CN1368991A - Thermoplastic vulcanizates from dynamically vulcanized TRU/apolar rubber blends - Google Patents

Thermoplastic vulcanizates from dynamically vulcanized TRU/apolar rubber blends Download PDF

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CN1368991A
CN1368991A CN00811477A CN00811477A CN1368991A CN 1368991 A CN1368991 A CN 1368991A CN 00811477 A CN00811477 A CN 00811477A CN 00811477 A CN00811477 A CN 00811477A CN 1368991 A CN1368991 A CN 1368991A
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blend
rubber
thermoplastic polyurethane
thermoplastic
polar
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D·利默肯斯
G·J·布莱斯
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Huntsman International LLC
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Huntsman International LLC
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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
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • 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
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

Abstract

Dynamically vulcanized blend comprising a thermoplastic polyurethane having at least 1 major Tg of less than 60 DEG C and an apolar rubber.

Description

Thermoplastic vulcanizates product from the acquisition of dynamic vulcanization TPU/ apolar rubber blends
Invention field
The thermoplastic vulcanizates product that the present invention relates to thermoplastic vulcanizates product (TPV) and relate more specifically to be produced by the blend that comprises thermoplastic polyurethane (TPU) and non-polar rubber, wherein rubber phase is a dynamic vulcanization.
The description of prior art
Thermoplastic elastomer is a class material that combines the processing characteristics of the performance of vulcanized rubber and ordinary hot thermoplastic plastic.The example of these materials is being well-known in the art.Usually, they are made up of segmented copolymer, have showed heterogeneous microstructure.The most well-known example is styrenic elastomer segmented copolymer such as styrene-butadiene-styrene (SBS), perhaps styrene-isoprene-phenylethene (SIS).Other example is polyamide elastomer and polyurethane elastomer segmented copolymer.Wonder more example, for example consult 13 chapters of " rubber Science and Technology (Science and Technology of Rubber) ", J.E.Mark etc., Eds., 2 NdEd.Academic Press, 1994.
Thermoplastic elastomer can also be produced by hard thermoplastic material of blend and rubber-like material.Example is natural rubber/polypropylene (NR/PP) blend (TPNR) and ethylene-propylene-diene monomer rubber/polypropylene (EDPM/PP) blend, is commonly referred to thermoplastic olefin (TPO).Many examples are at " Thermoplastic Elastomers from Rubber-Plastic Blends ", DE and BHOWMICK eds., and Ellis Horwood provides in 1990.
It is also known that, in the art, often can improve mutually by crosslinked in the hybrid technique process or vulcanized rubber based on the performance of the thermoplastic elastomer of rubber-inorganic filler plastic blending material.This method is called as dynamic vulcanization and has produced the material that is referred to as thermoplastic vulcanizates product (TPV) or elastomer alloy (EA) usually.Studied TPV (for example, Rubber Chem.Technol.53, p781, (1980), Rubber Chem.Technol.63, p.599 (1989), Rubber Chem.Technol.68, p351 (1995)) by Coran and colleague comprehensively.Prevailing TPV (consults for example US 3758643, US3806558) based on the EPDM/PP dynamic vulcanized comixture.
Disclose in undelegated patent application EP 98102213.0 still to comprise that (A) is not lower than 60 ℃ the rigid thermoplastic polyurethane of main Tg and the thermoplastic elastomer of composition that (B) has the rubber-like material of the Tg that is lower than 20 ℃, (A): (B) weight ratio is 85: 15 at the most.
The thermoplastic elastomer that thermoplastic polyurethane or TPU normally are made up of soft chain segment that produces from the reaction between macromolecular diol, vulcabond and the short-chain diol and hard segment.They have showed elasticity and thermoplasticity corresponds respectively to hard and soft two kinds of glass transition temperature Tg mutually with having shown hAnd Tg s
Term used herein ' second-order transition temperature ' or Tg are understood by those skilled in the art easily, and this notion is at the 2nd chapter of " Mechanical Properties of Polymers ", L.E.Nielsen, Chapman ﹠amp; Hall, London is fully explained in 1962, and can (DSC) determines as ' dsc ' by well-known method easily.Usually, Tg sBe to be lower than approximately-10 ℃ and Tg hBe higher than 50 ℃.
The blend of TPU and other thermoplastics is well-known in the art.For example, TPU and polyoxymethylene (POM), polyvinyl chloride (PVC), the blend of styrene-acrylonitrile (SAN) and acronitrile-butadiene-styrene (ABS) has commercial significance.
At ' Structure, Morphology and Physical Property ofDynamically Vulcanized Polyurethane/Nitrile Butadiene RubberBlends ' (Adv.Polym.Blends Alloys Technol.4, p.1-10,1993) in, Tao Tang etc. discloses has the dynamic vulcanization TPU/NBR blend that improves physicals, is because the synergy between TPU and NBR phase.NBR is a polar rubber; The blend of TPU and non-polar rubber is not disclosed.
General introduction of the present invention
Now, it has surprisingly been found that the Thermoplastic Vulcanizate with useful performance can produce by TPU and non-polar rubber material that melt blended and dynamic vulcanization has 1 a main Tg that is lower than 60 ℃ at least.Detailed description of the present invention
Therefore the present invention relates to and comprises the thermoplastic polyurethane with at least 1 the main Tg that is lower than 60 ℃ and the dynamic vulcanized comixture of non-polar rubber.
According to the present invention, rubber phase is dynamically vulcanized, and promptly vulcanizes in the blending technology process.The sulfuration of rubber phase can enoughly be proficient in the known composition of personnel of art technology and realize, for example uses sulfur system, accelerated sulfur system, superoxide, phenols etc.Preferably, use phenols and peroxide vulcanizing system.The general introduction of normally used vulcanization system can be at " Science and Technology of rubber (Science and Technology of Rubber) ", and 2 Nd.Ed.academic press finds in 1994.
Melt blended and dynamic vulcanization can obtain by using typical closed well known in the art or open type mixing machine.In addition, blend can be used and extrude, and for example in twin screw extruder, perhaps finishes in the batch mixing single screw extrusion machine.The general introduction of putting into practice the aspect of polymer blending can be at " blend polymer and alloy (Polymer Blends andAlloys) ", Folkes and Hope Eds, Chapman ﹠amp; Hall finds in (1993).
Thermoplastic polyurethane of the present invention passes through at 95-105, and the reaction by vulcabond and macromolecular diol and chainextender under the isocyanate index of preferred 98-102 obtains.
The thermoplastic polyurethane that is fit to can also be by the different urethane of blend obtains under the condition of amount of at least 1 the main Tg that is lower than 60 ℃ so that blend has.
Here employed term " isocyanate index " is meant the isocyanate group that is present in the formulation and the ratio of isocyanate reactive hydrogen atoms, provides with percentage ratio.In other words, isocyanate index is illustrated in the preparaton the actual isocyanic ester that uses with respect to the percentage ratio that is used for the required theoretical amount of isocyanate of the quantitative response of the isocyanate-reactive hydrogen that uses at formulation.
It should be noted that employed isocyanate index should be considered from the viewpoint of the actual elastic body formation method that involves isocyanate prepolymer composition and isocyanate-reactive composition here.For producing any isocyanate group that modified polyisocyanate (comprise and be referred to as in the art to be as the criterion or these isocyanate derivates of semi prepolymer) consumes or do not consider in the calculating of isocyanate index and go in the pilot study step for producing modified polyalcohol or polyamines and any active hydrogen of isocyanate reaction.Only being present in the actual elastic body forms the free isocyanate groups in stage and free isocyanate reactive hydrogen and (comprises and be considered those of water into if you are using).
TPU can be according to so-called single stage method, and semi prepolymer or prepolymer method by casting, are extruded or known any other method of personnel of being proficient in art technology is produced.
Employed macromolecular diol has the molecular weight between 500 and 20000, and so that TPU has at least 1 amount that is lower than 60 ℃ main Tg to be used, is generally the amount based on the 25-75 weight part of TPU gross weight.
Be defined as the soft segment content of thermoplastic polyurethane as the amount of the macromolecular diol of the wt% of thermoplastic polyurethane total amount.
Macromolecular diol can be selected from polyesteramide, polythioether, polycarbonate, polyacetal, polyolefine, polysiloxane and especially polyester and polyethers.
Operable polyether glycol comprises by the ring-type oxide compound, the product that the polycondensation under the existence of two necessary functional initiator therein of oxyethane for example, propylene oxide, butylene oxide ring or tetrahydrofuran (THF) obtains.The initiator compounds that is fit to contains 2 active hydrogen atoms and comprises water, butyleneglycol, ethylene glycol, propylene glycol, glycol ether, triglycol and dipropylene glycol.Can use initiator and/or ring-type hopcalite.
Especially the available polyether glycol comprise as in the prior art fully as described in, by oxyethane and propylene oxide for two functional initiator polyoxypropyleneglycol and poly-(ethylene oxide-propylene oxide) glycols of obtaining of addition simultaneously or in a sequence.What can mention is the random copolymers that has at the most 80% ethylene oxide content, have at the most the segmented copolymer of 25% ethylene oxide content and have at the most the random/segmented copolymer of 50% ethylene oxide content, based on the gross weight of alkylene oxide unit, especially have to those of the oxyethylene group of small part at the polymer chain end.It is poly-1 that other useful especially polyether glycol comprises that the polymerization by tetrahydrofuran (THF) (THF) obtains, the 4-butyleneglycol.
Operable polyester glycol comprises dibasic alcohol such as ethylene glycol, propylene glycol, glycol ether, 1,4-butyleneglycol, neopentyl glycol or 1, the 6-hexylene glycol, the perhaps mixture of these dibasic alcohol, with the ester derivative that becomes of dicarboxylic acid and they, for example Succinic Acid, pentanedioic acid and hexanodioic acid or their dimethyl ester, sebacic acid, Tetra hydro Phthalic anhydride, the reaction product of the hydroxy terminal that tetrachlorophthalic tetrachlorophthalic anhydrid or dimethyl terephthalate (DMT) or their mixture form.
Operable polythioether glycol comprises by independent condensation thiodiglycol or it and other glycol, the product that alkylene oxide or dicarboxylic acid condensation obtain.
Operable polycarbonate diol comprises by making glycol as 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol, glycol ether or Tetraglycol 99 and diaryl carbonate, for example diphenyl carbonate or the product that obtains with phosgene reaction.
Operable polyacetal glycol comprise by make glycol such as glycol ether, triglycol or hexylene glycol and formaldehyde reaction the preparation those.The polyacetal that is fit to can also prepare by the polymerizable cyclic acetal.
The polyolefin diols that is fit to comprises that the divinyl of hydroxy terminal all comprises polydimethylsiloxanediols diols with multipolymer and suitable silicone glycol.
Chainextender can be any two functional isocyanate reactive materials, preferred diol or the dissimilar blend with MW＜500.
The chainextender that is fit to comprises aliphatic diol, as ethylene glycol, and 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,2-propylene glycol, 1,3 butylene glycol, 2,3-butyleneglycol, 1, the 3-pentanediol, 1,2-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, glycol ether, dipropylene glycol and tripropylene glycol.The chainextender such as the 2-methyl isophthalic acid that between the OH base, have the chainextender of odd numbers of carbon atoms and have the branched chain structure, ammediol, 2,2-dimethyl-2, ammediol, 1, ammediol, 1, the 5-pentanediol also is fit to.
Also can use cycloaliphatic diol to resemble 1, the 4-cyclohexanediol, 1,2-cyclohexanediol, 1,4 cyclohexane dimethanol or 1,2-cyclohexanedimethanol and aromatic diol resemble quinhydrones two (hydroxyethyl ether) etc.
Organic multiple isocyanate can be selected from aliphatic series, cyclic aliphatic and araliphatic polyisocyanates, especially vulcabond, as hexamethylene diisocyanate, isophorone diisocyanate, hexanaphthene-1, the 4-vulcabond, 4,4 '-dicyclohexyl methane diisocyanate, and and right-(tetramethyl-benzene) dimethylene diisocyanate, especially aromatic polyisocyanate such as tolylene diisocyanate (TDI), phenylene diisocyanate and diphenylmethanediisocyanate most preferably.
Diphenylmethanediisocyanate can be substantially by pure 4,4 '-diphenylmethanediisocyanate or this vulcabond and one or more other organic multiple isocyanates, especially other diphenylmethanediisocyanate isomer, for example 2,4 '-isomer is optional together with 2, and 2 '-mixture of isomers is formed.Polyisocyanate component can also be by containing 4 of 85wt% at least, the polyisocyantates composition deutero-MDI-modification thing of 4 '-diphenylmethanediisocyanate.MDI modification thing is well-known in the art, can be used according to the invention especially comprise by carbodiimide-based being incorporated in the described polyisocyantates composition and/or product liquid by obtaining with one or more polyol reactions.
Preferably contain 4 of 90wt% at least, the polyisocyantates composition of 4 '-diphenylmethanediisocyanate.Contain 4 of 95wt% at least, the polyisocyantates composition of 4 '-diphenylmethanediisocyanate is most preferred.
Employed catalyzer can be any catalyzer as known in the art in the production of TPU, especially tertiary amine catalyst and metal catalyst such as Sn and Bi type catalyzer.
Being used for rubber of the present invention can be the general known any non-polar rubber in this area.Preferred rubber is only by C, H, O and/or N atom, more preferably only by C, H and O atom with most preferably only be made up of C and H atom.Preferably, do not have polar functional group such as C ≡ N ,-OH or-CO-O-exists.Yet, can admit of polar group in a small amount, as long as total polarity of rubber is not subjected to big influence.The example of the rubber that is fit to is (hydrogenation) divinyl rubber (BR), styrene butadiene rubbers (SBR), synthetic polyisoprene (IR), natural rubber (NR), isoprene-isobutylene rubber (IIR), ethylene-propylene rubber (EPR), ethylene-propylene-diene monomer rubber (EPDM) or think other non-polar rubber based on polyolefine or their mixture.
(hydrogenation) elastoprene or preferably based on the rubber of ethylene, propylene blend or multipolymer.Styrene butadiene ribber more preferably, synthetic polyisoprene, natural rubber or isoprene-isobutylene rubber, synthetic polyisoprene are most preferred.
The amount of the rubber that uses in blend is 10wt% at least, and based on the gross weight of rubber and urethane, preferably 25wt% and more preferably 50wt% at least at least are based on the gross weight of rubber and urethane.
In another embodiment of the invention, the performance of dynamic vulcanized comixture of the present invention is improved by using compatibilizing agent.In many cases, the performance of TPV can be also referred to as expanding material and be improved by using compatible additive.This compounds is well-known in the art, normally segmented copolymer or graft copolymer, and wherein block is made up of polymer material that must increase-volume.Expanding material can independently be produced and be added before or after blend, perhaps can be in the blend process produce in situ.Back one method is referred to as reactive compatibilization.The general introduction of the example of the expanding material that the polymkeric substance increase-volume is right with being used for different polymkeric substance is given in " Polymer Blends and Alloys ", Folkes and Hope Eds., Chapman﹠amp; Hall is in (1993).
Can be used for expanding material of the present invention can be non-reactive copolymer or non-reacted graft copolymer, for example comprises the polyester-rubber graft copolymer, the mutually compatible segmented copolymer compatible with rubber phase with another block with TPU of perhaps wherein a kind of block.Also can consider to use reactive compatibilizer, for example, wherein all or part of PU (or rubber) is modified mutually and can reacts mutually with rubber (or PU).These expanding materials add with the amount based on 10 weight parts at the most of blend gross weight usually.
Can also use the typical case to be used for the auxiliary agent and the additive of urethane and rubber technology.Can the sulfuration before, during or separately additive and auxiliary agent are added in TPU or the rubber phase afterwards.These auxiliary agents and additive comprise for example siloxanes-alkylene oxide copolymer of tensio-active agent, extending oil, fire retardant, softening agent, organic and mineral filler, pigment, antioxidant, UV stablizer, whipping agent, antideteriorant and inner pattern releasing agent applicable.
In the present invention, the hot expandable microsphere that contains (ring) aliphatic hydrocrbon also is the additive that is fit to.The drying that this microsphere generally is made up of the small spherical particles of the mean diameter with general 10-15 micron, the unexpanded or unexpanded microsphere of part.Ball is by sealing (ring) aliphatic hydrocrbon, and for example the resistance to air loss polymer shell of the fine droplet of liquid isobutane (for example being made up of vinyl cyanide or PVDC) forms.Be enough to when these microspheres that (for example 150 ℃-200 ℃) heat under the high temperature level of (ring) aliphatic hydrocrbon that softening thermoplastics shell and volatilization wherein seal, formed gas expansion shell and increased the volume of microsphere.When expanding, microsphere has the 3.5-4 diameter doubly of their initial diameters, result, their expanding volume than them at the original volume of unswollen state larger about 50-60 times.The example of these microspheres is EXPANCEL-DU microspheres (EXPANCEL is the trade mark of AKZO Nobel Industries) that the AKZO Nobel Industries of Sweden sells.
The invention still further relates to by melt blended and dynamic vulcanization and comprise that the thermoplastic polyurethane with at least a main Tg that is lower than 60 ℃ and the blend of non-polar rubber prepare the method for thermoplastic elastomer, and the thermoplastic elastomer that relates to acquisition like this.
Blend of the present invention is the liquid or solid form preferably.The especially preferred form of blend is a particulate solid.
Melt blended can carrying out in the independent process before dynamic vulcanization.
Advantage, purposes
Blend of the present invention can be used in the thermoplastic elastomer that preparation combines some advantages of typical TPU elastomerics and employed rubber.Because a large amount of possibility combinations is arranged, so can produce various materials with various performances.
The gained elastomerics can be used in many application, as sole, and shoe-pad, trolley part (panel board, window sealing material, air bag shell) or other are used as watchband, tool holder, cable insulation etc.
Embodiment
In an embodiment, use following test method:
Xiao A hardness: DIN 53505
Tensile strength: DIN 53504
Elongation at break: DIN 53504
Young's modulus: DIN53504
100% modulus: DIN 53504
Anti-skid: DIN 53375
Embodiment 1
In HAAKE Rheomix 3000P, under 180 ℃ and 50rpm with the synthetic polyisoprene (available from the Cariflex IR 310 of Shell) of 120g and the P4470T of 80g, promptly available from the poly-THF MDI type TPU blend of the 70 Shore A grades of HUNTSMAN ICI.After material melts fully (after about 5 minutes), add 7.2g available from 2 of Aldrich, 5-is two-(methylol)-p-cresol.Be blended in and carried out under the 80rpm 2 minutes, under 50rpm, carried out other 15 minutes.From mixing machine, discharge this material, cooling and pulverizing then.
This material uses HAAKE 252P single screw extrusion machine and the common PE screw rod with 1: 3 compression ratio to extrude.Set(ting)value is: 160 ℃: 170 ℃: 180 ℃, and die head temperature is 190 ℃.Screw speed is 50rpm.To the extruded material measurement performance.
The gained material has 52 Xiao A hardness, the tensile strength of 2.9Mpa and 440% elongation at break.
Embodiment 2
As producing TPV in embodiment 1, but the TPU that uses is P4485AT now, and it is 85 Shore A grades available from HUNTSMAN ICI, poly-THF-MDI type TPU.
The gained material has 55 Xiao A hardness, the tensile strength of 3.3Mpa and 490% elongation at break.
Embodiment 3
As preparing TPV in embodiment 2, but employed solidifying agent is 2,5-is two-and (methylol)-p-Cresol (' Purum ' level is available from Aldrich).Solidifying agent uses (phr: part/100 parts of rubber) with different levels.Some mechanical propertys of gained TPV provide in table 1.
Table 1
Phenols curing agent (phr) Young's modulus (MPa) Tensile strength (MPa) Elongation at break (%) Xiao A hardness
?3 ?4.4 ?2.2 ?375 ?53
?6 ?4.6 ?2.9 ?445 ?52
?6 ?2.5 ?3.3 ?490 ?55
?6 ?2.4 ?2.9 ?485 ?58
?6 ?2.4 ?2.3 ?355 ?47
Embodiment 4
As preparing TPV in embodiment 2, but TPU/ rubber weight ratio is 50/50 now, and employed solidifying agent is Trigonox  145-45 (peroxide firming agent that can obtain from Akzo Nobel) and blending temperature such variation as shown in table 2.Extruded material is compression molded into the 2mm slab.The power that applies is that 200kN continues 2 minutes, after this, and this plate of cooling between cooled plate.Some mechanical propertys of gained TPV are set forth in the table 2.
Table 2
The kneader temperature (℃) Trigonox  145-45 solidifying agent (phr) Tensile strength (Mpa) 100% modulus (MPa) Elongation at break (%) Xiao A hardness
?200 ?1.67 ?4.64 ?1.85 ?464 ?53
?200 ?2.78 ?5.1 ?1.88 ?504 ?52
?205 ?2.22 ?4.6 ?1.88 ?434 ?53
?205 ?2.22 ?4.38 ?1.84 ?427 ?53
?205 ?2.22 ?4.64 ?1.83 ?450 ?51
?210 ?1.67 ?5.15 ?2.04 ?455 ?53
?210 ?2.78 ?4.62 ?1.92 ?430 ?53
Embodiment 5
As producing TPV in embodiment 2, but employed solidifying agent is Trigonox  145-45, is held constant at the concentration of 4phr, and the kneader temperature is set in the amount of 205 ℃ and rubber as changing as shown in the table 3.Extruded material is as compression moulding among the embodiment 4.Some mechanical propertys of gained material are set forth in the table 3.
Table 3
Rubber mass in the blend (pbw) Tensile strength (MPa) 100% modulus (MPa) Elongation at break (%) Shore A hardness Abrasion (mg) Do anti-skid Wet anti-skid
?20 ?9.8 ?4.1 ?538 ?76 ?47 ?0.69 ?0.9
?30 ?7 ?3.3 ?428 ?71 ?74 ?1.35 ?1.17
?40 ?5.1 ?2.6 ?374 ?65 ?140 ?1.6 ?1.21
?50 ?5.15 ?2 ?455 ?53 ?216 ?2.27 ?2.05
Embodiment 6
As producing TPV in embodiment 2, but employed rubber is that EPDM is (available from the Keltan  4903 of DSM now; Ethylene content about 48%), and employed TPU is P4472DB, promptly available from the polyester polyol type TPU of the Xiao A hardness with about 72D of Huntsman ICI.Employed solidifying agent is the dicumyl peroxide of 3phr concentration.Some mechanical propertys of gained TPV are set forth in the table 4.
Table 4
Young's modulus (MPa) 22
Tensile strength (Mpa) 3.1
Elongation at break (%) 685
Xiao A hardness 76

Claims (20)

1. dynamic vulcanized comixture, it comprises thermoplastic polyurethane and the non-polar rubber with at least 1 the main Tg that is lower than 60 ℃.
2. according to the blend of claim 1, wherein rubber is selected from elastoprene, hydrogenated diene rubber or based on the rubber of ethylene, propylene blend or multipolymer.
3. according to the blend of claim 2, wherein rubber is selected from styrene butadiene ribber, synthetic polyisoprene, natural rubber, isoprene-isobutylene rubber or EPDM.
4. according to the blend of claim 3, wherein rubber is synthetic polyisoprene or EPDM.
5. according to each blend in the claim of front, wherein the amount of non-polar rubber is 10wt% at least, based on the gross weight of blend.
6. according to the blend of claim 5, wherein the amount of non-polar rubber is 25wt% at least, based on the gross weight of blend.
7. according to the blend of claim 6, wherein the amount of non-polar rubber is 50wt% at least, based on the gross weight of blend.
8. according to each blend in the claim of front, wherein thermoplastic polyurethane is based on diphenylmethanediisocyanate.
9. blend according to Claim 8, wherein diphenylmethanediisocyanate comprises 4 of 90wt% at least, 4 '-diphenylmethanediisocyanate.
10. according to each blend in the claim of front, wherein thermoplastic polyurethane is based on polyether glycol or polyester polyol or their mixture.
11. according to the blend of claim 10, wherein polyether glycol is the polytetramethylene polyvalent alcohol.
12. according to each blend in the claim of front, wherein the soft segment content of thermoplastic polyurethane is the 25-75 weight part, based on the gross weight of thermoplastic polyurethane.
13. according to each blend in the claim of front, it contains expanding material.
14. according to the blend of claim 13, wherein said expanding material is a reactive compatibilizer.
15. according to each blend in the claim of front, wherein vulcanization system is selected from the system that comprises phenols or superoxide.
16. a method for preparing thermoplastic elastomer, this method by melt blended and dynamic vulcanization according to the front claim each comprise the thermoplastic polyurethane with at least 1 the main Tg that is lower than 60 ℃ and the blend of non-polar rubber.
17. thermoplastic elastomer that obtains according to the method for claim 16.
18. one kind according to the blend that defines in each in claim 1-15, it is solid or liquid form.
19. according to the blend of claim 18, it is a particulate solid.
20. purposes that is used to prepare thermoplastic elastomer according to the blend that in each of claim 1-15 or 18-19, defines, the thermoplastic polyurethane and the non-polar rubber that wherein have at least 1 the main Tg that is lower than 60 ℃ are mixed, and dynamic vulcanization before thermoplastic elastomer is produced or in the process.
CN00811477A 1999-08-09 2000-07-10 Thermoplastic vulcanizates from dynamically vulcanized TRU/apolar rubber blends Pending CN1368991A (en)

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EP99115702 1999-08-09

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CN103131160A (en) * 2011-11-28 2013-06-05 福建省莆田市双源鞋业有限公司 Elastic trans- 1,4- polyisoprene (TPI) vibration-absorptive materials and toe vibration-absorptive sole
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CN103756287A (en) * 2014-01-24 2014-04-30 福州大学 Modified TPU (thermoplastic polyurethane) calendered film and preparation method thereof
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