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WO2000064985A1 - Preparation of a thermoplastic elastomer having a low hardness - Google Patents

Preparation of a thermoplastic elastomer having a low hardness Download PDF

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Publication number
WO2000064985A1
WO2000064985A1 PCT/NL2000/000177 NL0000177W WO0064985A1 WO 2000064985 A1 WO2000064985 A1 WO 2000064985A1 NL 0000177 W NL0000177 W NL 0000177W WO 0064985 A1 WO0064985 A1 WO 0064985A1
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Prior art keywords
rubber
oil
process according
thermoplastic elastomer
polar groups
Prior art date
Application number
PCT/NL2000/000177
Other languages
French (fr)
Inventor
Edwin Willems
Original Assignee
Dsm N.V.
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Filing date
Publication date
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU34646/00A priority Critical patent/AU3464600A/en
Publication of WO2000064985A1 publication Critical patent/WO2000064985A1/en

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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention relates to a process for the preparation of a thermoplastic elastomer containing a thermoplastic polymer with polar groups, a rubber and an oil, m which process the thermoplastic polymer with polar groups is mixed with the rubber and the oil and the rubber is dynamically vulcanized.
  • thermoplastic elastomers with dynamically vulcanized rubber are described in the "Handbook of Thermoplastic Elastomers, by B.M. Walker / C.P. Rader, chapter 4, Elastomeric Alloy Thermoplastic Vulcanisates Van Nostrand Remhold, New York 1988".
  • thermosettmg material When a rubber is vulcanized in the normal way, a product having the properties of a thermosettmg material is formed.
  • thermoplastic elastomers with dynamically vulcanized rubber contain vulcanized rubber, which is dispersed m the form of fine particles m a continuous phase of a thermoplastic polymer.
  • TPVs are special in that they have a number of properties of the thermoplastic polymer that forms the continuous phase. Thus, TPVs can be processed as thermoplastics and use can oe made of the customary techniques for shaping and reprocessing.
  • an oil is often added to the composition.
  • a drawback of the use of oil m a TPV containing a thermoplastic polymer with polar groups is that TPVs are formed in whicn the vulcanized rubber is poorly dispersed. It is even possible for the continuous phase to be formed not by the thermoplastic with polar groups, but by the rubber, so that the advantageous properties of the TPVs as a thermoplastic with respect to processability are lost.
  • the object of the present invention is to provide a process for the preparation of a thermoplastic elastomer containing a thermoplastic polymer with polar groups, a rubber and an oil m which the rubber is dynamically vulcanized, that does not have said drawback.
  • This object is achieved m that at least a part of the oil is added after the rubber has at least partly vulcanized.
  • the process according to tne present invention use can oe made of paraffmic, naphthenic as well as aromatic oils or of mixtures of these oils .
  • the total quantity of oil that is present m tne TPV after the process according to the invention has been carried out ranges, for instance, from 0.05 to 2.5 times the quantity of rubber present m the TPV.
  • the total quantity of ruiober amounts to between 0.1 and 1.6 times the quantity of rubber present m the TPV.
  • the total quantity of oil amounts to between 0.5 and 1.2 times the quantity of rubber present m the TPV.
  • the quantity of oil that is added after the rubber has at least partly vulcanized is between 50 and 100% of the total quantity of oil.
  • m which 100% of the oil is added after the rubber has at least partly vulcanized.
  • thermoplastic polymer with polar groups m the TPVs of the invention use can be made of all known thermoplastic polymers with polar groups. Examples of thermoplastic polymers with polar groups that are suitable for use m the process according to the present invention are: polyamides, polyesters, polyacrylates , polycaroonates and copoly ⁇ ther ester block polymers or mixtures of these polymers .
  • a polyamide or a polyester is used as thermoplastic polymer with polar groups.
  • polyamides that can be used m the process according to the present invention are: polyamide 6, polyamide 4,6, polyamide 6,6 and polyamide 11.
  • polyesters that can be used m the process according to the present invention are . polyethylene terephthalate and polybutylene terephthalate .
  • copolyether ester block copolymers with polar groups as thermoplastic polymer with polar groups, or to the use of a mixture of a copolyether ester block copolymer and a polyester.
  • TPVs can be prepared that have a very low hardness and a good compression set.
  • copolyether ester block copolymers that can be used m the process according to the invention are: copolybutylether butylene terephthalate block copolymer and copoly (1- methyl) ethylether butylene terephthalate block copolymer .
  • the quantity of the thermoplastic polymer with polar groups that is used m the process according to the invention ranges from 0.2 to 5.0 times the quantity of rubber present m the TPV.
  • the quantity of the thermoplastic polymer with polar groups ranges from 0.5 to 2.0 times the quantity of rubber present m the TPV.
  • Use can for instance be ma ⁇ e of the following rubbers or a mixture thereof.
  • SBR styrene butadiene rubber, copolymer of styrene and butadiene
  • NBR non ⁇ le rubber, copolymer of butadiene and acrylonitrile
  • IIR butyl ruboer, copolymer of isobutene and isoprene
  • BR butadiene rubber
  • SBS styrene butadiene block copolymer
  • SEBS styrene ethylene/butadiene styrene block copolymer
  • SIPS styrene isoprene block copolymer
  • the ⁇ -olefin can for instance be propylene, m these cases the rubber is called EPDM and EPM.
  • BR or a mixture of these rubbers is used as rubber m the process according to the invention.
  • EPDM rubber or a mixture of EPDM and EPM rubber or a mixture of EPDM, EPM and one or more of the following rubbers: SBS, SEBS and SIPS.
  • the TPV prepared according to the process of the invention for instance contains 5 - 250 parts of oil and 20 - 500 parts of thermoplastic polymer with polar groups per 100 parts of rubber.
  • the TPV according to the process of the invention contains 10 - 160 parts of oil and 50 - 200 parts of thermoplastic polymer with polar groups per 100 parts of rubber.
  • the TPV prepared according to the process of the invention can for instance contain additives.
  • sucn additives are fillers, reinforcing agents, dyestuffs, stabilizers and vulcanization agents.
  • the TPV prepared according to the process of the invention exists of the thermoplastic polymer with polar groups, the rubber, the oil and the additives.
  • the TPV prepared according to the invention substances can for instance be present to increase the compatibility between the rubber and the thermoplastic polymer with polar groups used.
  • these substances are maleic anhydride- modified, alkoxy silane-modifled, epoxy-modifled, acid- modified thermoplastic polymers and/or rubbers.
  • the dynamic vulcanization of the rubber used m the process according to the invention is carried out m the presence of a vulcanization agent, which is added to the mixture m a quantity known to one skilled m the art.
  • vulcanization agent m the dynamic vulcanization use can be made of the vulcanization agents that are known in literature.
  • a peroxide, a sulphur compound, a hydrosilane or a phenol resin is used as vulcanization agent .
  • At least part of the oil is added after the rubber has at least partly vulcanized.
  • tne quantity of vulcanized rubber is for instance between 50 - 100% of the total quantity of rubber present.
  • the rubber present is 100% vulcanized.
  • the extent to wnich tne rubber is vulcanized at the moment that at least part of the oil is added is determined by measuring the quantity of soluble rubber m boiling xylene.
  • the extent to wnicn the rubber is vulcanized is calculated using formula I : B
  • B the quantity of rubber dissolved m boiling xylene.
  • the process according to the invention can take place using the equipment known from literature for mixing rubbers with thermoplastics and oil m continuous and discontinuous processes.
  • the equipment for the process according to the present invention is an extruder or a batch kneader .
  • thermoplastic elastomers obtained by the use of the process according to the invention are suitable for all kinds of applications in shaped articles made from thermoplastic elastomers containing a thermoplastic polymer with polar groups, a rubber and an oil.
  • thermoplastic elastomers m which a low hardness and a good compression set over a wide temperature range are important .
  • thermoplastic elastomer with polar groups By the choice of the thermoplastic elastomer with polar groups to be used, the rubber and the oil and the quantities to be used of the substances, it is ensured that the TPV according to the invention has the material properties that are needed for the application.
  • nardness of tne TPV for this application preferably amounts to between 20 Shore A and 40 Shore D. Special preference is given to a TPV of which the hardness amounts to between 30 and 70 Shore A.
  • the compression set (ISO 815) of the TPV for this application amounts to between 10 and 50%.
  • the compression set (DIN 35517,
  • the shaped articles of the applications are made using the customary processing methods such as for instance: extrusion, blow moulding and injection moulding.
  • the TPVs according to the invention can be used m applications for the automotive industry, for instance: door profiles, bellows, cable sheathmgs, hoses, air bag covers, dashboard films, handles and soft-touch applications.
  • the quantity of oil (Sunpar ® 150) is added according to Table 2.
  • This composition is heated and mixed for 2 minutes at 230°C, then a quantity of 10 parts of phenol resin (SP 1045) is added, after which mixing is continued for 5 minutes. As soon as the phenol resin is added, the dynamic vulcanization of the rubber starts.
  • thermoplastic elastomer made has a lower hardness and a better compression set m comparison with A.
  • thermoplastic polymer that is present forms the continuous phase.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Process for the preparation of a thermoplastic elastomer containing a thermoplastic polymer with polar groups, a rubber and an oil in which the thermoplastic polymer with polar groups is mixed with the rubber and the oil and in which the rubber is dynamically vulcanized. At least a part of the oil is added after the rubber has at least partly vulcanized.

Description

PREPARATION OF A THERMOPLASTIC ELASTOMER HAVING A LOW HARDNESS
The invention relates to a process for the preparation of a thermoplastic elastomer containing a thermoplastic polymer with polar groups, a rubber and an oil, m which process the thermoplastic polymer with polar groups is mixed with the rubber and the oil and the rubber is dynamically vulcanized.
Such thermoplastic elastomers with dynamically vulcanized rubber are described in the "Handbook of Thermoplastic Elastomers, by B.M. Walker / C.P. Rader, chapter 4, Elastomeric Alloy Thermoplastic Vulcanisates Van Nostrand Remhold, New York 1988".
When a rubber is vulcanized in the normal way, a product having the properties of a thermosettmg material is formed.
The thermoplastic elastomers with dynamically vulcanized rubber (hereinafter referred to as TPVs) contain vulcanized rubber, which is dispersed m the form of fine particles m a continuous phase of a thermoplastic polymer.
TPVs are special in that they have a number of properties of the thermoplastic polymer that forms the continuous phase. Thus, TPVs can be processed as thermoplastics and use can oe made of the customary techniques for shaping and reprocessing.
To improve tne elastic properties and processing properties of TPVs, an oil is often added to the composition.
A drawback of the use of oil m a TPV containing a thermoplastic polymer with polar groups is that TPVs are formed in whicn the vulcanized rubber is poorly dispersed. It is even possible for the continuous phase to be formed not by the thermoplastic with polar groups, but by the rubber, so that the advantageous properties of the TPVs as a thermoplastic with respect to processability are lost.
The object of the present invention is to provide a process for the preparation of a thermoplastic elastomer containing a thermoplastic polymer with polar groups, a rubber and an oil m which the rubber is dynamically vulcanized, that does not have said drawback.
This object is achieved m that at least a part of the oil is added after the rubber has at least partly vulcanized.
Surprisingly, it has been found that when the process according to the present invention is used TPVs containing a thermoplastic polymer with polar groups, a rubber and an oil can be prepared with a good dispersion of the vulcanized rubber.
A further advantage of the process according to the present invention is that the TPVs can even be prepared with high oil contents while the TPVs still have a good processability as thermoplastics. Yet another advantage of the process according to the present invention is that the TPVs can be made that have a very low hardness and a good compression se .
As oil m the process according to tne present invention use can oe made of paraffmic, naphthenic as well as aromatic oils or of mixtures of these oils .
The total quantity of oil that is present m tne TPV after the process according to the invention has been carried out ranges, for instance, from 0.05 to 2.5 times the quantity of rubber present m the TPV. Preferaoly, the total quantity of ruiober amounts to between 0.1 and 1.6 times the quantity of rubber present m the TPV. With special preference the total quantity of oil amounts to between 0.5 and 1.2 times the quantity of rubber present m the TPV.
To prepare the TPVs with a good dispersion of the vulcanized rubber and a good processability as a thermoplastic, all or part of the oil for the process according to the invention is added after the rubber has at least partly vulcanized.
Preferably, the quantity of oil that is added after the rubber has at least partly vulcanized is between 50 and 100% of the total quantity of oil. Special preference is given to the process according to the invention, m which 100% of the oil is added after the rubber has at least partly vulcanized. As thermoplastic polymer with polar groups m the TPVs of the invention use can be made of all known thermoplastic polymers with polar groups. Examples of thermoplastic polymers with polar groups that are suitable for use m the process according to the present invention are: polyamides, polyesters, polyacrylates , polycaroonates and copolyεther ester block polymers or mixtures of these polymers .
Preferaoly, a polyamide or a polyester is used as thermoplastic polymer with polar groups. Examples of polyamides that can be used m the process according to the present invention are: polyamide 6, polyamide 4,6, polyamide 6,6 and polyamide 11. Examples of polyesters that can be used m the process according to the present invention are . polyethylene terephthalate and polybutylene terephthalate .
Special preference in this invention is given to the use of copolyether ester block copolymers with polar groups as thermoplastic polymer with polar groups, or to the use of a mixture of a copolyether ester block copolymer and a polyester. With these, TPVs can be prepared that have a very low hardness and a good compression set. Examples of copolyether ester block copolymers that can be used m the process according to the invention are: copolybutylether butylene terephthalate block copolymer and copoly (1- methyl) ethylether butylene terephthalate block copolymer . The quantity of the thermoplastic polymer with polar groups that is used m the process according to the invention ranges from 0.2 to 5.0 times the quantity of rubber present m the TPV. Preferably, the quantity of the thermoplastic polymer with polar groups ranges from 0.5 to 2.0 times the quantity of rubber present m the TPV.
In the preparation of TPVs according to the process of the invention many customary rubbers that are capable of dynamic vulcanization can be used as rubber.
Use can for instance be maαe of the following rubbers or a mixture thereof. SBR (styrene butadiene rubber, copolymer of styrene and butadiene) , NBR (nitπle rubber, copolymer of butadiene and acrylonitrile) , IIR (butyl ruboer, copolymer of isobutene and isoprene) or BR (butadiene rubber) . Other examples of rubbers that can be used in the process according to the invention are styrene containing block copolymers such as for instance: SBS (styrene butadiene block copolymer) , SEBS (styrene ethylene/butadiene styrene block copolymer) , SIPS (styrene isoprene block copolymer) . Yet other examples of rubbers that can be used m the process according to the invention are a copolymer of ethylene, an α-olefm and a third monomer or a mixture with a copolymer of ethylene and an α- olefin. The α-olefin can for instance be propylene, m these cases the rubber is called EPDM and EPM. Preferably, SBR, SBS, SEBS, SIPS, NBR, IIR,
BR or a mixture of these rubbers is used as rubber m the process according to the invention.
In the process according to the invention most preferably use is made of EPDM rubber or a mixture of EPDM and EPM rubber or a mixture of EPDM, EPM and one or more of the following rubbers: SBS, SEBS and SIPS.
The TPV prepared according to the process of the invention for instance contains 5 - 250 parts of oil and 20 - 500 parts of thermoplastic polymer with polar groups per 100 parts of rubber. Preferably, the TPV according to the process of the invention contains 10 - 160 parts of oil and 50 - 200 parts of thermoplastic polymer with polar groups per 100 parts of rubber.
In addition, the TPV prepared according to the process of the invention can for instance contain additives. Examples of sucn additives are fillers, reinforcing agents, dyestuffs, stabilizers and vulcanization agents.
Preferably the TPV prepared according to the process of the invention exists of the thermoplastic polymer with polar groups, the rubber, the oil and the additives.
Furthermore m the TPV prepared according to the invention substances can for instance be present to increase the compatibility between the rubber and the thermoplastic polymer with polar groups used. Examples of these substances are maleic anhydride- modified, alkoxy silane-modifled, epoxy-modifled, acid- modified thermoplastic polymers and/or rubbers. The dynamic vulcanization of the rubber used m the process according to the invention is carried out m the presence of a vulcanization agent, which is added to the mixture m a quantity known to one skilled m the art. As vulcanization agent m the dynamic vulcanization use can be made of the vulcanization agents that are known in literature. Preferably, a peroxide, a sulphur compound, a hydrosilane or a phenol resin is used as vulcanization agent . At least part of the oil is added after the rubber has at least partly vulcanized. At the moment that the oil is added tne quantity of vulcanized rubber is for instance between 50 - 100% of the total quantity of rubber present. Preferably, the rubber present is 100% vulcanized.
The extent to wnich tne rubber is vulcanized at the moment that at least part of the oil is added is determined by measuring the quantity of soluble rubber m boiling xylene. The extent to wnicn the rubber is vulcanized is calculated using formula I : B
X 100 % ( i :
where A: the total quantity of rubber
B: the quantity of rubber dissolved m boiling xylene. The process according to the invention can take place using the equipment known from literature for mixing rubbers with thermoplastics and oil m continuous and discontinuous processes.
Preferably, the equipment for the process according to the present invention is an extruder or a batch kneader .
The TPVs obtained by the use of the process according to the invention are suitable for all kinds of applications in shaped articles made from thermoplastic elastomers containing a thermoplastic polymer with polar groups, a rubber and an oil.
In particular this relates to applications of thermoplastic elastomers m which a low hardness and a good compression set over a wide temperature range are important .
By the choice of the thermoplastic elastomer with polar groups to be used, the rubber and the oil and the quantities to be used of the substances, it is ensured that the TPV according to the invention has the material properties that are needed for the application.
The nardness of tne TPV for this application preferably amounts to between 20 Shore A and 40 Shore D. Special preference is given to a TPV of which the hardness amounts to between 30 and 70 Shore A.
Preferably, the compression set (ISO 815) of the TPV for this application amounts to between 10 and 50%.
Preferably, the compression set (DIN 35517,
B) of the TPV for this application amounts to between 10 and 70%.
The shaped articles of the applications are made using the customary processing methods such as for instance: extrusion, blow moulding and injection moulding. The TPVs according to the invention can be used m applications for the automotive industry, for instance: door profiles, bellows, cable sheathmgs, hoses, air bag covers, dashboard films, handles and soft-touch applications.
Comparative experiment A
In a batch kneader a mixture of the following mass ratios is made:
100 parts of EPDM rubber (Keltan®, supplied by DSM) 75 parts of copolyether ester (Arnitel® EM 400, supplied by DSM)
10 parts of white pigment (Kronos® 2210, supplied by
Kronos)
1 part of stabilizer (Irgancx5' 1098, supplied by Ciba Geigy) .
After heating to 205°C and mixing, 10 parts of pnenol resin (SP 1045, supplied by Schenectady) are added and the dynamic vulcanization of tne rubber starts . This composition is mixed for 2 minutes at
205°C. Examples I - VI
The following experiments were carried out, with 6 x a composition according to A being made in a batch kneader.
After mixing for 2 minutes at 205°C, a quantity of oil (Sunpar , supplied by Sun Oil) according to Table 1 is added, followed by another 5 minutes' mixing.
Table 1
Figure imgf000011_0001
After cooling cf tne thermoplastic elastomer, the hardness and tne compression set are measured (see Table 3) . Comparative experiments B - G
The following six experiments were carried out, m which mixtures m tne following mass ratios were made on a batch kneader: 100 parts of EPDM rubber (Keltan®) 75 parts of copolyether ester (Arnitel® EM 400) 10 parts of white pigment (Kronos® 2210) 1 part of stabilizer (Irganox 1098) .
The quantity of oil (Sunpar® 150) is added according to Table 2.
This composition is heated and mixed for 2 minutes at 230°C, then a quantity of 10 parts of phenol resin (SP 1045) is added, after which mixing is continued for 5 minutes. As soon as the phenol resin is added, the dynamic vulcanization of the rubber starts.
Table 2
Figure imgf000012_0001
After cooling of the composition the hardness and the compression set are measured (see Table 3) .
Table 3, test results
Figure imgf000014_0001
Figure imgf000014_0002
From examples I - VI it is clear that when the quantity of oil increases the thermoplastic elastomer made has a lower hardness and a better compression set m comparison with A. In these thermoplastic elastomers the thermoplastic polymer that is present forms the continuous phase.
From comparative experiments B - G it is clear that B and C are still behaving as thermoplastics, but the compositions of experiments D - G no longer behave as thermoplastics because the rubber forms the continuous phase. Furthermore compositions B - G, with increasing quantities of oil, do prove to have a lower hardness, but the compression set remains virtually unchanged.

Claims

1. Process for the preparation of a thermoplastic elastomer containing a thermoplastic polymer with polar groups, a rubber and an oil, m which the thermoplastic polymer with polar groups is mixed with the rubber and the oil and m which the rubber is dynamically vulcanized, characterized m that at least part of the oil is added after the rubber has at least partly vulcanized.
2. Process according to claim 1, characterized m that the total quantity of oil m the thermoplastic elastomer is between 0.1 and 1.6 times the quantity of rubber present.
3. Process according to claim 1, characterized m that the total quantity of oil in the thermoplastic elastomer is between 0.5 and 1.2 times the quantity of rubber present.
4. Process according to claim 1, characterized in that between 50 and 100% of the oil is added after the rubber has at least partly vulcanized.
5. Process according to claim 1, characterized in that 100% of the quantity of oil is added after the rubber has at least partly vulcanized.
6. Process according to claim 1, characterized m that said thermoplastic polymer with polar groups is a polyamide, or a polyester, or a mixture of polyamide and a polyester.
7. Process according to claim 1, characterized m that said thermoplastic polymer with polar groups is a copolyether ester block copolymer, or is a mixture of a copolyether ester block copolymer and a polyester.
8. Process according to claim 1, characterized m that the rubber used is SBR, SBS, SEBS, SIPS, NBR, IIR, BR or a mixture of these rubbers.
9. Process according to claim 1, characterized m that the rubber is EPDM or a mixture of EPDM and EPM, or a mixture of EPDM, EPM and one or more of the following rubbers: SBS, SEBS and SIPS.
10. Process according to claim 1, characterized m that the quantity of thermoplastic polymer with polar groups m the thermoplastic elastomer is between 0.5 and 2.0 times the quantity of rubber present .
11. Thermoplastic elastomer obtainable by the process according to claims 1 - 10.
12. Shaped article containing a thermoplastic elastomer according to claim 11, characterized in that the hardness of said article is between 20 Shore A and 40 Shore D.
13. Shaped article containing a thermoplastic elastomer according to claim 11, characterized m that the hardness of said article is between 30 and 70 Shore A.
14. Shaped article containing a thermoplastic elastomer according to claim 11, characterized m that the compression set (ISO 815) of said article is between 10 and 50%.
15. Shaped article containing a thermoplastic elastomer according to claim 11, characterized m that the compression set (DIN 35517, B) of this article is between 10 and 70%.
PCT/NL2000/000177 1999-04-27 2000-03-17 Preparation of a thermoplastic elastomer having a low hardness WO2000064985A1 (en)

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Publication number Priority date Publication date Assignee Title
EP1299662B2 (en) † 2000-07-10 2009-05-06 Dichtungstechnik G. Bruss GmbH & Co. KG Shaft sealing ring
US8028656B2 (en) 2002-12-20 2011-10-04 Delaval Holding Ab Milking devices
GB2545326A (en) * 2015-11-11 2017-06-14 Hexcel Composites Ltd Composite material
CN110294927A (en) * 2018-03-23 2019-10-01 苏州纳绎博纳米科技有限公司 Thermoplastic nylon elastomer and preparation method thereof

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US3985702A (en) * 1975-05-27 1976-10-12 Shell Oil Company Dry blending and molding process
US4141863A (en) * 1976-06-11 1979-02-27 Monsanto Company Thermoplastic compositions of rubber and polyester
EP0659824A1 (en) * 1993-12-21 1995-06-28 Hüls Aktiengesellschaft Composites of thermoplastic polyester and thermoplastic polyesterelastomer without the use of an adhesion layer
EP0742268A2 (en) * 1995-05-12 1996-11-13 Advanced Elastomer Systems, L.P. Thermoplastic elastomers having improved high temperature performance

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Publication number Priority date Publication date Assignee Title
US3985702A (en) * 1975-05-27 1976-10-12 Shell Oil Company Dry blending and molding process
US4141863A (en) * 1976-06-11 1979-02-27 Monsanto Company Thermoplastic compositions of rubber and polyester
EP0659824A1 (en) * 1993-12-21 1995-06-28 Hüls Aktiengesellschaft Composites of thermoplastic polyester and thermoplastic polyesterelastomer without the use of an adhesion layer
EP0742268A2 (en) * 1995-05-12 1996-11-13 Advanced Elastomer Systems, L.P. Thermoplastic elastomers having improved high temperature performance

Cited By (4)

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US8028656B2 (en) 2002-12-20 2011-10-04 Delaval Holding Ab Milking devices
GB2545326A (en) * 2015-11-11 2017-06-14 Hexcel Composites Ltd Composite material
CN110294927A (en) * 2018-03-23 2019-10-01 苏州纳绎博纳米科技有限公司 Thermoplastic nylon elastomer and preparation method thereof

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