CA2087417A1 - Impact-resistant polyolefin molding composition - Google Patents
Impact-resistant polyolefin molding compositionInfo
- Publication number
- CA2087417A1 CA2087417A1 CA002087417A CA2087417A CA2087417A1 CA 2087417 A1 CA2087417 A1 CA 2087417A1 CA 002087417 A CA002087417 A CA 002087417A CA 2087417 A CA2087417 A CA 2087417A CA 2087417 A1 CA2087417 A1 CA 2087417A1
- Authority
- CA
- Canada
- Prior art keywords
- molding composition
- olefin
- weight
- carbon atoms
- polyolefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- 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
-
- 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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- 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
Abstract
Abstract of the disclosure:
Impact-resistant polyolefin molding composition A polyolefin molding composition essentially comprising 20 to 99% by weight, based on the molding composition, of an isotactic polyolefin which contains no atactic polymer chains, and 1 to 80% by weight, based on the molding composition, of a rubber having a glass transition temperature below -20°C is distinguished by a high impact resistance and hardness, even at low temperatures.
Impact-resistant polyolefin molding composition A polyolefin molding composition essentially comprising 20 to 99% by weight, based on the molding composition, of an isotactic polyolefin which contains no atactic polymer chains, and 1 to 80% by weight, based on the molding composition, of a rubber having a glass transition temperature below -20°C is distinguished by a high impact resistance and hardness, even at low temperatures.
Description
87~ ~Pi~
HOECHST AKTI~NGESELLSCH~FT HOE 92/F 008 Dr. ~Otb~
Description Impact~resistant polyolefin molding composition The i~vention relates to a polyolefin molding composition S of an i~otactic olefin homopolymer and/or slefin copoly-mer and a rubber, which has a high hardness and a high impact r~si~tance even at low temperatures.
Impact-resistant polyolefin molding compositions are known in principle. They are prepared by mixing, for example, polypropylene and a rubber, such as, for example~ ethylene/propylene rubber (EPM) or eth~lene/
propylene/diene rubber (EPDN), in the malt ~Al~gew.
Makromol. Ch~m. 185/186 (1991) 97; and Polymerd 28 (1987) 47).
According to the prior art, the polypropylene used comprises atactic polypropylene (~PP) to the extent of at least 2 - 10% by weight and polypropylene chains o~
widely varying chain length (N~/M~ = 5 - 10) ~o the extent of g0 - 9~%.
Alternatively, a propylene copolymer which also com-prise~, in addition to APP, pol~propylene chains and polymer chains of the comonomer having the build-up described abov2, propylene copolymer chains of varying copolymer contents and likewise varying chain lengths is al~o used a8 the polypropylene component.
Moreover ~o-called reactor blends are known. ~he~e are composed o~ ~PP, polypropylene and polymers o~ the comonomer of varying chain length, a~ well as ef propylene comonomer chains of varying chain length and comonomar con~ent~. They are prepared directly in the polymerization reactor in one or more polymerixation 2 ~
steps.
All these molding compo~ition~ have ~he co~mon feature that they have only an unsatisfactory rigidity~hardnes~
at the desired high impact resistance.
There was thu~ the object of di6covering a molding compo~ition which does not have the aclver~e properties known from the prior artO
Surprisingly/ it ha~ now been found that if polymer~ and copo~ymers which are free rom atactic polymer chains ~atactic polyolefin; called ~P0) and have a homogeneous mol~cular weight distribution (M~M~ i~ preferably le~s than 5~ are u~ed, the abovementioned disadvantages can be avoided.
The invention thus relates to a polyolefin molding composition essentially comprising 20 to 99~ by weight~
based on the molding composition, of an isotactic poly-olefin which contains no atactic polymer ohains and 1 to 80% by weight, based on the molding composition, of a rubber having a glas~ transition ~emperature below 20C.
The AP0-free i~otactic polyolefin to be used for the preparation of the po1yolefin molding composition accord-ing to the invention is a pol~mer having a narrow molecular weight distribution M~tM~ of ~ 5, preferably < 3.5, and a uniform chain build-up. Uniform chain build-up is understood as meaning a random distribution ofbuilding defect3 andtor comonomer~ in the polymer chain.
AP0-~ree l~otactic polyole~ins are to be understoocl as meaning tho~e polyolefins which es~en~ially comprise no atactic .pol~mer chain~. These are product~ (homo- and copolymers) which are prepared using highly stereo-speci~ic metallocene/aluminoxane cataly~t ~y~tellls.
Correspondin~ proce~ses are known and are de~cribed, for 2O~7 example, in ~P-A 302,424, EP-A 336,1271 EP-A 336,123 and DE-P 40 35 886Ø The isotactic polyolefins prepared by the processes mentioned comprise only very 6mall con tents, if any, of atactic polymer chains. ~s a rule, this conte~t i~ less than 1% by weight.
In principl2, it i5 also possible for polyolefins which have been prepared using con~entional Ziegler catalysts (MgCl2/TiCl4/elec~ron donor/Al~t3~ and c03npri~e noticeable APO content6 to be converted into polyolefins which are AP~-fre~ and ~herefore according to the invention by extraction of the ~P0 contents w.ith a hydrocarbon.
However, because of the associated involved proces~, i.Oe.
for raasons of cost, ~uch a procedure i~ ~ot very appro-pria$e.
The i~otactic polyolefin to be u~ed according to the i~ention either i~ an olefin homopolymer ha~in~ a molecular weight distribution M~/M~ c 5, preferably ~ 3.5, and an isotacticity index (II) of at least S5%, or an olefin copolymer having an M~/M~ of < 5, preferably ~ 3.5, and an isotacticity index of at l~ast 85%, or the poly-olefin i~ composed of an olefin homopolymer and an olefin copolymer in which the isotacticity index is a'c least 85%
and M~/M~ of the components is < 5, preferably < 3.5.
If the olefin polymer is an olefin homopolymer, it comprise6 unit~ of an olefin having at least 3 carbon atoms~ of the formula R~-CH=CH-Rb, in which Ra and * are identical or different and are a hydrogen atom or an alkyl xadical having 1 to 10, preferably 1 to 6 carbon atoms, or Ra and R~l with the carbon atoms ~oining them, ~orm a ring having 4 to 22 carbon atoms. Preferred olefin~ are propylene, l-butene, 4-methyl-1-pentene l-hexene, pentene and norbornene. Propylene i~
particularly preferred, i.e. the moldi.ng composition according to the invention comprise~, in particular, polypropylene.
2~7~ ~
If the olefin pol~mer i5 an olefin copolymer, it com-prises olefin uni~s defined above for the homopolymer and h~ving an isot2cticity index of a~ least 85~ to khe extent of 99.5 to 50, preferably 99 ~o 70% by weight~ and units of ethylene and/or another olefin of the aboYe definition as the comonomer to the extent of at least Q.5 to 50, preferably 1 to 30~ by weigh~. The comon~mer i~
incorporated rand~mly with a high regularity. Pre~erred comonomers are ethylene, 1-bu~ene, 4-methyl-1-pentene, 1-hexene, norbornone or pent~ne. Particularly preferred olefin comonomers comprise propylene unit.~ and ethylene comonomer units.
If the polyolefin comprises a mixture of olefin homopoly mer and olefin copolymer, the olefin homopolymer has the composition described above. The olefin copolymer com-prises an olefin as defined above for ~he olefin homo-polymer to the exten~ of 20 to 90% by weight, preferably 40 to 90~ by weigh~/ and uni~s of ethylene and/or at least one olefin as defined above for an olefin copolymer to the extent of 80 ~o 10% by weigh~, preferably 60 to 10% by weight. The comonomer is pref~rably incorporated randomly. The content of olefin homopolymer in the total polyolefin compo~ition in this case is 20 to 99~ by weight, preferably 40 to 95~ by weight, and the content of olefin copolymer i8 80 to 1~ by wei~ht, preferably 60 to 5~ by weight.
If it comprise~ two different pol~mer components, the polyolefin according to the invention is particularly preferably composed of 40 to 95% by weight of polypropylene (ba~ed on the total amount of polyole~in) ha~ing an i~otactici~y index of at least 85%, and 60 to 5~ by weigh~ (based on the total amount of polyolefin) of olefin copol~mer compri~in~ 40 to 90% by weight o~
propylene units and 60 to 10% by weight of ethylene units (in each ca~e ba~ed on the total amount of olefin aopoly-m~r).
2~7~L~ 7 5 ~
The molding composition according to the invention compri~es the i80tactic olefin polym~r in an amount of 20 to 99~ by weigh~, preferably 40 to 95% by weight.
1 to 80, preferably 5 to 60~ by weight of ~he molding composition according to the invention i~ a rubber having a glass transition te~perature below -20C. Sui~able rubbers are, for example, ~tyrene/butadiena rubbers, silicone rubbexs, ethylene/propylene xubbers (EPM) or ethylene/propylene/diene rubbers (~PDM). ~PM and EPDM
rubbers can additionally also compri~e up to 40% of polyethylene. 1,4-Hexadiene, norbornadiene or cyclopenta-diene can be pre~ent in an amoun~ of up ~o 10% by weight, based on the total amount of rubber, as the diene component.
The content of ethylene and propylene is not limited, as long as a glass transition temperature of the amorphous ~omponents of less than -20C is achie~ed.
A typical composition for commercially available EPM
rubbers i~, ~or example, 10-604 by weight of propylane unit~ and 90-40~ by weight of ethylene units. Of the ethylene units t 0-40~ by weigh* are a pure polyethylene content, and the remainder f~rms a copolymer content, together with the propylene~
EPD.M rubber~ are of corresponding composition, but 1-10%
by weight of a diene of the abovementioned type is al80 additionally incorporated in the copolymer content, in addition to propylene and ethylene. The melt viscosity of typical EPM and EPDM rubbers i6 between 0.5 and 3nO g/10 minuta~ (MFI 230/5).
The Mooney vi~co~ity (m2asured at 121~C, ML) i8 typi.cally between 20 and 80. The ten~ile stre~ at 60~ elongation i5 typically 10 300 p3i ~pounds/~uare inch, 1 p~i =
6B94.8 kg/m.second2 = 1 Pa).
2~7'.;L~7 Rubher~ which can typically be used are on the market, for example/ under the currently existing co~mercial names Vistalon, Ex~elor ~Exxon Chemicals), Dutral (Dutral S.A.), Nordel (DuPont~ ox Buna (Veba).
S In addition to the isotactic olein pol~mer and the rubber, the molding composition according to the inven-tion can also contain the cus~omary additives, for example stabilizer~, an~ioxidants, W absorbers, light prot~ction agents, metal deactivators, free radical ~cavengers fillers and reinforcing agents, compatibilizing agents~
plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatics and blowing agents.
The molding composition accoxding to the inYention can be prepared by the methods customary in plastic~ pxocessing for mixing polymers and additives.
One possibility is sintering in a high-speed mixer, if all the constituents of the molding compositlon are pulverulent.
Another possibility is the use of an extruder having mixing and kneading organs on the screw.
Finally, kneader6 such as are employed in the rubber and synthetic rubber industry are also suitable mixing machine~.
The mixing temperature depends on the particular composi-tion of the molding composition and can be determined by simple routine experiments.
~he molding compo~ition according to ~he invention i8 dlstinguished by a hi~h hardness, in combination with high impac~ re~istance, ln particular even a~ temper-atures below 0C. In general, this molding composition ~7l~17 can be used in the form of extruded, in~ection molded, foamed or blown moldings in all instance5 where high rigidity, hardne~s, dimensional stabili~y and scratch resistance in combination with high impact resistance, tear strength and flexural streng~h ar~ desired.
It can be used in automobile construct:ion, for example, for side lining strips, spoilers, seals, fender linings~
bumper materials, ~ruck and tractor fenders, scratch-xesistan~ automobile interior fit~ings or hub caps.
~he molding composition according ~o the ~nvention furthermore is al~o suitable, for ex2mple, for the production of ~ear-resistant films, memhrane filter~, fibers and filaments.
The following examples ars in~ended to illus~ra~e the invention in more detail.
II = iso~acticity index (by l3C-NMR spectroscopy) ni90 = average isotactic chain length (by 13C-NMR) npE = avexag2 polyethylene block l~ngth VN = viscosity number, measured at 135C a~ a 0 . 1 % s t r e n g t h s o l u t i o n i n decahydronaphthalene in a capillary vi~cometer MFI 230/5 = melt index at 230C7 5 kg load, in accordcmce with DIN 53 735 M~/M~ = polydispersity (measure of the chain length distribution) Determination of the melting points by DSC (20C/minute3 BIH = ball indentation hardnes~ (in accordance with DIN 53 456l pre~sed sheets 4 mm thick) 30 aKv = notched impact strength according to D~N
53 453, measured on ~tandard small bars (50 x 6 x 4 mm), taken from pressed sheets, with a V notch (flank angle 45r notch depth 1.3 mm, notch radiu~ 1 mm).
, , 2 ~
A ZSK 28 twin-screw extruder (Werner & Pfl~iderer) was used for the preparakion of the molding compositions.
Example 1 ~ molding composition comprising 90% by weight of iso-tactic polypropylene, ba ed on the total molding composi-tion, and 10% by weight of a rubber having the following composition was prepared by extrusion:
35.8~ by weight of propylene units and 64.2% by weight of ethylene units; 40.4~ by weight of the rubber c~mposition was polyethylene and 59.6% by weight was an ethylene/
propylene copolymer (EPM) CompriSiRg 60 . 0~ by weight of propylene units and 40.0% by weight of ethylene un:its.
The MFI 230/5 of the r~bber was 2 g/10 minutes, the Yiscosi~y number ~VN) was 236 cm3/g, ~he DSC melting point was 131C and ~he DSC glas~ tran ition temperaturQ wa~
-56C. The isotactic polypropylene used h~d an iso~acticity index ~II) of 96.0~, an nl~ of 49, an MFI
230/5 of 32 g/10 minutes and a melting point of 148UC;
further data were: M~ = 190,000 g/mol; M~N~ = 2.~, VN - 174 cm3/g, no AP0 content~ extractable with ether or heptane.
~ kg of the i~otactic pol~propylene powder were mixed with 1 kg of the rubber, and the mixture was stabilized against chemical degradation under extru~ion conditions with 10 g of pentaerythrityl tetrakis~3 (3,5-di-t-butyl-4-hydroxyphenyl)propionate]. The temperatures established in the five heating zones of the extruder were lZ0C
(intake~, 150C, 190C, 185C and 180UC ~die plate). The extruder ~crew was operated at 300 revolution~ per minute; the melt temperature o~ the mixture in the extruder was 210UC.
The following data were measured on the molding composi-tion thus produced:
2~)~7~
g MYI (230/5) = 31 g/10 minutes; V~ = 168 cm3/g;
BIH = 70 Nmm2; a~v = 10.1 mJmm~Z (23C3;
5 4 mJmm~2 (0C) and 4.3 mJmm (-20 C).
Melting point (DSC) = 128 and 148C, glass transition temperature Tg = -56C.
Comparison Example A
Instead of the APO-free (here APP~free; APP - atactic ; polypropylene) isotactic polypropylene of narrQw distri-bution according to the invention, a pol~propylene having the following da~a was employed under the ~ame conditions as in Example ls MFI (230/5) = 27 g/10 minutes; VN = 220 cm3ig;
M~ = 312,000 g/mol, M~/M~ = 8.5; ~PP content by heptane extraction: 2.3% by weight.
The molding composition thus obtain~d had the following data:
NEI (230/5) = 24 g~10 minutes; VN = 245 cm3/~;
BIH ... Nmm2; agV = ... mJmm2.
Melting point IDSC) = 128~164~C, glass transition temperature Tg = -56C.
Examples 2 - 4; Comparison Examples B - D
The procedure was as in Example 1 (Examples 2 4) or as in Comparison Example A (Comparison Examples B - D), but instead of 10% of rubber 15% (Example 2; Compari~on Example B), 25~ ~Example 3, Compari~on Example C) and 40%
(Bx~mple~4, Comparison Example D) of xubber was employed.
The reeults are ~ummarized in Table 1.
2 ~ 1 7 U r~u~ col- t~e~' E~ U` u~ , ~ , ul u~
.~
O O ~D ~r oo ~ r~ o ~ ~ ~D ~ ~D
C~
.,1 Uq ~ ~ ~ ~I ~ N
_~ ~ _~1 ~ 1 ~
S~ O U7 d' l ~D ~ D
_l t` O
U OD O~ ~1 ~ ~ ~1 ~
_- _~
p~ U~
_ cr u~ ~D CO O~ O~ a~
~F3 r-- ~1 ~ ~I M
~ ~ D
~ r ~~ o~ a~ ~o ~ O ~ ~~ ~ ~ ~1 O
P
2 ~ 8 7 ~ 7 ~ 11 Examples 5 - 8 Example~ 1 - 4 were repeated, but a product having the following data was used as the polypropylene according to the invention:
II = 96.1~; ni90 = 53; MFI 230/53 = 4 gtlO minutes;
melting poin~ = 151Ct M~ = 369,500, M~/M~ = 2.0;
VN - 2g3 cm3/g; no APP contents extractable with ether or heptane.
This polypropylene was processed by e~trusion with lO~ by weight (Example 5)~ 15% by weigh~ (Ex~mple 6), ~5~ hy weight (Example 7) and 40% by weight (Example 8) of the rubber to give molding compositions having ~he data summarized in Table 2.
Comparison Examples E - H
The procedure was as in Examples S to 8, but a polyprop-ylene which is not according to the invention and has the following data was ufied:
MFI ~230/5) = 9 g/lO minutes; VN = 302 cm3/g;
M~ = 288,000 g/mol, ~/M~ = 5.7; APP by heptane extrac-tion: 2.7% by weight.
The molding compositions thus obtained, VE (lO~, VF(15~), VG (25%) and VH having a 40% rubber content, had the data summarized in Table 2.
2 ~
O U~U~ ~U~ ~D~D r~u~
~ ,. u~ u~ u~ u~ ul u~ ul In E~ ~ l I l l l l I
c~
O U ~ d ' ~ 1 ~--I N ~ O
~4 U~ ~D U~ U~ ~ U~ U~
_l ~1 _1 ~ ~/ ~;
~ ~) o o~ cr~ co o~ o~ o e~
,1 ~ ~) ~3 N ~ ~ ~3 t~7 t`3 Cl ~I r-l r-~ _I ~ 1 _1 ~1 o U~ ~ C~ ~` C~ 1` ~ ~
U~ ~ U~ ~ ~ O
U u7 c, 1` Ir~ G~ In o~
1~ 0 r~ t~ o co ~r ~ o co ~0 _1 ~ ~P~
r~ ~3 n ~3 ~ Il'~ ~O O~ ~r 1'~) ao ~ ~D ~P CO Ot~
C~ ~ ~ C~l ~- ~ O ~D ~ CO ~ U~
4 f~ ~D ~O ~ U) In~r ~r ~
~ ~ O ~ ~' d' -I ~ n ~ ~ ~ D U~ 1~7 U~ ~D I
? El ~`1 N t'3 ~ t`~ ~ ~ t~l U~ _ ~ .~
H ~ ~ C~ U) U~ ~ a~ ~ ~
_~
~ In ~ ~D ~ I~ ~ CO ~
E~
2~7~
Example 9 Example 3 wa repea~edl but a produc~ having the follow-ing data was used as the polypropylene according to the invention:
II = 96.4%, nl30 = 60; MFI (230/5~ = 100 g/10 minutes;
~elting point = 148C, N~ = 154,500 g/mol, MwJMb = 2.2;
VN = 146 cm3/g; no APP contents extrac~able wi~h ether or heptane.
The following data were mea~ured on the molding composi-tion prepared by extru~ion with the rubber:
MFI ~230/5) - 79 dg/minutes; VN = 170 cm3/g;
BI~ = 72 Nmm~2; aKV = 28.6 (23C~, 17.5 (0C~ and 8.7 mJmm ~-20 C).
Ex~mple 10 Ex~nple 3 was repeated, but an ethylene/propylene copoly-mer having the following compo~ition and properties was used as the polyolefin according to ~he in~ention.
Ethylene content 4.3%, incorporation of ethylene with an average ethylene block length of npE ~ 1 o 2, i.e. the predominant ethylene content is incorporated in isolated units. The II of the propylene ~equences was 96.8~.
MFI (230/5) = 7.0 g/10 minutes; VN 289 cm3/g;
M~ = 402,000 g/mol, M~/M~ = 2Ø
No APP contents axtractable with ether or heptane.
2S The following data were measured on the molding composi tion prepared ~y extrusion with the r~bber:
MFI (230/5) - 3.5 g/10 min, VN = 272 cm3/g;
BIH = 50 Nmm2; aKV = 45.7 (23C), 27.9 (0C) and 18 4 mJ~n~2 t 20C) ~7~'7 - 14 _ Example 11 Example 3 was repeated, but an ethylene/propylene block copolymer which was prepared in two stages and had ~he following composition and properties was used as the polyolefin according to the invention:
12.5~ ethylene content; fractionation of the copolymer showed a composition of 76% of polypropylene having an II
of 96.8% and 24% of an ethylene/propylene copolymer with an ethylene content of 52~, the ethylene being incor-porated both as isolated units and in block form.
MFI (230t5) = 4.9 g/10 minutes; VN = 326 cm3/g;
N~ = 407,000 g/moll N~ = 3.1.
No APP contents extractable with ether or heptane.
The following data were measured on the molding composi-tion prepared by extru~ion with the rubber:
MFI (230~5) = 3.4 g/10 minutes; VN = 298 cm3/g;
BIH = 39 Nmm2; aKV: no fractures of the test specLmen down to -40 C.
HOECHST AKTI~NGESELLSCH~FT HOE 92/F 008 Dr. ~Otb~
Description Impact~resistant polyolefin molding composition The i~vention relates to a polyolefin molding composition S of an i~otactic olefin homopolymer and/or slefin copoly-mer and a rubber, which has a high hardness and a high impact r~si~tance even at low temperatures.
Impact-resistant polyolefin molding compositions are known in principle. They are prepared by mixing, for example, polypropylene and a rubber, such as, for example~ ethylene/propylene rubber (EPM) or eth~lene/
propylene/diene rubber (EPDN), in the malt ~Al~gew.
Makromol. Ch~m. 185/186 (1991) 97; and Polymerd 28 (1987) 47).
According to the prior art, the polypropylene used comprises atactic polypropylene (~PP) to the extent of at least 2 - 10% by weight and polypropylene chains o~
widely varying chain length (N~/M~ = 5 - 10) ~o the extent of g0 - 9~%.
Alternatively, a propylene copolymer which also com-prise~, in addition to APP, pol~propylene chains and polymer chains of the comonomer having the build-up described abov2, propylene copolymer chains of varying copolymer contents and likewise varying chain lengths is al~o used a8 the polypropylene component.
Moreover ~o-called reactor blends are known. ~he~e are composed o~ ~PP, polypropylene and polymers o~ the comonomer of varying chain length, a~ well as ef propylene comonomer chains of varying chain length and comonomar con~ent~. They are prepared directly in the polymerization reactor in one or more polymerixation 2 ~
steps.
All these molding compo~ition~ have ~he co~mon feature that they have only an unsatisfactory rigidity~hardnes~
at the desired high impact resistance.
There was thu~ the object of di6covering a molding compo~ition which does not have the aclver~e properties known from the prior artO
Surprisingly/ it ha~ now been found that if polymer~ and copo~ymers which are free rom atactic polymer chains ~atactic polyolefin; called ~P0) and have a homogeneous mol~cular weight distribution (M~M~ i~ preferably le~s than 5~ are u~ed, the abovementioned disadvantages can be avoided.
The invention thus relates to a polyolefin molding composition essentially comprising 20 to 99~ by weight~
based on the molding composition, of an isotactic poly-olefin which contains no atactic polymer ohains and 1 to 80% by weight, based on the molding composition, of a rubber having a glas~ transition ~emperature below 20C.
The AP0-free i~otactic polyolefin to be used for the preparation of the po1yolefin molding composition accord-ing to the invention is a pol~mer having a narrow molecular weight distribution M~tM~ of ~ 5, preferably < 3.5, and a uniform chain build-up. Uniform chain build-up is understood as meaning a random distribution ofbuilding defect3 andtor comonomer~ in the polymer chain.
AP0-~ree l~otactic polyole~ins are to be understoocl as meaning tho~e polyolefins which es~en~ially comprise no atactic .pol~mer chain~. These are product~ (homo- and copolymers) which are prepared using highly stereo-speci~ic metallocene/aluminoxane cataly~t ~y~tellls.
Correspondin~ proce~ses are known and are de~cribed, for 2O~7 example, in ~P-A 302,424, EP-A 336,1271 EP-A 336,123 and DE-P 40 35 886Ø The isotactic polyolefins prepared by the processes mentioned comprise only very 6mall con tents, if any, of atactic polymer chains. ~s a rule, this conte~t i~ less than 1% by weight.
In principl2, it i5 also possible for polyolefins which have been prepared using con~entional Ziegler catalysts (MgCl2/TiCl4/elec~ron donor/Al~t3~ and c03npri~e noticeable APO content6 to be converted into polyolefins which are AP~-fre~ and ~herefore according to the invention by extraction of the ~P0 contents w.ith a hydrocarbon.
However, because of the associated involved proces~, i.Oe.
for raasons of cost, ~uch a procedure i~ ~ot very appro-pria$e.
The i~otactic polyolefin to be u~ed according to the i~ention either i~ an olefin homopolymer ha~in~ a molecular weight distribution M~/M~ c 5, preferably ~ 3.5, and an isotacticity index (II) of at least S5%, or an olefin copolymer having an M~/M~ of < 5, preferably ~ 3.5, and an isotacticity index of at l~ast 85%, or the poly-olefin i~ composed of an olefin homopolymer and an olefin copolymer in which the isotacticity index is a'c least 85%
and M~/M~ of the components is < 5, preferably < 3.5.
If the olefin polymer is an olefin homopolymer, it comprise6 unit~ of an olefin having at least 3 carbon atoms~ of the formula R~-CH=CH-Rb, in which Ra and * are identical or different and are a hydrogen atom or an alkyl xadical having 1 to 10, preferably 1 to 6 carbon atoms, or Ra and R~l with the carbon atoms ~oining them, ~orm a ring having 4 to 22 carbon atoms. Preferred olefin~ are propylene, l-butene, 4-methyl-1-pentene l-hexene, pentene and norbornene. Propylene i~
particularly preferred, i.e. the moldi.ng composition according to the invention comprise~, in particular, polypropylene.
2~7~ ~
If the olefin pol~mer i5 an olefin copolymer, it com-prises olefin uni~s defined above for the homopolymer and h~ving an isot2cticity index of a~ least 85~ to khe extent of 99.5 to 50, preferably 99 ~o 70% by weight~ and units of ethylene and/or another olefin of the aboYe definition as the comonomer to the extent of at least Q.5 to 50, preferably 1 to 30~ by weigh~. The comon~mer i~
incorporated rand~mly with a high regularity. Pre~erred comonomers are ethylene, 1-bu~ene, 4-methyl-1-pentene, 1-hexene, norbornone or pent~ne. Particularly preferred olefin comonomers comprise propylene unit.~ and ethylene comonomer units.
If the polyolefin comprises a mixture of olefin homopoly mer and olefin copolymer, the olefin homopolymer has the composition described above. The olefin copolymer com-prises an olefin as defined above for ~he olefin homo-polymer to the exten~ of 20 to 90% by weight, preferably 40 to 90~ by weigh~/ and uni~s of ethylene and/or at least one olefin as defined above for an olefin copolymer to the extent of 80 ~o 10% by weigh~, preferably 60 to 10% by weight. The comonomer is pref~rably incorporated randomly. The content of olefin homopolymer in the total polyolefin compo~ition in this case is 20 to 99~ by weight, preferably 40 to 95~ by weight, and the content of olefin copolymer i8 80 to 1~ by wei~ht, preferably 60 to 5~ by weight.
If it comprise~ two different pol~mer components, the polyolefin according to the invention is particularly preferably composed of 40 to 95% by weight of polypropylene (ba~ed on the total amount of polyole~in) ha~ing an i~otactici~y index of at least 85%, and 60 to 5~ by weigh~ (based on the total amount of polyolefin) of olefin copol~mer compri~in~ 40 to 90% by weight o~
propylene units and 60 to 10% by weight of ethylene units (in each ca~e ba~ed on the total amount of olefin aopoly-m~r).
2~7~L~ 7 5 ~
The molding composition according to the invention compri~es the i80tactic olefin polym~r in an amount of 20 to 99~ by weigh~, preferably 40 to 95% by weight.
1 to 80, preferably 5 to 60~ by weight of ~he molding composition according to the invention i~ a rubber having a glass transition te~perature below -20C. Sui~able rubbers are, for example, ~tyrene/butadiena rubbers, silicone rubbexs, ethylene/propylene xubbers (EPM) or ethylene/propylene/diene rubbers (~PDM). ~PM and EPDM
rubbers can additionally also compri~e up to 40% of polyethylene. 1,4-Hexadiene, norbornadiene or cyclopenta-diene can be pre~ent in an amoun~ of up ~o 10% by weight, based on the total amount of rubber, as the diene component.
The content of ethylene and propylene is not limited, as long as a glass transition temperature of the amorphous ~omponents of less than -20C is achie~ed.
A typical composition for commercially available EPM
rubbers i~, ~or example, 10-604 by weight of propylane unit~ and 90-40~ by weight of ethylene units. Of the ethylene units t 0-40~ by weigh* are a pure polyethylene content, and the remainder f~rms a copolymer content, together with the propylene~
EPD.M rubber~ are of corresponding composition, but 1-10%
by weight of a diene of the abovementioned type is al80 additionally incorporated in the copolymer content, in addition to propylene and ethylene. The melt viscosity of typical EPM and EPDM rubbers i6 between 0.5 and 3nO g/10 minuta~ (MFI 230/5).
The Mooney vi~co~ity (m2asured at 121~C, ML) i8 typi.cally between 20 and 80. The ten~ile stre~ at 60~ elongation i5 typically 10 300 p3i ~pounds/~uare inch, 1 p~i =
6B94.8 kg/m.second2 = 1 Pa).
2~7'.;L~7 Rubher~ which can typically be used are on the market, for example/ under the currently existing co~mercial names Vistalon, Ex~elor ~Exxon Chemicals), Dutral (Dutral S.A.), Nordel (DuPont~ ox Buna (Veba).
S In addition to the isotactic olein pol~mer and the rubber, the molding composition according to the inven-tion can also contain the cus~omary additives, for example stabilizer~, an~ioxidants, W absorbers, light prot~ction agents, metal deactivators, free radical ~cavengers fillers and reinforcing agents, compatibilizing agents~
plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatics and blowing agents.
The molding composition accoxding to the inYention can be prepared by the methods customary in plastic~ pxocessing for mixing polymers and additives.
One possibility is sintering in a high-speed mixer, if all the constituents of the molding compositlon are pulverulent.
Another possibility is the use of an extruder having mixing and kneading organs on the screw.
Finally, kneader6 such as are employed in the rubber and synthetic rubber industry are also suitable mixing machine~.
The mixing temperature depends on the particular composi-tion of the molding composition and can be determined by simple routine experiments.
~he molding compo~ition according to ~he invention i8 dlstinguished by a hi~h hardness, in combination with high impac~ re~istance, ln particular even a~ temper-atures below 0C. In general, this molding composition ~7l~17 can be used in the form of extruded, in~ection molded, foamed or blown moldings in all instance5 where high rigidity, hardne~s, dimensional stabili~y and scratch resistance in combination with high impact resistance, tear strength and flexural streng~h ar~ desired.
It can be used in automobile construct:ion, for example, for side lining strips, spoilers, seals, fender linings~
bumper materials, ~ruck and tractor fenders, scratch-xesistan~ automobile interior fit~ings or hub caps.
~he molding composition according ~o the ~nvention furthermore is al~o suitable, for ex2mple, for the production of ~ear-resistant films, memhrane filter~, fibers and filaments.
The following examples ars in~ended to illus~ra~e the invention in more detail.
II = iso~acticity index (by l3C-NMR spectroscopy) ni90 = average isotactic chain length (by 13C-NMR) npE = avexag2 polyethylene block l~ngth VN = viscosity number, measured at 135C a~ a 0 . 1 % s t r e n g t h s o l u t i o n i n decahydronaphthalene in a capillary vi~cometer MFI 230/5 = melt index at 230C7 5 kg load, in accordcmce with DIN 53 735 M~/M~ = polydispersity (measure of the chain length distribution) Determination of the melting points by DSC (20C/minute3 BIH = ball indentation hardnes~ (in accordance with DIN 53 456l pre~sed sheets 4 mm thick) 30 aKv = notched impact strength according to D~N
53 453, measured on ~tandard small bars (50 x 6 x 4 mm), taken from pressed sheets, with a V notch (flank angle 45r notch depth 1.3 mm, notch radiu~ 1 mm).
, , 2 ~
A ZSK 28 twin-screw extruder (Werner & Pfl~iderer) was used for the preparakion of the molding compositions.
Example 1 ~ molding composition comprising 90% by weight of iso-tactic polypropylene, ba ed on the total molding composi-tion, and 10% by weight of a rubber having the following composition was prepared by extrusion:
35.8~ by weight of propylene units and 64.2% by weight of ethylene units; 40.4~ by weight of the rubber c~mposition was polyethylene and 59.6% by weight was an ethylene/
propylene copolymer (EPM) CompriSiRg 60 . 0~ by weight of propylene units and 40.0% by weight of ethylene un:its.
The MFI 230/5 of the r~bber was 2 g/10 minutes, the Yiscosi~y number ~VN) was 236 cm3/g, ~he DSC melting point was 131C and ~he DSC glas~ tran ition temperaturQ wa~
-56C. The isotactic polypropylene used h~d an iso~acticity index ~II) of 96.0~, an nl~ of 49, an MFI
230/5 of 32 g/10 minutes and a melting point of 148UC;
further data were: M~ = 190,000 g/mol; M~N~ = 2.~, VN - 174 cm3/g, no AP0 content~ extractable with ether or heptane.
~ kg of the i~otactic pol~propylene powder were mixed with 1 kg of the rubber, and the mixture was stabilized against chemical degradation under extru~ion conditions with 10 g of pentaerythrityl tetrakis~3 (3,5-di-t-butyl-4-hydroxyphenyl)propionate]. The temperatures established in the five heating zones of the extruder were lZ0C
(intake~, 150C, 190C, 185C and 180UC ~die plate). The extruder ~crew was operated at 300 revolution~ per minute; the melt temperature o~ the mixture in the extruder was 210UC.
The following data were measured on the molding composi-tion thus produced:
2~)~7~
g MYI (230/5) = 31 g/10 minutes; V~ = 168 cm3/g;
BIH = 70 Nmm2; a~v = 10.1 mJmm~Z (23C3;
5 4 mJmm~2 (0C) and 4.3 mJmm (-20 C).
Melting point (DSC) = 128 and 148C, glass transition temperature Tg = -56C.
Comparison Example A
Instead of the APO-free (here APP~free; APP - atactic ; polypropylene) isotactic polypropylene of narrQw distri-bution according to the invention, a pol~propylene having the following da~a was employed under the ~ame conditions as in Example ls MFI (230/5) = 27 g/10 minutes; VN = 220 cm3ig;
M~ = 312,000 g/mol, M~/M~ = 8.5; ~PP content by heptane extraction: 2.3% by weight.
The molding composition thus obtain~d had the following data:
NEI (230/5) = 24 g~10 minutes; VN = 245 cm3/~;
BIH ... Nmm2; agV = ... mJmm2.
Melting point IDSC) = 128~164~C, glass transition temperature Tg = -56C.
Examples 2 - 4; Comparison Examples B - D
The procedure was as in Example 1 (Examples 2 4) or as in Comparison Example A (Comparison Examples B - D), but instead of 10% of rubber 15% (Example 2; Compari~on Example B), 25~ ~Example 3, Compari~on Example C) and 40%
(Bx~mple~4, Comparison Example D) of xubber was employed.
The reeults are ~ummarized in Table 1.
2 ~ 1 7 U r~u~ col- t~e~' E~ U` u~ , ~ , ul u~
.~
O O ~D ~r oo ~ r~ o ~ ~ ~D ~ ~D
C~
.,1 Uq ~ ~ ~ ~I ~ N
_~ ~ _~1 ~ 1 ~
S~ O U7 d' l ~D ~ D
_l t` O
U OD O~ ~1 ~ ~ ~1 ~
_- _~
p~ U~
_ cr u~ ~D CO O~ O~ a~
~F3 r-- ~1 ~ ~I M
~ ~ D
~ r ~~ o~ a~ ~o ~ O ~ ~~ ~ ~ ~1 O
P
2 ~ 8 7 ~ 7 ~ 11 Examples 5 - 8 Example~ 1 - 4 were repeated, but a product having the following data was used as the polypropylene according to the invention:
II = 96.1~; ni90 = 53; MFI 230/53 = 4 gtlO minutes;
melting poin~ = 151Ct M~ = 369,500, M~/M~ = 2.0;
VN - 2g3 cm3/g; no APP contents extractable with ether or heptane.
This polypropylene was processed by e~trusion with lO~ by weight (Example 5)~ 15% by weigh~ (Ex~mple 6), ~5~ hy weight (Example 7) and 40% by weight (Example 8) of the rubber to give molding compositions having ~he data summarized in Table 2.
Comparison Examples E - H
The procedure was as in Examples S to 8, but a polyprop-ylene which is not according to the invention and has the following data was ufied:
MFI ~230/5) = 9 g/lO minutes; VN = 302 cm3/g;
M~ = 288,000 g/mol, ~/M~ = 5.7; APP by heptane extrac-tion: 2.7% by weight.
The molding compositions thus obtained, VE (lO~, VF(15~), VG (25%) and VH having a 40% rubber content, had the data summarized in Table 2.
2 ~
O U~U~ ~U~ ~D~D r~u~
~ ,. u~ u~ u~ u~ ul u~ ul In E~ ~ l I l l l l I
c~
O U ~ d ' ~ 1 ~--I N ~ O
~4 U~ ~D U~ U~ ~ U~ U~
_l ~1 _1 ~ ~/ ~;
~ ~) o o~ cr~ co o~ o~ o e~
,1 ~ ~) ~3 N ~ ~ ~3 t~7 t`3 Cl ~I r-l r-~ _I ~ 1 _1 ~1 o U~ ~ C~ ~` C~ 1` ~ ~
U~ ~ U~ ~ ~ O
U u7 c, 1` Ir~ G~ In o~
1~ 0 r~ t~ o co ~r ~ o co ~0 _1 ~ ~P~
r~ ~3 n ~3 ~ Il'~ ~O O~ ~r 1'~) ao ~ ~D ~P CO Ot~
C~ ~ ~ C~l ~- ~ O ~D ~ CO ~ U~
4 f~ ~D ~O ~ U) In~r ~r ~
~ ~ O ~ ~' d' -I ~ n ~ ~ ~ D U~ 1~7 U~ ~D I
? El ~`1 N t'3 ~ t`~ ~ ~ t~l U~ _ ~ .~
H ~ ~ C~ U) U~ ~ a~ ~ ~
_~
~ In ~ ~D ~ I~ ~ CO ~
E~
2~7~
Example 9 Example 3 wa repea~edl but a produc~ having the follow-ing data was used as the polypropylene according to the invention:
II = 96.4%, nl30 = 60; MFI (230/5~ = 100 g/10 minutes;
~elting point = 148C, N~ = 154,500 g/mol, MwJMb = 2.2;
VN = 146 cm3/g; no APP contents extrac~able wi~h ether or heptane.
The following data were mea~ured on the molding composi-tion prepared by extru~ion with the rubber:
MFI ~230/5) - 79 dg/minutes; VN = 170 cm3/g;
BI~ = 72 Nmm~2; aKV = 28.6 (23C~, 17.5 (0C~ and 8.7 mJmm ~-20 C).
Ex~mple 10 Ex~nple 3 was repeated, but an ethylene/propylene copoly-mer having the following compo~ition and properties was used as the polyolefin according to ~he in~ention.
Ethylene content 4.3%, incorporation of ethylene with an average ethylene block length of npE ~ 1 o 2, i.e. the predominant ethylene content is incorporated in isolated units. The II of the propylene ~equences was 96.8~.
MFI (230/5) = 7.0 g/10 minutes; VN 289 cm3/g;
M~ = 402,000 g/mol, M~/M~ = 2Ø
No APP contents axtractable with ether or heptane.
2S The following data were measured on the molding composi tion prepared ~y extrusion with the r~bber:
MFI (230/5) - 3.5 g/10 min, VN = 272 cm3/g;
BIH = 50 Nmm2; aKV = 45.7 (23C), 27.9 (0C) and 18 4 mJ~n~2 t 20C) ~7~'7 - 14 _ Example 11 Example 3 was repeated, but an ethylene/propylene block copolymer which was prepared in two stages and had ~he following composition and properties was used as the polyolefin according to the invention:
12.5~ ethylene content; fractionation of the copolymer showed a composition of 76% of polypropylene having an II
of 96.8% and 24% of an ethylene/propylene copolymer with an ethylene content of 52~, the ethylene being incor-porated both as isolated units and in block form.
MFI (230t5) = 4.9 g/10 minutes; VN = 326 cm3/g;
N~ = 407,000 g/moll N~ = 3.1.
No APP contents extractable with ether or heptane.
The following data were measured on the molding composi-tion prepared by extru~ion with the rubber:
MFI (230~5) = 3.4 g/10 minutes; VN = 298 cm3/g;
BIH = 39 Nmm2; aKV: no fractures of the test specLmen down to -40 C.
Claims (10)
1. A polyolefin molding composition essentially com-prising 20 to 99% by weighty based on the molding com-position, of an isotactic polyolefin which contains no atactic polymer chains and 1 to 80% by weight, based on the molding composition, of a rubber having a glass transition temperature below -20°C.
2. A molding composition as claimed in claim 1, wherein the isotactic polyolefin is an olefin homopolymer having an isotacticity index of at least 85%.
3. A molding composition as claimed in claim 1 or 2, wherein the isotactic polyolefin is an olefin homopolymer and comprises units of an olefin having at least 3 carbon atoms, of the formula Ra-CH=CH-Rb, in which Ra and Rb are identical or different and are a hydrogen atom or C1-C10-alkyl, or Ra and Rb, with the atoms joining them, form a ring having 4 to 22 carbon atoms.
4. A molding composition as claimed in one or more of claims 1 to 3, wherein the isotactic polyolefin is polypropylene.
5. A molding composition as claimed in claim 1, wherein the isotactic polyolefin is an olefin copolymer which comprises units of an olefin having at least 3 carbon atoms, of the formula Ra-CH=CH-Rb, in which Ra and Rb are identical or different and are a hydrogen atom or C1-C10-alkyl, or Ra and Rb, with the atoms joining them, form a ring having 4 to 22 carbon atoms, and having an isotacticity index of at least 85% to the extent of 99.5 to 50% by weight, and units of ethylene and/or an olefin of the formula Ra-CH=CH-Rb to the extent of 0.5 to 50% by weight.
6. A molding composition as claimed in claim 5, wherein the olefin copolymer is an ethylene/propylene copolymer.
7. A molding composition as claimed in claim 1, wherein the isotactic polyolefin is a mixture of a) 20 to 99% by weight of an olefin homopolymer which comprises units of an olefin having at least 3 carbon atoms, of the formula Ra-CH=CH-Rb, in which Ra and Rb are identical or different and are a hydrogen atom or C1-C10-alkyl, or Ra and Rb, with the atoms joining them, form a ring having 4 to 22 carbon atoms, and having an isotacticity index of at least 85%
and b) 80 to 1% by weight of an olefin copolymer which comprises units of an olefin having at least 3 carbon atoms, of the formula Ra-CH=CH-Rb, in which Ra and Rb are identical or different and are a hydrogen atom or C1-C10-alkyl, or Ra and Rb, with the atoms joining them, form a ring having 4 to 22 carbon atoms, and having an isotacticity index of at least 85% to the extent of 20 to 90% by weight, and units of ethylene and/or another olefin of the formula Ra-CH=CH-Rb to the extent of 80 to 10% by weight.
and b) 80 to 1% by weight of an olefin copolymer which comprises units of an olefin having at least 3 carbon atoms, of the formula Ra-CH=CH-Rb, in which Ra and Rb are identical or different and are a hydrogen atom or C1-C10-alkyl, or Ra and Rb, with the atoms joining them, form a ring having 4 to 22 carbon atoms, and having an isotacticity index of at least 85% to the extent of 20 to 90% by weight, and units of ethylene and/or another olefin of the formula Ra-CH=CH-Rb to the extent of 80 to 10% by weight.
8. A molding composition as claimed in one or more of claims 1 to 7, which additionally comprises stabilizers, antioxidants, UV absorbers, light protection agents, metal deactivators, free radical trapping agents, fillers and reinforcing agents, compatibilizing agents, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatics or blowing agents.
9. The use of a molding composition as claimed in one or more of claims 1 to 8 for the production of moldings.
10. A molding which can be produced from a molding composition as claimed in one or more of claims 1 to 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4201191 | 1992-01-18 | ||
| DEP4201191.4 | 1992-01-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2087417A1 true CA2087417A1 (en) | 1993-07-19 |
Family
ID=6449744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002087417A Abandoned CA2087417A1 (en) | 1992-01-18 | 1993-01-15 | Impact-resistant polyolefin molding composition |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0552681B1 (en) |
| JP (1) | JP3328674B2 (en) |
| KR (1) | KR100269835B1 (en) |
| AT (1) | ATE166909T1 (en) |
| AU (1) | AU669503B2 (en) |
| CA (1) | CA2087417A1 (en) |
| DE (1) | DE59308622D1 (en) |
| ES (1) | ES2116357T3 (en) |
| RU (1) | RU2107701C1 (en) |
| TW (1) | TW259804B (en) |
| ZA (1) | ZA93263B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7538158B2 (en) | 2003-03-06 | 2009-05-26 | Exxonmobil Chemical Patents Inc. | Thermoplastic elastomer composition having viscosity-enhanced and vulcanized elastomer dispersions |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0841370B1 (en) * | 1993-01-11 | 2003-05-02 | Mitsui Chemicals, Inc. | Propylene polymer compositions |
| US5460884A (en) * | 1994-08-25 | 1995-10-24 | Kimberly-Clark Corporation | Soft and strong thermoplastic polymer fibers and nonwoven fabric made therefrom |
| TW575588B (en) * | 1998-03-04 | 2004-02-11 | Carlo Scianna | Omnidirectional lighting device |
| US20020099107A1 (en) * | 2000-10-27 | 2002-07-25 | Tucker John David | Textile fibers made from strengthened polypropylene |
| DE102004036179A1 (en) * | 2004-07-26 | 2006-03-23 | Degussa Ag | Coolant line |
| CN109651708A (en) * | 2019-01-11 | 2019-04-19 | 福建省莆田市力能包装文具有限公司 | A kind of low temperature resistant anticracking material used based on documents pouch |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3700614A (en) * | 1971-05-07 | 1972-10-24 | Dart Ind Inc | High impact polypropylene blends |
| DE2642053C2 (en) * | 1976-09-18 | 1985-04-11 | Bayer Ag, 5090 Leverkusen | Thermoplastic rubber compounds |
| US4395519A (en) * | 1979-04-18 | 1983-07-26 | Mitsui Petrochemical Industries, Ltd. | Physically blended propylene polymer composition |
| JPS5641237A (en) * | 1979-09-10 | 1981-04-17 | Chisso Corp | Polyolefin composition for sheet |
| DE3808268A1 (en) * | 1988-03-12 | 1989-09-21 | Hoechst Ag | METHOD FOR PRODUCING A 1-OLEFIN POLYMER |
| IT1230133B (en) * | 1989-04-28 | 1991-10-14 | Himont Inc | PLASTIC-ELASTIC POLYPROPYLENE COMPOSITIONS |
| DE3942364A1 (en) * | 1989-12-21 | 1991-06-27 | Hoechst Ag | METHOD FOR PRODUCING A POLYPROPYLENE MOLDING MATERIAL |
-
1992
- 1992-12-15 TW TW081110046A patent/TW259804B/zh active
-
1993
- 1993-01-14 JP JP00532093A patent/JP3328674B2/en not_active Expired - Fee Related
- 1993-01-15 ZA ZA93263A patent/ZA93263B/en unknown
- 1993-01-15 EP EP93100566A patent/EP0552681B1/en not_active Expired - Lifetime
- 1993-01-15 AU AU31848/93A patent/AU669503B2/en not_active Ceased
- 1993-01-15 CA CA002087417A patent/CA2087417A1/en not_active Abandoned
- 1993-01-15 RU RU93004451A patent/RU2107701C1/en not_active IP Right Cessation
- 1993-01-15 DE DE59308622T patent/DE59308622D1/en not_active Expired - Lifetime
- 1993-01-15 ES ES93100566T patent/ES2116357T3/en not_active Expired - Lifetime
- 1993-01-15 AT AT93100566T patent/ATE166909T1/en not_active IP Right Cessation
- 1993-01-18 KR KR1019930000546A patent/KR100269835B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7538158B2 (en) | 2003-03-06 | 2009-05-26 | Exxonmobil Chemical Patents Inc. | Thermoplastic elastomer composition having viscosity-enhanced and vulcanized elastomer dispersions |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3328674B2 (en) | 2002-09-30 |
| EP0552681A1 (en) | 1993-07-28 |
| KR100269835B1 (en) | 2001-01-15 |
| RU2107701C1 (en) | 1998-03-27 |
| DE59308622D1 (en) | 1998-07-09 |
| AU3184893A (en) | 1993-07-22 |
| ES2116357T3 (en) | 1998-07-16 |
| EP0552681B1 (en) | 1998-06-03 |
| AU669503B2 (en) | 1996-06-13 |
| ATE166909T1 (en) | 1998-06-15 |
| TW259804B (en) | 1995-10-11 |
| KR930016488A (en) | 1993-08-26 |
| JPH05247277A (en) | 1993-09-24 |
| ZA93263B (en) | 1993-08-17 |
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