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WO2000064985A1 - Preparation d'un elastomere thermoplastique de faible durete - Google Patents

Preparation d'un elastomere thermoplastique de faible durete 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
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
oil
process according
thermoplastic elastomer
polar groups
Prior art date
Application number
PCT/NL2000/000177
Other languages
English (en)
Inventor
Edwin Willems
Original Assignee
Dsm N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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.

Landscapes

  • 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

L'invention concerne un procédé de préparation d'un élastomère thermoplastique contenant un polymère thermoplastique avec des groupes polaires, ainsi qu'un caoutchouc et une huile dans laquelle ledit polymère thermoplastique avec des groupes polaires est mélangé au caoutchouc et à cette huile, et vulcanisé de manière dynamique. Au moins une partie de l'huile est ajoutée une fois ledit caoutchouc au moins partiellement vulcanisé.
PCT/NL2000/000177 1999-04-27 2000-03-17 Preparation d'un elastomere thermoplastique de faible durete WO2000064985A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU34646/00A AU3464600A (en) 1999-04-27 2000-03-17 Preparation of a thermoplastic elastomer having a low hardness

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1011896A NL1011896C2 (nl) 1999-04-27 1999-04-27 Bereiding van een thermoplastisch elastomeer met lage hardheid.
NL1011896 1999-04-27

Publications (1)

Publication Number Publication Date
WO2000064985A1 true WO2000064985A1 (fr) 2000-11-02

Family

ID=19769089

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2000/000177 WO2000064985A1 (fr) 1999-04-27 2000-03-17 Preparation d'un elastomere thermoplastique de faible durete

Country Status (3)

Country Link
AU (1) AU3464600A (fr)
NL (1) NL1011896C2 (fr)
WO (1) WO2000064985A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1299662B2 (fr) † 2000-07-10 2009-05-06 Dichtungstechnik G. Bruss GmbH & Co. KG Bague d'etancheite
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 (zh) * 2018-03-23 2019-10-01 苏州纳绎博纳米科技有限公司 热塑性尼龙弹性体及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
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 (fr) * 1993-12-21 1995-06-28 Hüls Aktiengesellschaft Matériaux composites formés de polyester thermoplastique et d'élastomère thermoplastique de polyester sans couche adhésive
EP0742268A2 (fr) * 1995-05-12 1996-11-13 Advanced Elastomer Systems, L.P. Elastomères thermoplastiques ayant une résistance améliorée aux températures élevées

Patent Citations (4)

* Cited by examiner, † Cited by third party
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 (fr) * 1993-12-21 1995-06-28 Hüls Aktiengesellschaft Matériaux composites formés de polyester thermoplastique et d'élastomère thermoplastique de polyester sans couche adhésive
EP0742268A2 (fr) * 1995-05-12 1996-11-13 Advanced Elastomer Systems, L.P. Elastomères thermoplastiques ayant une résistance améliorée aux températures élevées

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1299662B2 (fr) † 2000-07-10 2009-05-06 Dichtungstechnik G. Bruss GmbH & Co. KG Bague d'etancheite
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 (zh) * 2018-03-23 2019-10-01 苏州纳绎博纳米科技有限公司 热塑性尼龙弹性体及其制备方法

Also Published As

Publication number Publication date
AU3464600A (en) 2000-11-10
NL1011896C2 (nl) 2000-10-30

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