylene contents of ethylene propylene diene terpolymers and this ethylene propylene diene terpolymers that (a) has about 25 about 300 Mooney viscosities [ML (1+4) 125 DEG C] is at least about 60wt%；(b) polyolefin elastomer.The existence of this polyolefin elastomer increases the rheological property of said composition to the degree not significantly attenuating other character (such as tensile break strength and compressive deformation).

Description

Comprise the compositions of EPDM and polyolefin elastomer, its preparation and purposes
Cross-Reference to Related Applications
The application relates to the U.S. serial 12/621,020 (attorney docket of submission on November 18th, 2009 2009EM237)。
Invention field
The present invention relates to polymer composition.More particularly it relates to comprise Ethylene-Propylene-Diene ternary polymerization Thing and the compositions of polyolefin elastomer, its preparation method, and goods prepared therefrom.
Background of invention
Comprise the processing to they final uses of the character of compositions of ethylene-propylene-diene terpolymer (EPDM) Performance has a direct impact.Consumer's application needs the compositions comprising EPDM by adding the multiple tune of the component compatible with EPDM Whole to obtain certain character.By the EPDM of a small amount of low mooney viscosity [ML (1+4) 125 DEG C], such as less than 25 is mixed relatively Relatively high Mooney viscosity [ML (1+4) 125 DEG C], be typically larger than 60 common EPDM to reach the mobility dramatically increased, thus Improve rheological property.But, this compositions typically results in widely used relatively costly.
The U.S. announces No.2011-0118404A1 and relates to natural rubber blends, its preparation method, and system prepared therefrom Product.Described natural rubber blends includes that at least one contains the propylene copolymer of the unit deriving from ethylene.Described natural rubber Blend can farther include one or more reinforcers, such as white carbon black.The existence of propylene copolymer is it is said that can improve resistance to The ozon ageing properties with natural rubber gum stock (gum stock).
" the Use of specialty elastomer Vistamaxx VM1100in an EPDM of Xiao Sheng Gum stock ", Rubber Industry, the 483-486 page, the 8th phase, volume 54,2007, it has been reported that certain is based on propylene Elastomer to join [ML (1+4) 125 DEG C] containing Mooney viscosity be the EPDM of about 80 and relatively low mooney viscosity [ML (1+4) 125 DEG C] in the EPDM gum stock of the EPDM of 17-23 to be not more than the amount part of 20phr with the total amount relative to two kinds of EPDM components Replace the EPDM of relatively low mooney viscosity.This replaces it is said that production cost can be reduced, and the heat of the original gum stock of the most basic holding is old Change and compressive deformation performance.This list of references concludes further that, at the rheological property of processing (such as, extrusion) period gum stock Substantially will not be changed by elastomer based on propylene.
Due to low mooney viscosity EPDM raw material quickly increases the most in recent years demand and relative nervous supply, it is desirable to tool There is the succedaneum of low mooney viscosity EPDM, its mobility being also used for improving the compositions comprising EPDM.Applicant have discovered that Some polyolefin elastomer, is based particularly on the elastomer of propylene, it is possible to provide comprise the EPDM with of a relatively high Mooney viscosity The mobility of composition for improved, especially when using with the amount of for example, less than about 20phr relative to described EPDM.Acquisition comprises The preferable mobility of EPDM composition and weaken other character indistinctively, such as fracture tensile strength and compressive deformation, be one Kind the most cost-effective method, hence in so that the present composition to subsequent applications, such as extrude advantageous particularly.
Summary of the invention
The compositions comprising EPDM, polyolefin elastomer, its preparation method, and goods prepared therefrom are provided.In one In embodiment, the present invention contains a kind of compositions, and it comprises: (a) Mooney viscosity [ML (1+4) 125 DEG C] is about 25-about 300 Ethylene-propylene-diene terpolymer and the ethylene contents of this EPDM be at least about 60wt%；(b) polyolefin elastomer.
In one embodiment, the present invention relates to a kind of method preparing compositions, it comprises the following steps: (a) will (i) Mooney viscosity [ML (1+4) 125 DEG C] be about the ethylene contents of EPDM and this EPDM of 25-about 300 be at least about 60wt% with (ii) polyolefin elastomer combines, and (b) forms described compositions.
Present invention also contemplates that a kind of goods, it comprises described herein or according to prepared by any means disclosed herein appointing Meaning compositions.Preferably, described goods are extruded product, mechanograph, flexible pipe, sheet material, film or overcoat.
In one embodiment, a kind of method that the present invention relates to Mooney viscosity reducing compositions, it includes following Step: (i) Mooney viscosity [ML (1+4) 125 DEG C] is about the ethylene-propylene-diene terpolymer of 25-about 300 and is somebody's turn to do by (a) The ethylene contents of ethylene-propylene-diene terpolymer is at least about 60wt%, and polyolefin elastomer is combined, and (b) with (ii) Form described compositions.
In a preferred embodiment, polyolefin elastomer is to derive from the unit of propylene and about 5-about containing at least about 60wt% 25wt% derives from the elastomer based on propylene of the unit of ethylene, gross weight meter based on described elastomer based on propylene, its Described in elastomer based on propylene there is the heat of fusion of below about 80J/g.In a preferred embodiment, described compositions Mooney viscosity [ML (1+4) 100 DEG C] than without described polyolefin elastomer but other side is identical for composition combination Mooney viscosity [ML (1+4) 100 DEG C] the low about 0-about 15 of thing.
Accompanying drawing is sketched
When Fig. 1 depicts that in compositions, EPDM content is 25wt%, compared with the first comparative example, the sample 1-3 of the present invention Mooney viscosity respective with sample 1a-3a [ML (1+4) 100 DEG C] (Fig. 1 a), mooney scorch, it is expressed as Mooney viscosity 125 DEG C improve the time (Fig. 1 b) of 5 units (T5), and reach the hardening time (Fig. 1 c) of 90% curing curve (T90) at 180 DEG C.
When Fig. 2 depicts that in compositions, EPDM content is 25wt%, compared with the first comparative example, the sample 1-3 of the present invention Tensile break strength and hot strength after the most aging with sample 1a-3a are remaining.
When Fig. 3 depicts that in compositions, EPDM content is 25wt%, compared with the first comparative example the present invention sample 1-3 and Compressive deformation (%) under each comfortable 25% flexure of sample 1a-3a.
When Fig. 4 depicts that in compositions, EPDM content is 20wt%, compared with the second comparative example, the sample 4-6 of the present invention Mooney viscosity respective with sample 4a-6a [ML (1+4) 100 DEG C] (Fig. 4 a), mooney scorch (Fig. 4 b), it is expressed as Mooney viscosity Improve the time of 5 units (T5) at 125 DEG C, and reach the hardening time (Fig. 4 c) of 90% curing curve (T90) at 180 DEG C.
Fig. 5 retouches when having understood that in compositions, EPDM content is 20wt%, compared with the second comparative example, and the sample 4-6 of the present invention Tensile break strength respective with sample 4a-6a and aging after hot strength remaining.
When Fig. 6 describes that in compositions, EPDM content is 20wt%, compared with the second comparative example, the sample 4-6 of the present invention With sample 4a-6a compressive deformation (%) under 25% flexure.
Detailed description of the invention
The multiple detailed description of the invention of the present invention and pattern now will be described, including preferred implementation and determining of using herein Justice.Give concrete preferred implementation although described further below, skilled person will understand that these are implemented Mode is exemplary, and the present invention can put into practice otherwise.Any refer to this " invention " can refer to be wanted by right Seek one or more present invention of restriction, but unnecessary be whole.The use of subhead is done merely for convenience, not Restricted the scope of the present invention.
As described herein, " polymer " is used to refer to homopolymer, copolymer, interpretation, terpolymer etc..
As described herein, when polymer is referred to as comprising monomer, described monomer is with this monomer polymeric species or this monomer Derivant form is present in described polymer.
As described herein, " elastomer " or " elastic composition " refers to any polymerization consistent with ASTM D1566 definition The compositions (blend of such as polymer) of thing or polymer.Elastomer includes the mixing blend of polymer, such as, be polymerized The melt blending of thing and/or reactor blend.This term can exchange with term used herein " rubber " and use.
As described herein, " phr " is the number of rubber parts per hundred parts, or " number ", and it is tolerance common in this area, Wherein measure the component in compositions relative to main elastomer component, based on elastomer or 100 parts of weight of rubber.
As described herein, compositions " does not contains " a kind of component and refers to that compositions substantially lacks this component, or with based on group The amount of the gross weight of compound below about 0.01wt% comprises this component.
The present invention relates to comprise ethylene-propylene-diene terpolymer (EPDM) and the compositions of polyolefin elastomer.Should Polyolefin elastomer, when with relative to EPDM for example, less than about 150phr, below about 100phr, below about 50phr, below about When certain amount of 20phr uses, the Mooney viscosity of the reduction of compositions can be realized with cost-effective method, and significantly cut Other character weak.
In one embodiment, the present invention contains a kind of compositions, and described compositions comprises: a) Mooney viscosity [ML (1+ 4) 125 DEG C] ethylene contents that is about the ethylene-propylene-diene terpolymer (EPDM) of 25-about 300 and this EPDM is at least About 60wt%；And b) polyolefin elastomer.In a preferred embodiment, described polyolefin elastomer is for comprising at least about 60wt% derives from the unit of propylene and about 5-about 25wt% derives from the elastomer based on propylene of unit of ethylene, based on described base In the gross weight meter of the elastomer of propylene, wherein said elastomer based on propylene has the heat of fusion of below about 80J/g.Preferably Ground, the Mooney viscosity [ML (1+4) 100 DEG C] of described compositions than without described polyolefin elastomer but for composition other side Mooney viscosity [ML (1+4) 100 DEG C] the low about 0-about 15 of the compositions that face is identical.
Ethylene-propylene-diene terpolymer
Embodiments of the present invention include ethylene-propylene-diene terpolymer (EPDM).In one embodiment, EPDM has the Mooney viscosity (ML [1+4] 125 DEG C) of about 25-about 300 and accounts for the ethylene contents of EPDM at least about 60wt%.Separately In one embodiment, EPDM has the Mooney viscosity (ML [1+4] 125 DEG C) of about 60-about 90, and optimal ethylene content accounts for EPDM about 60-about 75wt%.In still another embodiment, EPDM has the Mooney viscosity (ML [1+4] 125 DEG C) of about 70-about 75, and excellent Ethylene contents is selected to account for EPDM about 65-about 70wt%.In one embodiment, determining according to ASTM D1646, EPDM has (ML [1+4] 125 DEG C) about 25-about 300, preferably from about 50-about 150, more preferably 60-about 90, and most preferably from about 70-about 75 Mooney glue Degree.In some embodiments, EPDM have about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70 To about 75, about 80, about 85, about 90, about 95, about 100, about 105, about 110, about 115, about 120, about 125, about 130, about 135, about 140, about 145, about 150, about 155, about 160, about 165, about 170, about 175, about 180, about 185, about 190, about 195, about 200, About 205, about 210, about 215, about 220, about 225, about 230, about 235, about 240, about 245, about 250, about 255, about 260, about 265, about 270, about 275, about 280, about 285, about 290, about 295 or about 300, or the combination in any at the most recited numerical value In the range of Mooney viscosity (ML [1+4] 125 DEG C).In some embodiments, EPDM have account for EPDM about 60, about 61, about 62, about 63, about 64, about 65, to about 70, about 71, about 72, about 73, about 74, about 75, about 76, about 77, about 78, about 79, about 80, about 81, about 82, about 83, about 84, about 85, about 86, about 87, about 88, about 89, about 90, about 91, about 92, about 93, about 94, about 95, about 96, about 97, about 98, or about 99wt%, or the ethylene contents in the range of the combination in any of the most recited numerical value.In one In embodiment, EPDM is present in compositions of the present invention with the amount of about 10-about 45wt%.At some embodiment In, EPDM is present in described combination with the amount of about 10-about 15, about 20, about 25, about 30, about 35, about 40, about 45 or about 50wt% In thing.
In one embodiment, EPDM comprises at least 60wt% and derives from the unit of ethylene, preferably from about 60-about 75wt% and obtain From the unit of ethylene, and more preferably from about 65-about 70wt% derives from the unit of ethylene.This EPDM derives from the unit (or " two of diene Alkene ") amount in the range of about 0.3-about 15wt%, preferably from about 0.3-about 10wt%, more preferably from about 0.3-about 8wt% and optimum Select about 0.3-about 6wt%.Suitably diene comprises, such as: Isosorbide-5-Nitrae-hexadiene, 1,6-octadiene, 5-methyl isophthalic acid, 4-hexadiene, 3,7-dimethyl-1,6-octadiene, bicyclopentadiene (DCPD), ethylidene norbornene, norbornadiene (ENB), 5-vinyl- 2-norborene (VNB) and combinations thereof.Described diene most preferably ENB.Ethylene contents is determined by ASTM D3900, and does not has Revise diene content.The ENB content being incorporated to polymer is determined by FTIR, ASTM D6047.Comprise VNB terpolymer two Alkene content preferably by1H NMR measures.These methods measure available degree of unsaturation.Accordingly, because have unsaturated side base portion The diene divided has been converted, such as, by hydrogen, and be not detected in mensuration, and the amount of being incorporated to measured is likely lower than reality The amount of being incorporated on border.If ENB and VNB exists,13C NMR is preferably used for measuring diene content.
EPDM polymer as herein described preferably has the MWD of about 2-about 20.Side as described herein, common by this area Method, such as, be furnished with differential refraction rate (DRI) detector and Chromatix KMX-6 is online by GPC (gel permeation chromatography) On Waters 150 chromatograph of gel permeation of light scattering photometer, measure MWD (Mw/Mn).This system uses at 135 DEG C, adopts With 1,2,4-trichloro-benzenes, as flowing phase, use Shodex (Showa Denko America, Inc) polystyrene gel post 802,803,804 and 805.At " Liquid Chromatography of Polymers and Related Materials III " (J.Cazes edits, Marcel Dekker, 1981, p207) discusses this technology, the document is incorporated by reference into Herein.Coupled columns extension is not corrected；But, at the standard generally accepted, such as State Standard Bureau's polyethylene 1484 and the moon The data obtained on the polyisoprene (ethylene-propylene copolymer alternately) of the hydrogenation that ionic polymerization method produces show, to MWD This correction less than 0.05 unit.Mw/Mn is calculated by elution time.Use the LALLS software that commercially available Beckman/CIS customizes Combined standard gel infiltration software kit carries out numerical analysis.The citation of Mw/Mn represents, Mw is to use LALLS detector recording Value, Mn is then the value using above-mentioned DRI detector recording.
Preferably EPDM polymer triad steric regularity (its by13C NMR measures) it is 75% or bigger, 80% Or bigger, 82% or bigger, 85% or bigger, or 90% or bigger.The triad steric regularity of polymer is three phases The relative steric regularity of adjacent propylene units sequence, this sequence is the chain of key composition from the head to the tail, is expressed as m and r sequence Binary combination.For semi-amorphous copolymer, it is typically expressed as the number of unit specifying steric regularity and the institute in copolymer There is the ratio of propylene triad number.The triad steric regularity (mm mark) of this EPDM polymer can by propylene altogether Polymers13C NMR spectra and following formula measure.
Mm mark=PPP (mm)/(PPP (mm)+PPP (mr)+PPP (rr)),
Wherein PPP (mm), PPP (mr) and PPP (rr) represent in the following three propylene units chains being made up of head-to-tail bond By the peak area deriving from methyl of second unit:
PPP (mm):
PPP (mr):
PPP (rr):
As measured this EPDM polymer described in United States Patent (USP) No.5,504,17213C H NMR spectroscopy.With methyl carbon region (million/19-23 (ppm)) relevant spectrum is divided into first area (21.2-21.9ppm), second area (20.3- 21.0ppm) with the 3rd region (19.5-20.3ppm).With reference to periodical " Polymer ", volume 30 (1989), in page 1350 Article determines each peak in this spectrum.In the first region, the second unit in the three propylene units chains represented with PPP (mm) Methyl resonate.In the second area, the methyl of the second unit in the three propylene units chains represented with PPP (mr) occurs Resonance, and the methyl (PPE-methyl) of the propylene units that its adjacent cells is propylene units and ethylene unit resonate ( Near 20.7ppm).In the 3rd region, the methyl of the second unit in the three propylene units chains represented with PPP (rr) occurs altogether Shake, and the methyl (EPE-methyl) of the propylene units that its adjacent cells is ethylene unit resonates (near 19.8ppm). The computational methods of triad steric regularity are described in the technology shown in United States Patent (USP) No.5,504,172.From second area (2,1 and 1,3 two kinds) error peak area is inserted with the peak area deduction propylene of the total peak area in the 3rd region, it is possible to obtain based on The peak area of the 3 propylene units chains (PPP (mr) and PPP (rr)) of key composition from the head to the tail.Therefore, it can evaluate PPP (mm), PPP (mr) and the peak area of PPP (rr), such that it is able to the triad measuring the propylene units chain of key composition from the head to the tail stands Structure regularity.
In a preferred embodiment, EPDM polymer can have greater than or equal to about 0.5 joule every gram (J/g), and is less than Or equal to about 70J/g, preferably less than or equal to about 50J/g, preferably less than or equal to about 35J/g, preferably less than or equal to about Heat of fusion (the Δ H of 25J/gf).Preferably this EPDM polymer also has greater than or equal to about 1J/g, is preferably greater than or equal to about The heat of fusion of 2.5J/g, preferably greater than or equal to about 5J/g.Thermodynamics heat of fusion number can be determined by differential scanning calorimetry (DSC) According to, its step is as follows.Remove about 200 DEG C-230 DEG C compactings with in ambient temperature (under 25 DEG C and 50% humidity 24 with punch die Hour) under the polymer sheet of about 6-about 10mg of cooling.This sample is at room temperature annealed 80-100 hour.Annealing terminates Time, this sample is placed in differential scanning calorimeter (Perkin Elmer 7 Series Thermal Analysis System) and is cooled to-50 DEG C to-70 ℃.This sample is heated to the final temperature of 200 DEG C-220 DEG C subsequently with the speed of 20 DEG C/min.Thermal output is recorded as this sample and melts Melting the area of below peak curve, this melting peak curve typically reaches peak value at 30 DEG C-175 DEG C, and the temperature of 0 DEG C-200 DEG C Occur.The thermal output represented with joule is measuring of heat of fusion.
In a preferred embodiment, EPDM polymer has 0.5-40, preferably 1-30, and the % knot of more preferably 5-25 Crystalline substance degree, wherein % degree of crystallinity is according to DSC step measurements as herein described.Used herein, the crystallization of propylene-ethylene polymer Degree also can be expressed by percent crvstallinity.The maximum amount level of polyacrylic heat energy is estimated in 189J/g (that is, 100% degree of crystallinity etc. In 189J/g).In another embodiment, the propylene-ethylene polymer of the disclosure has preferably shorter than 40%, preferably from about 0.25%-about 25%, more preferably from about 0.5%-about 22%, and the degree of crystallinity of most preferably from about 0.5%-about 20%.
Except such crystallinity level, this EPDM polymer preferably has single, wide melting transition.Fusing point is defined as The temperature that maximum heat absorbs in sample fusion range.But, this EPDM polymer can be melted in main peak adjacent display secondary Peak, but with purpose herein, this secondary melting peaks is considered as single fusing point together, wherein summit be considered as this propylene- Polyvinyl fusing point (Tm).This EPDM polymer preferably has about 25 DEG C-105 DEG C, preferably 25 DEG C-about 85 DEG C, and preferably 25 DEG C-about 75 DEG C, preferably from about 25 DEG C-about 65 DEG C, more preferably from about 30 DEG C-about 80 DEG C, more preferably from about 30 DEG C-about 70 DEG C and more preferably from about The fusing point of 30 DEG C-about 60 DEG C.
Suitably EPDM polymer is with VISTALONTMTrade name commercially available (ExxonMobil Chemical Company, Houston, TX, USA).
Polyolefin elastomer
As described herein, term " polyolefin elastomer " refers to be derived from, by least 50wt%, the polymerization that the unit of alkene forms Thing elastomer, its example includes ethylene and C3-16Alpha-olefin, and combinations thereof.The example of this alkene includes ethylene, propylene, 1- Butylene, isobutene., 2-butylene, cyclobutane, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 3-methyl-1-butene, 4- Methyl isophthalic acid-butylene, cyclopentenes, 1-hexene, cyclohexene, 1-octene, 1-decene, 1-dodecylene etc..These can be individually or with it In two or more be applied in combination.In some preferred implementation, polyolefin elastomer comprises at least 50wt% Derive from those of unit of ethylene or propylene or butylene.
This polyolefin elastomer can be that (unit deriving from comonomer randomly divides random copolymer along main polymer chain Cloth), block copolymer (unit deriving from comonomer occurs along long sequence), or wherein any variant.Copolymer random The existence of degree or triad steric regularity can be by known in the art and as herein described13C NMR measures, such as, 18J.POLY.SCI.:POLY.LETT.ED. the 389-394 page (1980).
In some embodiments, the lower limit of the Shore A hardness of this polyolefin elastomer be about 10, about 20, about 30, about 40, about 50, or about 60 be about 70 to the upper limit, about 75, about 80, about 85, about 90, or about 95, it is measured by ASTM D2240.
In one or more preferred implementations, this polyolefin elastomer has greater than about 0.1g/10min, about 0.5g/ 10min, about 1g/10min, about 2g/10min, about 5g/10min, or about 10g/10min, and preferably up to about 20g/10min, about 40g/10min, about 80g/10min, about 100g/10min, or the melt flow rate (MFR) (MFR) of about 200g/10min, its by ASTMD1238 measures, at 230 DEG C, and 2.16kg.
In some embodiments, the polyolefin elastomer of the present invention have at least about 100%, at least about 200%, at least About 300%, and at most about 800%, about 1000% or about 2000%, and the elongation at break of preferably from about 100%-about 2000%, It is measured by ASTM D412.
In some embodiments, the polyolefin elastomer of the present invention has about 0.83g/cm3-about 0.9g/cm3, preferably from about 0.85g/cm3-about 0.89g/cm3, about 0.86g/cm3-about 0.88g/cm3, or about 0.86g/cm3-about 0.87g/cm3Density, its Measured by ASTM D1505.
In some embodiments, the polyolefin elastomer of the present invention has about 8MPa-about 100Mpa 1% secant (73 ° F) (23 DEG C) bending modulus, it is measured by ASTM D790.
In some embodiments, the polyolefin elastomer used by the present invention, with below about 150phr, is preferably lower than about 100phr, more preferably below about 50phr, the most preferably less than amount of about 20phr exist.In embodiments of the present invention, This polyolefin elastomer is with relative to the EPDM amount existence more than 0phr and below about 20phr, such as, about 1phr, about 2phr, about 3phr, about 4phr, about 5phr, about 6phr, about 7phr, about 8phr, about 9phr, about 10phr, about 11phr, about 12phr, about 13phr, about 14phr, about 15phr, about 16phr, about 17phr, about 18phr, about 19phr.
In a preferred embodiment, the polyolefin elastomer of the present invention is to comprise at least about 60wt% to derive from the unit of propylene About 5-about 25wt% derives from the elastomer based on propylene of the unit of ethylene, gross weight based on described elastomer based on propylene Amount, wherein said elastomer based on propylene has the heat of fusion of below about 80J/g.It is somebody's turn to do elastomer based on propylene for deriving from third The unit of alkene and derive from ethylene or C4-10The copolymer of the unit of at least one alpha-olefin.Due to adjacent isotactic propylene list Fusing point first and as herein described, should have limited degree of crystallinity by elastomer based on propylene.With height isotactic polypropylene phase Ratio, the degree of crystallinity and the fusing point that are somebody's turn to do elastomer based on propylene are inserted the introducing of error by propylene and reduce.Should bullet based on propylene Gonosome is typically free of the intermolecular inhomogeneities of any essence in steric regularity and comonomer composite, and does not generally also have Any essence inhomogeneities of intramolecular compositions distribution.
Derive from ethylene or C4-10The unit of at least one alpha-olefin or comonomer can about 1-about 35wt%, or about 5-is about 35wt%, preferably from about 7-about 32wt%, more preferably from about 8-about 25wt%, even more preferably about 8-about 20wt%, and most preferably from about The amount of 8-about 18wt% is present in this elastomer based on propylene.Co-monomer content can be adjusted and make bullet based on propylene Gonosome has the heat of fusion of below about 80J/g, the fusing point of about 105 DEG C or less, and the isotactic poly third of about 2%-about 65% The degree of crystallinity of alkene, and the MFR of about 2-about 20g/10min.
Elastomer based on propylene can comprise more than one comonomer.Have more than one comonomer based on propylene The preferred implementation of elastomer include propylene-ethylene-octene, propylene-ethylene-hexene, and propylene-ethylene-butene polymerization Thing.Ethylene or C is derived from some more than one4-10In the embodiment that the comonomer of at least one alpha-olefin exists, a kind of The amount of comonomer can less than the about 5wt% of elastomer based on propylene, but the total amount of the comonomer of the elastomer of propylene It is about 5wt% or more.
In a preferred embodiment, comonomer is ethylene, 1-hexene, or 1-octene.In one embodiment, this base Elastomer in propylene comprises the unit deriving from ethylene.5-about 25wt% should be can include about, preferably from about by elastomer based on propylene 8-about 20wt%, or the unit deriving from ethylene being somebody's turn to do elastomer based on propylene of about 9-about 16wt%.At some embodiments In, should elastomer based on propylene substantially by deriving from propylene and ethylene unit forms, i.e. elastomer based on propylene is not with allusion quotation The amount that Impure forms in the ethylene used in the course of the polymerization process and/or propene feed streams exists type, or to incite somebody to action this The amount of the heat of fusion, fusing point, degree of crystallinity or the melt flow rate (MFR) that affect copolymer based on propylene in matter contains any other and is total to Poly-monomer, or do not contain any other comonomer being intentionally added in polymerization technique.
Elastomer based on propylene can have (its by13C NMR measures) at least about 75%, at least about 80%, at least about The triad steric regularity of three propylene units of 82%, at least about 85%, or at least about 90%.Preferably, should be based on third The elastomer of alkene has about 50-about 99%, about 60-about 99%, more preferably from about 75-about 99%, or Unit three of about 80-about 99% Group steric regularity.In some embodiments, should elastomer based on propylene can have about 60-97% triad stand structure rule Whole degree.
Elastomer based on propylene has an about 80J/g or less, preferably from about 70J/g or less, about 50J/g or less, or The heat of fusion (" H of about 35J/g or lessf") (it is measured by DSC).Should can have lower limit about by elastomer based on propylene 0.5J/g, about 1J/g, or the H of about 5J/gf.Such as, HfValue can from 1.0,1.5,3.0,4.0,6.0 or 7.0J/g to 30,35, 40,50,60,70,75 or 80J/g.
Elastomer based on propylene can have (according to DSC step measurements as herein described) and be about 2-about 65%, preferably from about 0.5-about 40%, preferably from about 1-about 30%, and the percent crvstallinity of the isotactic polypropylene of more preferably from about 5-about 35%.Third The peak of the heat energy of alkene (i.e. 100% degree of crystallinity) is estimated as 189J/g.In some embodiments, copolymer has and is less than The degree of crystallinity of the isotactic polypropylene in the range of 40%, about 0.25-about 25%, or about 0.5-about 22%.Should be based on propylene The embodiment of elastomer can have lower limit and be about 4 or about 6 upper limits and be about 8 or the Tacticity Index m/r of about 10 or about 12. In some embodiments, should have isotacticity index more than 0% by elastomer based on propylene, or the upper limit was about 50% or about 25%, and lower limit is about in the range of 3% or about 10%.
In some embodiments, by the combined polymerization of propylene and one or more comonomers limited amount reduce based on The degree of crystallinity of the elastomer of propylene, described comonomer is selected from: ethylene, C4-20Alpha-olefin, and polyenoid.In these copolymers, The amount of the unit deriving from propylene being present in this elastomer based on propylene be elastomer based on propylene the upper limit about 95wt%, About 94wt%, about 92wt%, about 90wt%, or about 85wt%, to lower limit about 60wt%, about 65wt%, about 70wt%, about 75wt%, about 80wt%, about 84wt%, or the scope of about 85wt%.
Optional polyenoid can be any hydrocarbon structure with at least two unsaturated bond, and wherein said unsaturated bond is at least One of be easily incorporated into polymer.Such as, optional polyenoid is selected from straight chain acyclic alkene, such as Isosorbide-5-Nitrae-hexadiene and 1,6-pungent two Alkene；Branched-chain acyclic alkene, such as 5-methyl isophthalic acid, 4-hexadiene, 3,7-dimethyl-1,6-octadiene, and 3,7-dimethyl-1,7- Octadiene；Monocycle alicyclic olefin, such as 1，4-cyclohexadiene, 1,5-cyclo-octadiene, and 1,7-ring 12 carbon diene；Multi-ring Alicyclic condense and bridged rings alkene, such as tetrahydro indenes, norbornadiene, methyl-tetrahydro indenes, bicyclopentadiene, bicyclo-- (2.2.1)-hept-2,5-diene, norbornadiene, alkenyinorbornene, alkylidene radical norborene, cycloalkenyl group norborene and Cylcoalkyliene norbornenes is (such as 5-methylene-2-norbornene, 5-ethidine-2-norborene, 5-acrylic-2-norborneol Alkene, 5-isopropylidene-2-norborene, 5-(4-cyclopentenyl)-2-norborene, 5-cyclohexylidene base-2-norborene and 5- Vinyl-2-norborene)；And the substituted olefine of cycloalkenyl group, such as VCH, pi-allyl cyclohexene, vinyl Cyclo-octene, 4 vinyl cyclohexene, allyl cyclodecene, vinyl cyclododecene, divinylbenzene and Fourth Ring (A-11, 12)-5,8-dodecylene.It is present in the amount of the optional unit deriving from polyenoid of this elastomer based on propylene in the range of upper It is limited to about 15%, about 10%, about 7%, about 5%, about 4.5%, about 3%, about 2.5% or about 1.5%, be about 0% to lower limit, About 0.1%, about 0.2%, about 0.3%, about 0.5% or about 1%, gross weight based on described elastomer based on propylene.Excellent Select in embodiment, any unit (as described herein, " diene ") deriving from diene should not contained by elastomer based on propylene.
Should can have the unimodal melting transition measured by DSC by elastomer based on propylene.In one embodiment, this is total to Polymers has main peak and changes about 90 DEG C or lower, changes being about 110 DEG C or higher along with wide end of melting.Peak value is " molten Point " (" Tm") it is defined as the temperature that maximum heat absorbs in sample fusion range.But, this copolymer can show at main peak adjacent Show secondary melting peaks, and/or at end of melting transformation.For the purpose of this disclosure, this secondary melting peaks is by together Being considered as single fusing point, wherein summit is considered as the fusing point of this propylene-ethylene polymer, wherein the highest being recognized in these peaks For being the T of this elastomer based on propylenem.Should can have T by elastomer based on propylenemBe about 110 DEG C or lower, about 105 DEG C or Lower, about 100 DEG C or lower, about 90 DEG C or lower, about 80 DEG C or lower, or about 70 DEG C or lower.In one embodiment, Should have T by elastomer based on propylenemIt is about 25 DEG C-about 105 DEG C, preferably from about 60 DEG C-about 105 DEG C, about 70 DEG C-about 105 DEG C, or About 90 DEG C-about 105 DEG C.
Should can have about 0.850-about 0.900g/cm by elastomer based on propylene3, preferably from about 0.860-about 0.880g/cm3 Density, it is at room temperature measured by ASTM D1505.
Should can have (it is measured at 230 DEG C of 2.16kg) at least about 2g/ by ASTM D1238 by elastomer based on propylene The MFR of 10min.In one embodiment, should have about 2-about 20g/10min, about 2-about 10g/ by elastomer based on propylene 10min, or the MFR of about 2-about 5g/10min.
Should can have below about 2000%, below about 1000% by elastomer based on propylene, or below about 800% fracture was stretched Long rate, it is measured by ASTM D412.
Should can have about 5 by elastomer based on propylene, 000-about 5,000,000g/ rubs, preferably from about 10,000-about 1, 000,000g/ rubs, and more preferably from about 50,000-about 400, the weight average molecular weight (M that 000g/ rubsw)；It is about 2,500-about 250, 000g/ rubs, preferably from about 10,000-about 250, and 000g/ rubs, and more preferably from about 25,000-about 250, the number-average molecular weight that 000g/ rubs (Mn)；And/or about 10,000-about 7,000,000g/ rubs, preferably from about 80,000-about 700, and 000g/ rubs, and more preferably from about Z-average molecular weight (the M that 100,000-about 500,000g/ rubsz).Should can have an about 1.5-about 20 by elastomer based on propylene, or about 1.5-about 15, preferably from about 1.5-about 5, and more preferably from about 1.8-about 3, and the molecular weight distribution of most preferably from about 1.8-about 2.5 (“MWD”)。
The elastomer being preferably based on propylene can be bought with following trade name: VISTAMAXXTM(ExxonMobil Chemical Company, Houston, TX, USA), VERSIFYTM(The Dow Chemical Company, Midland, Michigan, USA), TAFMERTMXM or NOTIOTMSome trade mark of (Mitsui Company, Japan), and SOFTELTM(lotus Blue Basell Polyolefins) some trade mark.It is applicable to the commercial bullet based on propylene of the specific trade mark of the present invention Gonosome can be measured by the method that this area is common easily.
Compositions of the present invention, such as, masterbatch, it may include one or more different elastomers based on propylene, Namely be based on propylene elastomer each there is one or more different performances, the most different comonomers or comonomer Content.This combination of multiple elastomer based on propylene is within.
In some embodiments, elastomer based on propylene is the elastomer including propylene-degree of crystallinity, DSC measure Fusing point equal to or less than 105 DEG C, and heat of fusion is about 5J/g-about 30J/g.This derives from the unit of propylene with about 80-about The amount of 90wt% exists, gross weight based on described elastomer based on propylene.This derives from the unit of ethylene with about 9-about 18wt%, such as, about 9, about 9.5, about 10, about 10.5, about 11, about 11.5, about 12, about 12.5, about 13, about 13.5, about 14, about 14.5, about 15, the amount of about 15.5, about 16, about 16.5, about 17, about 17.5, about 18wt% exists, based on described based on propylene The gross weight of elastomer.
Elastomer based on propylene can comprise copolymer, described copolymer according to WO02/36651, United States Patent (USP) No.6, 992,158, and/or prepared by the step described in WO00/01745, its content is incorporated herein by.Producing should be based on propylene The preferred method of elastomer can in United States Patent (USP) No.7,232,871 and 6, find in 881,800, its content is by quoting also Enter herein.The present invention is not limited to prepare this any specific polymerization of elastomer based on propylene, and polymerization process is also It is not limited to the reaction vessel of Special Category.
The exemplary polyolefin elastomer that the present invention uses includes elastomer based on ethylene, and it has one or more Following character:
(1) ethylene contents is about 60wt%-about 90wt%, preferably from about 65wt%-about 85wt%, and preferably from about 65wt%-is about 80wt%, preferably from about 65wt%-about 75wt%；
(2) ethylene contents is about 80mol%-about 96mol%, preferably from about 82mol%-about 92mol%, preferably from about 82mol%-about 88mol%, preferably from about 84mol%-about 86mol%；
(3) propylene content is about 10wt%-about 20wt%；
(4) 1-butylene content is about 15wt% or more, preferably from about 20wt% or more, preferably from about 25wt% or more；
(5) 1-ahexene content is about 20wt% or more, preferably from about 25wt% or more, preferably from about 30wt% or more；
(6) 1-octene content is about 25wt% or more, preferably from about 30wt% or more, preferably from about 35wt% or more；
(7) density is about 0.9g/cm3Or lower, preferably 0.89g/cm3Or lower, preferably 0.88g/cm3Or it is lower, preferably 0.87g/cm3Or lower, preferably 0.86g/cm3Or lower, preferably 0.83g/cm3Or more, preferably 0.84g/cm3Or more, excellent Select 0.85g/cm3Or more, preferably 0.855g/cm3Or more, preferably from about 0.83g/cm3-about 0.9g/cm3, preferably from about 0.85g/ cm3-about 0.89g/cm3, preferably from about 0.85g/cm3-about 0.88g/cm3, or preferably from about 0.85g/cm3-about 0.87g/cm3；
(8) heat of fusion (Hf) it is about 90J/g or lower, preferably from about 70J/g or lower, preferably from about 50J/g or lower, preferably About 30J/g or lower, preferably from about 10J/g-70J/g, preferably from about 10J/g-about 50J/g, preferably from about 10J/g-about 30J/g；
(9) degree of crystallinity is about 40% or lower, preferably from about 30% or lower, preferably from about 20% or lower, and at least about 5%, preferably from about 5%-about 30%, preferably from about 5%-about 20%；
(10) fusing point (Tm, peak the first melt) be about 100 DEG C or lower, preferably from about 90 DEG C or lower, preferably from about 80 DEG C or Lower, preferably from about 70 DEG C or lower, preferably from about 60 DEG C or lower, preferably from about 50 DEG C or lower；
(11) crystallization temperature (Tc, peak) and it is about 90 DEG C or lower, preferably from about 80 DEG C or lower, preferably from about 70 DEG C or lower, Preferably from about 60 DEG C or lower, preferably from about 50 DEG C or lower, preferably from about 40 DEG C or lower；
(12) glass transition temperature (Tg) be about-20 DEG C or lower, preferably from about-30 DEG C or lower, preferably from about-40 DEG C or Lower；
(13)MwAbout 30,000g/mol-about 2,000,000g/mol, preferably from about 50,000g/mol-about 1,000, 000g/mol, preferably from about 90,000g/mol-about 500,000g/mol；
(14)Mw/MnIt is about 1-about 40, preferably from about 1.4-about 20, preferably from about 1.6-about 10, preferably from about 1.8-about 3.5, preferably About 1.8-about 2.5；
(15) branch index (g') is about 0.9 or higher, preferably from about 0.95 or higher, preferably from about 0.99 or higher；With
(16) melt index (MI) (MI) is about 0.1g/10min-about 100g/10min, preferably from about 0.3g/10min-about 60g/ 10min, preferably from about 0.5g/10min-about 40g/10min, preferably from about 0.7g/10min-about 20g/10min.
In some preferred implementation, elastomer based on ethylene comprises one or more C of at least 30wt%4-20Alkene Hydrocarbon comonomer, such as, 1-butylene, 1-hexene, and/or 1-octene.In some embodiments, elastomer based on ethylene can For random copolymer, statistical copolymer, block copolymer, or their blend.The present invention is not limited to preparation should be based on Any specific polymerization of elastomer of ethylene.In certain preferred implementation, metallocene catalyst system is used to produce Elastomer based on ethylene.
The elastomer based on ethylene that the present invention uses includes those can bought: EXACT with following trade nameTM (Exxon Mobil Chemical Company, Houston, TX, USA), ENGAGETMAnd INFUSETM(The Dow Chemical Company, Midland, Michigan, USA), and TAFMERTMSome board of (Mitsui Company, Japan) Number.
Filler
The compositions of the present invention optionally includes one or more fillers, such as calcium carbonate, clay, Muscovitum, titanium dioxide Silicon and silicate, Talcum, titanium dioxide, starch, and other filler such as wood powder, and white carbon black.This filler component can be with 150- The level of 350phr is present in this EPDM, such as 180-320phr.In some embodiments, two or more white carbon blacks combination Using, such as, Regal 85 is the white carbon black with multiple granularity.That of the white carbon black that combination also includes changing based on surface area A bit.Similarly, also using the different types of white carbon black through different disposal.Such as, chemically treated white carbon black can with without chemistry The white carbon black processed combines.This white carbon black can typically be present in this EPDM with the level of 120-280phr, preferably 150-250phr.
In one or more embodiments, the compositions of the present invention can include one or more clays scaled off. The clay (also referred to as " nanoclay ") scaled off is common, and their characteristic, preparation and with polymer be blended Method be disclosed in following patent, such as, JP2000-109635,2000-109605,11310643；DE 19726278；WO 98/53000；United States Patent (USP) No.5,091,462,4,431,755,4,472,538, and 5,910,523.Expandable stratiform is glued Soil material can include naturally occurring or synthetic phyllosilicate, especially smectic clays, such as montmorillonite, nontronite, beidellite, conjunction One-tenth clay, saponite, hectorite, saponite, sauconite, wheat hydrocarbon silicon sodium stone, kenyaite, magnesium-rich smectite etc., and Vermiculitum, Halloysite, aluminate oxide, brucite etc..These lamellar claies generally comprise granule, and it contains and hasOrMultiple silicate platelets of thickness, be bonded together and containing the tradable cation existed at interlayer surface Such as Na+, Ca+2, K+, or Mg+2。
This lamellar clay can pass through organic molecule (sweller) and process and carry out intercalation and peeling, and described organic molecule can be Cation carries out ion-exchange reactions in the presence of laminated silicate interlayer surface.Suitably sweller includes that cationic surface is lived Property agent, such as ammonium, alkylamine or alkylammonium (primary, secondary, tertiary and quaternary), aliphatic or sulfonium derivant, aromatic series or aryl fat Fat race amine, phosphine and sulfide.Desired amines (or corresponding ammonium ion) is to have structure R1R2R3Those of N, wherein R1, R2, and R3It is C1-C20Alkyl or olefine, they can be identical or different.In one or more embodiments, Exfoliant is so-called long chain tertiary amine, at least a part of which R1It is C14-C20Alkyl or olefine.
Another kind of sweller includes being covalently bound to those of interlayer surface.These include that the structure of polysilane is for-Si (R’)2R2, wherein R ' occurs it being identical or different every time, and selected from alkyl, alkoxyl or TMOS, and R2For with compound The organic free radical of the matrix polymer compatible of material.
Other suitable sweller includes the protonated amino acid containing 2-30 carbon atom and salt thereof, such as 12-amino Dodecylic acid, epsilon-caprolactams and similar material.Suitably the technique of sweller and intercalation phyllosilicate is in United States Patent (USP) No.4,472,538,4,810,734,4,889, disclosed in 885, and WO92/02582.
The clay of clay or peeling can be incorporated to compositions enough to improve the amount of compositions mechanical performance or barrier property In, such as, hot strength or air/oxygen permeability to gas.Amount is generally in the scope of 0.5-15wt%；Or the scope of 1-10wt%； Or the scope of 1-5wt%, polymer content based on described compositions.Express with the number of every cental rubber, this clay or stripping The clay fallen can exist with 1-30phr；Or exist with 3-20phr.In one or more embodiments, the clay of this peeling is The clay of alkylamine-peeling.
White carbon black can be produced by Organic substance imperfect combustion.The manufacture of white carbon black has two kinds of main production technologies: oil oven work Skill and thermal process.In oil oven technique, fuel burns to produce fine carbon powder in the case of air excess.There is several different life Produce part: reaction；Filter and separate；Pelletize；With dry.Thermal process is similar, but it is continuous print stove technique.U.S.'s material Material test association (ASTM) establishes white carbon black taxonomic hierarchies, ASTM D1765 based on granularity and surface oxidation.Surface oxidation degree Affect the hardening time of black filled rubber compound." N " represents conventional solidified white carbon black and " S " refers to low solidification white carbon black.At N or After S, the first number of three figure place suffix determines that granularity and remaining two numbers are assigned arbitrarily.
White carbon black enhancing characteristic in rubber is attributable to the surface chemistry of size, shape and aggregated structure, shape and group Poly structure surface chemistry, described aggregate structure is formed by being substantially in the form of spherical and chemical bonding each other primary particles.Charcoal Two black key properties are surface area and structure.Surface area reversely depends on the size of primary particles, and is polymer physics The tolerance of the usable area of effect.Surface area is 10-140m2The scope of/g, has by ASTM D4820 along with thermal black Measure based on N2 adsorption (N2SA) minimum.Surface area is also by cetab (CTAB) absorptiometry 's.The structure of white carbon black depends on the size of the primary granule in these aggregations and agglomerating (grouping).At the beginning of in aggregation Grade particles is the most, and the structure of white carbon black is the highest, and this is owing to the more complicated shape of white carbon black and voidage (porous).Structure exists 35-130cm3The scope of/100gm, it is by dibutyl phthalate (DBP) the oil absorptiometry of ASTM D2414.Use The trade mark of white carbon black is at Rubber Technology, described in the scope of 59-85 page of (1995) N110-N990.More desirably, may be used The embodiment of the white carbon black being applied to such as tire tread is the N229 provided in ASTM (D3037, D1510, and D3765), N351, N339, N220, N234 and N110.The embodiment of the white carbon black being applied to such as tyre wall be N330, N351, N550, N650, N660, and N762.The embodiment of the white carbon black being applied to such as liner or the inner tube of a tyre be N550, N650, N660, N762, N990 etc..
Compositions can include white carbon black, and it has less than 35m2The surface area of/g and less than 90cm3The phthalic acid of/100gm Dibutyl ester.Suitably white carbon black also can have lower limit about 7m2/g、10m2/ g, or 15m2/ g to the upper limit about 25m2/g、30m2/ g or 35m2The scope of the surface area of/g.Suitably white carbon black also can have lower limit about 7m2/g、10m2/ g, or 23m2/ g to the upper limit about 25m2/ g、26m2/ g, or 28m2The scope of the surface area of/g.Suitably white carbon black also can have at least 25cm3/ 100gm and less than 90cm3/ 100gm, less than 80cm3/ 100gm, less than 70cm3/ 100gm, less than 65cm3/ 100gm, or less than 60cm3The adjacent benzene of/100gm Dibutyl carboxylic acid oil absorbs.The dibutyl phthalate oil of white carbon black absorbs and is alternatively lower limit about 30cm3/ 100gm, 35cm3/ 100gm, or 40cm3/ 100gm to the upper limit about 60cm3/ 100gm, 70cm3/ 100gm, or 80cm3The scope of/100gm.Suitably White carbon black may include but be not limited to N550, N762, N774, N907, N990, Regal 85, and Regal 90.
Processing aid
The compositions of the present invention optionally includes one or more processing aids.Suitably processing aid can include but not It is limited to, plasticizer, viscosifier, extender, chemical amendment, levelling agent and peptizer (such as mercaptan), oil and sulfuration plant Oil, mineral oil, paraffin oil, Polybutene oil, naphthenic oil, aromatic oil, wax, resin, Colophonium, or other has and paraffin or mineral oil Synthetic fluid etc. etc. the low pour point that compares, relatively low emission.The example of some business processing aids is SUNDEXTM(Sun And FLEXON Chemicals)TM(ExxonMobil Chemical Company)。
Preferably plasticizer includes polyalphaolefin (PAO), high-purity hydrocarbon fluid compositions (HPFC) and the base of Group III Material, such as described in the WO2004/014998 those.Preferably PAO includes the oligomer of decene and decene and dodecylene Co-oligomer.Preferably PAO can buy with following trade name: SuperSynTM, SpectraSynTMPAO, and ELEVASTTMExxonMobil Chemical Company。
Suitably Polybutene oil has the M less than 15,000g/moln.Preferably polybutene oil plant also includes deriving from have 3-8 carbon atom, the homopolymer of unit of alkene of preferred 4-6 carbon atom or copolymer.In still another embodiment, poly-fourth Alkene is C4The homopolymer of residual liquid or copolymer.The preferably embodiment of low-molecular weight polymer referred to as " polybutene " polymer exists Described in documents below, such as, Synthetic Lubricants and High-Performance Functional Fluids, 357-392 page (Leslie R.Rudnick&Ronald L.Shubkin, ed., Marcel Dekker1999) (under Wen Zhongwei " polybutene processing oil " or " polybutene ").
In one or more embodiments, Polybutene oil can be copolymer, and it is including at least the list of derived from isobutylene Unit, and optionally derive from the unit of 1-butylene, and/or derive from the unit of 2-butylene.In one or more embodiments, poly-fourth Alkene is the homopolymer of isobutene., or isobutene. and 1-butylene or the copolymer of 2-butylene, or isobutene. and 1-butylene and 2-butylene Terpolymer, wherein the unit of derived from isobutylene accounts for the 40-100wt% of copolymer, and the unit deriving from 1-butylene accounts for copolymerization The 0-40wt% of thing, and the unit deriving from 2-butylene accounts for the 0-40wt% of copolymer.In one or more embodiments, poly-fourth Alkene is copolymer or terpolymer, and wherein the unit of derived from isobutylene accounts for the 40-99wt% of copolymer, derives from the list of 1-butylene Unit accounts for the 2-40wt% of copolymer, and the unit deriving from 2-butylene accounts for the 0-30wt% of copolymer.In still another embodiment, Polybutene is the terpolymer of Unit three, and wherein the unit of derived from isobutylene accounts for the 40-96wt% of copolymer, derives from 1-butylene Unit account for the 2-40wt% of copolymer, and the unit deriving from 2-butylene accounts for the 2-20wt% of copolymer.Still another embodiment party In formula, polybutene is isobutene. and the homopolymer of 1-butylene or copolymer, and wherein the unit of derived from isobutylene accounts for homopolymer or altogether The 65-100wt% of polymers, and the unit deriving from 1-butylene accounts for the 0-35wt% of copolymer.
Polybutene processing oil typically has less than 10,000g/mol, less than 8,000g/mol, or less than 6,000g/mol Number-average molecular weight (Mn).In one or more embodiments, Polybutene oil has more than 400g/mol, and more than 700g/ Mol, or the number-average molecular weight more than 900g/mol.Can be preferred embodiment any lower limit of this paper and the group of any upper limit Close.Such as, in one or more describe the embodiment of polybutene, described polybutene has 400g/mol-10,000g/ Mol, and 700g/mol-8, the number-average molecular weight of 000g/mol.The useful range of viscosities of polybutene processing oil is at 100 DEG C 10-6,000cSt (centistoke), or 35-5,000cSt at 100 DEG C, or more than 35cSt at 100 DEG C, or be more than at 100 DEG C 100cSt。
The compositions of the present invention can include the polybutene as mixture of one or more kinds, itself or adding bullet to It is blended before gonosome, or is blended together with elastomer.The amount of polybutene processing oil mixture and characteristic (such as viscosity, MnDeng) also Alterable is to realize some other viscosity or molecular weight.By this way, the physical property of compositions can be controlled.More specifically Ground, phrase " polybutene processing oil ", or " polybutene processing oil (plural) " include advising for obtaining scope as herein disclosed Fixed any desired viscosity or the single oil plant of molecular weight (or other character) or the compositions of two or more oil plants.
In one embodiment, processing oil can be present in compositions with the 60-170phr of EPDM, implements at another Mode is 70-160phr, and is 85-145phr in still another embodiment.
Firming agent and accelerator
The compositions of the present invention optionally includes being generally used for one or more other components of elastomer blend and adding Add agent, such as pigment, accelerator, crosslinking and curing materials, antioxidant, antiozonant etc..
Crosslinking and firming agent include sulfur, zinc oxide and fatty acid.Generally, polymer composition can be by adding firming agent Molecule cross-links, such as sulfur, metal-oxide (i.e. zinc oxide), organo-metallic compound, and radical initiator etc. is subsequently heated. Especially, the following is conventional solidified dose will worked in the present invention: ZnO, CaO, MgO, Al2O3、CrO3、FeO、Fe2O3、 And NiO.These metal-oxides can be with respective metal stearate complex (such as Zn (stearic acid)2, Ca (stearic acid)2, Mg (stearic acid)2, and Al (stearic acid)3), or be used in combination with stearic acid and sulphur compound.This is used for natural rubber rubber blend The method of sulfuration also apply be applicable to the compositions of the present invention.
Accelerator includes amine, guanidine, Thiourea, thiazoles, thiurams, sulfenamide, sulfenamide Class, thiocarbamates, xanthic acid esters etc..By being joined by a certain amount of accelerator, compositions realizes solidification The acceleration of method.The mechanism of the accelerated cure of the compositions comprising EPDM relates at firming agent, accelerator, activator and polymer Between complicated interaction.It is desirable that all available firming agent are connecting two polymer chains and are strengthening polymer base The formation of effective cross-bond of the overall strength of matter is consumed.Many accelerators are known in the art, and include but do not limit In following compound: stearic acid, diphenylguanidine (DPG), tetramethylthiuram disulfide (TMTD), tetra-sulfurized pair pentamethylene Flos Cymbidii Ensifolii Nurse (DPTT), 4,4 '-dithio morpholine (DTDM), tetrabutylthiuram disulfide (TBTD), benzothiazole disulfide (MBTS), the double sodothiol dihydrate of hexa-methylene-1,6-, 2-(morpholinothio) benzothiazole (MBS or MOR), the blend (MOR90) of 90%MOR and 10%MBTS, N tert butyl benzothiazole 2 sulfenamide (TBBS), and N- Oxydiethylene thiocarbamoyl-N-oxydiethylene sulfenamide (OTOS), 2 ethyl hexanoic acid zinc (ZEH), N, N'-diethyl thiourea.
Curing system includes those components promoted or affect elastomer curative described above, such as metal, accelerator, Sulfur, and the reagent that other this area is common, and described above.In one or more embodiments described, sulfur curable body The compositions that system comprises sulfur and sulfur donor and the present invention is used together, and wherein relative to EPDM, sulfur, with less than 5phr, is preferably shorter than The amount of 61phr exists, and at least one sulfur donor exists with the amount less than 5phr relative to EPDM.In a preferred implementation In, sulfur donor comprises at least one of TMTD and DPTT.
Character
It is an object of the invention to improve rheological property, but simply effectively lose other character, such as, stretch Fracture strength and compressive deformation, this is favourable in the application of such as extruded product.
In one embodiment, in the compositions of the present invention, polyolefin elastomer is excellent to be below about 150 relative to EPDM Choosing below about 100phr, more preferably less than about 50phr, more preferably less than about 20phr, such as, about 19phr, about 18phr, about 17phr, about 16phr, about 15phr, about 14phr, about 13phr, about 12phr, about 11phr, about 10phr, about 9phr, about 8phr, The amount of about 7phr, about 6phr, about 5phr, about 4phr, about 3phr, about 2phr, about 1phr exists, and the compositions of the present invention has ratio Without described polyolefin elastomer, but the Mooney viscosity [ML (1+4) 100 DEG C] of the compositions that other side is identical for composition Low about 0-about 15, about 0-about 10, or the Mooney viscosity [ML (1+4) 100 DEG C] of about 0-about 5.As described herein, compositions " does not contains Described polyolefin elastomer but for composition other side identical " refer to that referred to compositions has and the present composition The identical composition of same ratio (phr), except the polyolefin elastomer in the present composition is by the compositions referred to EPDM substitute (see, e.g., comparison 1 compare embodiment 1-3 and 1a-3a).Preferably, this polyolefin elastomer be comprise to Few about 60wt% derives from the unit of propylene and about 5-about 25wt% derives from the elastomer based on propylene of unit of ethylene, based on institute Stating the gross weight of elastomer based on propylene, wherein said elastomer based on propylene has the heat of fusion of below about 80J/g.Door Buddhist nun's viscosity, as described herein, can be according to ASTM D1646, at 100 DEG C, the form of ML (1+4) is measured, except as otherwise noted.
In another embodiment, compositions described herein has than the stretching containing described Polyolefin elastomer composition Fracture strength is low by most about 15%, and preferably up to about 10%, the tensile break strength of more preferably up to about 5%, but its just composition For be identical, it is measured by ISO 37 at 23 DEG C.
In still another embodiment, compositions described herein has than the compositions without described polyolefin elastomer Compressive deformation height at most about 30% under 25% flexure, preferably up to about 20%, the compressive deformation of more preferably up to about 10%, But it is compositionally identical, it is measured by ISO 815A in different temperatures and time point.
The method of preparation compositions
Additionally provide the method preparing the present composition.In one embodiment, the present invention includes preparing compositions Method, it comprises the following steps: (a) (i) Mooney viscosity [ML (1+4) 125 DEG C] is about 25-about 300 EPDM and should The ethylene contents of EPDM is at least about 60wt% and (ii) polyolefin elastomer combines, and (b) forms described compositions.Preferably In embodiment, this polyolefin elastomer is to comprise at least about 60wt% to derive from the unit of propylene and about 5-about 25wt% derives from second The elastomer based on propylene of the unit of alkene, gross weight meter based on described elastomer based on propylene, wherein said based on third The elastomer of alkene has the heat of fusion of below about 80J/g.Preferably, said composition have than without described polyolefin elastomer but Mooney viscosity [the ML of Mooney viscosity [ML (1+4) 100 DEG C] the low about 0-about 15 of the compositions that other side is identical for composition (1+4)100℃]。
Can be by any suitable mixing arrangement (such as BanburyTMBlender, BrabenderTMBlender, or excellent Selection of land blender/extruder or mill) in combine the component of the present composition to mix the component of the present composition.Mixed Carry out at a temperature of elastomer that conjunction can use in far above compositions and/or the fusing point of rubber, allow with enough speed Graphite and/or clay exfoliation and become the most uneven dispersion to form compositions.
Suitably mixing rate may range from about 10RPM-about 100RPM.In one or more embodiments, described Mixing rate can be about 10RPM, about 15RPM, about 20RPM, about 25RPM, about 30RPM, about 35RPM, about 40RPM, about 45RPM, About 50RPM, about 55RPM, about 60RPM, about 65RPM, about 70RPM, about 75RPM, about 80RPM, about 85RPM, about 90RPM, about 95RMP and about 100RPM.
In one or more embodiments, mixing temperature may range from about 40 DEG C-about 340 DEG C.At one or more In embodiment, mixing temperature may range from about 80 DEG C-300 DEG C.In one or more embodiments, the model of mixing temperature Enclosing can be lower limit about 30 DEG C, 40 DEG C, or 50 DEG C are arrived the upper limit about 70 DEG C, 170 DEG C, or 340 DEG C.At one or more embodiments In, the scope of mixing temperature can be that lower limit about 80 DEG C, 90 DEG C or 100 DEG C arrive the upper limit about 120 DEG C, 250 DEG C, or 340 DEG C.One Kind or numerous embodiments in, the scope of mixing temperature can be lower limit about 85 DEG C, 100 DEG C, or 115 DEG C arrive the upper limit about 270 DEG C, 300 DEG C or 340 DEG C.
In at least one detailed description of the invention, can in the speed of noticeably greater than 20-90 second, or until temperature from 40 DEG C to 60 DEG C, one or more elastomers of mixing 70%-100%.Then, the white carbon black more than about 1/2 can be added, and remaining is elastic Body (if any) is in blender, and mixes sustainable, until temperature is from 90 DEG C to 150 DEG C.Then, can add remaining White carbon black and other filler, and processing oil, and mix sustainable until temperature is from 140 DEG C to 190 DEG C.Can be by a mill until Complete final product mix in flakes and allow to be cooled to 60 DEG C-100 DEG C when adding firming agent.
Application
The present invention contains the goods using the method for the present invention to produce and the goods of the compositions comprising the present invention.Goods Example includes but not limited to, extruded product, such as weather strip for automobile, non-vehicle sealing strip, architectural shape etc.；Mechanograph, example Such as strip of paper used for sealing, packing ring etc.；Flexible pipe, such as air hose, hot flexible pipe, rubber hose, industrial hose etc.；Roofing board；Film；Or outside cable Set etc..
Present invention also contemplates that the method reducing compositions Mooney viscosity, it comprises the following steps: (a) is by (i) Mooney viscosity The ethylene-propylene-diene terpolymer of [ML (1+4) 125 DEG C] about 25-about 300 and this Ethylene-Propylene-Diene ternary are altogether The ethylene contents of polymers is at least about 60wt% and is combined with (ii) polyolefin elastomer, and (b) forms described compositions, preferably institute State compositions than the Mooney viscosity [ML without described polyolefin elastomer but other side is identical for composition compositions (1+4) 100 DEG C] Mooney viscosity [ML (1+4) 100 DEG C] of low about 0-about 15.In a preferred embodiment, polyolefin elastomer is Comprise at least about 60wt% and derive from the unit of propylene and about 5-about 25wt% derives from the elastomer based on propylene of unit of ethylene, Gross weight meter based on described elastomer based on propylene, wherein said elastomer based on propylene has below about 80J/g's Heat of fusion.
Other embodiment can farther include:
1. a compositions, comprises:
A () Mooney viscosity [ML (1+4) 125 DEG C] is about the ethylene-propylene-diene terpolymer (EPDM) of 25-about 300 And the ethylene contents of this EPDM is at least about 60wt%；With
(b) polyolefin elastomer.
2. the compositions described in paragraph 1, wherein said EPDM exists with the amount of the about 10-about 50wt% of said composition.
3. the compositions described in paragraph 1 or 2, wherein said polyolefin elastomer derives from propylene for comprising at least about 60wt% Unit and about 5-about 25wt% derive from the elastomer based on propylene of unit of ethylene, based on described elastomer based on propylene Gross weight meter, wherein said elastomer based on propylene has the heat of fusion of below about 80J/g.
4. the compositions described in paragraph 3, wherein said elastomer based on propylene has about 2g/10min-about 20g/ The MFR (ASTM D1238,2.16kg, 230 DEG C) of 10min.
5. the compositions described in paragraph 1-4 either segment, wherein said polyolefin elastomer is to be below about relative to EPDM The amount of 150phr exists.
6. the compositions described in paragraph 1-5 either segment, wherein said polyolefin elastomer is to be below about relative to EPDM The amount of 100phr exists.
7. the compositions described in paragraph 1-6 either segment, wherein said polyolefin elastomer is to be below about relative to EPDM The amount of 50phr exists.
8. the compositions described in paragraph 1-7 either segment, wherein said polyolefin elastomer is to be below about relative to EPDM The amount of 20phr exists.
9. the compositions described in paragraph 1-8 either segment, it comprises filler, processing aid, firming agent and accelerator further At least one of.
10. the compositions described in paragraph 1-9 either segment, it comprises sulfur further.
Compositions described in 11. paragraph 1-10 either segment, wherein said sulfur exists with the amount being less than 5phr relative to EPDM.
Compositions described in 12. paragraph 1-11 either segment, it comprises sulfur donor further.
Compositions described in 13. paragraphs 12, wherein said sulfur donor includes tetramethylthiuram disulfide and tetra-sulfurized pair At least one pentamethylene thiuram.
Compositions described in 14. paragraphs 12 or 13, wherein said sulfur donor exists with the amount being less than 5phr relative to EPDM.
Compositions described in 15. paragraph 1-14 either segment, the Mooney viscosity [ML (1+4) 100 DEG C] of wherein said compositions Than the Mooney viscosity [ML (1+4) 100 without described polyolefin elastomer but the compositionally compositions that other side is identical DEG C] low about 0-about 15.
At least one compositions described in 16. paragraph 1-15 either segment, what wherein said compositions had the following properties that: I () tensile break strength is than the stretching without described polyolefin elastomer but the compositionally compositions that other side is identical Fracture strength is low by most about 15%；(ii) compressive deformation is than without described polyolefin elastomer but compositionally other side The compressive deformation height at most about 30% of the compositions that face is identical.
17. 1 kinds of methods preparing compositions, it comprises the following steps:
The ethylene contents that (i) has EPDM and this EPDM that Mooney viscosity [ML (1+4) 125 DEG C] is about 25-about 300 is At least about 60wt% and (ii) polyolefin elastomer combine, and
Form described compositions.
Method described in 18. paragraphs 17, wherein said polyolefin elastomer is to comprise at least about 60wt% to derive from propylene Unit and about 5-about 25wt% derives from the elastomer based on propylene of the unit of ethylene, based on described elastomer based on propylene Gross weight meter, wherein said elastomer based on propylene has the heat of fusion of below about 80J/g.
Method described in 19. paragraphs 17 or 18, farther includes the step making described compositions form goods.
Method described in 20. paragraph 17-19 either segment, Mooney viscosity [ML (1+4) 100 DEG C] ratio of wherein said compositions Without described polyolefin elastomer but the Mooney viscosity [ML (1+4) 100 DEG C] of the compositionally compositions that other side is identical Low about 0-about 15.
At least one method described in 21. paragraph 17-20 either segment, what wherein said compositions had the following properties that: (i) Tensile break strength is than the tension failure without described polyolefin elastomer but the compositionally compositions that other side is identical Intensity the most at most about 15%；(ii) compressive deformation is than without described polyolefin elastomer but compositionally other side phase The compressive deformation height at most about 30% of same compositions.
22. 1 kinds of goods, it comprises the compositions described in paragraph 1-16 either segment.
Goods described in 23. paragraphs 19, wherein said goods are extruded product, mechanograph, flexible pipe, sheet material, film or overcoat.
24. 1 kinds of compositionss, it comprises:
A () amount is that the Mooney viscosity [ML (1+4) 125 DEG C] of the about 20-about 25wt% of described compositions is about 60-about The ethylene-propylene-diene terpolymer of 90wt%, and the ethylene contents of this ethylene-propylene-diene terpolymer is about 60-about 75wt%；
B () is about the elasticity based on propylene of 5-about 15phr relative to described ethylene-propylene-diene terpolymer, amount Body, described elastomer comprises at least 60wt% propylene and about 5-about 25wt% ethylene, based on described elastomer based on propylene Gross weight meter, wherein said elastomer based on propylene has the heat of fusion of below about 80J/g；
C () is about the sulfur of 0.5phr relative to described ethylene-propylene-diene terpolymer, amount；
D () is about the tetramethylthiuram disulfide of 1phr relative to described ethylene-propylene-diene terpolymer, amount 's；With
E () is about the tetra-sulfurized pair pentamethylene of 1.5phr relative to described ethylene-propylene-diene terpolymer, amount Thiuram.
The method of 25. 1 kinds of Mooney viscosities reducing compositions, comprises the following steps:
(i) Mooney viscosity [ML (1+4) 125 DEG C] is about the ethylene-propylene-diene terpolymer of 25-about 300 and is somebody's turn to do The ethylene contents of ethylene-propylene-diene terpolymer is at least about 60wt% and is combined with (ii) polyolefin elastomer, and
Form described compositions.
Method described in 26. paragraphs 25, the described compositions wherein formed have than without described polyolefin elastomer but Compositionally Mooney viscosity [the ML of Mooney viscosity [ML (1+4) 100 DEG C] the low about 0-about 15 of the compositions that other side is identical (1+4)100℃]。
Method described in 27. paragraphs 25 or 26, wherein said polyolefin elastic derives from propylene for comprising at least about 60wt% Unit and about 5-about 25wt% derive from the elastomer based on propylene of unit of ethylene, based on described elastomer based on propylene Gross weight meter, wherein said elastomer based on propylene has the heat of fusion of below about 80J/g.
At least one method described in 28. paragraph 25-27 either segment, what wherein said compositions had the following properties that: (i) Tensile break strength than without described polyolefin elastomer but compositions tension failure that compositionally other side is identical is strong Spend low by most about 15%；(ii) compressive deformation than without described polyolefin elastomer but compositionally other side identical The compressive deformation height at most about 30% of compositions.
Embodiment
Discussion before can further describing according to following non-limiting examples 1 and 2.Embodiment 1 is by sample 1-3 The effect of the polyolefin elastomer (such as based on propylene elastomer) comprising the unit deriving from ethylene, institute is shown with 1a-3a State the polyolefin elastomer component as the compositions of the present invention comprising 25wt%EPDM.EPDM by sample 1-3 based on third The elastomer portion of alkene is replaced, but the amount of EPDM 1a-3a in the sample keeps identical.For sake of comparison, it is provided that first Comparative example (" comparison 1 ") comprises 25wt%EPDM with explanation but does not contains the effect of the compositions of polyolefin elastomer.Embodiment 2 is led to Cross sample 4-6 and 4a-6a and show the polyolefin elastomer (such as, elastomer based on propylene) comprising the unit deriving from ethylene Effect, described polyolefin elastomer is as the component of the present composition of the EPDM comprising 20wt%.EPDM is by sample 4-6 In elastomer portion based on propylene replace, but the amount of EPDM keeps identical in sample 4a-6a.For the mesh contrasted , also provide for the second comparative example (" comparison 2 ") and comprise 20wt%EPDM with explanation but compositions without polyolefin elastomer Effect.
By in the 3.2L banbury with tangential rotors, operating under 50rpm, batch mixed prepares each sample, Except compositions firming agent is to be blended in roller mill.Start-up temperature is 50 DEG C to 70 DEG C.The mixing circulation of masterbatch is entered by table 1 below OK.As described herein, " toppling over " is that feeling the pulse with the finger-tip material is discharged from blender, and " wrench " be lift plunger while carry out mixing with Masterbatch is made to invert completely.Wrench and contribute to being incorporated in the clay hanging on plunger during adding blender to.
Table 1: masterbatch mixing cycle
Time (min) Order of addition
0 EPDM+VistamaxxTM 6102
1' 2/3 white carbon black+ZnO
2' 1/3 carbon+oil plant+CaCO3+ other
3' Wrench-1
5' Wrench-2 (the need to)
Topple at 140 DEG C
Table 2 provides VistalonTM5601 and VistamaxxTMThe typical performance of 6102.
Table 2:VistalonTM5601 and VistamaxxTMThe typical performance of 6102
Embodiment 1
Table 3 below is listed for preparing the first comparative example (without elastomer based on propylene), sample 1-3 and sample 1a- The component of 3a and the formula of respective amount.Test sample is by pressing mold and uses standard test protocols to assess.Test sample is solid at 180 DEG C Change 8min.Measuring physical property, such as Mooney viscosity [ML (1+4) 100 DEG C], mooney scorch, hardening time, tension failure are strong Degree, hot strength are remaining and compressive deformation and is shown under 25% flexure in fig. 1-3.
Table 3: the formula (phr) of comparison 1 and sample 1-3 and 1a-3a
Fig. 1 depicts compared with the first comparative example, sample 1-3 and the respective Mooney viscosity of sample 1a-3a [ML (1+4) 100 DEG C] (Fig. 1 a), mooney scorch, it is expressed as Mooney viscosity and improves the time (Fig. 1 b) of 5 units (T5) at 125 DEG C, with 180 DEG C reach the hardening time (Fig. 1 c) of 90% curing curve (T90).Fig. 2 depicts compared with the first comparative example, sample 1-3 and sample Tensile break strength and hot strength after product 1a-3a is the most aging are remaining.Fig. 3 depicts compared with the first comparative example, sample Under each comfortable 25% flexure of 1-3 and sample 1a-3a, (%) is at (70 DEG C, 22h), (70 DEG C, 168h), (100 DEG C, 72h) and (125 DEG C, 72h) compressive deformation.
Embodiment 2
Table 4 below is listed for preparing the second comparative example (" comparison 2 ", without polyolefin elastomer), sample 4-6 and sample The component of 4a-6a and the formula of respective amount.Test sample uses standard test protocols assessment.Measure physical property such as Mooney to glue Degree [ML (1+4) 100 DEG C], mooney scorch, hardening time, tensile break strength, hot strength remnants and compressive deformation are 25% Under flexure, and show in figs. 4-6.
Table 4: the formula (phr) of comparison 2 and sample 4-6 and 4a-6a
Fig. 4 depicts compared with the second comparative example, sample 1-3 and the respective Mooney viscosity of sample 1a-3a [ML (1+4) 100 DEG C] (Fig. 4 a), mooney scorch, it is expressed as Mooney viscosity and improves the time (Fig. 4 b) of 5 units (T5) at 125 DEG C, with 180 DEG C reach the hardening time (Fig. 4 c) of 90% curing curve (T90).Fig. 2 describes compared with the second comparative example, embodiment 1-3 and Tensile break strength and hot strength after embodiment 1a-3a is the most aging are remaining.Fig. 3 describes compared with the second comparative example, Embodiment 1-3 and embodiment 1a-3a each comfortable 25% flexure under (%) (70 DEG C, 22h), (70 DEG C, 168h), (100 DEG C, 72h) and the compressive deformation of (125 DEG C, 72h).
As shown in figures 1 to 6, polyolefin elastomer joins in the compositions comprising EPDM, and without polyolefin elastomer Compositions is compared, and Mooney viscosity [ML (1+4) 100 DEG C] is reduced about 0-about 15.This allows the mobility of material to increase, therefore Make extrusion subsequently be easier to and more efficiently.Mooney scorch and hardening time are also increased slightly.Although additionally, observing The lower tensile break strength reduced of 25% flexure and the compressive deformation of increase, but both changes are all in very limited amount of scope In, hint does not has significant difference for performance loss.
Multiple terms defined above.For the term used in the most undefined claim, association area people Member should give the broadest definition of this term, as described term reflects at least one printed publication or granted patent. Additionally, all patents and patent applications cited herein, test procedure (such as ASTM method), and other file is fully incorporated Consistent with the present invention to these disclosure contents and for wherein allowing the degree of all permissions of this introducing as reference.
When numerical lower limits listed herein and numerical upper limits, cover from any lower limit to the scope of any upper limit.To the greatest extent Pipe specifically describes the illustrated embodiment of the present invention, it is to be understood that various other improves for people in the art Member will be apparent from and easily can be made by those skilled in the art, without departing from enlightenment and the scope of the present invention. Therefore, it is not intended that scope of the following claims to be limited to embodiment as herein described and explanation, and this claim quilt It is interpreted as comprising the feature of all patent novelties being present in the present invention, including all features, its neck that be the invention belongs to The technical staff in territory is considered as equivalent.
The most describe the present invention with reference to numerous embodiments and specific embodiment.According to detailed description above, It may occur to persons skilled in the art that many variants.All this obvious variants at the complete of claims it is contemplated that In the range of.

Claims (23)

1. a compositions, it comprises:
(a) Mooney viscosity [ML (1+4) 125 DEG C] be the ethylene-propylene-diene terpolymer of 25-300 and this ethylene-propylene- The ethylene contents of diene terpolymer is at least 60wt%；With
B () elastomer based on propylene, comprises gross weight meter at least 60wt% based on described elastomer based on propylene and derives from The unit of propylene and 5-25wt% derive from the unit of ethylene, and wherein said elastomer based on propylene has melting less than 80J/g Heat-transformation.
2. the compositions described in claim 1, wherein said ethylene-propylene-diene terpolymer is with the 10-of described compositions The amount of 50wt% exists.
3. the compositions described in claim 1, wherein said elastomer based on propylene is had and is existed by ASTM D1238 2.16kg, the melt flow rate (MFR) of 230 DEG C of 2g/10min-20g/10min recorded.
4. the compositions described in claim 1, wherein said polyolefin elastomer is with relative to described Ethylene-Propylene-Diene three The membered copolymer amount less than 150phr exists.
5. the compositions described in claim 1, wherein said elastomer based on propylene is with relative to described ethylene-propylene-two The alkene terpolymer amount less than 100phr exists.
6. the compositions that claim 1 is described, wherein said elastomer based on propylene with relative to described ethylene-propylene- The diene terpolymer amount less than 50phr exists.
7. the compositions described in claim 1, wherein said elastomer based on propylene is with relative to described ethylene-propylene-two The alkene terpolymer amount less than 20phr exists.
8. the compositions described in any one of claim 1-7, comprises in filler, processing aid, firming agent and accelerator further At least one.
9. the compositions described in any one of claim 1-7, comprises sulfur further.
10. the compositions described in claim 9, wherein said sulfur is with low relative to described ethylene-propylene-diene terpolymer Amount in 5phr exists.
Compositions described in 11. any one of claim 1-7, comprises sulfur donor further.
Compositions described in 12. claim 11, wherein said sulfur donor comprises tetramethylthiuram disulfide and tetra-sulfurized pair At least one in pentamethylene thiuram.
Compositions described in 13. claim 11, wherein said sulfur donor is with relative to described Ethylene-Propylene-Diene ternary altogether The polymers amount less than 5phr exists.
Compositions described in 14. any one of claim 1-7, Mooney viscosity [ML (1+4) 100 DEG C] ratio of wherein said compositions Without described polyolefin elastomer but the Mooney viscosity [ML (1+4) 100 DEG C] of the compositionally compositions that other side is identical Low 0-15.
At least one compositions described in 15. any one of claim 1-7, what wherein said compositions had the following properties that: (i) Tensile break strength is than the tension failure without described polyolefin elastomer but the compositionally compositions that other side is identical Intensity as little as many 15%；(ii) compressive deformation than without described polyolefin elastomer but compositionally other side identical The compressive deformation up to many 30% of compositions.
16. 1 kinds of methods preparing compositions, it comprises the following steps:
(a) by (i) ethylene-propylene-diene terpolymer and (ii) elastomer-bonded based on propylene,
The Mooney viscosity [ML (1+4) 125 DEG C] of this ethylene-propylene-diene terpolymer is 25-300, and this ethylene-propylene- The ethylene contents of diene terpolymer is at least 60wt%,
This elastomer based on propylene comprises gross weight meter at least 60wt% based on described elastomer based on propylene and derives from third The unit of alkene and 5-25wt% derive from the unit of ethylene, and wherein said elastomer based on propylene has the fusing less than 80J/g Heat, and
B () forms described compositions.
Method described in 17. claim 16, comprises the step making described compositions form goods further.
Method described in 18. claim 16 or 17, Mooney viscosity [ML (1+4) 100 DEG C] ratio of wherein said compositions does not contains Described polyolefin elastomer but Mooney viscosity [ML (1+4) 100 DEG C] the low 0-of the compositionally compositions that other side is identical 15。
At least one method described in 19. claim 16 or 17, what wherein said compositions had the following properties that: (i) stretches Fracture strength is than the tensile break strength without described polyolefin elastomer but the compositionally compositions that other side is identical As little as many 15%；(ii) compressive deformation is than without described polyolefin elastomer but group that compositionally other side is identical The compressive deformation of compound up to many 30%.
20. 1 kinds of goods, it comprises the compositions described in any one of claim 1-15.
Goods described in 21. claim 20, wherein said goods are extruded product, mechanograph, flexible pipe, sheet material, film or overcoat.
22. 1 kinds of compositionss, it comprises:
A () amount is the ethylene-the third that Mooney viscosity [ML (1+4) 125 DEG C] is 60-90wt% of the 20-25wt% of described compositions Alkene-diene terpolymer, and the ethylene contents of this ethylene-propylene-diene terpolymer is 60-75wt%；
B () is relative to the elastomer based on propylene that described ethylene-propylene-diene terpolymer amount is 5-15phr, described base Elastomer in propylene comprises gross weight meter at least 60wt% propylene based on described elastomer based on propylene and 5-25wt% Ethylene, wherein said elastomer based on propylene has the heat of fusion less than 80J/g；
C () is the sulfur of 0.5phr relative to described ethylene-propylene-diene terpolymer amount；
D () is the tetramethylthiuram disulfide of 1phr relative to described ethylene-propylene-diene terpolymer amount；With
E () is the Bis(pentamethylene)thiuram tetrasulfide of 1.5phr relative to described ethylene-propylene-diene terpolymer amount.
The method of 23. 1 kinds of Mooney viscosities reducing compositions, comprises the following steps:
(a) by (i) ethylene-propylene-diene terpolymer and (ii) elastomer-bonded based on propylene,
The Mooney viscosity [ML (1+4) 125 DEG C] of this ethylene-propylene-diene terpolymer is 25-300, and this ethylene-propylene- The ethylene contents of diene terpolymer is at least 60wt%,
This elastomer based on propylene comprises gross weight meter at least 60wt% based on described elastomer based on propylene and derives from third The unit of alkene and 5-25wt% derive from the unit of ethylene, and wherein said elastomer based on propylene has the fusing less than 80J/g Heat, and
B () forms described compositions, Mooney viscosity [ML (1+4) 100 DEG C] ratio of the described compositions wherein formed is without described Polyolefin elastomer but Mooney viscosity [ML (1+4) 100 DEG C] the low 0-15 of the compositionally compositions that other side is identical.
CN201280071176.5A 2012-03-09 2012-03-09 Comprise the compositions of EPDM and polyolefin elastomer, its preparation and purposes Expired - Fee Related CN104245822B (en)

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