CN1010588B - Polymer composition - Google Patents
Polymer compositionInfo
- Publication number
- CN1010588B CN1010588B CN 85106770 CN85106770A CN1010588B CN 1010588 B CN1010588 B CN 1010588B CN 85106770 CN85106770 CN 85106770 CN 85106770 A CN85106770 A CN 85106770A CN 1010588 B CN1010588 B CN 1010588B
- Authority
- CN
- China
- Prior art keywords
- composition
- silane
- polymer
- crosslinkable
- multipolymer
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 229920000642 polymer Polymers 0.000 title claims description 10
- 239000000126 substance Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 24
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910000077 silane Inorganic materials 0.000 claims abstract description 8
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 trifluorochloroethylene, tetrafluoroethylene Chemical group 0.000 claims description 42
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 229920000620 organic polymer Polymers 0.000 claims description 20
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229920000578 graft copolymer Polymers 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- 229920001567 vinyl ester resin Polymers 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 150000002170 ethers Chemical group 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 150000002978 peroxides Chemical class 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 abstract 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 9
- 238000003856 thermoforming Methods 0.000 description 9
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229920001973 fluoroelastomer Polymers 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004700 high-density polyethylene Substances 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 229920000092 linear low density polyethylene Polymers 0.000 description 6
- 239000004707 linear low-density polyethylene Substances 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003707 silyl modified polymer Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229920001038 ethylene copolymer Polymers 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001733 carboxylic acid esters Chemical group 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002942 palmitic acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to a cross-linking thermoplastic polymer composition which comprises components cross linked preferably by heating or using a chemical treating method such as polyolefin components containing peroxide or silane modified polyolefin and a fluorocarbon polymer. The composition can be made into useful manufactured products by thermal forming, for example an insulated cable. However, the fluorocarbon polymer (such as a copolymer of 1, 1-difluoroethylene and hexafluoropropylene) makes the surface smoothness of the manufactured products improved.
Description
The present invention relates to crosslinkable thermoplastic polymer composition, said composition can thermoforming, and for example extrusion moulding is crosslinked afterwards, obtains the product of improvement in performance.
More particularly the present invention relates to the composition of thermoplastic polymer, be suitable for after being thermoformed into finished product or work in-process, carrying out crosslinked with heating method or method of chemical treatment.The known composition of this class comprises polymer composition and the silane modified polymer that contains superoxide, and the former is suitable for carrying out with the method for heating " thermoforming product " crosslinked, and the temperature of heating will be higher than hot-forming temperature; And silane modified polymer is suitable for usually after thermoforming, in the presence of silicon alcohol condensation catalyst, carries out crosslinked with the method for water treatment.
In the presence of superoxide, can be with the new LDPE (film grade) of high-pressure process production and the multipolymer of ethylene vinyl acetate with the example of the crosslinked thermoplastic polymer of heat treating method, high density polyethylene(HDPE) and linear low density polyethylene, for example, the peroxide modified usable polymers powder of crosslinkable thermoplastic polymer or particle are with being made by the complete suitable organo-peroxide blend of physics dispersive.Such as at the mixing section of forcing machine or similarly disperse in the device, then with these mixture thermoformings (such as, extrude with a mouth mould) obtain special-shaped product.These goods are being higher than heat treated under the hot-forming temperature so that peroxide breakdown and make crosslinked polymer.In this technology, the selection of suitable superoxide, depend primarily on following factor, promptly, this superoxide should be metastable under hot-forming temperature, and should be higher than hot-forming temperature and be lower than under the polymer unwinds temperature, decompose and be preferably lower than under the temperature that the goods of being produced begin loss of dimensional stability, so that cause the crosslinked of polymkeric substance.For example, this class methods have been described among GB-A-865384 and the US-A-4101512 at GB-A-831126.
The thermoplasticity silane modified polymer contains the organic polymer (linking to each other with silicon) of hydrolyzable group, and it is by hydrolytic crosslinking, and is for example, under the water effect, particularly for example, crosslinked in the presence of silicon alcohol condensation catalyst.For example, the crosslinkable silane-modified copolymers can make by unsaturated organic monomers and the unsaturated silane compound copolymerization that contains the hydrolyzable base.Narrated the example of this analog copolymer at GB-A-20228531 and GB-A-2039513, these two patents state under comparatively high temps and pressure, in the presence of radical polymerization causes, with the method for ethene and olefinic unsaturated silane compound copolymerization crosslinkable multipolymer.In GB-A-1415194, also narrated the preparation method of this analog copolymer, promptly be preferably under the lower temperature and pressure, Ziegler (Ziegler) catalyzer with certain regulation, make ethene or optionally contact preparation crosslinkable multipolymer with the silane compound of terminal unsaturation with other olefinic unsaturated comonomer.
The method of the silane-modified organic polymer of other known this kind of preparation crosslinkable has: the radical initiator graft copolymerization on organic polymer of olefinic unsaturated silane compound.In GB-A-1357549, GB-A-1234034 and GB-A-1286460, narrated this method.Grafting copolymerization process has formed well-known " MONOSIL " and (RTM) has produced the basis of the industrial production technology of cross-linkable thermoplastic polymkeric substance.In step " MONOSIL " of well-known manufacturing cross-linkable composition (RTM) in the method, in the presence of radical initiator and silicon alcohol condensation catalyst, the olefinic unsaturated silane compound is grafted on the organic polymer.In this method, the processing of graft reaction and polymer product is carried out simultaneously, for example, this organic polymer, unsaturated silane compound, initiator and silicon alcohol condensation catalyst (optionally using other universal additive simultaneously) are added in the forcing machine, graft reaction promptly take place in the device and directly extrude the crosslinkable product.
Use conventional thermoforming technology, for example, extrusion moulding, methods such as injection molding, blow molding and blown film processing, the crosslinkable organic polymer can be processed into many useful goods.
In the cross-linkable thermoplastic composition of the above-mentioned type, the problem that runs into is when carrying out thermoforming and make useful goods, because heat or mechanical influence or through moisture or the existence of other impurity, said composition can take place crosslinked prematurely.In " dead zone " of forcing machine or mouthful mould, for example, in the melt movable mold, form the space of eddy current or stagnation, also can take place crosslinked.Too early crosslinked meeting in the thermoplasticity polymerization melt makes final thermoformed articles produce defective, for example, has at the product surface of extrusion moulding significantly to resemble sheltering a little flake and the striped spot.
The present invention aims to provide improved cross-linkable thermoplastic polymer composition.
Another object of the present invention provides a kind of cross-linkable thermoplastic polymkeric substance, and the surface smoothness of the product after extruding improves to some extent.
The invention provides a kind of composition of crosslinkable thermoplastic polymer, it contains and is suitable for being characterized in heating or the crosslinked a kind of component of chemically treated method, contains fluorocarbon polymer in composition.
The present invention further provides a kind of method of making crosslinkable thermoplastic compounds.This method is some to be suitable for chemistry or heat treated and crosslinked component is carried out blend with fluorocarbon polymer together.
The present invention further provides a kind of method of producing crosslinkable thermoplastic article.This method is suitable for after thermoforming with heating or chemical treatment method by some and the crosslinkable thermoplastic polymer that crosslinked component is formed is goods through being thermoformed into.Be characterized in, in composition, contain fluorocarbon polymer.
Be suitable for heating or chemical treatment and crosslinked component is called as " crosslinkable component " hereinafter.
Employed fluorocarbon polymer in the composition of the present invention can form melt and extrude blend with the crosslinkable component in the composition.The fusing point of fluorocarbon polymer and softening temperature are preferably in 100 to 300 ℃ the scope, and preferable scope is 150 to 250 ℃.The carbon fluorine homopolymer and the multipolymer of narration are specially adapted to this patent in the United States Patent (USP) 3125547.The ratio of fluorine atom and carbon atom was at least 1: 2 in this class homopolymer and the multipolymer.For example, they comprise, one or more monomeric homopolymer and multipolymers in vinylidene fluoride, vinyl fluoride, trifluorochloroethylene, tetrafluoroethylene and the R 1216.The multipolymer of these fluorinated olefin and non-fluorinated olefins can be applied in the composition of this patent, it is that the telomer of tetrafluoroethylene, the telomer and the elastic ratio of carbon fluorine of trifluorochloroethylene were at least 1: 2 with the obvious example of carbon atom polymkeric substance that the multipolymer that is provided requires fluorine atom, can be applicable to the carbon fluorine body of this patent, the multipolymer of R 1216 and vinylidene fluoride for example.
In the composition of the present invention, the content of employed fluorocarbon polymer is benchmark with the weight of crosslinkable component, and its scope is preferably in 0.03 to 0.4% 0.002 to 2.0%.When crosslinkable component used in the present invention was a kind of silane-modified polymkeric substance, the optimal consumption of fluorocarbon polymer was a benchmark with the weight of crosslinkable component, should be between 100 to 450ppm.
Using the blending technology that adopts usually to sneak into fluorocarbon polymer in the cross-linkable composition of this patent goes.For example, can directly sneak into fluorocarbon polymer in the silane-modified polymkeric substance, maybe can be blended in a kind of polymer materials and go, this polymer materials is used to form the base-material of superoxide-crosslinkable component, another kind method, be fluorocarbon polymer can with the thermoplastic polymer blend, for example, with the new LDPE (film grade) blend, make the master batch enriched material, this master batch can be blended in the linked and go, or is blended in the precursor of crosslinkable composition and goes, for example, with before oxide compound mixes, be blended in the base-material of peroxide crosslinkable polymkeric substance and remove (" base " porioxide crossli-nkablepolymer).
Used crosslinkable component in the composition of this patent, for example, it can be a kind of thermally cross-linkable mixture, and it is made up of organic polymer and that above-mentioned class organo-peroxide, or a kind of can the reaction with water or the crosslinked silane-modified polymkeric substance of other chemical action continuation.When crosslinkable component is made up of organic polymer and organo-peroxide, the best polyolefine of organic polymer, or the multipolymer of a kind of alkene and one or more other alkene or unsaturated ester.Especially desirable organic polymer is (high pressure) new LDPE (film grade), high-density linear polyethylene, LLDPE, ethylene/alkyl acrylate copolymer (for example ethylene/ethyl acrylate), the multipolymer (for example ethylene/ester vinyl acetate) of ethylene alkenyl esters and the blend of using always of these polymkeric substance and/or multipolymer.
In these crosslinkable components, the concentration of superoxide is the general concentration that adopts in the technology normally, and the content of superoxide for example adds the total weight of organic polymer with superoxide, normally in the scope of 0.05-10%, preferably between 0.1 to 5.0%.
When crosslinkable component is made up of silane-modified polymkeric substance, it can be, for example by alefinically unsaturated compounds with have the multipolymer that the unsaturated silane compound of hydrolyzable base forms, being grafted to the unsaturated silane compound of hydrolyzable group on organic polymer or the multipolymer and the graft copolymer that forms, or with the improved multipolymer that contains the hydrolyzable silane base of transesterification (for example, referring to FP4752).Best silane modified polymer is, in the presence of radical initiator, the multipolymer that optionally same or a plurality of alpha-olefins, vinyl ester, alkyl (methyl) acrylate, unsaturated nitrile, unsaturated ethers (as vinyl ether) make with a kind of undersaturated silane compound copolymerization together.Equally, best graft copolymer is at radical initiator, for example, under the existence of organo-peroxide, unsaturated silane compound is grafted to polyethylene or ethene with one or more alpha-olefins, vinyl ester, alkyl (methyl) acrylate, (for example, vinyl ether prepare on) the multipolymer, graft reaction is to finish by unsaturated silane compound is heated with the multipolymer of polyethylene or ethene for unsaturated nitrile or unsaturated ethers.The multipolymer of polyethylene or ethene can comprise, new LDPE (film grade) for example, low density ethylene-hydrocarbon copolymer (for example LLDPE), high density polyethylene(HDPE), ethylene/acrylic acid vinyl ester copolymers, ethylene/vinyl acetate or ethylene-propylene rubber(EPR) (EPR).
Silane-modified polymkeric substance can exist under the situation " at the scene " to make at other composition of composition of this patent, for example, in the presence of radical polymerization initiator, undersaturated silane compound is grafted on the ethylene copolymer of polyethylene or above-mentioned type.
With ethylene copolymer, or preferably to have general formula with the silane compound of polyethylene or ethylene copolymer graft copolymers be R
1SiR
2The compound of nY3-n, R in general formula
1Represent a kind of ethylenically unsaturated hydrocarbons base or-oxyl (hgdrocarbyloxy group); R
2Expression aliphatic saturated hydrocarbon base; Y represents the hydrolyzable organic radical, and n represents 0,1 or 2.Be used to prepare multipolymer or the best unsaturated silane compound of graft copolymer is a vinyltrimethoxy silane, vinyltriethoxysilane and vinyl nitrilotriacetic base silane.
In this patent composition, particularly suitable is the multipolymer that obtains by following multipolymer method as the silane-modified polymkeric substance of crosslinkable composition.Promptly by ethene, or add in addition more optionally that can to reach 40%(by weight be benchmark with ethene) monomer, carry out copolymerization with unsaturated silane compound, the monomer that adds can from one or more vinyl ester or (methyl) acrylate select, and unsaturated silane compound can vinyl trialkyl oxysilane and vinyltriacetoxy silane in select, at pressure 500-4000 crust, temperature is in 150-400 ℃ scope, when having radical polymerization initiator to exist, carry out copolyreaction.
Preferably a kind of multipolymer of silane-modified polymkeric substance or graft copolymer, wherein the copolymerization units content of silane compound by weight the percentage ratio meter should be 0.1-10%, preferably at 0.5-5%.
Be applicable to that being described in more detail of silane modified polymer of the present invention can be with reference to GB-A-2028831, GB-A-2039513, GB-A-1357549, GB-A-1415194, GB-A-1286460, GB-A-1234034, US-A-3225018 and EP4752.
The thermoforming process that is adopted among the present invention can be, for example is extruded into, extrudes coating, blow moulded, injection-molded, blown film, slot cast (Slot-casting), etc.This method is particularly suitable for producing extruded product or extrudes coated articles, for example manages 2, flexible pipe and insulated conductor and cable.
In preferred representative instance of the present invention, master batch is made up of master batch, base material polymer and fluorocarbon polymer and some additive.The example of base material polymer has, the multipolymer of new LDPE (film grade), LLDPE or ethene and alkyl acrylate; Additive for example has oxidation inhibitor, filler, metal passivator (salicylaldoxime), lubricant, anhydrous stopper, whipping agent.Fire retardant and pigment.
The present invention at length provides a kind of cross-linkable composition, and it comprises:
(A) crosslinkable thermoplasticity composition, it is a kind of silane-modified organic polymer, has hydrolyzable base on its Siliciumatom.
(B) a foregoing class fluorocarbon polymer and
(C) silane condensation catalyzer, it is dialkyl tin (IV) carboxylic esters preferably.The present invention further also comprises the master batch that is used for being added to crosslinkable composition (A), and this master batch contains fluorocarbon polymer (B) and silicon alcohol condensation catalyst (C) and some thermoplasticity base-material polymkeric substance (D) and forms.Alkyl in alkyl tin (IV) carboxylicesters preferably contains the alkyl of 1～12 carbon atom, for example, and propyl group, butyl, hexyl, octyl group or decyl.Carboxylic acid ester groups in tin compound can be provided by following compounds, and example 2 has aliphatics or aromatic monocarboxylic acid or di-carboxylic acid.Best dialkyl tin compound comprises dibutyltin dilaurate, dibutyl tin two palmitates, dibutyl tin SUNSOFT Q-182S, dioctyl tin dilaurate and dibutyl tin maleic acid ester.Carboxylicesters functional group in dialkyl tin (IV) carboxylicesters is that dicarboxylic acid provides, and is (for example dibutyl tin maleic acid ester) well with this carboxylicesters.In general, dialkyl tin carboxylate's consumption should be so that its concentration in cross-linkable composition is: in the crosslinkable component every mole of silyl 0.001 to 3.0mole, preferably 0.003 to 0.05mole.In master batch, the content of tin compound is benchmark as if the weight with master batch, should account for 0.1 to 70%, is preferably 0.3% to 20%.The content of fluorocarbon polymer is in the master batch, for example, is benchmark with the master batch, accounts for 0.01 to 95%, preferably accounts for 0.1-20%.Therefore random thermoplasticity base-material polymkeric substance (D) can be a kind of suitable organic polymer, and it has consistency with the crosslinkable composition, can be melted blend in wherein.Example as this base material polymer (D) has universal new LDPE (film grade), ethylene-vinyl acetate copolymer, ethylene-acrylic acid vinyl ester copolymers, LLDPE and high density polyethylene(HDPE).
The compositions and methods of the invention can be used to be manufactured on crosslinkable goods after the thermoforming, and the character of these goods improves to some extent, and for example, has improved surface elasticity, reduce the incidence of gel defective.
Following Example explanation the present invention.
Example 1 and example 2 are to this experiment 1A and 2A
Prepare master batch by following method, that is: with VitonA fluoroelastomer particle (Dupont) 2 weight parts, 98 parts of LLDPE (LL101 AA BP Chemicals), prepare burden in Werner and Pfeiderer Z SK30 twin screw extruder and extrude, screw speed is 200 rev/mins.Extruder temperature is 150 ℃ near the hopper section, and the head place brings up to 190 ℃.Forcing machine is extruded billot, obtains spherical master batch through pelletizing.
Spherical master batch (5 weight parts, be equivalent in final blend, contain the VitonA of 1000ppm), dry blending together with 95 parts new LDPE (film grade) (BP chemicals manufacturing), be added to then in the hopper of Maillefer forcing machine, the screw diameter of forcing machine is 30mm, length-to-diameter ratio is 30: 1, has a compression mould head that applies the 1.5mm copper wire.The temperature distribution of forcing machine and die orifice is 150-160-170-180-190-190-190 ℃, 30 rev/mins of screw speeds, and copper wire extruded velocity (take off speed) is 10 meters/minute, the outside diameter of cable of extruding is 2.7mm.With vinyltrimethoxy silane (90 weight part), the mixture (M) of dicumyl peroxide (dicumylperoxide) (7.6 parts) and dibutyltin dilaurate (2.4 weight part) is pumped into the hopper neck, makes the mixture (M) that contains 1.8 parts of weights in per 100 parts of resins of above-mentioned adding.Except not adding the VitonA master batch, all the other conditions are consistent with last example to this test.The cable batten carried out crosslinked in 1 hour 80 ℃ curing in water.Then according to IEC540(200 ℃, 20Ncm
-2, 15 minutes) and carry out hot tensile test, carry out tension test according to IEC540.
Viton A is a kind of multipolymer, and its general formula is (CF
2CH
2)
n(CF
2-CFCF
3)
m, here n/m is about 7/3.DFDM2951 and 5951 is trades mark of polyethylene (low density), is that B Pchemicals makes.
Example 1 and example 2 have proved that fluoroelastomer has reduced the forcing machine energy consumption, have improved surface luster, do not reduce the mechanical property of cable.
Example 3-5 and simultaneous test 3A
In example 3,4 and 5, Viton A fluoroelastomer (Dupont) is incorporated in the master batch in all proportions.In simultaneous test, do not mix Viron A in the master batch.Table 2 has been listed the definite prescription of master batch.Press the batching of table 2,,, their blend are extruded make master batch at 200 rev/mins screw speed F with the twin screw extruder of Werner and Pfleidezer ZSK30.Every batch of the total amount of composition prepared is 10kg in each example and each test.The material angle temperature of forcing machine is 140 ℃ at the section near hopper, brings up to 190 ℃ at the head place.Extrude billot, obtain spherical field refining glue through pelletizing.
Spherical field refining glue (5 weight part) and 95 parts silyl-modified polymkeric substance are with dry blending together, this silyl-modified polymkeric substance is by ethene and vinyltrimethoxy silane, what copolymerization obtained under High Temperature High Pressure in the presence of radical initiator.In the silyl-modified polymkeric substance (EVTMS), the vinyltrimethoxy silane of copolymerization accounts for 1.8% of multipolymer composition by weight.The melting index of this polymkeric substance (190 ℃, the 2.16kg load) is 0.7, and density is 923kg/m
2
The concentration of fluoroelastomer is respectively 500,250 and 100ppm in example 3,4 and 5.
Be added in the hopper of Francis-Skaw forcing machine doing mixed thing, this extruder screw diameter is 2 inches, and length-to-diameter ratio is 23: 1, and the mould internal diameter is 2.2mm, and the copper wire of 0.6mm diameter passes through therein.200 ℃ of die temperatures, 50 rev/mins of screw speeds.Except that the speed of the copper cash that applies with 200 meters/minute involves, the cable size of extruding is 2.05mm.Clearly, in moulding, example 2,3,4 and 5 than example 3A mould trickling (drool) is more still less extruded cable and is immersed in constant temperature carries out slaking in 80 ℃ water-bath.
By composition of the present invention, even showing cable, the cable visual observation that example 3,4 and 5 is extruded extrudes back 1 hour, its surface is (3 and 4 to 5 is better) of level and smooth light still.And on the other hand, the cable surface of extruding according to the composition of simultaneous test 3A seems coarse many coarse particles that have simultaneously.
The stretching and the thermomechanical property basically identical of whole battens, this shows that fluoroelastomer does not weaken crosslinking reaction.
Fluoroelastomer sneak into the energy consumption that can significantly reduce forcing machine.
Claims (13)
1, a kind of thermoformable crosslinkable polymer composition, said composition contains:
(a) a kind of crosslinkable thermoplastic component, it is a kind of silane-modified organic polymer, is connected with hydrolyzable group on its Siliciumatom,
(b) in a kind of fluorocarbon polymer of the weight 0.002% to 2.0% of crosslinkable component and
(c) a kind of silanol condensation catalyst.
2, according to the composition of claim 1, the fusing point of wherein said fluorocarbon polymer or softening temperature are in 100～300 ℃ scope.
3, according to the composition of claim 1 or 2, the fluorine atom of wherein said fluorocarbon polymer was at least 1: 2 with the ratio of carbon atom.
4, according to the composition of claim 1 or 2, wherein said fluorocarbon polymer is one or more monomeric homopolymer or multipolymers in vinylidene fluoride, vinyl fluoride, trifluorochloroethylene, tetrafluoroethylene and the R 1216.
5, according to the composition of claim 1 or 2, wherein said fluorocarbon polymer is the multipolymer of R 1216 and vinylidene fluoride.
6, according to the composition of claim 1, the content of wherein said fluorocarbon polymer in described crosslinkable component weight between 0.03% to 0.4%.
7, according to the composition of claim 1, the content of wherein said fluorocarbon polymer in described crosslinkable component weight between the 100ppm to 450ppm.
8, according to the composition of claim 1, wherein said silane-modified organic polymer is the multipolymer by a kind of ethylenically unsaturated compounds and a kind of unsaturated silane compound copolymerization that contains hydrolyzable group are obtained.
9, according to the composition of claim 1, wherein said silane-modified organic polymer is to obtain by a kind of unsaturated silane compound that contains hydrolyzable silane group is grafted on a kind of organic polymer or the multipolymer, and wherein said organic polymer or multipolymer are selected from the multipolymer that polyethylene or ethene and one or more alpha-olefins, vinyl ester, (methyl) alkyl acrylate, undersaturated nitrile or unsaturated ethers form.
10, according to Claim 8 or 9 composition, wherein said unsaturated silane compound is selected from vinyltrimethoxy silane, vinyltriethoxysilane and vinyltriacetoxy silane.
11, according to Claim 8 or 9 composition, wherein said multipolymer or graft copolymer contain 0.1% to 10%(weight) polymeric form silane compound unit.
12, a kind of that extrude or extrude the goods of coating, it contains by the composition that is proposed in the claim 1 through extruding and the further crosslinked and product that obtains of heating or chemical treatment.
13, a kind of preparation method of thermoformable compositions crosslinkable, this method comprises each component is blended into together, wherein said component comprises: (a) crosslinkable thermoplastic component, this component is a kind of silane-modified organic polymer, there is hydrolysable group to be connected on this polymkeric substance with Siliciumatom, (b) in the weight of crosslinkable component, a kind of fluorocarbon polymer of 0.002% to 2.0% and (c) a kind of silanol condensation catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85106770 CN1010588B (en) | 1984-07-20 | 1985-09-09 | Polymer composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB848418591A GB8418591D0 (en) | 1984-07-20 | 1984-07-20 | Polymer composition |
| CN 85106770 CN1010588B (en) | 1984-07-20 | 1985-09-09 | Polymer composition |
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| Publication Number | Publication Date |
|---|---|
| CN85106770A CN85106770A (en) | 1987-03-11 |
| CN1010588B true CN1010588B (en) | 1990-11-28 |
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|---|---|---|---|
| CN 85106770 Expired CN1010588B (en) | 1984-07-20 | 1985-09-09 | Polymer composition |
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| CN100386362C (en) * | 2005-06-13 | 2008-05-07 | 上海三爱富新材料股份有限公司 | Catalyst composition and preparation method of fluorine silicon contained polymer |
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