AU622482B2 – Plastoelastomeric polyolefinic compositions and process for preparing them according to dynamic vulcanization methods
– Google Patents
AU622482B2 – Plastoelastomeric polyolefinic compositions and process for preparing them according to dynamic vulcanization methods
– Google Patents
Plastoelastomeric polyolefinic compositions and process for preparing them according to dynamic vulcanization methods
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Publication number
AU622482B2
AU622482B2
AU41323/89A
AU4132389A
AU622482B2
AU 622482 B2
AU622482 B2
AU 622482B2
AU 41323/89 A
AU41323/89 A
AU 41323/89A
AU 4132389 A
AU4132389 A
AU 4132389A
AU 622482 B2
AU622482 B2
AU 622482B2
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Australia
Prior art keywords
weight
propylene
polypropylene
ethylene
terpolymer
Prior art date
1988-09-13
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AU41323/89A
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AU4132389A
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Inventor
Vittorio Braga
Michele Manica
Emilio Martini
Federico Milani
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Solvay Specialty Polymers Italy SpA
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Ausimont SpA
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1988-09-13
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1989-09-12
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1992-04-09
1989-09-12
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1990-03-22
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1992-04-09
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1992-04-09
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patent/AU622482B2/en
2009-09-12
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Classifications
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
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
C08L2205/00—Polymer mixtures characterised by other features
C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
C08L23/10—Homopolymers or copolymers of propene
C08L23/12—Polypropene
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
C08L2312/00—Crosslinking
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
Description
COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION Form FOR OFFICE USE 622482 Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: ft’ 4 fJ 4 4 4 I 4 4 *1 9., 4* t tf 4l 9
‘I
IL
Related Art: TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: Actual Inventor: Address for Service: AUSIMONT S.r.l.
31, Foro Buonaparte, Milan, ITALY Vittorio BRAGA, Michele MANICA, Emilio MARTINI, Federico MILANI GRIFFITH HACK CO.
71 YORK STREET SYDNEY NSW 2000
AUSTRALIA
Complete Specification for the invention entitled: PLASTOELASTOMERIC POLYOLEFINIC COMPOSITIONS AND PROCESS FOR PREPARING THEM ACCORDING TO DYNAMIC VULCANIZATION METHODS The following statement is a full description of this invention, including the best method of performing it known to me/us:-
L-
-2- The present invention relates to plastoelastomeric polyolefinic compositions, consisting of mixes of at least partially vulcanized EP or EPDM rubber with at least an olefinic plastomeric thermoplastic polymer, and obtained by dynamic vulcanization of the corresponding mixes containing said rubber in the non-vulcanized state.
The. preparation of compositions based on thermoplastic polymers and vulcanized rubbers by means of the dynamic vulcanization method is known in the art and is describ- ||ed in particular in U.S. patents Nos. 3,578,643; 3,862,106; 3,037,954 and 3,806,558.
According to said method, vulcanization of the elastomeric component is made to occur during the step of mixing or mastication with a plastomeric polymer in the molten state, by means of cross-linking agents, which are usual- -3 ly of the conventional type, such as e.g. peroxides, azide compounds, mixtures of sulphur with zinc oxide, substituted ureas, thiocarbamates etc. If in the so-treated mixture there is a sufficient amount of plastomeric polymer, the composition, on conclusion of the vulcanization of the elastomeric component, retains good processability characteristics in hot conditions also if it contains high proportions of vulcanized elastomer.
According to French patent No. 2,408,632, poly- .i are obtained olefinic plastoelastomeric compositions /y means of dynamic vulcanization methods, which utilize, as a cross-linking agent, a halogenated phenolic resin, or a phenolic resins which is not halogenated but is associated with halogen donors, in combination with a metal oxide (activator).
According to said patent, the mix of EPDM rubber and olefinic polymer, wherein the phenolic resin content ranges from 5 to 20% with respect to the rubber, is subjected to mastication at a temperature sufficient to melt the olefinic polymer, then the activator is added and mastication is continued at a temperature at which the elastomeric component cross-linking occurs. The metal oxide, in particular the zinc oxide, favours in this case the complete cross- -linking of the elastomer, which is one of the objects of the process of said patent.
4 f- 1 Generally, the products obtained according to the above-cited processes exhibit good elastomeric characteristics at room temperature. However, these characteristics, in particular the compression set values, decay as the temperature rises, so as to jeopardize the practical utilization of the products above the melting point of the plastomer.
It is further known from U.S. Patent 3,957,919 to prepare thermoplastic elastomers by subjecting a blend of an EPDH interpolymer with polypropylene and substantial amounts of polyethylene to a cross-linking reaction by means of face radical generating agents, while submitted to hot working.
According to said preparation, polyethylene is preferentially cross-linked and grafted to the EPDH interpolymer, thereby protecting polypropylene from radical attack, depredation and cross-linking or grafting reactions. The products thus obtained possess improved T molding characteristics, but exceeding low elastic properties much as elongation at break, tension set and compression set, especially at high temperatures.
The Applicant has now found polyolefinic J plastoelastomeric compositions, which, besides exhibiting an excellent processability in hot conditions and having r general characteristics comparable with the ones of the best plastoelastomeric compositions of the prior art, are endowed, with respect to those compositions, with better elastic characteristics at high temperatures.
7349S:smt ,t K. i 4a Said compositions, which represent one of the objects of the present invention, comprise an intimate mixture of the following components, in the indicated percentages by weight, referred to the whole mixture: A) 10-50%, but preferably 20-30%, of not cross-linked polypropylene, B) 2-10%, but preferably 5-10%, of an ethylene/propylene elastomeric not cross-linked copolymer, or of an ethylene/propylene/diene elastomeric not cross-linked terpolymer, C) 30-45%, but preferably 35-40%, of a polymeric product which is insoluble in xylene at a temperature of 135 0
C,
comprising polypropylene and ethylene/propylene copolymer or ethylene/propylene/diene terpolymer, D) 5-58%, but preferably 10-50%, of an extender oil.
Optionally, cross-linked or not cross-linked polyethylene can be present in said composition in amounts lower than 4% by weight on the weight of the polymer composition.
i IThe above-specified compositions may optionally contain also inorganic and/or organic non polymeric products such as ZnO, Si02, TiO 2 kaolin, carbon black, stabilizers, anti-ageing agents, catalysts, accelerators, cross-linking coadjuvants or decomposition products thereof.
C
7 349S:smt 5 The polypropylene as per point may be a homopolymer, or a copolymer of propylene with up to 10% by weight of copolymerized ethylene.
The copolymers and terpolymers defined at point may contain from 25 to 60% by weight, but preferably from 30 to 45% by weight, of propylene, and from 0 to 5% by weight of units deriving from one or more conjugated or non-conjugated dienic monomers, such as for example indene, 1,3-butadiene, 1,4-hexadiene, norbornadiene, ethylidenenorbornene, cyclopentadiene.
They are preparable by copolymerization of monomers carried out in the presence of Ziegler catalysts, according of the methods of the art. Examples of Ziegler catalysts are the catalysts prepared by contacting a compound of a Ct IC i I C I
C
C it C C( jo {tf1 CC I
C
C C (c$ctL
C
i c i
B
i i’ 7349S:smt 6- S I 6metal belonging to group IVa, Va, VIa or Vila of the Mendelejeff periodic system, such as e.g. a Ti, V or Cr halide with organometallic compounds of a metal of group I, II or III of the periodic system, containing at least a metal-carbon bond, alkyls such as e.g. Al alkyls and Al alkyl halides.
If the molecular weight of the elastomeric copolymer or terpolymer exhibits a rather high value, corresponding to/l/values higher than 3.5 dl/g, of particular advantage for the compositions of the invention have proved to be those copolymers and terpolymers, the macromolecular structure of which is substantially free from head-to-head, c’ tail-to-tail inversions of the propylenic unit.
‘.It is known in this connection that propylene can enter the polymeric chain according to primary or secondary insertions, as is described for example by I. Pasquon and U.
Giannini in “Catalysis Science Technology” vol. 6, pages 65-159, J.R. Anderson N. Doudart, Springer Verlag, Berlin, 1984.
“Propylene enchainment inversion” means the insertion variation (from primary to secondary) that the propylene molecule may exhibit in the macromolecule.
Method for determining the distribution of the ethylene-propylene sequences, and in particular the absence of the above-mentioned invention in the ethylene-propylene I; r -7- 7 -fcopolymers, are well known in literature. Said methods include well defined modalities for qualitative and quantitative analyses, based on the Nuclear Magnetic Resonance of 13C, according to what is described for example by J.C. Randall in “Polymer sequence determination by C 13-NMR method” (Academic Press, N.Y. 1977) and in “Macromolecules”, 11, 33, (1978), or by H.N. Cheng in “Macromolecules”, 17, 1950 (1984) or by C.J. Charman et al in “Macromolecules”, 10, 536 (1977).
Such modalities are transferable also to ethylene/propylene/ C 1 S diene terpolymers, in which diene is present in relatively CtC t C t ti: ‘low amounts, generally lower than 10% by weight.
The ethylene-propylene copolymers and ethylene- -propylene-(conjugated or non-conjugated) diene terpolymers, the macromolecules of which are substantially free from pro- C 1t pylene enchainment inversions, are characterized by very low 13 absorption values in the 1C-NMR spectrum (obtained in orthodichlorobenzene solution at a temperature of 120 0 C, using dimethyl sulphoxide (DMSO) as a reference) at about 34.9, 35.7 and 27.9 ppm (chemical shift, referred to tetramethylsilane (TMS) which are typical of the presence of sequences of the type CH CH 3 3 3 HC–CH CH -CH– (head-to-head inversion or tail-to-tail inversion of type X) i ii ii 8 and of the type CH
CH
3 3 HC– CH 2 2 2 2 (head-to-head inversion or tail-to-tail inversion of type X 4 The substantial absence of propylene enchainment inversions in such copolymers and terpolymers is apparent from the fact that at least one of the two parameters X and 2 and preferably both, exhibits a value equal to or lower than 0.02.
As is known, parameters X and X represent the Sfraction of methylene sequences,having 2 and 4 uninterrupted methylene groups between two consecutive methyl or methine groups in the polymeric chain, with respect to the total of 13 uninterrupted methylene sequences determined by C NMR.
St The value of said fraction is calculated according to the method described by J.C. Randall in “Macromolecules” 11, 33 (1978).
Copolymers and terpolymers endowed with such characteristics are known. They are preparable by polymerization of the corresponding monomer mixtures in the presence of Ziegler catalysts based on titanium compounds optionally carried on magnesium halide, and on aluminium organometal compounds. Catalysts of this kind are described for example in U.S. patent No. 4,013,823, in published European patent 9 application No. 202,550, in Italian patent No. 1,173,40 and in Italian patent application Nos. 20,203 A/81, 20,386 21,872 A/86, 21,510 A/87 in the name of the Applicant hereof.
The polymeric product, which is insoluble in xylene at 135 0 C and which constitutes component of the compositions according to the invention, substantially comprises the products derived from the cross-linking of components and and possibly the grafting products of components and either cross-linked or not cross-linked, the ones on the others.
Generally, the polypropylene content in said component ranges from 5 to 20% and preferably from 10 to by weight referred to the weight of the whole composition.
Component consists of an oil of the type which is usually utilized to carry out the extension of rubbers in general, and it can be an aromatic, naphthenic or, preferably, paraffinic oil.
Generally, in the plastoelastomeric compositions of the invention the elastomeric phase appears to be dispersed in the continuous plastomeric phase in the form of particles of size not greater than 10 microns, with at least thereof have size lower than 5 microns.
The plastoelastomeric compositions, which are one of the objects of the present invention, are preparable by 7349S:smt 4 10 subjecting to mastication or to other shearing stresses, in the presence of a peroxide cross-linking agent and of particular cross-linking coadjuvants, as defined hereinafter, a polymeric mixture comprising from 20 to by weight, but preferably from 60 to 25% by weight of polypropylene and from 80 to 20% by weight, but preferably from 40 to 75% by weight of an ethylene-propylene elastomeric copolymer or of an ethylene-propylene-diene elastomeric terpolymer, at a temperature which is sufficient to melt the polypropylene and at which the cross-linking of o, about 50-85% by weight of the starting elastomer amount 7 0 0 4 o occurs.
@00066 Optionally, amounts or polyethylene lower than 4% by weight on the weight of the polymeric mixture can be present therein.
Whenever used herein, the term “cross-linking”, as 0o0 referred to the starting elastomer, comprises both the P actual cross-linking or vulcanization reaction of the *elastomer and the reaction which may lead to the grafting of the cross-linked or not cross-linked elastomer on the t polypropylene (or plastomeric phase) as a consequence of the reaction promoted by the cross-linking system utilized.
As cross-linking agents, use is made of organic peroxides, preferably of those which exhibit a halving time of the order of 10-200 seconds at a temperature ranging from 1000 to 240 0 C, at which the vulcanization reaction is made to occur.
77349S:smt i 1: 1 i D) 5-58% of an extender oil.
8. A process for preparing the plastoelastomeric polyolefinc compositions according to claim 1, which comprises the following consecutive steps: 2 “i N? 10a Examples of said peroxides are dicumyl peroxide, a a ‘–bis(t.butylperoxy)-m- and/or -p-diisopropylbenzene, and l,l-di-t.butylperoxide-3,5,5-trimethylcyclohexane.
The peroxide amount utilized in the vulcanization generally ranges from 0.1 to 10% by weight, but preferably from 0.2 to 5% by weight calculated on the elastomeric component.
To the vulcanization system to be utilized in the preparation of the compositions according to the invention belong, along with the abovesaid peroxides, also coadjuvants consisting of furan derivatives selected among furfuryliden acetone, the esters of the furfurylidene malonic acid, the condensation products of 8 (alpha-furlaerolein) with cyclic ketones, and the compounds having general formulae or
(II).
0 m wherein R 1
R
2 equal to or different from each other, can be H or CI-C 3 alkyl, where X is a radical of formula: -CHO, -COOH, -CHONH 2 -CN, -NO 2 -COOCO-, -COOR, CO-, -CH COCH COOR,
CN(COOR)
2 where R is an aryl containing 6 to 8 carbon atoms, or an alkyl containing 1 to 4 carbon atoms, n 1 or 2, m a number equal to the free valence of X, z 0 or 1 S49S:smt -f -C N -CN, -NO 2 -COOCO-, -COOR, -CH 2
COCH
2
COOR,
CN(COOR)
2 where R is an aryl containing 6 to 8 carbon atoms, or an alkyl containing 1 to 4 carbon atoms, n 1 or 2, m a number equal to the free valence of X, z 0 or 1
A
SI
S./3
C
I
11 -C N-N C– 0 0 R’
R”
(II)
(6 1 f E where R’ and like or different from each other, may be hydrogen, or alkyl radicals containing from 1 to 4 C, or cycloalkyl radicals containing from 5 to 8 C and preferably from 6 to 8 C.
Said coadjuvants are utilized in amounts corresponding to about 5-60% by weight, but preferably to 10-30% by weight with respect to the utilized peroxide.
1′ liI u i i i i 7349S:smt present invention are 1,5-difurfuryl-1,4-pentadiene-3-one and difurfuralaldazine.
Further examples are B-(alpha-furyl)-acrolein; B-(alpha-furyl)acrylonitrile; B-(alpha-furyl) acrylic acid and esters thereof; bis-furfuryldene acetone; alpha-ethyl-B-(alpha) acrolein; the products obtained from the condensation of B-(alpha-furyl acrolein) with cyclic ketones can be prepared according to what is described in “Berichte”, 76, 676 (1943).
The abovesaid compounds are known in the art.
formulThey are preparable, for example, according to what is described in US patent No. 3301837.
Thus, another object of the present invention is a process for preparing plastoelastomeric polyolefinic compositions, which comprises, in the order, the following operative steps -(alpha-furyl acrolein) with cyclic 1) preparing an intimate mixture, comprising, in bed iby weight: from 20 to 80%, but preferably from 60 to 25% ofart.
polypropylene or of a copolymer ording propylene with described in US patent No. 3301837.
Thus, another object of the present invention is a process for preparing plastoelastomeric polyolefinic i1) preparing an intimate mixture, comprising, in by 1 up to 10% by weight of ethylene; 7349S:smt 7349S:smt V I.
ketones~~~ ia :epeae codn owa sdsrbdi !Brct” i I7 y !e |]veai copjnd “r “n :h 1 7349 es Ir !rprbe exmpe :*orin ‘owa __crbe .n _S ‘^en No. 33*- VULCANIZATION METHODS The following statement is a full description of this invention, including the best method of performing it known to me/us:r> 13 from 80 to 20%, but preferably from 75 to 40% of an ethylene-propylene elastomeric copolymer or ethylene-propylene-diene elastomeric terpolymer; from 0.1 to 10%, calculated on said elastomeric copolymer or terpolymer, of an organic peroxide as a vulcanizing agent; from 5 to 60%, calculated on said organic peroxide, of at least a compound comprised in one of preceding formulas and as a vulcanization coadjuvants; optionally, an amount lower than 4% on the total polymeric products of polyethylene; 2) heating the mixture, during the mixing step or during the mastication step or during the step in which it is subjected to other shearing stresses, to a temperature ranging from 160 0 C to 240 0 C, wherefore melting of the L polypropylene and cross-linking of about 50-85% by weight of the originally present elastomeric copolymer or terpolymer take place; 3) adding to the resulting product, by means of intimate mixing, a paraffin extender oil in an amount ranging from 6 to 100 parts by weight and preferably from 20 to parts by weight for 100 parts of said product.
i 734 9S:smt L elastomeric cmponent is made to occur during the step of mixing or mastication with a plastomeric polymer in the molten state, by means of cross-linking agents, which are usual- -14 The mixture elastomeric product specified under (b) contains from 25 to 60%, preferably from 30 to 45% by weight of copolymerized propylene, and from 0 to 5% by weight of units deriving from one or more conjugated or non conjugated dienic monomers as mentioned hereinbefore. It may have a molecular weight corresponding tol /values ranging from 2 to 8 dl/g, but preferably ranging from 3 to 5 dl/g, extremes included.
If the molecular weight of the elastomeric component corresponds to 4 lvalues higher than 3.5 dl/g, such component is preferably selected from ethylene/propylene/(diene) copolymers and terpolymers, in the structure of which head- -to-head, tail-to-tail inversions of the propylenic unit, as e amentioned hereinafter, are substantially missing. More adand preferably ranging from 10 to 15. The R1xR 2 represents, i2 as is known, the product between the reactivity ratios of ethylene (R
I
and of propylene said product being calcul ated from the sequence distribution in such copolymers and terpolymers through 13C NMR analysis, according to known methods.
W
vantageously, sadcp9mr n eroyesaeslce t -linking of the elastomer, which is one of the objects of the process of said patent.
15 In order to reduce to practice the process of the invention it is possible to use, instead of the individual components and of the abovesaid mixture, an intimate mixture of polypropylene and of elastomeric ethylene-propylene copolymer or elastomeric ethylene-propylene-diene terpolymers,as is obtainable in a single polymerization step of the monomers by polymerizing for example, according to US patent 4,399,054, first the propylene up to the desired amount and subsequently a mixture of ethylene and propylene, optionally containing the dienic monomer, in the proper ratio.
To the mixture so obtained, the vulcanization components as defined under and will be subsequently ad- S 1 ded.
Other vulcanization co-agents or coadjuvants (for example liquid polybutadiene, triallyl cyanurate) besides thermal stabilizers, antioxidants, mineral fillers,dyes, may in any case be added to the mixture of reaction components from to cited above.
In the range of the operative conditions illustrated hereinbefore, by varying, according to techniques accessible to those skilled in the art, the amounts of the rea-
S
gents and of the components of the polymeric mixture, it is possible to obtain, after cross-linking, products having high- Ser or lower quantitative ratios between components (B) I O’o IS exap- iui poyuadee ti1ycaurt)beie elastic characteristics at high temperatures.
I
7349S:smt and as defined above. In particular, the use of higher amounts of coadjuvant permits to obtain higher amounts of cross-linked polypropylene. In particular, to the vulcanized compositions coming from operative step it is possible to add variable amounts of polypropylene as is defined in in order, for example, to correct the product hardness.
Generally, the polypropylene amount belonging to the product, which is insoluble in xylene at 135 0 C, accounts for 20 to 70%, preferably-for 30 to 50% by weight of the polypropylene contained in the starting mixture subjected to cross-linking.
The elastomeric copolymer or terpolymer belonging to said insoluble product amounts to 50 85%, but preferably to 70 -85% by weight of the copolymer or terpolymer contained in said starting mixture.
The following examples are given to better illustrate the present invention, without being however a limitation thereof.
EXAMPLE 1 In a Banbury internal mixer there were intimately mixed for 5 minutes, at a temperature gradually rising from 800 to 180 0 C, 26 parts by weight of homopolymer polypropylene having a M.I. (230 0 C, 2.16 kg) 1 and a I.I.
92%, with 74 parts by weight of an ethylene/propylene C i ?iI~
II
I I 4 4 7349S:smt
I
17 17 copolymer, containing 38% by weight of copolymerized propylene, obtained by bulk polymerization of the monomers at 40 0
C,
using a titanium catalyst similar to the one described in example 1 of European patent application No. 262,987, and Al triisobutyl as a co-catalyst. Such copolymer exhibited the following characteristics S head-to-head, tail-to-tail inversions of the propylene unit: substantially absent (X2 X 0.018%); 2 4 R x R 8; 1 2 Mw/Mn 11; 3.8 dl/g.
The mixture was then discharged and granulated by using a Bandera single-screw extruder.
The granules were then sent to a laboratory two-screw extruder produced by A.P.V. having a length/diameter (L/D) ratio equal to 25 and a diameter of 127 mm, equipped with conveyance and masticating elements, by means of which a residence time of 60 seconds was obtained, and which was operating at a temperature from 1600 to 240°C. 2% by weight of Peroximon F40 and 0.37% by weight of di-furfural-aldazine, referred to the polypropylene/elastomer mixture, were simultaneously conveyed into said extruder.
At about 2/3 of the extruder length, the elastomer cross- -linking reaction was concluded. At such extruder point, i t 7349S:smt 1 18 p. of polypropylene of the same type as the starting polypropylene, 3 p.w. of ZnO, 0.5 p.w. of mercaptobenzoimidazole and 0.2 p.w. of polymerized 2,2,4-triethyl-l,2-dihydroquinone, then 74 p.w. of paraffin extender oil, preheated to 200 0
C,
were added. The mix was then discharged from said extruder into a second single-screw extruder (L/D 8, D 20 mm), where it was compacted, degassed, further homogenized and sent to a liquid-ring top cutting unit for being transformed 0o o into pellets.
*e I The resulting product was subjected, in the order, to the following analysis procedures.
S 1) Extraction with xylene at 135 0 C for 5 hours and separation of the residue by filtration from the resulting solution, using a Gooch heated-wall filter.
2) Determination of the polypropylene amount present in such residue by means of infrared analysis and, by difference, of the amount of cross-linked copolymer or terpolymer.
3) Determination, in the solution obtained from the above- S’ -mentioned extraction, of the content of polypropylene as such (not cross-linked and not grafted on the elastomeric component) by cooling of such solution, wherefore precipitation of polypropylene occured, which was filtered at 23°C and washed with xylene at 23 0
C.
4) Determination of the content of not cross-linked elasr ethylene-propylene sequences, and in particular the absence of the above-mentioned invention in the ethylene-propylene -19tomeric copolymer and terpolymer, carried out by coagulating with acetone the xylene solution deriving from the separation of polyproylene as such, according to procedure and by separating the coagulated product.
Determination of the paraffin oil content carried out by evaporating under vacuum the acetone/xylene mixture deriving from procedure 4).
The analysis gave the following results, expressed in by weight on the thermoplastic composition: not cross-linked elastomeric copolymer 7% polypropylene as such residue insoluble in xylene at 135 0 C 38% polypropylene contained in the insoluble residue (on the total of the composition) 8% extender oil 37% The characteristics of the obtained product, determined on specimens obtained in an injection molding press, were as follows: SHORE hardness 70 (ISO 868) 2 Tensile strength (kg/cm (ISO 37) Elongation at break (ISO 37) Compression set (10 h at 170 0 C) (ISO 815).
In the obtained composition the elastomeric phase appears to h be highly dispersed, with particle size lower than micron, at least 50% thereof having a size lower than micron.
EXAMPLE 2 It was operated as is described in the preceding 7349S:smt CH CH 3 I 3 3 HC–CH CH -CH- 2 2 (head-to-head inversion or tail-to-tail inversion of type X 2 i axample, using polypropylene and ethylene/propylene copolymer in the form of a product directly obtained by polymerization carried out according to the following modalities.
A 20 1 autoclave,equipped with proper instruments and containing 13 1 of n.pentane, was fed, at a temperature of 20 0
C,
with 0.26 g of a catalyst based on MgC12 and TiCl 4 having spheroidal shape and prepared according to example 1 described in US patent 4,399,054, along with 21.6 g of Al (isobutyl)3.
S The autoclave was brought to a temperature of 60°C and propylene, withdrawn from a proper cylinder thermoregulated at was introduced under stirring up to a pressure of atm. While maintaining constant both temperature and prest sure, propylene was fed till about 1300 g of polypropylene were produced. Degassing was then carried out in order to remove the solvent and the unreacted propylene,bringing the temperature in the autoclave again to 20°C. While maintaining the polymer mass under stirring and operating at a temperature of 20 0 C, the autoclave was fed with a 50/50 by weight mixture of ethylene/propylene withdrawn from cylinders thermoregulated at 40 0 C, till a pressure of 9.5 atm. was reached. Controlling the cylinder weight loss, about 3,730 g of ethylene/propylene copolymer in the gaseous phase were so produced in 4.5 hours. After gradual degassing in order pounds. Catalysts of this kind are described for example in U.S. patent No. 4,013,823, in published European patent
II
21 to remove the unreacted monomers, the autoclave was opened and 5,030 g of spheroidal polymer were discharged therefrom.
The polymer so obtained has a propylene content equal to 54% and aI/lequal to 3.7 dl/g. The copolymeric component of such mix consisted of an ethylene/propylene copolymer containing 38% by weight of copolymerized propylene having the following characteristics Shead-to-head, tail-to-tail enchainment of propylene substantially absent (X X 0.019), R x R 2 1 2 Mw/Mn 12, 3.8 dl/g.
Said synthesis product was converted to pellets by means of a head-cut single-screw extruder, to facilitate the product S feeding to the APV extruder of the preceding example.
The test was conducted as is described in example 1 as regards both the arrangement in the APV extruder and the addition of cross-linking agents, co-agents, polypropylene and extender oil.
The analyses of the resulting product gave the following resuits: elastomeric not cross-linked copolymer 6% polypropylene as such 16% residue insoluble to extraction in xylene at 135°C 37% 73 49S:smt T-*iiJ– 22 polypropylene content in the insoluble residue 9% (on the total) extender oil 38% The product characteristics determined on test pieces obtained in an injection press, according to the ISO standards indicated hereinabove, were as follows SHORE hardness A 69 Tensile strength (MPa) 7.4 Elongation at break 360 Compression set (10 h at 1700C) 57 The particle size of the dispersed elastomeric phase turned out to be lower than 10 microns, with at least 50% of the particles having size lower than 5 microns.
EXAMPLE 3 It was operated under the same conditions as in example 1 and with the same reagents amounts, but using an ethylene/propylene copolymer containing 38% by weight of propylene, prepared by means of a homogeneous catalyst system based on VOC13 and A1 2
(C
2
H
5 3 C1 3 as is described in example 1 of Italian patent No. 866,519. Such copolymer exhibited the following characteristics:
R
1 x R 2 0.5; Mw/Mn 3; head-to-head inversions, tail-to-tail inversions of the propylene unit expressed by values of SX X 4 0.05; 2 4 2.7 dl/g.
The analysis of the obtained product gave the following results, expressed as by weight: ;3 7 3 49S:smt to occur.
7349S:smt r A 4 7 -23 elastomeric not cross-linked copolymer 4% polypropylene as such residue insoluble in xylene at 135 0 C 36% polypropylene contained in the insoluble residue 5% (on the total) extender oil 37% The characteristics of the obtained product, determined on test pieces obtained in an injection press according to the ISO standards indicated hereinabove, were as follows SHORE hardness A 69 Tensile strength (MPa) Elongation at break 400 Compression set (10 h at 1700C) The size of the dispersed elastomeric particles was lower than 10 microns.
EXAMPLE 4 It was operated as in example 1 with the exception Sthat a paraffin extender oil was incorporated into the ethylene/propylene copolymer upon mixing with polypropylene.
The obtained product exhibited the following characteristics: elastomeric not cross-linked copolymer 22% polypropylene as such 19% residue insoluble in xylene at 135 0 C after a 5-hour extraction 16% polypropylene contained in the insoluble residue 4% (on the total) 7349S:smt /Y ^349S:smt .4: 24 extender oil The characteristics of the obtained product, determined on test pieces obtained in an injection press according to the above-indicated ISO standards were as follows SHORE hardness A 67 Tensile strength (MPa) Elongation at break 250 Compression set (10 h at 170 0 C) 72.
The size of the elastomeric dispersed particles was lower than 10 microns, with more than 50% of the particles having size lower than 5 microns.
EXAMPLE It was operated as in example 1, using an ethylene/ S propylene copolymer contained 47% by weight of copolymerized propylene, obtained by operating with a titanium catalyst similar to the one of example 7 of European patent application No. 262,987 and with Al triisobutyl as co-catalyst, and having the following characteristics: head-to-head inversions, tail-to-tail inversions of the propylene unit expressed by values of X 2 0.02;
X
4 =0.05; 4- Rx R 9; 1 2 Mw/Mn 11; 3.5 dl/g, and using, as cross-linking coadjuvant, 1.5-difurfuryl-l,4pentadien-3-one in an amount equal to 0.3% by weight referred to the mix of the two polymers.
7349S:smt i 1 -1 7349S:smt 24a The analysis of the obtained product gave the following results expressed as by weight of the thermoplastic composition: elastomeric not cross-linked copolymer 8% residue insoluble in xylene at 135 0 C after a 5-hour extraction 36% polypropylene as such 16% polypropylene contained in the insoluble residue 7% (on the total) extender oil 37% The characteristics of the obtained product, determined on test pieces obtained in an injection press were as follows: SHORE hardness A Tensile strength (MPa) Elongation at break 370 Compression set (10 h at 170 0 C) 57.
The size of the dispersed elastomeric particles turned out to be lower than 10 microns at least 50% of the particles having size lower than 5 microns.
EXAMPLE 6 It was operated as in the preceding example, but substituting the mix of propylene and ethylene/propylene copolymer prepared by mixing in a Banbuty mixer, by a product directly obtained by reaction according to the following modalities: 0.31 g of a catalyst based on MgCl 2 and TiCl4, having a spheroidal shape and prepared according to example 1 described in U.S. patent No. 4,399,054, along with 259 g of 7349S:smt 7349S:smt Al(isoBu) were introduced at a temperature of 20 0 C into a 3 autoclave properly equipped with instruments and containing 13 1 of n.pentane.
The autoclave was brought at a temperature of 600C and propylene, withdrawn from a proper cylinder thermoregulated at 0 C, was introduced, under stirring, up to a pressure of atm. While temperature and pressure were maintained constant, propylene was fed until about 1450 g of polypropylene were produced. Then it was degassed to remove the solvent and the unreacted propylene, bringing the temperature in the autoclave again to 20 0 C. While maintaining the polymer mass under stirring and operating at a temperature of 200C, a C 2-C3 mixture (40/60 by weight), withdrawn from cylinders thermoregulated at 400C, was introduced into the autoclave till reaching a pressure of 9.5 atm. Checking the cylinder weight loss, about 3,850 g of polymer were produced in 4.5 h in gaseous phase. It was gradually degassed in order to remove the unreacted monomers and the autoclave was opened, S from which 5,300 g of polymer in spheroidal shape were discharged.
The polymer so obtained had a propylene content equal to 60.5% by weight. The copolymeric component of the product so obtained was composed of an ethylene/propylene copolymer having a propylene content of 47% and exhibiting the following C 7349S:smt -26 characteristics: head-to-head, tail-to-tail inversions of propylene: substantially absent (X 2 0.018); SR x R 2 7; w/Mn 3.8 dl/g.
Said synthesis product was transformed to pellets by means of a head-cut, single-screw extruder, to favour the feeding to the APV extruder.
The test was conducted as is described in example 5 as regards both the APV extruder and the addition of cross-linking agents, co-agents, polypropylene and oil.
The analysis gave the following results, expressed in by weight of the thermoplastic composition: not cross-linked elastomeric copolymer 8% polypropylene as such residue insoluble to the extraction in xylene at 1350C 36% I polypropylene content in the insoluble residue 8% (on the total) extender oil 38%.
The characteristics of the product obtained, determined on test pieces produced by injection molding, were as follows: SHORE hardness A 69
L
Il u I.Jt IIJU6I U II III Ju l u uAJ II I W 13 terpolymers through C NMR analysis, according to known methods.
iii 27 tensile strength (MPa) 6.8 elongation at break 380 compression set (10 h at 170 0 C) 58.
The dispersed elastomeric particle size was lower than microns, with more than 50% of the particles having size lower than 5 microns.
EXAMPLE 7 Operating under the same conditions as in example and with the same component amounts but using an ethylene/ propylene copolymer containing 40% of propylene, prepared by means of a catalyst composed of VOC1 3 and Al-triisobutyl, following the modalities described in example 3, and having Sthe following characteristics:
R
1 R2 4; Mw/Mn S- head-to-head, tail-to-tail inversions of the propylene unit expressed by X 2 0.13, X 0.06; 3.2 dl/g, a composition was obtained, which, after cross-linking, was subjected to analysis and revealed the following composition: not cross-linked elastomeric copolymer polypropylene as such 19% residue insoluble to the extraction in xylene at 135 0 C residue 5.8% (on the total) extender oil 39% The characteristics of the resulting product, determined on 1 7349S:smt p he tail- t i o o th p n un t e pre sed y X .13, X. 0. 6; I” possible to obtain, after cross-linking, products having highjer or lower quantitative ratios between components
(B)
28 1 test pieces produced by injection molding process, were as follows SHORE hardness A 68 Tensile strength (MPa) 6.7 Elongation at break 410 Compression set (10 h at 1700C) 71 The dispersed elastomeric particle size was not higher than microns, with at least 50% of the particles having size lower than 5 microns.
EXAMPLE 8 Example 5 was repeated, with the only difference that an ethylene/propylene/l,4-butadiene terpolymer prepared by means of a Ti-catalyst similar to the one described in example 1 of Italian patent application No. 21,510 A/87 in the name of the Applicant hereof, was utilized as an elastomeric component, using aluminium triisobutyl as a co-catalyst, and having the following characteristics propylene 46% by weight 1,4-butadiene 1.5% by weight head-to-head, tail-to-tail inversions expressed by X 2 0.018 and by X 4 0.008 Mw/Mn 9 3.7 dl/g.
The analysis of the composition, carried out after crosslinking, gave the following results: not cross-linked elastomeric copolymer 6% polypropylene as such 13% 7349S:smt 800 to 180°C, 26 parts by weight of homopolymer puiypropylene having a M.I. (2300C, 2.16 kg) 1 and a I.I. 92%, with 74 parts by weight of an ethylene/propylene i- 29 r residue insoluble to the extraction with xylene at 135 0 C after 5 hours polypropylene content in the insoluble residue extender oil 38% The characteristics of the product obtained, determined on test pieces prepared by an injection molding process were as follows: SHORE hardness A tensile strength (MPa) 7.2 elongation at break 350 compression set (10 h at 170 0 C) The size of the elastomeric dispersed particles was lower than 10 microns, with at least 50% of said particles having size lower than 5 microns.
EXAMPLE 9 (comparative test) Example 8 was repeated, but without using furfuryl-1,4-pentadien-3-one as a vulcanization coadjuvant.
The analysis of the composition after cross-linking gave the following results, expressed in by weight: not cross-linked elastomeric terpolymer 21% polypropylene as such 22% residue insoluble in xylene at 135 0 C after 5 h 14% S polypropylene content in the insoluble residue 1% (on the total) extender oil 39% The composition characteristics were as follows SHORE hardness A 64 7349:smt
A
7349S:smt* muilaneously conveyed into sala extruaer.
At about 2/3 of the extruder length, the elastomer cross- -linking reaction was concluded. At such extruder point, i i t tensile strength (MPa) 3.1 elongation at break 250 compression set (10 h at 170 0 C) EXAMPLE 10 (comparative test) Example 1 was repeated, using, instead of di-furfural aldazine, 0.4% by weight of triallyl cyanurate as a cross-linking co-agent.
The resulting product exhibited the following %-composition: not cross-linked elastomeric copolymer 8% polypropylene as such 29% residue insoluble in xylene at 135 0 C after 5 h 21% polypropylene content in the insoluble residue 2% (on the total of the composition) extender oil 37% The product characteristics were as follows SHORE hardness A 68 tensile strength (MPa) elongation at break 300 compression set (10 h at 170 0 C) 92.
poyprpylee a suc 29 re idu ins lub e in xyln t 13 °C fter5 h 21% poyproylen conent n th inslubl tensile.I- st en t (M a)5.
-1
Claims (13)
1. Plastoelastomeric polyolefinic compositions, compris- ing an intimate mixture of the following components, in the indicated percentage by weight A) 10-50% of not cross-linked polypropylene, B) 2-10% of an ethylene/propylene elastomeric not cross-linked copolymer, or of an ethylene/propyl- ene/diene elastomeric not cross-linked terpolymer, C) 30-45% of a polymeric product insoluble in xylene at 135°C, comprising polypropylene and ethylene/ propylene copolymer or ethylene/propylene/diene terpolymer, D) 5-58% of an extender oil.
2. The compositions according to claim 1, wherein the elastomeric copolymer or terpolymer are characterized by a substantial absence, in their macromolecular structure, of head-to-head, tail-to-tail inversions of the propylene unit.
3. The compositions according to claims 1 and 2, wherein the amount of component ranges from 20 to 30% by weight.
4. The compositions according to claims 1 to’ 3, wherein the amount of component ranges from 5 to 10% by weight. CA C I C I Ar C C Ct reached. Controlling the cylinder weight loss, about ,/Ju g of ethylene/propylene copolymer in the gaseous phase were so produced in 4.5 hours.
After gradual degassing in order 1 32 The compositions according to claims 1 to 4, wherein the amount of component ranges from 35 to 40% by weight.
6. The compositions according to claims .i to 5, wherein the amount of polypropylene contained in the insoluble polymeric product ranges from 5 to 20% by weight referred to the composition.
7. The compositions according to claims 1 to 5, wherein the amount of polypropylene contained in the insoluble polymeric product ranges from 10 to 15% by weight referred to the composition.
8. A process for preparing the plastoelastomeric poly- olefinc compositions according to claim 1, which com- prises the following consecutive steps: 1) preparing an intimate mixture comprising, in by weight: from 20 to 80% of polypropylene or of a copo- lymer of propylene with up to 10% by weight of ethylene; from 80 to 20% of an ethylene/propylene elas- tomeric copolymer or of an ethylene/propylene/ diene elastomeric terpolymer; from 0.1 to l0%,referred to said elastomeric copolymer or terpolymer, of an organic peroxide *t: iI ,I r Ilrr rlv~~ III J polypropylene as such 16% residue insoluble to extraction in xylene at 135 0 C 37% I 33 -33- as a vulcanizing agent; from 5 to 60% referred to said organic peroxide, of at least one compound selected among furfuryliden acetone, the esters of furfurylidene malonic acid, the condensation products of 8(alpha-furylacrolein) with cyclic ketones and the compounds having general formulae (CH 2 -CR 1 =CR 2 (I) 0 wherein R 1 R 2 equal to or different from each other, can be H or C1-C 3 alkyl, where X is a radical of formula: -CHO, -COOH, -CHONH 2 -CN, -NO 2 -COOCO-, -COOR, -CH COCH COOR, CN(COOR) 2 where R is an aryl containing 6 to 8 carbon atoms, or an alkyl containing 1 to 4 carbon atoms, n 1 or 2, m a number equal to the free valence of X, z 0 or 1 -C N-N (II) 0 0′ R’ R” where R’ and equal to or different from each other, may be hydrogen, or alkyl radicals containing 1 to 4 carbon atoms, or cycloalkyl radicals containing 5 to 8 carbon atoms; 7349S:smt b LI9 7349S:smt 34 41 $4 4 4i optionally, an amount lower than 4% on the total polymeric material, of polyethylene. 2) heating the mixture, during mixing, or mastication, or while it is subjected to other shearing stresses, to a temperature ranging from 160 0 C to 240 0 C, wherefore melting or polypropylene and cross-linking of about 50-85% by weight of the originally present elastomeric copolymer or terpolymer occurs; 3) adding to the resulting product, by means of intimate mixing, an extender oil in an amount ranging from 6 to 100 parts by weight referred to said product. r i I -r j X E r i i I” -_ii 7349S:smt
9. The process according to claim 8, wherein the elastomeric copolymer or terpolymer has a molecular weight corresponding to values of ranging from 3 to 5 dl/g.
The process according to claim 8, wherein the elastomeric copolymer or terpolymer are characterized by the absence, in the macromolecular structure, of head-to-head, tail-to-tail inversions of the propylene unit.
11. The process according to claims 8 to 10, wherein the elastomeric copolymer or terpolymer exhibits an average value of product R 1 x R 2 higher than 2 and values of the Mw/Mn ratio equal to at least 6.
12. A plastoelastomeric polyolefinic composition as claimed in claim 1 substantially as herein described with reference to any one of examples 1-8.
13. A process for the preparation of a plastoelastomeric polyolefinic composition as claimed in claim 1 substantially as herein described with reference to any one of examples 1-8. Dated this llth day of September 1989 AUSIMONT S.r.1. By their Patent Attorney GRIFFITH HACK CO. I 7349S:smt
AU41323/89A
1988-09-13
1989-09-12
Plastoelastomeric polyolefinic compositions and process for preparing them according to dynamic vulcanization methods
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DE4214170A1
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1992-04-30
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IT1264555B1
(en)
*
1993-08-03
1996-10-02
Himont Inc
SLUSH MOLDING PROCESS OF POLYOLEFINIC COMPOSITIONS POWDERS
IT1274746B
(en)
1994-08-30
1997-07-24
Enichem Elastomers
VULCANIZED POLYOLEFINIC PLASTOELASTOMERIC COMPOSITION AND PROCEDURE FOR ITS PREPARATION
CN1051229C
(en)
*
1994-11-30
2000-04-12
南京金宁信息技术研究所
Preparation method of active dried earthworm powder
IT1274469B
(en)
1995-05-11
1997-07-17
Spherilene Spa
DYNAMICALLY VULCANIZABLE POLYOLEFINIC COMPOSITIONS
US5571868A
(en)
*
1995-06-15
1996-11-05
Exxon Chemical Patents Inc.
Calendered elastomeric articles
EP0913427A1
(en)
*
1997-11-01
1999-05-06
Bernhard Rustige GmbH und Co. Kommanditgesellschaft
Thermoplastic multiphase polymeric composition
DE19748976A1
(en)
*
1997-11-06
1999-05-20
Danubia Petrochem Polymere
Thermoplastic elastomers with high strength, elasticity and good colorability and the high impact polymer blends made from them
JP2000026696A
(en)
*
1998-07-14
2000-01-25
Sumitomo Wiring Syst Ltd
Flame retardant and abrasion resistant resin composition
US20030144415A1
(en)
2002-01-29
2003-07-31
Dsm N.V.
Process for the preparation of a thermoplastic elastomer comprising a partially vulcanized rubber concentrate
BR0305247A
(en)
2002-06-13
2004-09-21
Basell Poliolefine Spa
Process of preparing ethylene copolymers
IL156870A0
(en)
2003-07-10
2004-02-08
Carmel Olefines Ltd
Process for making thermoplastic vulcanizates
US7868096B2
(en)
*
2003-09-17
2011-01-11
Exxonmobil Chemical Patents Inc.
Thermoplastic vulcanizates and processes for making the same
EP2032647B1
(en)
*
2006-06-23
2013-07-24
Basell Poliolefine Italia S.r.l.
Polyolefin thermoplastic vulcanizate elastomers
CA2598342C
(en)
*
2006-09-08
2014-10-14
Lanxess Inc.
Peroxide cured thermoplastic vulcanizates comprising butyl rubber
JP6459780B2
(en)
*
2014-07-31
2019-01-30
住友化学株式会社
Thermoplastic elastomer composition and molded article thereof
KR20180039664A
(en)
*
2015-08-11
2018-04-18
스미또모 가가꾸 가부시끼가이샤
A method for producing an ethylene-? -Olefin-based copolymer rubber, a rubber composition, and an ethylene-? -Olefin-based copolymer rubber
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*
2018-02-28
2020-10-20
中国铁道科学研究院金属及化学研究所
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PROCEDURE FOR THE PREPARATION OF POLYOLEFINIC PLASTIC-ELASTOMERIC COMPOSITIONS, BY DYNAMIC VULCANIZATION
JPS5825340A
(en)
*
1981-08-07
1983-02-15
Mitsui Petrochem Ind Ltd
Production of partially crosslinked rubber/resin composition
CA1261505A
(en)
*
1984-05-02
1989-09-26
Akira Uchiyama
Thermoplastic elastomer composition
IT1207498B
(en)
*
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1989-05-25
Himont Inc
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IT1203607B
(en)
*
1985-12-20
1989-02-15
So F Ter Spa
PROCEDURE FOR PREPARING PLASTO-ELASTOMERIC COMPOSITIONS BASED ON POLYOLEFINS AND EPDM TERPOLYMERS AND PLASTIC-ELASTOMERIC COMPOSITIONS SO OBTAINED
JPS6339942A
(en)
*
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2003-04-10
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