CN101081907A - Oriented thermoplastic elastomer thin film and preparation method thereof - Google Patents
Oriented thermoplastic elastomer thin film and preparation method thereof Download PDFInfo
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- CN101081907A CN101081907A CN 200710137331 CN200710137331A CN101081907A CN 101081907 A CN101081907 A CN 101081907A CN 200710137331 CN200710137331 CN 200710137331 CN 200710137331 A CN200710137331 A CN 200710137331A CN 101081907 A CN101081907 A CN 101081907A
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- nylon
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- dynamic vulcanization
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 23
- 239000010409 thin film Substances 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 claims abstract description 28
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical class CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001971 elastomer Polymers 0.000 claims abstract description 22
- 239000000806 elastomer Substances 0.000 claims abstract description 14
- 239000004952 Polyamide Substances 0.000 claims abstract description 5
- 229920002647 polyamide Polymers 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 34
- 238000007766 curtain coating Methods 0.000 claims description 22
- 239000004677 Nylon Substances 0.000 claims description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 229920001778 nylon Polymers 0.000 claims description 20
- 150000001408 amides Chemical class 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000007664 blowing Methods 0.000 claims description 14
- 238000004073 vulcanization Methods 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 12
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 239000004902 Softening Agent Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- 229920002292 Nylon 6 Polymers 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical group CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 2
- 229920000577 Nylon 6/66 Polymers 0.000 claims description 2
- 229920000007 Nylon MXD6 Polymers 0.000 claims description 2
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 238000010096 film blowing Methods 0.000 claims 2
- 238000005266 casting Methods 0.000 abstract description 6
- 230000035699 permeability Effects 0.000 abstract description 5
- 238000000071 blow moulding Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 8
- -1 polyhexamethylene hexanediamide Polymers 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000232 polyglycine polymer Polymers 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 235000012222 talc Nutrition 0.000 description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
- 241000197192 Bulla gouldiana Species 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 241000282941 Rangifer tarandus Species 0.000 description 1
- 239000004959 Rilsan Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001743 benzylic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006039 crystalline polyamide Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The oriented thermoplastic elastomer film with low permeability and high fatigue resistance is produced with the mixture of halogenated isobutene elastomer and dynamically vulcanized polyamide, and through flow casting or blow molding. During the production, the shearing speed in the mold lip for flow casting or blow molding is regulated properly to control the molecule arrangement inside the film and make the film possess planar birefraction (PBR) not smaller than 0.002.
Description
The application is that application number is dividing an application of 03826102.2 application.
Technical field
The present invention relates to the oriented thermoplastic elastomer thin film and preparation method thereof of the fatigue resistance of a kind of perviousness with reduction and raising.More particularly, the present invention relates to the thermoplastic elastomer thin film preparation of compositions method that a kind of gas permeability reduces and planar orientation improves and use it to prepare the method for pneumatic tyre.
Background technology
EP722850B1 discloses a kind of low-osmosis thermoplastic elastomer composition, it in pneumatic tyre excellent ground as gas-barrier layer.This thermoplastic compounds comprises for example mixture of polymeric amide or polymeric amide of low-permeability thermoplastic matrix, wherein is dispersed with low-permeability rubber, for example bromo poly-(iso-butylene-altogether-p-methylstyrene) (being BIMS).Subsequently, in EP857761A1 and EP969039A1, the viscosity ratio quilt between thermoplastic matrix and the rubber dispersion is clear and definite so that obtain phase continuity in thermoplasticity and thin rubber dispersion.Recognize that in EP969039A1 less rubber dispersion gives the criticality of acceptable wearing quality in these thermoplastic elastomers, particularly they are in pneumatic tyre during as the liner purposes.
Can realize the impermeable further raising of these low-osmosis thermoplastic elastomers by forcing at planar orientation.In WO 0214410, briefly disclose and in thermoplastic elastomer thin film, introduced orientation to improve performance and to reduce perviousness.Testing data is not provided in this patent application.And the method described in this application relates to the film of discussing by hypothesis to be had strain vulcanization characteristics and suitable stretching kinetics and comes to make the cast film diaxial orientation through drawing-off, tentering and thermofixation.In the present invention, give thermoplastic elastomer cast film planar orientation by film casting and/or film blow moulding simply, be used to improve film performance.This thermoplastic elastomer thin film does not have suitable stretching kinetics that it is orientated through ensuing diaxial orientation process.
Summary of the invention
The oriented thermoplastic elastomer thin film that the purpose of this invention is to provide the fatigue resistance of a kind of gas permeability with reduction and raising also provides the preparation method of this film.
According to the present invention, the oriented thermoplastic elastomer thin film of the fatigue resistance of a kind of perviousness with reduction and raising is provided, it comprises (A) halogenated isobutylene elastomer and (B) polymeric blends of the dynamic vulcanization of polymeric amide, this film is to make by curtain coating or the polymeric blends above the blowing under certain condition, described condition make adjustable throttle prolong or blowing with the velocity of shear at die lip place with the molecular arrangement in the control film, the planar birefringence of gained film (PBR) is more than or equal to 0.002 thus, and preferred PBR is 0.004 or bigger.
Summary of the invention
In this specification sheets below and claims, singulative " ", " one " and " this " comprise plural indicator, unless context clearly explanation in addition.
The present invention relates to the oriented thermoplastic elastomer thin film and preparation method thereof of the fatigue resistance of a kind of perviousness with reduction and raising.
More particularly, the present invention relates to prepare the film casting of the thermoplastic elastomer thin film that a kind of planar orientation improves and the method for blow moulding and this film preparation pneumatic tyre of use.
The preferred planar double refraction of oriented thermoplastic elastomer thin film is more than or equal to 0.002.This orientation can apply by the blow-up ratio during speed of rolling during increase curtain coating and the blowing or the blowing of increase film.
The accompanying drawing summary
To understand the present invention better from the explanation of 1 statement with reference to the accompanying drawings, Fig. 1 has shown the planar orientation of film and the relation between its perviousness.
Composition for thermoplastic elastomer is through the halogenated isobutylene elastomer of dynamic vulcanization and polyamide compound.
" " this paper refers to the sulfidation that engineering resin and vulcanizable elastomer vulcanize to dynamic vulcanization to term under the condition of high shear. As a result, vulcanizable elastomer is crosslinked and be dispersed in the engineering resin matrix as " microgel " particulate simultaneously.
Dynamic vulcanization equipment for example roller mill, Banbury blender, continuous mixing device, kneading machine or mix in the extruder (for example double screw extruder) elastomeric solidification temperature or on temperature under mix these components and carry out. The unique property of the composition of dynamical cure is, although elastomeric component can solidify fully, these compositions can by conventional thermoplastic resin processing technology such as extrude, processing and the reprocessing such as injection mo(u)lding, extrusion modling. Waste or flash can be remedied and reprocess.
In a preferred embodiment, halogenated isobutylene elastomer component comprises isobutene and to the copolymer of ring-alkylated styrenes, for example described in the european patent application 0 344 021. These copolymers preferably have basically uniformly, and composition distributes. Alkyl in the ring-alkylated styrenes part is preferably included the alkyl with 1-5 carbon atom, uncle's haloalkyl of a 1-5 carbon atom, secondary haloalkyl and composition thereof. A kind of preferred copolymer comprises isobutene and p-methylstyrene.
Suitable halogenated isobutylene elastomer component comprises that number-average molecular weight Mn is at least about 25,000, preferably at least about 50,000, preferably at least about 75,000, preferably at least about 100,000, preferably at least about 150,000 copolymer (for example bromo isobutene-p-methylstyrene copolymer). The ratio that this copolymer also can have weight average molecular weight (Mw) and a number-average molecular weight (Mn) is Mw/Mn less than about 6, preferably less than about 4, be more preferably less than about 2.5, most preferably less than about 2.0. In another embodiment, suitable halogenated isobutylene elastomer component comprises that 125 ℃ of lower Mooney viscosities (1+4) (measuring by ASTM D 1646-99) are 25 or larger, preferred 30 or larger, more preferably 40 or larger copolymer (for example bromo isobutene-p-methylstyrene copolymer).
The brominated copolymer of preferred isobutene and p-methylstyrene comprises that having 5-12 % by weight p-methylstyrene, 0.3-1.8mol% brominated p-methylstyrene and the Mooney viscosity 125 ℃ under is those of 30-65 (1+4) (by ASTM D 1646-99 mensuration).
Halogenated isobutylene elastomer component of the present invention (A) can by isobutene and take the total amount of comonomer as the basis about 0.5-25% weight, preferred about 2-20% weight to ring-alkylated styrenes, the polymerization of preferred p-methylstyrene is made by halo afterwards. Take the total amount of copolymer as the basis, the content of halogen (for example, Br and/or Cl, preferred Br) is preferably less than about 10% weight, more preferably from about 0.1-7% weight.
The described copolymerization for example known way described in disclosed European patent application EP-34402/1A on November 29th, 1989 carries out, and described halo for example the known way described in the United States Patent (USP) 4548995 carry out.
Halogenated isobutylene elastomer preferably has at least about 25,000, and more preferably at least about 100,000 number-average molecular weight (Mn) with preferably less than about 10, being more preferably less than about 8 the weight-average molecular weight Mw and the ratio of number-average molecular weight (Mn) is Mw/Mn.
Can be used for polymeric amide of the present invention is polyamide thermoplastic (nylon), and it is included in the crystallization that has the repetition amide units in the polymer chain or the high molecular solid binary multipolymer or the terpolymer of resin.Polymeric amide can by with one or more ε lactan for example hexanolactam, pyrrolidone, lauryl lactam and amino undecane lactan or amino acid polymerization make, perhaps can be by diprotic acid and diamine condensation are made.Fiber forms and the nylon of molding graae all is suitable.The example of these polymeric amide has the condensation product (Ni Long11) of the amino undecanoic acid of polycaprolactam (nylon 6), polylauryllactam (nylon 12), polyhexamethylene hexanediamide (nylon-66), polyhexamethylene azelaoyl amine (nylon-6 9), polyhexamethylene sebacamide (nylon-610), polyhexamethylene isophthaloyl amine (nylon-6 IP), nylon 612, nylon 46, nylon MXD 6, nylon 6/66 and 11-.Other case description of gratifying polymeric amide (particularly softening temperature is lower than those of 275 ℃) is at Kirk-Othmer, Encyclopedia ofChemical Technology, v.10, page 919 and Encyclopedia of PolymerScience and Technology, Vol.10 is among the pages 392-414.The polyamide thermoplastic of commercially available acquisition can be used for practice of the present invention valuably, wherein preferred softening temperature or the line style crystalline polyamide of fusing point between 160 ℃-230 ℃.
The amount that can be used for elastomerics of the present invention (A) and polymeric amide (B) preferably is respectively 95-25 weight part and 5-75 weight part, more preferably is respectively 90-25 weight part and 10-75 weight part, and prerequisite is that component (A) and total amount (B) are 100 weight parts.
Except above-mentioned neccessary composition, elastic composition of the present invention can contain sulfuration or linking agent, sulfuration or crosslinked accelerator, various oil, protective agent, toughener, softening agent, tenderizer or be mixed into other various additives in the conventional rubber usually.These compounds can mix and vulcanize and can be used to subsequently vulcanize or crosslinked composition to make by ordinary method.The add-on of these additives can be the amount that adds usually in the past, as long as their not negative impacts purpose of the present invention.
Embodiment
Further describe the present invention by following examples now, but the present invention is not limited to these embodiment.
The product of following commercially available acquisition is used for the component that these embodiment use.
1. resin Composition
The mixture of nylon 1:N11 (Rilsan BESN O TL) and N6/66 (Ube 5033B)
Nylon 2:N6/66 (CM6001FS)
Additive 1: softening agent; N-butylbenzenesulfonamide, expanding material; AR201
Additive 2: stablizer; Irganox 1098, Tinuvin 622LD and CuI
2. rubber components
BIMS: the brominated copolymer of iso-butylene and p-methylstyrene, to sell by ExxonMobil Chemical Company with trade name EXXPRO89-4, mooney viscosity is about 45, about 5 weight % p-methylstyrenes and about 0.75mol% bromine
DM16D: hexadecyldimethyl benzyl ammonium amine (Akzo Nobel)
6PPD:N-(1, the 3-dimethylbutyl)-N '-phenyl-P-pHENYLENE dI AMINE
ZnO: zinc oxide solidifying agent
St-acid: stearic acid solidifying agent
ZnSt: Zinic stearas solidifying agent
MBTS: benzothiazole based bisulfide
3. rubber granulation anti-hard caking agent
Talcum: hydrated magnesium silicate (Ciba)
ZnO: zinc oxide
Igafos:Igafos 168 antioxidants (Ciba)
Following is the measuring method that is used to estimate embodiment and comparative example:
A) measure volume averaging equivalent dispersion diameter and number average equivalent dispersion diameter
Adopt and dynamically to knock phase place AFM and estimate dispersion size and distribution of sizes in these films.The Reichert cryotome that use has a diamond knife freezes bubble with all film samples and cuts (cryoface) under-150 ℃.Bubble is cut sample be housed in the moisture eliminator under the drying nitrogen that flows and be heated to room temperature, do not have moisture.Use dynamic percussion mode AFM (DI-3000, Digital Instrument) to make sample operation 24 hours after cutting freezing to steep with rectangle 225-μ m silicon support.All are dynamically knocked phase place AFM Photomicrograph is transformed into tiff format and uses PHOTOSHOP (Adobe Systems) to handle to strengthen image.All images is measured and all to be to use commercial graphic processing tool box (Reindeer Games) to carry out as the annex of PHOTOSHOP.The result of determining image is write as text, is used for carrying out data processing by EXCEL (Microsoft) subsequently.Following calculating number average dispersion diameter Dn:
Dn＝Σ(n
1D
1)/Σ(n
1)
D
1Be the equivalent diameter of single dispersion, n
1Be that equivalent diameter is D
1The quantity of dispersion.Following expression volume averaging dispersion diameter Dv:
Dv＝Σ(n
1D
1 4)/Σ(n
1D
1 3)
Wherein, n
1Be that equivalent diameter is D
1The quantity of dispersion.
B) the tensile fatigue cycle
With film with carcass stock compound forces together with binder layer and solidified 10 minutes down at 190 ℃.Stamp out JIS No.2 dumbbell shape then and be used for-20 ℃, 6.67Hz and 40% strained serviceability test.
C) through the oxygen permeability of Mocon
Using Mocon OX-TRAN 2/61 perviousness determinator to carry out oxygen permeability under 60 ℃ measures.
D) through the main specific refractory power of Metricon
Use Metricon under the operative wavelength of 632.8nm, to measure 3 main specific refractory poweres.Following calculating planar birefringence, PBR, and mean refractive index, n:
PBR＝(n1+n2)/2-n3 (3)
n＝(n1+n2+n3)/3 (4)
Here, n1, n2 and n3 are respectively longitudinally, laterally and the specific refractory power of film vertical direction.
Embodiment 1-8
In the Banbury Banbury mixer, BIMS and solidifying agent pre-compounded are also used the anti-hard caking agent granulation, then it is mixed with nylon.In twin screw extruder, under 230 ℃, carry out mixing and the dynamic vulcanization of nylon and BIMS.Then with these mixture curtain coatings or be blow molded into film." diameter disk is also nursed one's health under 60 ℃ in vacuum oven and is spent the night, and measures perviousness afterwards by these film punching presses 2.Use Mocon OX-TRAN 2/61 perviousness determinator to measure the oxygen penetration number of these films under 60 ℃.
Use the main specific refractory power of these films of Metricon prism coupling measuring apparatus along 3 main directions.Operative wavelength is the 632.8nm that is produced by the low power He-Ne laser apparatus.Use this three main specific refractory poweres, can following calculating mean refractive index:
<n>＝(n1+n2+n3)/3
Wherein＜and n〉be mean refractive index.1,2 and 3 be meant respectively vertically, laterally with vertical (vertical) direction with pellicular front.The opposite planar orientation can be represented (referring to US 5385704) with planar birefringence that defines below or PBR
PBR＝(n1+n2)/2-n3
In embodiment 1-8, use as shown in table 1 adds nylon 1 matrix that softening agent and expanding material are arranged.Have softening agent nylon 1 matrix viscosity near with the coupling of BIMS.MBTS is a cure retarder, and DM16D is a viscosity enahncers.They can and influence it and the reactive compatibilization of nylon with phenmethyl (benzylic) bromine reaction of BIMS.Because BIMS and nylon combine improvement with this interface between MBTS and the DM16D, the nylon that therefore influences during film casting or the blowing is orientated.As shown in table 1, roll speed with identical casting head by increase and reduce cast film thickness, make planar orientation increase and the corresponding reduction of perviousness.Although can not measure the perviousness of blown film owing to film surface adhesive, rolling speed by increase under the situation that does not change die head and blow-up ratio reduces film thickness, makes planar orientation increase once more.Adding MBTS and DM16D makes orientation reduce.On the whole, between PBR and perviousness, has strong dependency.Because we use identical nylon matrix by his-and-hers watches 1 all listed films, therefore represent the density of nylon and the mean refractive index of degree of crystallinity to keep constant.The result marks on Fig. 1, and wherein embodiment 4,7 and 8 PBR (referring to figure #4, #7 and #8) are not within the scope of the invention.
Table 1
| |
1 | 2 | 3 | 4* 3 | 5 | 6 | 7* 3 | 8* 3 |
| Prescription (weight part) | ||||||||
| BIMS | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| |
0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.5 |
| |
0 | 0 | 0 | 0 | 0 | 0 | 1 | 0 |
| ZnO | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
| St-acid | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 |
| ZnSt | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| |
68 | 68 | 68 | 68 | 68 | 68 | 68 | 68 |
| |
21 | 21 | 21 | 21 | 21 | 21 | 21 | 21 |
| |
0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Method | ||||||||
| Curtain coating | Curtain coating | Curtain coating | Curtain coating | Curtain coating | - | - | Curtain coating | Curtain coating |
| Blowing | - | - | - | - | Blowing | Blowing | - | - |
| Performance | ||||||||
| Thickness (μ m) | 130 | 180 | 230 | 280 | 130 | 180 | 150 | 150 |
| <n> | 1.5170 | 1.5165 | 1.5165 | 1.5167 | 1.5175 | 1.5184 | 1.5175 | 1.516 |
| PBR(10 -3) | 4.91 | 3.95 | 3.02 | 1.25 | 2.24 | 2.11 | 1.85 | 1.4 |
| Perviousness * 1 | 10.8 | 11.8 | 12.7 | 12.8 | nm* 2 | nm* 2 | 13.5 | 14.6 |
* 1: unit is cc*mil/ (m
2-day-mmHg)
* 2: because surperficial bonding coat and undetermined.
* 3: the comparative example
Embodiment 9-13
In embodiment 9-13, use nylon 1 matrix, but do not have softening agent and expanding material.6PPD can be the solidifying agent that passes through under 230 ℃ mixing temperature through the crosslinked BIMS of phenmethyl bromine, therefore, removes them with reactive compatibilization.DM16D be also with the viscosity enahncers of the BIMS of the phenmethyl bromine reaction of BIMS.Use DM16M and 6PPD to improve the interface in conjunction with can significantly reducing planar orientation and improving film permeation, as shown in table 2.The results are shown in Fig. 1.In any case, between PBR and perviousness, can find good dependency.With comparing in the table 1, higher refractive index value has reflected that nylon matrix does not have the fact of softening agent.Therefore, wish higher density and high index.
Table 2
| |
9 | 10 | 11* 1 | 12* 1 | 13* 1 |
| Prescription (weight part) | |||||
| BIMS | 100 | 100 | 100 | 100 | 100 |
| |
0 | 0 | 1.0 | 2.0 | 3.0 |
| |
0 | 0.6 | 0 | 0 | 0 |
| ZnO | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
| St-acid | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 |
| ZnSt | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| |
95 | 95 | 95 | 95 | 95 |
| |
0 | 0 | 0 | 0 | 0 |
| |
0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| Method | |||||
| Curtain coating | Be | Be | Be | Be | Be |
| Performance | |||||
| <n> | 1.5184 | 1.5174 | 1.5175 | 1.5170 | 1.5171 |
| PBR(10 -3) | 3.2 | 2.25 | 1.1 | 0.98 | 1.1 |
| Perviousness | 5.31 | 6.43 | 7.05 | 7.69 | 7.47 |
* 1: the comparative example
Embodiment 14-19
In embodiment 14-19, use nylon 2 matrix, do not have N11 and do not have softening agent.When mixing with nylon 2, need viscosity modifier, for example DM16D and 6PPD mate and thin BIMS rubber dispersion so that good viscosity to be provided.The concentration that the listed anti-hard caking agent of table 3 uses is 0.5-1phr.As described in Table 3, use ZnO can remarkably influenced to be orientated as anti-hard caking agent.This anti-hard caking agent can play solidifying agent, therefore, removes the phenmethyl bromine so that itself and nylon reactive compatibilization from BIMS.From BIMS, remove a large amount of phenmethyl bromines and can reduce the ability that interface junction between nylon and the BIMS dispersion merge to reduce processing film method oriented nylon.Yet, kept the overall relevancy between PBR and the perviousness.With comparing in the table 2, higher refractive index value is the result of used N6/66 matrix.These results also are shown in Fig. 1.
Table 3
| |
14 | 15 | 16* 1 | 17 | 18 | 19 |
| Prescription (weight part) | ||||||
| BIMS | 100 | 100 | 100 | 100 | 100 | 100 |
| |
0 | 0 | 0 | 1.0 | 1.0 | 0 |
| 6PPD | 0.5 | 0.5 | 0.5 | 0 | 0 | 0.5 |
| Granulation | Talcum | Irgafos | ZnO | Talcum | Irgafos | Talcum |
| ZnO | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
| St-acid | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 |
| ZnSt | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| |
98 | 98 | 98 | 98 | 98 | 98 |
| |
0 | 0 | 0 | 0 | 0 | 0 |
| |
0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 |
| Method | ||||||
| Curtain coating/blowing | Curtain coating | Curtain coating | Curtain coating | Curtain coating | Curtain coating | Blowing |
| Performance | ||||||
| <n> | 1.5215 | 1.5216 | 1.5215 | 1.5222 | 1.5217 | 1.5219 |
| PBR(10 -3) | 6.1 | 5.15 | 1.4 | 4.55 | 3.25 | 5.4 |
| Perviousness | 1.38 | 1.51 | 1.92 | 1.27 | 1.37 | 1.42 |
* 1: the comparative example
Claims (11)
1, the oriented thermoplastic elastomer thin film of the fatigue resistance of a kind of perviousness with reduction and raising, it comprises (A) halogenated isobutylene elastomer and (B) polymeric blends of the dynamic vulcanization of polymeric amide, this film is to make by curtain coating or the above-mentioned polymeric blends of blowing under certain conditions, described condition make to regulate curtain coating or blowing with the velocity of shear at die lip place with the molecular arrangement in the control film, the planar birefringence of gained film is more than or equal to 0.002 thus.
2, oriented thermoplastic elastomer thin film as claimed in claim 1, wherein the amount of (A) halogenated isobutylene elastomer be the 95-25 weight part and (B) amount of polymeric amide be the 5-75 weight part, prerequisite is that the total amount of component (A) and component (B) is 100 weight parts.
3, oriented thermoplastic elastomer thin film as claimed in claim 1 or 2, wherein halogenated isobutylene elastomer is bromo poly-(iso-butylene-be total to-p-methylstyrene).
4, oriented thermoplastic elastomer thin film as claimed in claim 1 or 2, wherein polymeric amide is a polyamide thermoplastic, it is included in the crystallization that has the repetition amide units in the polymer chain or the high molecular solid binary multipolymer or the terpolymer of resin.
5, oriented thermoplastic elastomer thin film as claimed in claim 1 or 2, wherein polymeric amide is at least a following member that is selected from: nylon 6, nylon 66, Ni Long11, nylon 69, nylon 12, NYLON610, nylon 612, nylon 46, nylon MXD 6 and nylon 6/66.
6. each the method for oriented thermoplastic elastomer thin film of preparation claim 1-5, wherein halogenated isobutylene elastomer is the brominated copolymer of iso-butylene and p-methylstyrene, wherein with before polymeric amide mixes, in Banbury mixer with p-methylstyrene and solidifying agent pre-compounded, use the anti-hard caking agent granulation then
Afterwards,, form the blend polymer of dynamic vulcanization with the p-methylstyrene dynamic vulcanization of polymeric amide and granulation,
Then, to contain this dynamic vulcanization blend polymer, softening agent and stablizer the mixture curtain coating or be blow molded into film, wherein by increasing the speed of rolling in curtain coating or the blowing process, perhaps, apply on the blend polymer that is orientated dynamic vulcanization by increasing the blow-up ratio in the film blowing process.
7. the method for claim 6 wherein by increasing the speed of rolling in the curtain coating process, applies on the blend polymer that is orientated dynamic vulcanization.
8. the method for claim 6 wherein by increasing the speed of rolling in the blowing process, applies on the blend polymer that is orientated dynamic vulcanization.
9. the method for claim 6 wherein by increasing the blow-up ratio in the film blowing process, applies on the blend polymer that is orientated dynamic vulcanization.
10. the method for claim 6, wherein anti-hard caking agent is a zinc oxide.
11. the method for claim 6, wherein softening agent is a N-butylbenzenesulfonamide.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311955A (en) * | 2014-10-14 | 2015-01-28 | 任柏成 | Anti-caking moisture-absorbing film material for citric acid packaging |
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2003
- 2003-03-06 CN CN 200710137331 patent/CN101081907A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311955A (en) * | 2014-10-14 | 2015-01-28 | 任柏成 | Anti-caking moisture-absorbing film material for citric acid packaging |
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