CA1336627C - Moulding compound made of elastomeric polyolefin rubbers, polyethylene and/or ethylene copolymers and additives, and elastic sealing strips made therefrom - Google Patents
Moulding compound made of elastomeric polyolefin rubbers, polyethylene and/or ethylene copolymers and additives, and elastic sealing strips made therefromInfo
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- CA1336627C CA1336627C CA000608515A CA608515A CA1336627C CA 1336627 C CA1336627 C CA 1336627C CA 000608515 A CA000608515 A CA 000608515A CA 608515 A CA608515 A CA 608515A CA 1336627 C CA1336627 C CA 1336627C
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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
- C08L23/04—Homopolymers or copolymers of ethene
-
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
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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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
Abstract
A description is given of a moulding compound made of elastomeric polyolefin rubbers, polyethylene and/or ethylene copolymers and additives, the said compound containing, out of 100 parts of polyolefin rubber, 25 to 100 parts by weight of polyethylene and/or ethylene copolymers having an MFI (melt-flow-index) (190/2,16) of less than 0.1 (g/10 min), and between 16 and 28 parts by weight of a mineral oil. Also described is an elastic sealing strip, more particularly a roof-sealing strip, made from the said moulding compound by calendering or extruding.
Description
The invention relates to a moulding compound made of elastomeric polyolefin rubbers, polyethylene and/or ethylene copolymers and additives and to an elastic sealing strip made therefrom.
Strip- and foil-material for providing seals in above-ground, below-groud and engineering work must possess a series of different properties to ensure that structures remain watertight and weatherproof. These properties include high mechanical strength and adequate elongation both at room-temperatures and at temperatures of up to about 80C, long-term stability, the ability to join large areas to each other, resistance to ageing and biological resistance. Sealing strips varying widely in composition, based upon thermoplastic synthetic materials, vulcanizable or vulcanized elastomers, and thermoplastic synthetic materials having elastomeric properties are already known, but although they have advantageous properties, they also have disadvantages (see for example: DE-AS 15 70 352, DE-AS
15 95 442, DE-OS 22 19 147, DE-24 10 572-Al, DE-24 15 850-Al, DE-25 10 162-Al, DE-26 21 825-B2, DE-26 28 741-Al and DE-26 57 272-Al).
Although known thermoplastic sealing strips, based for example upon soft polyvinylchloride, polyisobutylene, acrylic polymers, or thermoplastics modified with bitumen may be simply and effectively applied to seams, they are sensitive to the effects of heat. Attempts are made to counteract these disadvantages by calender-coating or lining fabrics or fleeces made of textile- or glass-fibres, but this has been only partly successful.
Although known sealing strips made of vulcanizable synthetic materials, e.g. based upon chloroprene-rubber, ethylene-propylene-diene-terpolymers, chlorosulphonated polyethylene-rubber, or butyl-rubber meet mechanical-strength-requirements at room-temperature and are weather--1- ~
proof, they have considerable disadvantages in that unvulcanized foils (e.g. EP-OS 0 082 490) do not meet mechanical demands at elevated temperatures and vulcanized sealing strips cannot be welded together, but can be permanently united only with difficulty by means of adhesive, adhesive-tape or the like (see for example DE-OS
25 10 162).
There has recently been a change from the plastic sealing strips described hereinbefore, made of a layer of one material, possibly with a reinforcing insert, to multilayer sealing strips made of vulcanizable materials the outer layers being either unvulcanized or being vulcanized only to the extent that they can be welded by heat, by a solvent, or by a solvent-welding agent, and at least one vulcanized layer being provided, see for example AT-PS 290 612 and DE-OS 26 28 741. The disadvantage, however, is that the process is dependent upon the type and amount of vulcanizing accelerator used and the time required for complete vulcanization.
DE-OS 22 19 147 discloses a sealing strip based upon EPDM. In addition to EDPM it contains polyethylene, polyisobutylene and fillers. At room-temperature, elonga-tion at rupture amounts to between 500 and 600%. At elevated temperature such foils exhibit very low tensile strength and elongation at rupture.
DE-OS 24 10 572 discloses a sealing strip based upon polystyrene-polybutadiene-block copolymers having a maximal elongation at rupture of 210% at 80C. Such foils have unsatisfactory resistance to light and ozone.
Also known from DE-OS 26 21 825 is a sealing foil based upon polystyrene-polybutadiene-block copolymers with additions of chlorosulphonated polyethylene with very high elongation at rupture up to 660% at 80C. However, when fillers are added, this value drops to less than 300%. It may also be gathered from this reference that the addition of polyethylene instead of chlorosulphonated PE produces poor elongation at rupture at ~0C.
DE-OS Z~ 57 272 discloses a thermoplastic compound for sealing foils. For the purpose of achieving satisfactory strength at elevated temperatures, this compound contains, in addition to 100 parts by weight of EPDM, between 50 and 150 parts by weight of a polyethylene 10having an M~I (190/2,16) of between 0.Z and 50 (g/10 min), and between 30 and 50 parts of carbon black and possibly bitumen, mineral oil, chalk and lubricants. These foils exhibit tensile strengths of up to 4.7 (N/mm2) and elongations at rupture of up to 420~ at 70C.
15These mechanical values are inadequate for many practical applications. For instance, strips according to DE-OS 26 57 272 achieve elongations at rupture in excess o~
300% only if they contain large amoun-ts of polyethylene.
Sealing strips made of moulding compounds containing large amounts of PE are so stiff that they cannot be used for roof-sealing.
It is the purpose of the present invention to make available a moulding compound suitable for producing extruded or calendered strips with improved elongation at rupture at 80C. The said strips are to have satisfactory tensile strength at 80C, preferably greater than 0. 7 (N/mm ), an elongation of rupture in excess of 600% at 80C, and as little stiffness as possible.
The invention accomplishes this purpose by means of a moulding compound (i.e. composition) containing per 100 parts by weight of polyolefin rubber:
- 25 to 150 parts by weight of polyethylene and/or ethylene copolymers having an MFI (190/2,16) of less than o.1 (g/10 min) according to DIN 53 735;
35- between 16 to 28 parts by weight of a mineral oil.
` ` 1 336627 The moulding compound may contain additional components, more particularly inorganic fillers, carbon blacks,lubricants and/or stabilizers.
In this connection, it is essential to the invention to use, on the one hand, a special polyethylene having a very low MFI (190/2,16) of less than 0.1 (g/10 min), more particularly an MFI ( 190/5) of less than 0.1 (g/10 min), and preferably an MFI (190/21,6) of less than 5 (g/10 min) according to DIN 53 735 and, on the other hand, between 16 and 28 parts by weight of a mineral oil per 100 parts by weight of polyolefin rubber.
It was found, surprisingly enough that the PE
types selected according to the invention develop their advantageous properties - improved elongation at rupture at 80C - to an adequate degree, only in the presence of specific amounts of a mineral oil.
It is preferable to use between 25 and 50 parts by weight of polyethylene per 100 parts by weight of polyolefin rubber. With less than 25 parts by weight of polyethylene per 100 parts by weight of polyolefin rubber, tensile strength and elongation at rupture at 80C are too low, whereas with more than 50 parts by weight of polyethylene per 100 parts by weight of polyolefin rubber, the resulting strip is too stiff for many applications, e.g. roof-sealing.
Regardless of this, however, it is possible to add to the amount of polyethylene according to the invention further amounts of polyethylene having a higher MFI, without impairing the favourable elongation at rupture at 80 C.
The use of elastomeric vulcanizable, but unvul-canized, polyolefin rubbers imparts to the sealing strip according to the invention advantageous properties such as heat-welding and resistance to weathering and ageing.
Because of their great strength and elongation at rupture, they require no reinforcing layers. Since no vulcanizing ; ,i accelerators are used, there are also no storage problems, such as undesirable slow curing. Furthermore, any necessary repairs to a mechanically damaged location can be effected by welding-on a fresh strip with hot gas.
In order to obtain roof-sealing strip having a predominantly resilient feel, i.e. little stiffness, the compound should preferably contain between 25 and 50 parts by weight of the selected type of polyethylene per 100 parts by weight of polyolefin rubber. If increased stiffness causes no problems during processing, e.g. in the case of garbage-dumps or tank-installations, the compound may contain larger amounts of polyethylene, since this still provides very high tensile strength and elongation at rupture at 80C.
In order to obtain sealing strip with high mechanical properties, especially resistance to cold, resistance to perforation even at high temperatures, low shrinkage, high tensile strength, elongation and dimensional stability, the elastomeric synthetic materials used are partly crystalline ethylene-propylene terpolymers or partly crystalline ethylene-propylene copolymers, or mixtures thereof.
Within the meaning of the present invention, polyolefin rubbers, upon which the thermoplastic compounds according to the invention are based, are to be understood tom~n pol~ which ~n benade from ethylene, a~v~La~ly one or more ~C-olefins having 3 to 8 C-atoms, preferably propylene, and possibly one or more multiple olefins, with the aid of so-called Ziegler-Natta catalaysts which may also contain activators and modifiers, in solution or dispersion, at temperatures of between -30 and +100C, e.g. by the method according to DE-AS 15 70 352, DE-AS 15 95 442, DE-AS 17 20 450 or DE-OS 24 27 343.
t 336627 These include saturated polyolefin rubbers which consist of 15 to 90~ by weight, preferably 30 to 75~ by weight of ethylene and of 85 to 10% by weight, preferably 70 to 25~ by weight of propylene and/or butene-(l), and unsaturated polyolefin rubbers which, in addition to ethylene and propylene or butene-(l), consist of a multiple olefin, the amount thereof being such that the rubbers contain between 0.5 and 30 double bonds / 1.000 C-atoms.
Especially preferred multiple olefins are cis- and trans-hexadiene-(1.4), dicyclopentadiene, 5-methylene-, 5-ethylidene- and 5-isopropylene-2-norbornenes.
It is preferable to use an EPM having an ethylene content in excess of 65~ by weight and a propylene content of less than 35% by weight, or an EPDM having an ethylene content in excess of 65~ by weight and a propylene content of less than 30~ by weight, and a maximum of 8~ by weight of diene components, preferably less than 5~ by weight of diene components. The diene components may be ethylidene-norbornenes, for example. The degree of partial crystal-linity of the EPDM- and/or EPM-types used is determined according to the DSC method in the differential-scan calorimeter measured melt-curve. The maximum of the melt-peak, measured as the temperature TS in C according to the DSC curve, is known as the endothermal peak which may be very narrow or may also include a larger area. In the case of ethylene-propylene-terpolymers, the temperature TS is in the vicinity of 50C. The amount of heat required for melting, known as H50, also measured according to the DSC
heat, provides information as to the presence of crystalline blocks in the ethylene-propylene-terpolymer or the ethylene-propylene-copolymer. Such partlycrystalline EPDM- or EPM-types, having a melting heat of at least 10 (J/g), are preferred according to the invention.
Advantageously, when the polyethylene and/or ethylene copolymers used are contained in amounts between 25 and 50 parts by weight, the tensile strength at 80C may be greater tha 0.8 (N/mm2), preferably greater than 1.0 (N/mm ), according to DIN 53 455.
Advantageously, the rubber may comprise a partly crystalline sequential rubber and comprise at least a polymer bulk-strength of 5 (N/mm2).
In choosing suitable elastomeric synthetic materials, especially of the EPDM- and EPM-types, the strength thereof is of importance. According to the invention, they should have a tensile strength, measured according to DIN 53 455, of at least 5 (N/mm ).
Suitable polyolefins, to be added to the compounds according to the invention, are, in the first place, crystalline and partly crystalline modifications of polyethylene having densities of 0.905 to 0.975 (g/cm3) and an MFI (190/2,16) of less than 0.1 (g/10 min). However, it is also possible to use partly crystalline copolymers of ethylene with other ~-olefins within the limits of this specification, which contain 0.5 to 30~ by weight of comonomers.
Suitable mineral oils are those having kinematic viscosities of between 50 x 10 6 (m2/s) (50 cSt) and 5 x 10 3 (m2/s) (5.000 cSt) at 20C, preferably 200 x 10 6 (m2/s) (200 cSt) and 3 x 10 3 (m2/s) (3.000 cSt) at 20C and a density of 0.84 to 0.98 (g/cm3). The oils may contain both paraffinic, naphthenic or aromatic bound carbon atoms.
Advantageously, the moulding composition according to the invention may further comprise inorganic fillers, carbon blacks, lubricants and/or stabilizers.
Preferably, said composition may comprise, per 100 parts by weight of polyolefin rubber:
~,~
- between 20 and 80 parts by weight of an inorganic filler;
- between 10 and 50 parts by weight of carbon black;
- between 0.5 and 5 parts by weight of lubricants and/or stabilizers.
The choice of suitable fillers is of critical importance for plastic layers and additives which co-operate synergistically and improve the properties of the sealing strip, especially the mechanical properties. An essential component in this connection is semi-active or active carbon black, so-called reinforcing carbon black, the layers containing between 10 and 50 parts by weight, preferably between 20 and 45 parts by weight of carbon black per 100 parts by weight of polyolefin rubber. It is possible to use carbon blacks made by the furnace-method which have an average particle-size of between 30 and 60 (~m) and a BET
surface of between 30 and 60 (m /g).
As a reinforcing filler and, at the same time, in order to cheapen the product, it is preferable to use ZS
- 7a -.
, ,~
silica, e.g. a mixture of silicic-acid anhydride and kaolinite, the grain sizes being less than 20 (~um) and the grain-size of at least 40~ of the mixture being less than 2 ( ~m)- However, it is also possible to replace up to 2/3 of the silica with other equally finely granular fillers such as chalk, kaolin, talcum, baryte, glass-fibres or mixtures thereof.
The layers of sealing strip also contain stabilizers and anti-ageing agents, based more particularly upon sterically hindered phenolic antioxidants, phenolic phosphites, thioesters of aliphatic carboxylic acids and the like. The following may be used as processing lubricants:
metal soaps, for example calcium soaps, calcium-stearate, zinc-stearate. Montanic-acid esters and/or hydrogenated hydrocarbons may be used as aids to processing.
The properties of the sealing strip according to the invention are adapted to the demands of the construction industry. In addition to being serviceable at room-temperature, it is also serviceable at temperatures down to -60C and up to about +80C. It is also weatherproof and biologically resistant. In addition to this, the strip is easy to process and watertight seams can be produced by hot-air welding which is simple and in common use in construction work.
The moulding compounds are mixed either continuously in a screw-mixer or intermittently in a closed kneading machine, e.g. a stamping kneader. With temperatures in the mixer between 130 and 200C, the mixture is caused to melt. The compound leaves the mixer as a pasty, plasticized, still not fully homogenized mass which is then passed to a roughing mill for further mixing and processing at temperatures of between 170 and 185C. The compound may then be passed to a strainer where it is finally homogenized and filtered. Upon leaving the strainer, the temperature of the compound is about 200C and may now be fed to an L- or F-type calender.
When fed to the roll-gap of the calender, the temperature of the compound is between 185 and 190C, while the temperature upon leaving the final calender-roll is still 180 C. This procedure has the advantage of producing a homogeneous, bubble-free product and is specially adapted to the mixtures and moulding compounds used to produce sealing strip. It is possible to obtain take-off speeds, i.e. calender-output speeds, of between 10 and 20 (m/min) with the materials used and the foil-thicknesses selected.
However, the mass prepared for calendering may also be converted into granules. It may then be extruded or injection-moulded to form sealing strips or parts.
The following examples according to the invention, and comparison-examples, are intended to explain the present invention.
Reference is also made to Fig. 1 which shows, as example without limitative manner, a diagram of the elongation at rupture of the compound.
EXAMPLES 1 to 7 The following mixture is charged at 60C into a Werner & Pfleiderer stamping-kneader and is kneaded to a mass-temperature of 185C:
100.0 parts by weigth of ethylene-propylene-diene rubber (EPDM 1) 30.0 parts by weight of polyethylene 22.0 parts by weight of extender oil H 90 45.0 parts by weight of Sillitin*Z 82 siliceous chalk 38.0 parts by weight of Corax*N 550 FEF carbon black 1.8 parts by weight of lubricants and stabilizers.
* Sillitin and Corax are trade marks.
The EPDM used is a rubber consisting of 66~ by weight of ethylene, 27% by weight of propylene and 7~ by weight of ethylene-norbornenes with a polymer bulk-strength of 12 (N/mm ) and a melting heat of 26 (J/g).
The MFI (190/2,16) of the polyethylene types used were varied between about 0.05 and 8 (g/10 min) as follows:
EXAMPLE 1: MFI (190/2,16) = 0,05 ~g/10 min], EXAMPLE 2: MFI (190/2,16) = 0,1 ~g/10 min], EXAMPLE 3: MFI (190/2,16) = 0,5 Cg/lO min~, EXAMPLE 4: MFI (190/2,16) = 1 ~/10 min], EXAMPLE 5: MFI (190/2,16) = 2 ~g/10 min~, EXAMPLE 6: MFI (190/2,16) = 5 Cg/10 min~
EXAMPLE 7: MFI (190/2,16) = 8 Cg/10 min~, In Fig. 1, the elongation at rupture at 23 C
(RD 23), and the elongation at rupture at 80 C (RD 80), as measured according to DIN 53 455, are shown in relation to the MFI of examples 1 to 7. The figure shows that the elongation at rupture increases at 23C and slightly at a lower melting index, whereas the elongation at rupture at 80 C assumes adequate values from an MFI of 0.1 (g/10 min).
This extreme dependency of the elongation at rupture at 80 C
upon the MFI was totally unexpected.
EXAMPLES 8 to 11 The following mixture is charged, at 60C, into a Werner & Pfleiderer type stamping-kneader and is kneaded to a mass-temperature of 185C.: 0 100.0 parts by weight of ethylene-propylene-diene rubber (EPDM 1) 27.0 parts by weight of polyethylene 22.0 parts by weight of extender oil H 90 45.0 parts by weight of Sillitin Z 82 siliceous chalk 1~
~ - I 336627 38.0 parts by weight of Corax N 550 FEF carbon black 1.8 parts by weight of lubricants and stabilizers.
The EPDM 1 used is a rubber consisting of 669d by weight of ethylene, 2796 by weight of propylene and 7% by 5 weight of ethylidene norbornenes with a polymer bulk-strength of 12 (N/mm ) and a melting heat of 26 (J/g).
The polyethylenes used in Examples 8 to 11 are described in Table 1 below by their MFI (190/2 ,16), their density and their polymerization-type. In this Table:
LD: signifies low-density polyethylene LLD: signifies linear low-density polyethylene HD: signifies high-density polyethylene.
The materials kneaded in the manner described hereinbefore are fed to a 190C roughing mill, then to a calender having a roll-temperature of between 180 and Z00C
and are calendered into a 1 mm thick foil. Also shown in Table 1 are the following values for these foils: tensile strength at 23C (RF 23), tensile strength at 80C (RF 80), elongation at rupture at 23C (RD 23), and elongation at 20 rupture at 80 C (RD 80).
EXAMPLES 12 to 15 Examples 12 to 15 are comparison-examples taken from DE-OS 26 57 272 (examples 1, 2, 4 and 5). In contrast 25 to Examples 8 to 11, tensile strength and elongation at rupture are measured, not at 80C, but at 70C. The values in Table 1 are therefore shown in brackets. Compositions are also shown in Table 1.
30 EXAMPLES 16 to 18 The amounts and qualities shown in Table 1 are prepared according to Example 8 and are made into foils by calendering. Strength and elongation values are shown in Table 1.
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As may be ganhered from the examples in Table 1, the tensile strengths in comparison examples 9 to 18 at 23C
have very high values in spite of differences in composi-tion. At elevated temperatures of 80 and 70C, however, elongation at rupture values decline drastically, down to Example 8 in which a PE having a very high molecular weight = a low MFI is used. It is therefore impossible to draw conclusions from elongation values at 23C as to the behaviour of the materials at elevated temperatures, for example at 80C. It was all the more surprising that the improvements in properties shown could be achieved by the special polyethylene type according to the invention.
EXAMPLES 19 to 33 The qualities and types listed in Table 2 below are as described in Example 8, but with an ethylene-propylene-diene rubber (EPDM 2) containing 67% by weight of ethylene, 30% by weight of propylene and 3% by weight of ethylidene norbornenes, with a polymer bulk-strength of 13.5 (N/mm ) and a melting heat of 30 (J/g), processed into foils and measured.
In the case of comparison-examples 20, 21, 22, 24 and 25, the MFI values of which for the polyethylene lie outside the invention, values for elongation at rupture at 80 C were low. Higher values were obtained only in Example 23, in which the MFI value of the polyethylene used is within the limits of the invention, but without reaching the preferred range in excess of 600%.
Examples 30, 32 and 33 show that satisfactory elongation at rupture at 80C cannot be obtained with too little mineral oil, nor by increasing the proportion of the polyethylene type according to the invention.
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I~ r~ r~ r~ ~ I~ ~ o U~ o o U~ r~ r~ o . a~ o ~ 0 ~ o ~, A mixture consisting of:
100.0 parts by weight of ethylene-propylene diene rubber (EPDM 2) 25.0 parts by weight of polyethylene MFI (190/5) < 0.1 (g/10 min) 25.0 parts by weight of polyethylene MFI (190/2,16) of 1 (g/10 min) 22 . 0 parts by weight of extender oil H 90 45 . 0 parts by weight of Sillitin Z 82 siliceous chalk 38.0 parts by weight of Corax N 550 FEF carbon black 1.8 parts by weight of lubricants and stabilizers 15 is prepared as described in Example 8 and is made into 1 mm foil by calendering. The measured properties were:
RF 23C : 19. 5 N/mm RD 23C : 1060%
RF 80C : 1.2 N/mm RD 80 C : 800~
As shown by the measurement obtained, additional amounts of polyethylene with a higher MFI can be added to the amounts of polyethylene according to the invention without impairing the required high elongation at rupture at 80C. (see Fig. 1 )
Strip- and foil-material for providing seals in above-ground, below-groud and engineering work must possess a series of different properties to ensure that structures remain watertight and weatherproof. These properties include high mechanical strength and adequate elongation both at room-temperatures and at temperatures of up to about 80C, long-term stability, the ability to join large areas to each other, resistance to ageing and biological resistance. Sealing strips varying widely in composition, based upon thermoplastic synthetic materials, vulcanizable or vulcanized elastomers, and thermoplastic synthetic materials having elastomeric properties are already known, but although they have advantageous properties, they also have disadvantages (see for example: DE-AS 15 70 352, DE-AS
15 95 442, DE-OS 22 19 147, DE-24 10 572-Al, DE-24 15 850-Al, DE-25 10 162-Al, DE-26 21 825-B2, DE-26 28 741-Al and DE-26 57 272-Al).
Although known thermoplastic sealing strips, based for example upon soft polyvinylchloride, polyisobutylene, acrylic polymers, or thermoplastics modified with bitumen may be simply and effectively applied to seams, they are sensitive to the effects of heat. Attempts are made to counteract these disadvantages by calender-coating or lining fabrics or fleeces made of textile- or glass-fibres, but this has been only partly successful.
Although known sealing strips made of vulcanizable synthetic materials, e.g. based upon chloroprene-rubber, ethylene-propylene-diene-terpolymers, chlorosulphonated polyethylene-rubber, or butyl-rubber meet mechanical-strength-requirements at room-temperature and are weather--1- ~
proof, they have considerable disadvantages in that unvulcanized foils (e.g. EP-OS 0 082 490) do not meet mechanical demands at elevated temperatures and vulcanized sealing strips cannot be welded together, but can be permanently united only with difficulty by means of adhesive, adhesive-tape or the like (see for example DE-OS
25 10 162).
There has recently been a change from the plastic sealing strips described hereinbefore, made of a layer of one material, possibly with a reinforcing insert, to multilayer sealing strips made of vulcanizable materials the outer layers being either unvulcanized or being vulcanized only to the extent that they can be welded by heat, by a solvent, or by a solvent-welding agent, and at least one vulcanized layer being provided, see for example AT-PS 290 612 and DE-OS 26 28 741. The disadvantage, however, is that the process is dependent upon the type and amount of vulcanizing accelerator used and the time required for complete vulcanization.
DE-OS 22 19 147 discloses a sealing strip based upon EPDM. In addition to EDPM it contains polyethylene, polyisobutylene and fillers. At room-temperature, elonga-tion at rupture amounts to between 500 and 600%. At elevated temperature such foils exhibit very low tensile strength and elongation at rupture.
DE-OS 24 10 572 discloses a sealing strip based upon polystyrene-polybutadiene-block copolymers having a maximal elongation at rupture of 210% at 80C. Such foils have unsatisfactory resistance to light and ozone.
Also known from DE-OS 26 21 825 is a sealing foil based upon polystyrene-polybutadiene-block copolymers with additions of chlorosulphonated polyethylene with very high elongation at rupture up to 660% at 80C. However, when fillers are added, this value drops to less than 300%. It may also be gathered from this reference that the addition of polyethylene instead of chlorosulphonated PE produces poor elongation at rupture at ~0C.
DE-OS Z~ 57 272 discloses a thermoplastic compound for sealing foils. For the purpose of achieving satisfactory strength at elevated temperatures, this compound contains, in addition to 100 parts by weight of EPDM, between 50 and 150 parts by weight of a polyethylene 10having an M~I (190/2,16) of between 0.Z and 50 (g/10 min), and between 30 and 50 parts of carbon black and possibly bitumen, mineral oil, chalk and lubricants. These foils exhibit tensile strengths of up to 4.7 (N/mm2) and elongations at rupture of up to 420~ at 70C.
15These mechanical values are inadequate for many practical applications. For instance, strips according to DE-OS 26 57 272 achieve elongations at rupture in excess o~
300% only if they contain large amoun-ts of polyethylene.
Sealing strips made of moulding compounds containing large amounts of PE are so stiff that they cannot be used for roof-sealing.
It is the purpose of the present invention to make available a moulding compound suitable for producing extruded or calendered strips with improved elongation at rupture at 80C. The said strips are to have satisfactory tensile strength at 80C, preferably greater than 0. 7 (N/mm ), an elongation of rupture in excess of 600% at 80C, and as little stiffness as possible.
The invention accomplishes this purpose by means of a moulding compound (i.e. composition) containing per 100 parts by weight of polyolefin rubber:
- 25 to 150 parts by weight of polyethylene and/or ethylene copolymers having an MFI (190/2,16) of less than o.1 (g/10 min) according to DIN 53 735;
35- between 16 to 28 parts by weight of a mineral oil.
` ` 1 336627 The moulding compound may contain additional components, more particularly inorganic fillers, carbon blacks,lubricants and/or stabilizers.
In this connection, it is essential to the invention to use, on the one hand, a special polyethylene having a very low MFI (190/2,16) of less than 0.1 (g/10 min), more particularly an MFI ( 190/5) of less than 0.1 (g/10 min), and preferably an MFI (190/21,6) of less than 5 (g/10 min) according to DIN 53 735 and, on the other hand, between 16 and 28 parts by weight of a mineral oil per 100 parts by weight of polyolefin rubber.
It was found, surprisingly enough that the PE
types selected according to the invention develop their advantageous properties - improved elongation at rupture at 80C - to an adequate degree, only in the presence of specific amounts of a mineral oil.
It is preferable to use between 25 and 50 parts by weight of polyethylene per 100 parts by weight of polyolefin rubber. With less than 25 parts by weight of polyethylene per 100 parts by weight of polyolefin rubber, tensile strength and elongation at rupture at 80C are too low, whereas with more than 50 parts by weight of polyethylene per 100 parts by weight of polyolefin rubber, the resulting strip is too stiff for many applications, e.g. roof-sealing.
Regardless of this, however, it is possible to add to the amount of polyethylene according to the invention further amounts of polyethylene having a higher MFI, without impairing the favourable elongation at rupture at 80 C.
The use of elastomeric vulcanizable, but unvul-canized, polyolefin rubbers imparts to the sealing strip according to the invention advantageous properties such as heat-welding and resistance to weathering and ageing.
Because of their great strength and elongation at rupture, they require no reinforcing layers. Since no vulcanizing ; ,i accelerators are used, there are also no storage problems, such as undesirable slow curing. Furthermore, any necessary repairs to a mechanically damaged location can be effected by welding-on a fresh strip with hot gas.
In order to obtain roof-sealing strip having a predominantly resilient feel, i.e. little stiffness, the compound should preferably contain between 25 and 50 parts by weight of the selected type of polyethylene per 100 parts by weight of polyolefin rubber. If increased stiffness causes no problems during processing, e.g. in the case of garbage-dumps or tank-installations, the compound may contain larger amounts of polyethylene, since this still provides very high tensile strength and elongation at rupture at 80C.
In order to obtain sealing strip with high mechanical properties, especially resistance to cold, resistance to perforation even at high temperatures, low shrinkage, high tensile strength, elongation and dimensional stability, the elastomeric synthetic materials used are partly crystalline ethylene-propylene terpolymers or partly crystalline ethylene-propylene copolymers, or mixtures thereof.
Within the meaning of the present invention, polyolefin rubbers, upon which the thermoplastic compounds according to the invention are based, are to be understood tom~n pol~ which ~n benade from ethylene, a~v~La~ly one or more ~C-olefins having 3 to 8 C-atoms, preferably propylene, and possibly one or more multiple olefins, with the aid of so-called Ziegler-Natta catalaysts which may also contain activators and modifiers, in solution or dispersion, at temperatures of between -30 and +100C, e.g. by the method according to DE-AS 15 70 352, DE-AS 15 95 442, DE-AS 17 20 450 or DE-OS 24 27 343.
t 336627 These include saturated polyolefin rubbers which consist of 15 to 90~ by weight, preferably 30 to 75~ by weight of ethylene and of 85 to 10% by weight, preferably 70 to 25~ by weight of propylene and/or butene-(l), and unsaturated polyolefin rubbers which, in addition to ethylene and propylene or butene-(l), consist of a multiple olefin, the amount thereof being such that the rubbers contain between 0.5 and 30 double bonds / 1.000 C-atoms.
Especially preferred multiple olefins are cis- and trans-hexadiene-(1.4), dicyclopentadiene, 5-methylene-, 5-ethylidene- and 5-isopropylene-2-norbornenes.
It is preferable to use an EPM having an ethylene content in excess of 65~ by weight and a propylene content of less than 35% by weight, or an EPDM having an ethylene content in excess of 65~ by weight and a propylene content of less than 30~ by weight, and a maximum of 8~ by weight of diene components, preferably less than 5~ by weight of diene components. The diene components may be ethylidene-norbornenes, for example. The degree of partial crystal-linity of the EPDM- and/or EPM-types used is determined according to the DSC method in the differential-scan calorimeter measured melt-curve. The maximum of the melt-peak, measured as the temperature TS in C according to the DSC curve, is known as the endothermal peak which may be very narrow or may also include a larger area. In the case of ethylene-propylene-terpolymers, the temperature TS is in the vicinity of 50C. The amount of heat required for melting, known as H50, also measured according to the DSC
heat, provides information as to the presence of crystalline blocks in the ethylene-propylene-terpolymer or the ethylene-propylene-copolymer. Such partlycrystalline EPDM- or EPM-types, having a melting heat of at least 10 (J/g), are preferred according to the invention.
Advantageously, when the polyethylene and/or ethylene copolymers used are contained in amounts between 25 and 50 parts by weight, the tensile strength at 80C may be greater tha 0.8 (N/mm2), preferably greater than 1.0 (N/mm ), according to DIN 53 455.
Advantageously, the rubber may comprise a partly crystalline sequential rubber and comprise at least a polymer bulk-strength of 5 (N/mm2).
In choosing suitable elastomeric synthetic materials, especially of the EPDM- and EPM-types, the strength thereof is of importance. According to the invention, they should have a tensile strength, measured according to DIN 53 455, of at least 5 (N/mm ).
Suitable polyolefins, to be added to the compounds according to the invention, are, in the first place, crystalline and partly crystalline modifications of polyethylene having densities of 0.905 to 0.975 (g/cm3) and an MFI (190/2,16) of less than 0.1 (g/10 min). However, it is also possible to use partly crystalline copolymers of ethylene with other ~-olefins within the limits of this specification, which contain 0.5 to 30~ by weight of comonomers.
Suitable mineral oils are those having kinematic viscosities of between 50 x 10 6 (m2/s) (50 cSt) and 5 x 10 3 (m2/s) (5.000 cSt) at 20C, preferably 200 x 10 6 (m2/s) (200 cSt) and 3 x 10 3 (m2/s) (3.000 cSt) at 20C and a density of 0.84 to 0.98 (g/cm3). The oils may contain both paraffinic, naphthenic or aromatic bound carbon atoms.
Advantageously, the moulding composition according to the invention may further comprise inorganic fillers, carbon blacks, lubricants and/or stabilizers.
Preferably, said composition may comprise, per 100 parts by weight of polyolefin rubber:
~,~
- between 20 and 80 parts by weight of an inorganic filler;
- between 10 and 50 parts by weight of carbon black;
- between 0.5 and 5 parts by weight of lubricants and/or stabilizers.
The choice of suitable fillers is of critical importance for plastic layers and additives which co-operate synergistically and improve the properties of the sealing strip, especially the mechanical properties. An essential component in this connection is semi-active or active carbon black, so-called reinforcing carbon black, the layers containing between 10 and 50 parts by weight, preferably between 20 and 45 parts by weight of carbon black per 100 parts by weight of polyolefin rubber. It is possible to use carbon blacks made by the furnace-method which have an average particle-size of between 30 and 60 (~m) and a BET
surface of between 30 and 60 (m /g).
As a reinforcing filler and, at the same time, in order to cheapen the product, it is preferable to use ZS
- 7a -.
, ,~
silica, e.g. a mixture of silicic-acid anhydride and kaolinite, the grain sizes being less than 20 (~um) and the grain-size of at least 40~ of the mixture being less than 2 ( ~m)- However, it is also possible to replace up to 2/3 of the silica with other equally finely granular fillers such as chalk, kaolin, talcum, baryte, glass-fibres or mixtures thereof.
The layers of sealing strip also contain stabilizers and anti-ageing agents, based more particularly upon sterically hindered phenolic antioxidants, phenolic phosphites, thioesters of aliphatic carboxylic acids and the like. The following may be used as processing lubricants:
metal soaps, for example calcium soaps, calcium-stearate, zinc-stearate. Montanic-acid esters and/or hydrogenated hydrocarbons may be used as aids to processing.
The properties of the sealing strip according to the invention are adapted to the demands of the construction industry. In addition to being serviceable at room-temperature, it is also serviceable at temperatures down to -60C and up to about +80C. It is also weatherproof and biologically resistant. In addition to this, the strip is easy to process and watertight seams can be produced by hot-air welding which is simple and in common use in construction work.
The moulding compounds are mixed either continuously in a screw-mixer or intermittently in a closed kneading machine, e.g. a stamping kneader. With temperatures in the mixer between 130 and 200C, the mixture is caused to melt. The compound leaves the mixer as a pasty, plasticized, still not fully homogenized mass which is then passed to a roughing mill for further mixing and processing at temperatures of between 170 and 185C. The compound may then be passed to a strainer where it is finally homogenized and filtered. Upon leaving the strainer, the temperature of the compound is about 200C and may now be fed to an L- or F-type calender.
When fed to the roll-gap of the calender, the temperature of the compound is between 185 and 190C, while the temperature upon leaving the final calender-roll is still 180 C. This procedure has the advantage of producing a homogeneous, bubble-free product and is specially adapted to the mixtures and moulding compounds used to produce sealing strip. It is possible to obtain take-off speeds, i.e. calender-output speeds, of between 10 and 20 (m/min) with the materials used and the foil-thicknesses selected.
However, the mass prepared for calendering may also be converted into granules. It may then be extruded or injection-moulded to form sealing strips or parts.
The following examples according to the invention, and comparison-examples, are intended to explain the present invention.
Reference is also made to Fig. 1 which shows, as example without limitative manner, a diagram of the elongation at rupture of the compound.
EXAMPLES 1 to 7 The following mixture is charged at 60C into a Werner & Pfleiderer stamping-kneader and is kneaded to a mass-temperature of 185C:
100.0 parts by weigth of ethylene-propylene-diene rubber (EPDM 1) 30.0 parts by weight of polyethylene 22.0 parts by weight of extender oil H 90 45.0 parts by weight of Sillitin*Z 82 siliceous chalk 38.0 parts by weight of Corax*N 550 FEF carbon black 1.8 parts by weight of lubricants and stabilizers.
* Sillitin and Corax are trade marks.
The EPDM used is a rubber consisting of 66~ by weight of ethylene, 27% by weight of propylene and 7~ by weight of ethylene-norbornenes with a polymer bulk-strength of 12 (N/mm ) and a melting heat of 26 (J/g).
The MFI (190/2,16) of the polyethylene types used were varied between about 0.05 and 8 (g/10 min) as follows:
EXAMPLE 1: MFI (190/2,16) = 0,05 ~g/10 min], EXAMPLE 2: MFI (190/2,16) = 0,1 ~g/10 min], EXAMPLE 3: MFI (190/2,16) = 0,5 Cg/lO min~, EXAMPLE 4: MFI (190/2,16) = 1 ~/10 min], EXAMPLE 5: MFI (190/2,16) = 2 ~g/10 min~, EXAMPLE 6: MFI (190/2,16) = 5 Cg/10 min~
EXAMPLE 7: MFI (190/2,16) = 8 Cg/10 min~, In Fig. 1, the elongation at rupture at 23 C
(RD 23), and the elongation at rupture at 80 C (RD 80), as measured according to DIN 53 455, are shown in relation to the MFI of examples 1 to 7. The figure shows that the elongation at rupture increases at 23C and slightly at a lower melting index, whereas the elongation at rupture at 80 C assumes adequate values from an MFI of 0.1 (g/10 min).
This extreme dependency of the elongation at rupture at 80 C
upon the MFI was totally unexpected.
EXAMPLES 8 to 11 The following mixture is charged, at 60C, into a Werner & Pfleiderer type stamping-kneader and is kneaded to a mass-temperature of 185C.: 0 100.0 parts by weight of ethylene-propylene-diene rubber (EPDM 1) 27.0 parts by weight of polyethylene 22.0 parts by weight of extender oil H 90 45.0 parts by weight of Sillitin Z 82 siliceous chalk 1~
~ - I 336627 38.0 parts by weight of Corax N 550 FEF carbon black 1.8 parts by weight of lubricants and stabilizers.
The EPDM 1 used is a rubber consisting of 669d by weight of ethylene, 2796 by weight of propylene and 7% by 5 weight of ethylidene norbornenes with a polymer bulk-strength of 12 (N/mm ) and a melting heat of 26 (J/g).
The polyethylenes used in Examples 8 to 11 are described in Table 1 below by their MFI (190/2 ,16), their density and their polymerization-type. In this Table:
LD: signifies low-density polyethylene LLD: signifies linear low-density polyethylene HD: signifies high-density polyethylene.
The materials kneaded in the manner described hereinbefore are fed to a 190C roughing mill, then to a calender having a roll-temperature of between 180 and Z00C
and are calendered into a 1 mm thick foil. Also shown in Table 1 are the following values for these foils: tensile strength at 23C (RF 23), tensile strength at 80C (RF 80), elongation at rupture at 23C (RD 23), and elongation at 20 rupture at 80 C (RD 80).
EXAMPLES 12 to 15 Examples 12 to 15 are comparison-examples taken from DE-OS 26 57 272 (examples 1, 2, 4 and 5). In contrast 25 to Examples 8 to 11, tensile strength and elongation at rupture are measured, not at 80C, but at 70C. The values in Table 1 are therefore shown in brackets. Compositions are also shown in Table 1.
30 EXAMPLES 16 to 18 The amounts and qualities shown in Table 1 are prepared according to Example 8 and are made into foils by calendering. Strength and elongation values are shown in Table 1.
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As may be ganhered from the examples in Table 1, the tensile strengths in comparison examples 9 to 18 at 23C
have very high values in spite of differences in composi-tion. At elevated temperatures of 80 and 70C, however, elongation at rupture values decline drastically, down to Example 8 in which a PE having a very high molecular weight = a low MFI is used. It is therefore impossible to draw conclusions from elongation values at 23C as to the behaviour of the materials at elevated temperatures, for example at 80C. It was all the more surprising that the improvements in properties shown could be achieved by the special polyethylene type according to the invention.
EXAMPLES 19 to 33 The qualities and types listed in Table 2 below are as described in Example 8, but with an ethylene-propylene-diene rubber (EPDM 2) containing 67% by weight of ethylene, 30% by weight of propylene and 3% by weight of ethylidene norbornenes, with a polymer bulk-strength of 13.5 (N/mm ) and a melting heat of 30 (J/g), processed into foils and measured.
In the case of comparison-examples 20, 21, 22, 24 and 25, the MFI values of which for the polyethylene lie outside the invention, values for elongation at rupture at 80 C were low. Higher values were obtained only in Example 23, in which the MFI value of the polyethylene used is within the limits of the invention, but without reaching the preferred range in excess of 600%.
Examples 30, 32 and 33 show that satisfactory elongation at rupture at 80C cannot be obtained with too little mineral oil, nor by increasing the proportion of the polyethylene type according to the invention.
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I~ r~ r~ r~ ~ I~ ~ o U~ o o U~ r~ r~ o . a~ o ~ 0 ~ o ~, A mixture consisting of:
100.0 parts by weight of ethylene-propylene diene rubber (EPDM 2) 25.0 parts by weight of polyethylene MFI (190/5) < 0.1 (g/10 min) 25.0 parts by weight of polyethylene MFI (190/2,16) of 1 (g/10 min) 22 . 0 parts by weight of extender oil H 90 45 . 0 parts by weight of Sillitin Z 82 siliceous chalk 38.0 parts by weight of Corax N 550 FEF carbon black 1.8 parts by weight of lubricants and stabilizers 15 is prepared as described in Example 8 and is made into 1 mm foil by calendering. The measured properties were:
RF 23C : 19. 5 N/mm RD 23C : 1060%
RF 80C : 1.2 N/mm RD 80 C : 800~
As shown by the measurement obtained, additional amounts of polyethylene with a higher MFI can be added to the amounts of polyethylene according to the invention without impairing the required high elongation at rupture at 80C. (see Fig. 1 )
Claims (12)
1. A moulding composition made of elastomeric polyolefin rubbers, polyethylene and/or ethylene copolymers, mineral oils and additives, wherein the moulding composition comprises per 100 parts by weight of polyolefin rubber:
- 25 to 150 parts by weight of polyethylene and/or ethylene copolymers having an MFI (190/2,16) of less than 0.1 (g/10 min) according to DIN 53 735;
- between 16 to 28 parts by weight of a mineral oil.
- 25 to 150 parts by weight of polyethylene and/or ethylene copolymers having an MFI (190/2,16) of less than 0.1 (g/10 min) according to DIN 53 735;
- between 16 to 28 parts by weight of a mineral oil.
2. A moulding composition according to claim 1, wherein the additives are selected from the group consisting of:
- inorganic fillers;
- carbon blacks;
- lubricants and/or stabilizers.
- inorganic fillers;
- carbon blacks;
- lubricants and/or stabilizers.
3. A moulding composition according to claim 2, wherein it comprises, par 100 parts by weight of polyolefin rubber:
- between 20 and 80 parts by weight of an inorganic filler;
- between 10 and 50 parts by weight of carbon black;
- between 0.5 and 5 parts by weight of lubricants and/or stabilizers.
- between 20 and 80 parts by weight of an inorganic filler;
- between 10 and 50 parts by weight of carbon black;
- between 0.5 and 5 parts by weight of lubricants and/or stabilizers.
4. A moulding composition according to claim 1, wherein the polyethylene and/or ethylene copolymers have an MFI (190/5) of less than 0.1 (g/10 min) and an MFI
(190/21.6) of less than 5 (g/10 min) according to DIN 53 735.
(190/21.6) of less than 5 (g/10 min) according to DIN 53 735.
5. A moulding composition according to claim 1, wherein the rubber comprises a partly crystalline sequential rubber and comprises at least a polymer bulk-strength of 5 (N/mm2).
6. A moulding composition according to claim 1, wherein the polyethylene and/or ethylene copolymers are contained in amounts of between 25 and 50 parts by weight, the tensile strength at 80°C being greater than 0.8 (N/mm2), according to DIN 53 455.
7. A moulding composition according to claim 1, wherein the ethylene copolymers contain between 0.5 and 20%
by weight of C3-C8 olefins as comonomers.
by weight of C3-C8 olefins as comonomers.
8. A moulding composition according to claim 2, wherein it contains as fillers, between 40 and 60 parts by weight of inorganic fillers.
9. A moulding composition according to claim 2, wherein the carbon blacks are reinforcing or semi-reinforcing carbon blacks in amounts between 20 and 40 parts by weight per 100 parts by weight of polyolefin rubber.
10. A moulding ocmposition according to claim 2, wherein it contains, as filler, between 40 and 60 parts by weight of inorganic fillers selected from the group consisting of chalk, kaolin, talcum, baryte, silica and glass fibres mixed with silica.
11. Use of a moulding composition as defined in claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, for the preparation of elastic sealing strip by calendering or extrusion.
12. Use according to claim 11, wherein the elastic sealing strip has an elongation at break according to DIN 53 455 at 80°C greater than 600% and a tensile strength according to DIN 53455 greater than 0,7 (N/mm2) at 80°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3827904A DE3827904A1 (en) | 1988-08-17 | 1988-08-17 | MOLDING MATERIAL OF ELASTOMER POLYOLEFINKAUUGUKEN, POLYETHYLENE AND / OR ETHYLENE COPOLYMERS AND ADDITIVES AS WELL AS ELASTIC SEAL RAIL MANUFACTURED THEREOF |
| DEP3827904.5 | 1988-08-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1336627C true CA1336627C (en) | 1995-08-08 |
Family
ID=6361030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000608515A Expired - Fee Related CA1336627C (en) | 1988-08-17 | 1989-08-16 | Moulding compound made of elastomeric polyolefin rubbers, polyethylene and/or ethylene copolymers and additives, and elastic sealing strips made therefrom |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5177139A (en) |
| EP (1) | EP0429504B1 (en) |
| JP (1) | JP2879112B2 (en) |
| CA (1) | CA1336627C (en) |
| DE (2) | DE3827904A1 (en) |
| DK (1) | DK172499B1 (en) |
| HU (1) | HU209959B (en) |
| NO (1) | NO180542C (en) |
| WO (1) | WO1990002154A1 (en) |
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| US5286798A (en) * | 1990-10-04 | 1994-02-15 | Bridgestone/Firestone, Inc. | Polymer blends for heat seamable roof sheeting |
| EP0543306B1 (en) * | 1991-11-18 | 1997-07-16 | Bridgestone Corporation | Mineral filled heat seamable roof sheeting |
| US5256228A (en) * | 1991-12-06 | 1993-10-26 | Bridgestone Corporation | Heat seamable roof sheeting with highly crystalline thermoplasticity promoters and methods for covering roofs |
| CA2119286A1 (en) * | 1993-04-15 | 1994-10-16 | Hubert S. Smith, Iii | Internally lubricated elastomers for use in biomedical applications |
| FR2721319B1 (en) * | 1994-06-17 | 1996-08-30 | Reydel Sa | Polyolefin elastomeric powder composition, its manufacturing process, molded article obtained by its implementation. |
| US5871171A (en) * | 1994-09-23 | 1999-02-16 | Terry Kenney | Molded product of recycled plastic and rubber |
| DE19745700A1 (en) * | 1997-10-16 | 1999-04-22 | Buna Sow Leuna Olefinverb Gmbh | Thermoplastic, elastomeric molding composition useful for production of tubing, bellow and seals |
| FR2855829B1 (en) * | 2003-06-06 | 2005-09-09 | Valois Sas | VALVE JOINT AND FLUID PRODUCT DISPENSING DEVICE COMPRISING SUCH A JOINT |
| CA2603166C (en) * | 2005-03-29 | 2014-08-05 | Intellmat, Llc | Fly ash and cinder strengthened thermoplastic |
| US8419405B2 (en) * | 2009-09-23 | 2013-04-16 | Revolutionary Plastics, Llc | System for forming a composition with an optimized filler |
| US9290645B2 (en) | 2011-03-04 | 2016-03-22 | Polyone Corporation | Cycle time reduction masterbatches and their use in thermoplastic compounds |
| WO2012166651A2 (en) | 2011-05-27 | 2012-12-06 | Revolutionary Plastics, Llc | Method to heuristically control formation and properties of a composition |
| WO2013043454A2 (en) * | 2011-09-21 | 2013-03-28 | Polyone Corporation | Sustainable theromplastic compounds |
| WO2013082024A1 (en) | 2011-11-29 | 2013-06-06 | Revolutionary Plastics, Llc | Low density high impact resistant composition and method of forming |
| US9481768B1 (en) | 2013-03-15 | 2016-11-01 | Revolutionary Plastics, Llc | Method of mixing to form composition |
| JP6165192B2 (en) * | 2015-05-22 | 2017-07-19 | ダウ グローバル テクノロジーズ エルエルシー | Thermoplastic elastomers for low temperature and wet applications |
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| FR2076302A5 (en) * | 1970-01-08 | 1971-10-15 | Kleber Colombes | |
| CA1107885A (en) * | 1976-11-01 | 1981-08-25 | Roger C. Cotton | Compositions comprising polybytene, epom and polyolefin |
| DE2657272A1 (en) * | 1976-12-17 | 1978-06-29 | Huels Chemische Werke Ag | THERMOPLASTIC MASS |
| DE2657274A1 (en) * | 1976-12-17 | 1978-06-29 | Huels Chemische Werke Ag | THERMOPLASTIC MASS |
| DE2822815C2 (en) * | 1977-05-26 | 1994-02-17 | Mitsui Petrochemical Ind | Process for the preparation of a partially vulcanized thermoplastic composition |
| US4774277A (en) * | 1982-03-26 | 1988-09-27 | Exxon Research & Engineering Co. | Blends of polyolefin plastics with elastomeric plasticizers |
| CA1261505A (en) * | 1984-05-02 | 1989-09-26 | Akira Uchiyama | Thermoplastic elastomer composition |
| US4722973A (en) * | 1985-04-10 | 1988-02-02 | Nippon Oil Co., Ltd. | Thermoplastic elastomer composition |
| JP2570358B2 (en) * | 1988-02-03 | 1997-01-08 | 住友化学工業株式会社 | Thermoplastic elastomer composition |
| KR920003034B1 (en) * | 1988-06-21 | 1992-04-13 | 동양나이론 주식회사 | Resin making material |
-
1988
- 1988-08-17 DE DE3827904A patent/DE3827904A1/en not_active Ceased
-
1989
- 1989-08-11 US US07/654,612 patent/US5177139A/en not_active Expired - Fee Related
- 1989-08-11 JP JP1508581A patent/JP2879112B2/en not_active Expired - Lifetime
- 1989-08-11 EP EP89909190A patent/EP0429504B1/en not_active Expired - Lifetime
- 1989-08-11 DE DE89909190T patent/DE58905854D1/en not_active Expired - Fee Related
- 1989-08-11 WO PCT/EP1989/000946 patent/WO1990002154A1/en active IP Right Grant
- 1989-08-11 HU HU895001A patent/HU209959B/en not_active IP Right Cessation
- 1989-08-16 CA CA000608515A patent/CA1336627C/en not_active Expired - Fee Related
-
1991
- 1991-02-06 DK DK199100201A patent/DK172499B1/en active
- 1991-02-12 NO NO910561A patent/NO180542C/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04500085A (en) | 1992-01-09 |
| DK172499B1 (en) | 1998-10-26 |
| NO180542C (en) | 1997-05-07 |
| DK20191D0 (en) | 1991-02-06 |
| HUT62634A (en) | 1993-05-28 |
| EP0429504B1 (en) | 1993-10-06 |
| DK20191A (en) | 1991-02-06 |
| NO910561D0 (en) | 1991-02-12 |
| DE58905854D1 (en) | 1993-11-11 |
| US5177139A (en) | 1993-01-05 |
| NO910561L (en) | 1991-02-12 |
| HU209959B (en) | 1994-12-28 |
| JP2879112B2 (en) | 1999-04-05 |
| HU895001D0 (en) | 1991-08-28 |
| WO1990002154A1 (en) | 1990-03-08 |
| EP0429504A1 (en) | 1991-06-05 |
| NO180542B (en) | 1997-01-27 |
| DE3827904A1 (en) | 1990-03-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |