CA1134533A - Process for the manufacture of a moldable composition on the basis of polypropylene - Google Patents
Process for the manufacture of a moldable composition on the basis of polypropyleneInfo
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- CA1134533A CA1134533A CA000331350A CA331350A CA1134533A CA 1134533 A CA1134533 A CA 1134533A CA 000331350 A CA000331350 A CA 000331350A CA 331350 A CA331350 A CA 331350A CA 1134533 A CA1134533 A CA 1134533A
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- mfi
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- propylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-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
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
PROCESS FOR THE MANUFACTURE OF A MOLDABLE COMPOSITION ON
THE BASIS OF POLYPROPYLENE
Abstract of the disclosure:
A ternary polypropylene molding composition having an improved impact strength is obtained by first preparing a masterbatch from polyethylene and an ethylene/propylene copolymer (rubber mixture) and then mixing the masterbatch with propylene, whereby the melt indices MFI (230/5) of the rubber mixture and MFI (230/5) of polypropylene are in a relation
THE BASIS OF POLYPROPYLENE
Abstract of the disclosure:
A ternary polypropylene molding composition having an improved impact strength is obtained by first preparing a masterbatch from polyethylene and an ethylene/propylene copolymer (rubber mixture) and then mixing the masterbatch with propylene, whereby the melt indices MFI (230/5) of the rubber mixture and MFI (230/5) of polypropylene are in a relation
Description
~34~i33
- 2 - HOE 78~F 137 This invention relates to a process for the manufac-ture of a thermoplastic~ moldable composition on the basis of polypropylene, a rubber-like materiaI of an ethylene-propylene copolymer and polyethylene.
In addition to some very favorable properties such as, for example, a relatively low density, an outstanding resistance to elevated temperatures and to aqueous and non aqueous liquids, polypropylene exhibits less favorable pro-perties such as unsatisfactory impact strength at tempera-tures below room temperature, especially below 0C. A suf-ficient impact strength is, however, important, especially if the material is used for making crates, suitcases, parts for motor-cars and the like. High density polyethylene from which shaped structures of this type are generally made has a good impact strength, but it is less resistant to high temperatures and its resistance to crack formation is not satisfactory.
It has been proposed to use mixtures of polypropyIene and polyethylene. It has been found, however~ that the im-pact strength of such mixtures is scarcely improved uponthat of polypropylene. Moreover, shaped articles made from mixtures of this type tend to become turbid and mat even if bent to a slight degree only~. -To improve the impact strength of polypropylene at tem-peratures below room temperature amorphous copolymers of ethylene and propylene or other rubber-like polymers, for example polyisobutylene, have been added. The tensile strength and the stiffness of the mixtures of this kind 29 are, however, still insufficient.
. . . . .
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_ 3 _ HOE 78~F 137 It has been proposed to mix polypropylene with poly-ethylene and a rubber-like component (cf. GB-PS 1,154,447, GB-PS 1,065,566 and US-PS 3,256,367). Ternary mixtures of this type have betSer properties than binary mixtures. They can be produced by known methods, for example by simultane-ous kncading of the components in twin-shaft kneaders, rol~
ler mills and extruders. In some cases the so-called master~
batch technlque is used, i.e. the two polymers present in a small proportion in the moldable composition, Shat is po-lyethylene and rubber-like component, are first homogene-ously mixed with each other and the blend is then mixed with the desired amount of propylene (cf. US-PS 3,256,367).
According to another known process a solution of a po-lymer mixture is prepared and then the solvent is removed by rapid evaporation (cf. DE-OS 2,152,7~6). In this pro-cess considerable amounts of solvent are required and,~
therefore, it is unsuitable for industrial application.
The manufacture of impact resistant moldable thermo- ~ -plastic compositions on the basis of propylene by polymeri-zation fails in that very often high proportions of solub-le polymers are formed and thus high amounts of monomers are lost.
A drawback o~ the known processes for the manufacture of ternary, impact resistant and moldable polyproplyene compositions resides in the fact that compositions having an optimum impact strength are obtained incidentally only or with high research expenditure.
It has now been found that ternary moldable polypro-29 pylene compositions having an optimum impact strength can ~:: .
::
In addition to some very favorable properties such as, for example, a relatively low density, an outstanding resistance to elevated temperatures and to aqueous and non aqueous liquids, polypropylene exhibits less favorable pro-perties such as unsatisfactory impact strength at tempera-tures below room temperature, especially below 0C. A suf-ficient impact strength is, however, important, especially if the material is used for making crates, suitcases, parts for motor-cars and the like. High density polyethylene from which shaped structures of this type are generally made has a good impact strength, but it is less resistant to high temperatures and its resistance to crack formation is not satisfactory.
It has been proposed to use mixtures of polypropyIene and polyethylene. It has been found, however~ that the im-pact strength of such mixtures is scarcely improved uponthat of polypropylene. Moreover, shaped articles made from mixtures of this type tend to become turbid and mat even if bent to a slight degree only~. -To improve the impact strength of polypropylene at tem-peratures below room temperature amorphous copolymers of ethylene and propylene or other rubber-like polymers, for example polyisobutylene, have been added. The tensile strength and the stiffness of the mixtures of this kind 29 are, however, still insufficient.
. . . . .
:'. . - ,. : .:
:
` ~3~S3~
_ 3 _ HOE 78~F 137 It has been proposed to mix polypropylene with poly-ethylene and a rubber-like component (cf. GB-PS 1,154,447, GB-PS 1,065,566 and US-PS 3,256,367). Ternary mixtures of this type have betSer properties than binary mixtures. They can be produced by known methods, for example by simultane-ous kncading of the components in twin-shaft kneaders, rol~
ler mills and extruders. In some cases the so-called master~
batch technlque is used, i.e. the two polymers present in a small proportion in the moldable composition, Shat is po-lyethylene and rubber-like component, are first homogene-ously mixed with each other and the blend is then mixed with the desired amount of propylene (cf. US-PS 3,256,367).
According to another known process a solution of a po-lymer mixture is prepared and then the solvent is removed by rapid evaporation (cf. DE-OS 2,152,7~6). In this pro-cess considerable amounts of solvent are required and,~
therefore, it is unsuitable for industrial application.
The manufacture of impact resistant moldable thermo- ~ -plastic compositions on the basis of propylene by polymeri-zation fails in that very often high proportions of solub-le polymers are formed and thus high amounts of monomers are lost.
A drawback o~ the known processes for the manufacture of ternary, impact resistant and moldable polyproplyene compositions resides in the fact that compositions having an optimum impact strength are obtained incidentally only or with high research expenditure.
It has now been found that ternary moldable polypro-29 pylene compositions having an optimum impact strength can ~:: .
::
3~3~
- 4 - HOE 78/F 137 be obtained in simple manner by maintaining in the compo-sition a definite proporti.on of the melt index of polypro-pylene to that of the mixture of polyethylene with the rubber-elastic material.
Therefore, it is the object of the present invention to provide a process for the manufacture of a moldable polypropylene composition comprising 90 to 60 % by weight of polypropylene, 4 to 30 % by weight of polyethylene and ;~
6 to 30 ~ by weight of a rubber~elastic ethylene-propy1ene copolymer by mixing and homogenizing the polyethylene with the ethylene-propylene copolymer to give a rubber mixture, mixing the rubber mixture with the polypropylene~with sub-sequent granulation, which comprises mixing a rubber mix-ture and a polypropylene, the melt indices MFI (230t5) of rubber mixture (RM) to MFI (230/5) of polypropylene (PP) of which are in a relation of MFI ~230/5) - PP
- 2 to 15, preferably 3 to 8.
MFI (230/5) RM
In accordance with the process of the invention first a homogeneous mixture of a polyethylene and a rubber-like material is prepared and the mixture obtained is then mixed with a suitabie polypropylene.
Polyethylenes to be used in the process of the inven~
tion are ethylene homopolymers and copolymers with up to 10 ~ by weight of a 1-olefin having from 3 to 6 carbon atoms~ for example propylene, butene~1, pentene-1 or hexene-1.
The aforesaid polymers have a density of from 0.91 to 3.97 g/cc and a melt index MFI (190/5) of from 0.1 to 20, ; .
', ' ; ' ' :' ~ ' ' ~ ' ' ' , ~3~5~3~
Therefore, it is the object of the present invention to provide a process for the manufacture of a moldable polypropylene composition comprising 90 to 60 % by weight of polypropylene, 4 to 30 % by weight of polyethylene and ;~
6 to 30 ~ by weight of a rubber~elastic ethylene-propy1ene copolymer by mixing and homogenizing the polyethylene with the ethylene-propylene copolymer to give a rubber mixture, mixing the rubber mixture with the polypropylene~with sub-sequent granulation, which comprises mixing a rubber mix-ture and a polypropylene, the melt indices MFI (230t5) of rubber mixture (RM) to MFI (230/5) of polypropylene (PP) of which are in a relation of MFI ~230/5) - PP
- 2 to 15, preferably 3 to 8.
MFI (230/5) RM
In accordance with the process of the invention first a homogeneous mixture of a polyethylene and a rubber-like material is prepared and the mixture obtained is then mixed with a suitabie polypropylene.
Polyethylenes to be used in the process of the inven~
tion are ethylene homopolymers and copolymers with up to 10 ~ by weight of a 1-olefin having from 3 to 6 carbon atoms~ for example propylene, butene~1, pentene-1 or hexene-1.
The aforesaid polymers have a density of from 0.91 to 3.97 g/cc and a melt index MFI (190/5) of from 0.1 to 20, ; .
', ' ; ' ' :' ~ ' ' ~ ' ' ' , ~3~5~3~
5 - HOE 78~F 137 preferably 0.1 to 10 gJ10 min.
The rubber-like material is a statistical copolymer-from 30 to 80 % by ~eight of ethylene and 20 to 70 ~ of propylene, preferably 40 to 65 % by weight of ethylene and 35 to 60 g by weight of propylene. The material may fur-ther contain, incorporated by polymerization, up to 10 %
by weight, calculated on the total amount of the monomers, of at least one other comonomer containing at least two non conjugated C = C-bonds, suoh as ethylene norbornene, dicyclopentadiene and 1,4-hexadiene.
The aforesaid copolymers have a density of from 0.85 to 0.89 g/cc, their MFI (230/5) is in the range of from 0.05 to 10, preferably 0.1 to 6, g/10 min.
The polypropylene polymer to be used in the piocess of the invention is either a homopolymer or a copolymer of propylene with up to 15 % by weight of an 1-olefin having ~rom 2 to 6 carbon atoms, for example ethylene, butene or hexene. - ~
The mixture ol polyethylene and the rubber-like mate-rial can be prepared in any kneader, roll mill and thelike, in which the two components can be finely divided and distributed in each other. Kneaders of this type are 9 for example, so-called internal mixers as used in rubber industries. These machines consist of a heatable housing in which paddles of a speclal design rotate in opposite direction and the feeding hopper is closed by a plunger.
As further example twin shaft kneaders are mentioned which ressemble extruders and likewise consist of a heatable 29 housing in which the paddles rotate in opposite direction, .~
.
-` 3.. ~3~3
The rubber-like material is a statistical copolymer-from 30 to 80 % by ~eight of ethylene and 20 to 70 ~ of propylene, preferably 40 to 65 % by weight of ethylene and 35 to 60 g by weight of propylene. The material may fur-ther contain, incorporated by polymerization, up to 10 %
by weight, calculated on the total amount of the monomers, of at least one other comonomer containing at least two non conjugated C = C-bonds, suoh as ethylene norbornene, dicyclopentadiene and 1,4-hexadiene.
The aforesaid copolymers have a density of from 0.85 to 0.89 g/cc, their MFI (230/5) is in the range of from 0.05 to 10, preferably 0.1 to 6, g/10 min.
The polypropylene polymer to be used in the piocess of the invention is either a homopolymer or a copolymer of propylene with up to 15 % by weight of an 1-olefin having ~rom 2 to 6 carbon atoms, for example ethylene, butene or hexene. - ~
The mixture ol polyethylene and the rubber-like mate-rial can be prepared in any kneader, roll mill and thelike, in which the two components can be finely divided and distributed in each other. Kneaders of this type are 9 for example, so-called internal mixers as used in rubber industries. These machines consist of a heatable housing in which paddles of a speclal design rotate in opposite direction and the feeding hopper is closed by a plunger.
As further example twin shaft kneaders are mentioned which ressemble extruders and likewise consist of a heatable 29 housing in which the paddles rotate in opposite direction, .~
.
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- 6 - HOE j~/F 137 and knead the material while conveying it from the feeding hopper to the delivery point. Other suitable ~ixers are -two roll mills as used in rubber industries and PVC pro cessing in which two heated rolls rotate in opposite direc-tion to each other at different speeds. The charged mate-rial is plasticized in the roller gap and thus homogenized.
Mixing and homogenization is effected at a temperature depending on the machine type used, in general the tempera-ture ranges from 150 to 280C, preferably 170 to 2~0C.
The mixing time also depends on the type of machine used and is in general in the range of from 0.5 to 15 minutes, preferably 1 to 10 minutes.
The mixing ratio of polyethylene to rubber-like com- -ponent is in the range of from 6:1 to 0.3:1, preferably ~ 15 4:1 to 0.5:1 psrts by weight.
; The rubber mixture obtained has a melt lndex MFI
(230/5)-RM in the range of from 0.05 to 10, preferably~0.1 ~ to 6 g~10 mln. Accordingly, the polypropylene lS chosen in - such a manner that the relation of the MFI (230/5~-PP to :~
the MFI (230/5)-RM is as follows:
MFI l230~5) - PP
- = 2 to 15, preferably 3 to 8 MFI ~230/5) - RM
It is likewise possible, of course, to proceed in the opposite order of suceession and to choose a suitable rub-ber mixture for a glven polypropylene. This can be done by a few simple tests to determine the MFI (230~5) of a sui-table rubber mixture.
Polypropylene and rubber mixture are mixed in a ratio of 1.5 - 9:1, preferably 2 - 8:1, with the addition of ~: :
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Mixing and homogenization is effected at a temperature depending on the machine type used, in general the tempera-ture ranges from 150 to 280C, preferably 170 to 2~0C.
The mixing time also depends on the type of machine used and is in general in the range of from 0.5 to 15 minutes, preferably 1 to 10 minutes.
The mixing ratio of polyethylene to rubber-like com- -ponent is in the range of from 6:1 to 0.3:1, preferably ~ 15 4:1 to 0.5:1 psrts by weight.
; The rubber mixture obtained has a melt lndex MFI
(230/5)-RM in the range of from 0.05 to 10, preferably~0.1 ~ to 6 g~10 mln. Accordingly, the polypropylene lS chosen in - such a manner that the relation of the MFI (230/5~-PP to :~
the MFI (230/5)-RM is as follows:
MFI l230~5) - PP
- = 2 to 15, preferably 3 to 8 MFI ~230/5) - RM
It is likewise possible, of course, to proceed in the opposite order of suceession and to choose a suitable rub-ber mixture for a glven polypropylene. This can be done by a few simple tests to determine the MFI (230~5) of a sui-table rubber mixture.
Polypropylene and rubber mixture are mixed in a ratio of 1.5 - 9:1, preferably 2 - 8:1, with the addition of ~: :
.~ i . - . .
. .. ~ ~ -' ~3~3~3
- 7 - HOE 78/F 137 the usual stabilizers9 antioxidants, pigments, fillers, lu-bricants and tha like and the mixture obtained is granulat-ed. For mixing the usual mixers can be used and for granu-lation one of the known granulation extruders is used, most-ly a twin screw extruder with mixing and kneading zones.
The polypropylene composition obtained in this manner consists of from 90 to 60, preferably 80 to 70 ~ by weight of polypropylene, from 4 to 30, preferably 6 to 24, % by weight of polyethylene and 6 to 30, preferably 6 to 24, %
by weight of the rubber-like copolymer from ethylene and propylene which may contain one or several further oomo-nomers. The polymers are defined above.
The polypropylene composition according to the inven~
tion is characterized by a very good impact strength at tem-peratures below room temperature, particularly below 0C.
To test the moldable compositions obtained by the pro-cess of the invention the following methods were used.
MFI (230/5) g/10 min DIN 53 735 20 ball indentation hardness DIN 53 456 30 sec-value N/mm2 test load 132.4 N
and 358.1 N
notched impact strength mJ/mm2 DIN 53 453 KV cm 25 falling test a falIing weight of 1 kg the tip of which has a diameter of 12 mm is al-lowed to fall on the sheet clamped in a frame and the height is measured at which 50 % of the sheets are not broken.
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The polypropylene composition obtained in this manner consists of from 90 to 60, preferably 80 to 70 ~ by weight of polypropylene, from 4 to 30, preferably 6 to 24, % by weight of polyethylene and 6 to 30, preferably 6 to 24, %
by weight of the rubber-like copolymer from ethylene and propylene which may contain one or several further oomo-nomers. The polymers are defined above.
The polypropylene composition according to the inven~
tion is characterized by a very good impact strength at tem-peratures below room temperature, particularly below 0C.
To test the moldable compositions obtained by the pro-cess of the invention the following methods were used.
MFI (230/5) g/10 min DIN 53 735 20 ball indentation hardness DIN 53 456 30 sec-value N/mm2 test load 132.4 N
and 358.1 N
notched impact strength mJ/mm2 DIN 53 453 KV cm 25 falling test a falIing weight of 1 kg the tip of which has a diameter of 12 mm is al-lowed to fall on the sheet clamped in a frame and the height is measured at which 50 % of the sheets are not broken.
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- 8 - HOE 78~F 137 The following examples illustrate the invention.
E X A M P L E 1 and COMPARATIVE EXAMPLE A-In a twin-shaft kneader (twin screw extruder) having a screw diarneter D of 35 mm and a screw length L of 17 D
with mixing zone at the feeding side of` the cylinder, 2 parts of an ethy]ene-propylene copolymer consisting of 44 g by weight of ethylene units and 56 ~ by weight of propylene units and having a RSV value of 3.03 dl/g and a MFI (230/5) of 1.3 g/10 min are mixed at a cylinder tempe~ -10 rature of 230C with 1 part of a polyethylene having a den- ;
sity of 0.974 g/cm3 and a MFI (190/5) of l.6 g~10 min and the extruded mixture is granulated. The rubber mixture I ob-tained has a MFI (230/5) of 2.2 g/10 min.
In the same manner, a rubber mixture II for Compara-tive Rxample A is prepared from 2 parts of an ethylene~pro-pylene copolymer consisting of 41 g by weight of ethylene units and 59 % by weight of propylene units and having~a MFI ~230/5) of 0.45 g/10 min and 1 part of the aforesaid polyethylene. The mixture obtained has a MFI (230~5) of 0.~ g/10 min.
Each time 80 parts of a polypropylene having a density - of o.go6 g/cc and a MFI (230/5) of 8.9 g~10 min are mixed in a twin screw extruder (D = 35 mm, L = 17 D, 23QC, 70 rpm) with 20 parts of rubber mixture I and II, respectively9 and granulated. Test specimens are made from the granules by compression molding and injection molding and the speci-mens are used tQ measure the properties listed in Table 1.
It can be seen that the molding compositions prepared 29 according to the invention (with rubber mixture I) is cha-: . ~
:, - -~ . -.. , . ~.
,, racterized by an impro~ed impact strength at all tempera-tures.
E X A M P L E 2 and COMPARATIVE EXAMPLE B:
~ _ .
The rubber mixtures I and II Or Example 1 are used.
Each time 20 parts thereof are mixed with 80 parts each of polypropy.lene having a density of 0.903 g/oc and a MFI
(230~5) of 2.3 g/10 min and granules are prepared therefrom under the conditions of Example 1. The test specimens;are found to have the values indlcated in Table 2.
;~ 10 In this case, the molding composition containing rub~
ber mixture II compIies with the prerequisites of the in-vention and the mechanical properties thereof are superior to those of the other composition, especially as regards the notched impact strength at temperatures below 0C.
E X A M P L E 3 and COMPARATIVE EXAMPLE C:
In an internal mixer 1 part of a copolymer consîsting Or 41 ~ by weight of ethylene units and 59 ~ by weight~of propylene units having a MFI (230/5) of 0.45 g/10 min;and 1 part of a polyethylene having a density of 0.945 g/cc and a MFI (190/5) of 3 g!10 mîn are mixed for 5 minùtes at 170C. On a heated two roller mill the mixture is transformed into a rough sheet from which square granules are made. The rubber mixture III obtaîned in this manner has a MFI (230/5) of 0.3 g/10 minutes.
80 parts of a polypropylene having a density of 0.903 g/cc and a MFI (230/5) of 2.1 g/10 min are mixed as des-; cribed in Example 1 with 20 parts of rubber mîxture III and the mixture îs granulated. A molding composition a is ob-29 tained having the properties indicated in Table 3.
,~: :
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~l3~i3~3 - 10 _ HOE i3/F 137 When rubber mixture III i~ blen~ed, in the same pro-portion and under identical conditions, with a polypropy-lene having a density of 0.908 g~cc and a MFI (230~5) of ~;
18.7 g/10 min, a molding composition b is obtained which : :
does not comply with the conditions of the invention and the properties of which are less favorable. The measured values are also indicated in Table 3 (Comparative Example ~-C). ~:
E X A M P L E 4: : .
..
Under the conditions of Example 1, a rubber mlxture IV is prepared from 6 parts of a copolymer conslsting of :
44 % by weight of ethylene units and 56 ~ by weight of: :~
propylene units (MFI 230/5 = 1.5 g/10 min) and 4 parts of a polyethylene having a density of 0.947 g/cc and a MFI
(190/5) of 1.6 g/10 min. The MFI (230/5) of the rubber mixture is 2.0 g/10 min.
Under the same conditions a further rubber mixture .
V is prepared from 6 parts of a terpolymer consisting of : ~ 70 ~ by weight of ethylene units, 24.4 ~ by weight of pro-pylene units and 5.6 % by weight of ethylene-norbornene units and having a MFI of 0.1 g/10 min and 4 parts of a polyethylene having a density of 0.948 g/cc and a MFI
(190/5) of 1.5 g/10 min. Hixture V has a MFI ~230/5) of . 0.2 g~10 min).
: 25 Each time 90 parts of a polypropylene having a densi-; -ty of 0.903 g/cc and a MFI (230/5) of g.5 g/lQ min and con-~ taining 6.4 ~ by weight of ethylene units incorporated by .:, . " . .. . .
: polymerization are mixed with 10 parts of rubber mixture - 29 IV or Y, respectively as described in Example 1 and each . ~
~ ~ . . . ' ' ': ,' .~ :
~ HOE 78/F 137 _ _ I molding composition is granulated. The test specimens made therefrom have the values indicated in Table 4.
E X A M P L E 5 with COMPARATIVE EXAMPLE E:
, In the internal mixer as used in Example 3, 8 parts of a polyethylene having a density of 0~951 g/cc and a MFI
(190/5) of 0.15 g/10 min are mixed for 4 minutes at 180C
with 2 parts of a copolymer consisting of 61 ~ by weight of ethylene units and 39 % by weight of propylene units and ~
having a density of 0.86 g/cc and a MFI (230/5) of 0.22 g/
10 min and the mixture obtained is granulated. The rubber mix~ure VI obtained has a MFI (230/5) of 0.52 g/10 min~.
Each time 40 parts of the rubber mixture are mixed~
under the conditions of Example 1 with 60 parts of a poly-propylene having a density of 0.904 g/cc and a MFI (230/5) of 2.7 g/10 min and a polypropylene havln~ a density of 0.907 g/cc and a MFI (230/5) of 17.8 g/10 min, respective-ly, and the molding compositions obtained are granulated.
The test specimens prepared from molding compositions a and b have the values indicated in Table 5.
~ .
~3~ ^3 T2ble 1 Compositon :
with rubber with rubber mixture Imixture II
(= Comparative Example A) MFI (230/5)~RM 2.2 ~,4 :~:
(rubber mixture) g~10 min MFI (230/5)-PP 8.9 8.9 g~10 min MFI-PP
: - 4.0522.3 MFI-RM :
" ~ . . _ . . . _ _ . . _ _ MFI (230/5) of composition 6.6 7.3 g/10 min ball indentation hardness 49.4 l~6.3 N/mm2 notched impact strength mJ/mm ~20C 28.8 21.4 0C 17.9 14.4 -20C 9.3 5.1 . _ . . _ . _ _ _ . .
~: :
:
~:
:~
:: :
~ ' ~:
:
3~3 - 13 - HOE 78~F 737 Table 2 _ Compositon with rubber with rubber mixture I mixture II
(= Comparative Rxample B~
MFI (230~5)-RM 2.2 0.4 ~rubber mixture) g/10 min MFI (230/5)-PP 2.3 2.3 g/10 min MFI-PP 1.04 5.75 MFI-RM
MFI (230/5) of composition 2.6 2.9 g/70 min ball indentation hardness 40.5 43 N/mm notched impact strength mJ/mm ~20C 33 35 O C 17.4 20.7 ~20C ~ 6.4 13.5 -4~C 4.3 ~.8 .
:
.
. ~ . _ . .. _ _ , .. . ... . . . . . . . _ , : `
3~3 _ ~4 HOE 78/F 137 Table 3 Compositon a b ~= Comparative Example C) MFI (230/5)~RM 0.3 0.3 (rubber mixture) g/10 min MFI (230/5)-pp 2.1 1807 g/10 min MFI-PP
. 7.0 62.4 MFI-RM
MFI (230/5) of composition 5,3 17.2 g/10 min ball indentation hardness 45 50.4 Nimm2 . : ' :
notched impact strength mJtmm ~20C 37.7 11.4 ' 0C 23.7- 9.6 :/ plate falling test cm ~30C 100 . 50 ., ~ .
, . ' :, , ~
:
';
`
~, ' ' ' .
.. . .
' ~ , '. :
..
~o3~¢~133 - 15 ~ HOE 78~F 137 Table L~
Compositon with rubber with ru~ber mixture IV mixture V
(= Comparative Example D) _____ MFI t230/5) RM 2.0 0.2 ~rubber mixture) g/10 min MFI (230/5)-PP 9.5 9.5 g~10 min MFI-PP
4.75 47.5 MFI RM
-MFI (230~5) of composition 9.L~ 6.7 g/10 min ball indentation hardness51.2 50 2 :
~: . N/mm : notched impact strength ;~ mJ/mm2 20C ; 34.1 : : ~9.8~ :
0C ~ 16.7 5~.&~
~-20C 10.7 :4.5 -40C : 9.2 3.0:
: :. :
.
~:::: : : : :
, ~: .
.~ . .
Table 5 Compositon a b ~= Comparative Example E) MFI (230/5)-RM 0.52 0.52 (rubber mixture) g/10 min MFI (230/5)-PP 2.7 17.8 g~10 min : .
MFI-PP
5.2 34.3 ::
: . MFI-RM
ball indentation hardness 63.5 61 N/mm . - plate falling test : cm ~ ~ : 0C 135 ~10 30C 110 60 :~:
60C ~ 80 : 15 :: :
:
.
. ..
..
.~ .
- - , - -.
.
- -.
: . . :
E X A M P L E 1 and COMPARATIVE EXAMPLE A-In a twin-shaft kneader (twin screw extruder) having a screw diarneter D of 35 mm and a screw length L of 17 D
with mixing zone at the feeding side of` the cylinder, 2 parts of an ethy]ene-propylene copolymer consisting of 44 g by weight of ethylene units and 56 ~ by weight of propylene units and having a RSV value of 3.03 dl/g and a MFI (230/5) of 1.3 g/10 min are mixed at a cylinder tempe~ -10 rature of 230C with 1 part of a polyethylene having a den- ;
sity of 0.974 g/cm3 and a MFI (190/5) of l.6 g~10 min and the extruded mixture is granulated. The rubber mixture I ob-tained has a MFI (230/5) of 2.2 g/10 min.
In the same manner, a rubber mixture II for Compara-tive Rxample A is prepared from 2 parts of an ethylene~pro-pylene copolymer consisting of 41 g by weight of ethylene units and 59 % by weight of propylene units and having~a MFI ~230/5) of 0.45 g/10 min and 1 part of the aforesaid polyethylene. The mixture obtained has a MFI (230~5) of 0.~ g/10 min.
Each time 80 parts of a polypropylene having a density - of o.go6 g/cc and a MFI (230/5) of 8.9 g~10 min are mixed in a twin screw extruder (D = 35 mm, L = 17 D, 23QC, 70 rpm) with 20 parts of rubber mixture I and II, respectively9 and granulated. Test specimens are made from the granules by compression molding and injection molding and the speci-mens are used tQ measure the properties listed in Table 1.
It can be seen that the molding compositions prepared 29 according to the invention (with rubber mixture I) is cha-: . ~
:, - -~ . -.. , . ~.
,, racterized by an impro~ed impact strength at all tempera-tures.
E X A M P L E 2 and COMPARATIVE EXAMPLE B:
~ _ .
The rubber mixtures I and II Or Example 1 are used.
Each time 20 parts thereof are mixed with 80 parts each of polypropy.lene having a density of 0.903 g/oc and a MFI
(230~5) of 2.3 g/10 min and granules are prepared therefrom under the conditions of Example 1. The test specimens;are found to have the values indlcated in Table 2.
;~ 10 In this case, the molding composition containing rub~
ber mixture II compIies with the prerequisites of the in-vention and the mechanical properties thereof are superior to those of the other composition, especially as regards the notched impact strength at temperatures below 0C.
E X A M P L E 3 and COMPARATIVE EXAMPLE C:
In an internal mixer 1 part of a copolymer consîsting Or 41 ~ by weight of ethylene units and 59 ~ by weight~of propylene units having a MFI (230/5) of 0.45 g/10 min;and 1 part of a polyethylene having a density of 0.945 g/cc and a MFI (190/5) of 3 g!10 mîn are mixed for 5 minùtes at 170C. On a heated two roller mill the mixture is transformed into a rough sheet from which square granules are made. The rubber mixture III obtaîned in this manner has a MFI (230/5) of 0.3 g/10 minutes.
80 parts of a polypropylene having a density of 0.903 g/cc and a MFI (230/5) of 2.1 g/10 min are mixed as des-; cribed in Example 1 with 20 parts of rubber mîxture III and the mixture îs granulated. A molding composition a is ob-29 tained having the properties indicated in Table 3.
,~: :
' ., :
~l3~i3~3 - 10 _ HOE i3/F 137 When rubber mixture III i~ blen~ed, in the same pro-portion and under identical conditions, with a polypropy-lene having a density of 0.908 g~cc and a MFI (230~5) of ~;
18.7 g/10 min, a molding composition b is obtained which : :
does not comply with the conditions of the invention and the properties of which are less favorable. The measured values are also indicated in Table 3 (Comparative Example ~-C). ~:
E X A M P L E 4: : .
..
Under the conditions of Example 1, a rubber mlxture IV is prepared from 6 parts of a copolymer conslsting of :
44 % by weight of ethylene units and 56 ~ by weight of: :~
propylene units (MFI 230/5 = 1.5 g/10 min) and 4 parts of a polyethylene having a density of 0.947 g/cc and a MFI
(190/5) of 1.6 g/10 min. The MFI (230/5) of the rubber mixture is 2.0 g/10 min.
Under the same conditions a further rubber mixture .
V is prepared from 6 parts of a terpolymer consisting of : ~ 70 ~ by weight of ethylene units, 24.4 ~ by weight of pro-pylene units and 5.6 % by weight of ethylene-norbornene units and having a MFI of 0.1 g/10 min and 4 parts of a polyethylene having a density of 0.948 g/cc and a MFI
(190/5) of 1.5 g/10 min. Hixture V has a MFI ~230/5) of . 0.2 g~10 min).
: 25 Each time 90 parts of a polypropylene having a densi-; -ty of 0.903 g/cc and a MFI (230/5) of g.5 g/lQ min and con-~ taining 6.4 ~ by weight of ethylene units incorporated by .:, . " . .. . .
: polymerization are mixed with 10 parts of rubber mixture - 29 IV or Y, respectively as described in Example 1 and each . ~
~ ~ . . . ' ' ': ,' .~ :
~ HOE 78/F 137 _ _ I molding composition is granulated. The test specimens made therefrom have the values indicated in Table 4.
E X A M P L E 5 with COMPARATIVE EXAMPLE E:
, In the internal mixer as used in Example 3, 8 parts of a polyethylene having a density of 0~951 g/cc and a MFI
(190/5) of 0.15 g/10 min are mixed for 4 minutes at 180C
with 2 parts of a copolymer consisting of 61 ~ by weight of ethylene units and 39 % by weight of propylene units and ~
having a density of 0.86 g/cc and a MFI (230/5) of 0.22 g/
10 min and the mixture obtained is granulated. The rubber mix~ure VI obtained has a MFI (230/5) of 0.52 g/10 min~.
Each time 40 parts of the rubber mixture are mixed~
under the conditions of Example 1 with 60 parts of a poly-propylene having a density of 0.904 g/cc and a MFI (230/5) of 2.7 g/10 min and a polypropylene havln~ a density of 0.907 g/cc and a MFI (230/5) of 17.8 g/10 min, respective-ly, and the molding compositions obtained are granulated.
The test specimens prepared from molding compositions a and b have the values indicated in Table 5.
~ .
~3~ ^3 T2ble 1 Compositon :
with rubber with rubber mixture Imixture II
(= Comparative Example A) MFI (230/5)~RM 2.2 ~,4 :~:
(rubber mixture) g~10 min MFI (230/5)-PP 8.9 8.9 g~10 min MFI-PP
: - 4.0522.3 MFI-RM :
" ~ . . _ . . . _ _ . . _ _ MFI (230/5) of composition 6.6 7.3 g/10 min ball indentation hardness 49.4 l~6.3 N/mm2 notched impact strength mJ/mm ~20C 28.8 21.4 0C 17.9 14.4 -20C 9.3 5.1 . _ . . _ . _ _ _ . .
~: :
:
~:
:~
:: :
~ ' ~:
:
3~3 - 13 - HOE 78~F 737 Table 2 _ Compositon with rubber with rubber mixture I mixture II
(= Comparative Rxample B~
MFI (230~5)-RM 2.2 0.4 ~rubber mixture) g/10 min MFI (230/5)-PP 2.3 2.3 g/10 min MFI-PP 1.04 5.75 MFI-RM
MFI (230/5) of composition 2.6 2.9 g/70 min ball indentation hardness 40.5 43 N/mm notched impact strength mJ/mm ~20C 33 35 O C 17.4 20.7 ~20C ~ 6.4 13.5 -4~C 4.3 ~.8 .
:
.
. ~ . _ . .. _ _ , .. . ... . . . . . . . _ , : `
3~3 _ ~4 HOE 78/F 137 Table 3 Compositon a b ~= Comparative Example C) MFI (230/5)~RM 0.3 0.3 (rubber mixture) g/10 min MFI (230/5)-pp 2.1 1807 g/10 min MFI-PP
. 7.0 62.4 MFI-RM
MFI (230/5) of composition 5,3 17.2 g/10 min ball indentation hardness 45 50.4 Nimm2 . : ' :
notched impact strength mJtmm ~20C 37.7 11.4 ' 0C 23.7- 9.6 :/ plate falling test cm ~30C 100 . 50 ., ~ .
, . ' :, , ~
:
';
`
~, ' ' ' .
.. . .
' ~ , '. :
..
~o3~¢~133 - 15 ~ HOE 78~F 137 Table L~
Compositon with rubber with ru~ber mixture IV mixture V
(= Comparative Example D) _____ MFI t230/5) RM 2.0 0.2 ~rubber mixture) g/10 min MFI (230/5)-PP 9.5 9.5 g~10 min MFI-PP
4.75 47.5 MFI RM
-MFI (230~5) of composition 9.L~ 6.7 g/10 min ball indentation hardness51.2 50 2 :
~: . N/mm : notched impact strength ;~ mJ/mm2 20C ; 34.1 : : ~9.8~ :
0C ~ 16.7 5~.&~
~-20C 10.7 :4.5 -40C : 9.2 3.0:
: :. :
.
~:::: : : : :
, ~: .
.~ . .
Table 5 Compositon a b ~= Comparative Example E) MFI (230/5)-RM 0.52 0.52 (rubber mixture) g/10 min MFI (230/5)-PP 2.7 17.8 g~10 min : .
MFI-PP
5.2 34.3 ::
: . MFI-RM
ball indentation hardness 63.5 61 N/mm . - plate falling test : cm ~ ~ : 0C 135 ~10 30C 110 60 :~:
60C ~ 80 : 15 :: :
:
.
. ..
..
.~ .
- - , - -.
.
- -.
: . . :
Claims (6)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a moldable polypropy-lene composition comprising 90 to 60% by weight of a propylene homopolymer or copolymer, 4 to 30% by weight of an ethylene homopolymer or copolymer and 6 to 30% by weight of a rubber-elastic ethylene-propylene copolymer in which the ethylene homo-polymer or copolymer is mixed and homogenized with the ethylene-propylene copolymer to give a rubber mixture, the rubber mixture is mixed with the propylene homopolymer or copolymer with subse-quent granulation, and in which the melt indices MFI (230/5) of the rubber mixture (RM) to MFI (230/5) of the propylene homo-polymer or copolymer (PP) have a relation of MFI (230/5) - PP
= 2 to 15.
MFI (230/5) - RM
= 2 to 15.
MFI (230/5) - RM
2. A process of claim 1 in which the relation MFI (230/5) - PP
is from 3 to 8.
MFI (230/5) - RM
is from 3 to 8.
MFI (230/5) - RM
3. A process as claimed in claim 1 in which the ethylene copolymer is a copolymer of ethylene with up to 10% by weight of a l-olefin having from 3 to 6 carbon atoms.
4. A process as claimed in claim 1, claim 2 or claim 3 in which the ethylene-propylene copolymer is a copolymer of from 30 to 80% of ethylene and 20 to 70% by weight of propylene.
5. A process as claimed in claim 1, claim 2 or claim 3 in which the ethylene-propylene copolymer is a copolymer of from 40 to 65% by weight of ethylene and 35 to 60% by weight of propy-lene.
6. A process as claimed in claim 1, claim 2 or claim 3 in which the propylene copolymer is a copolymer of propylene with up to 15% by weight of a 1-olefin having from 2 to 6 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2828763.0 | 1978-06-30 | ||
| DE19782828763 DE2828763A1 (en) | 1978-06-30 | 1978-06-30 | METHOD FOR PRODUCING A POLYPROPYLENE MOLD |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1134533A true CA1134533A (en) | 1982-10-26 |
Family
ID=6043202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000331350A Expired CA1134533A (en) | 1978-06-30 | 1979-06-29 | Process for the manufacture of a moldable composition on the basis of polypropylene |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0006620B1 (en) |
| JP (1) | JPS557892A (en) |
| AU (1) | AU525407B2 (en) |
| CA (1) | CA1134533A (en) |
| DE (2) | DE2828763A1 (en) |
| NO (1) | NO792197L (en) |
| ZA (1) | ZA793253B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3012804C2 (en) * | 1980-04-02 | 1982-05-27 | Dynamit Nobel Ag, 5210 Troisdorf | Ternary thermoplastic molding composition containing polypropylene copolymers |
| DE3012805C2 (en) * | 1980-04-02 | 1983-04-28 | Dynamit Nobel Ag, 5210 Troisdorf | Ternary injection molding compounds based on ethylene-propylene copolymers or EPDM, polypropylene and polyethylene |
| DE3012763C2 (en) * | 1980-04-02 | 1983-05-19 | Dynamit Nobel Ag, 5210 Troisdorf | Ternary thermoplastic molding composition containing ethylene-propylene copolymer |
| CN107987326B (en) * | 2017-12-18 | 2020-10-02 | 南漳富元鼎航空器材配件有限公司 | Composite rubber of ethylene propylene diene monomer and natural rubber and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3256367A (en) * | 1962-08-14 | 1966-06-14 | Union Carbide Corp | Polypropylene compositions having improved impact strength containing polyethylene and ethylene-propylene copolymer |
| FR1456359A (en) * | 1964-12-28 | 1966-10-21 | Dow Chemical Co | Polypropylene compositions of improved impact resistance and their preparation |
| DE1694037A1 (en) * | 1966-03-16 | 1971-07-15 | Eastman Kodak Co | Polypropylene molding compounds |
| US3627852A (en) * | 1967-02-02 | 1971-12-14 | Asahi Chemical Ind | Impact resistant polymer compositions |
| NL162113C (en) * | 1970-10-23 | 1980-04-15 | Stamicarbon | PROCESS FOR PREPARING POLYPROPENE COMPOSITIONS WITH IMPROVED MECHANICAL PROPERTIES |
| GB1402049A (en) * | 1972-12-22 | 1975-08-06 | Stamicarbon | Polypropylene compositions having mechanical properties |
| DE2417093B2 (en) * | 1974-04-08 | 1979-09-27 | Hoechst Ag, 6000 Frankfurt | Process for the production of polypropylene molding compounds |
-
1978
- 1978-06-30 DE DE19782828763 patent/DE2828763A1/en not_active Withdrawn
-
1979
- 1979-06-28 AU AU48475/79A patent/AU525407B2/en not_active Withdrawn - After Issue
- 1979-06-28 DE DE7979102154T patent/DE2962553D1/en not_active Expired
- 1979-06-28 EP EP79102154A patent/EP0006620B1/en not_active Expired
- 1979-06-29 ZA ZA793253A patent/ZA793253B/en unknown
- 1979-06-29 CA CA000331350A patent/CA1134533A/en not_active Expired
- 1979-06-29 NO NO792197A patent/NO792197L/en unknown
- 1979-06-29 JP JP8155179A patent/JPS557892A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE2962553D1 (en) | 1982-06-03 |
| DE2828763A1 (en) | 1980-01-10 |
| EP0006620A1 (en) | 1980-01-09 |
| ZA793253B (en) | 1980-07-30 |
| JPS557892A (en) | 1980-01-21 |
| EP0006620B1 (en) | 1982-04-21 |
| AU525407B2 (en) | 1982-11-04 |
| NO792197L (en) | 1980-01-03 |
| AU4847579A (en) | 1980-01-03 |
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