NO303545B1 - Impact resistant materials based on vinyl chloride polymers and their use in profile extrusion - Google Patents
Impact resistant materials based on vinyl chloride polymers and their use in profile extrusion Download PDFInfo
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- NO303545B1 NO303545B1 NO920421A NO920421A NO303545B1 NO 303545 B1 NO303545 B1 NO 303545B1 NO 920421 A NO920421 A NO 920421A NO 920421 A NO920421 A NO 920421A NO 303545 B1 NO303545 B1 NO 303545B1
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- Prior art keywords
- vinyl chloride
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- ethylene
- polymers
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229920000642 polymer Polymers 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims description 37
- 238000001125 extrusion Methods 0.000 title claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 8
- 239000000194 fatty acid Substances 0.000 claims abstract description 8
- 229930195729 fatty acid Natural products 0.000 claims abstract description 8
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 8
- 229920001519 homopolymer Polymers 0.000 claims abstract description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 30
- 239000005977 Ethylene Substances 0.000 claims description 30
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 claims description 28
- 238000004132 cross linking Methods 0.000 claims description 5
- 235000010216 calcium carbonate Nutrition 0.000 abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 4
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 description 12
- 229920000915 polyvinyl chloride Polymers 0.000 description 8
- 239000004800 polyvinyl chloride Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000007900 aqueous suspension Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Dental Preparations (AREA)
- Materials For Medical Uses (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Foreliggende oppfinnelse vedrører slagfaste materialer basert på vinylklorid-polymerer, og anvendelse av slike. Mer spesielt vedrører den materialer basert på vinylklorid-polymerer som omfatter vinylklorid-polymerer podet på forsterkende polymerer, og også anvendelse av disse materialer til profil-ekstrudering. The present invention relates to impact-resistant materials based on vinyl chloride polymers, and their use. More particularly, it relates to materials based on vinyl chloride polymers comprising vinyl chloride polymers grafted onto reinforcing polymers, and also the use of these materials for profile extrusion.
For ekstrudering av polyvinylklorid-profiler, så som profiler for rammer for anvendelse utendørs, er det velkjent å benytte materialer som omfatter forsterkende polymerer, vanligvis elastomere av natur, så som for eksempel alkylakrylat-polymerer eller alternativt etylen/vinylacetat-kopolymerer. Disse materialer oppnås enten ved ytre blanding av polyvinylklorid med forsterkende polymerer av den ovennevnte type, eller ved anvendelse av polyvinylklorid som er modifisert "in situ" ved polymerisering med poding av vinylklorid på slike forsterkende polymerer. Uavhengig av innlemmings-metoden for de forsterkende polymerer, omfatter vanligvis materialer basert på polyvinylklorid som er spesielt anbefalt for ekstrudering av profiler for rammer for utendørs anvendelse, tilnærmet fra 6 til 10 vektdeler av forsterkende polymer pr. 100 vektdeler av de totale polymere bestanddeler i materialet, og også noen få prosent av fettsyre-belagt kalsiumkarbonat med fin partikkel-størrelse. Med slike materialer er det vanligvis mulig å tilfredsstille kvalitets-kravene for vindusrammer som er fastsatt i visse land, så som for eksempel det tyske kvalitets-kravet RAL som fastsetter en slagfasthet ved et enkelt U-formet innsnitt på en presset småplate som er 4 mm tykk (i henhold til DIN-standard 53453) på mer enn 20 kJ/m<2>og en slagfasthet ved et dobbelt V-formet innsnitt (i henhold til DIN-standard 53753) på mer enn 40 kJ/m<2>. Ikke desto mindre vil de forsterkende polymerer vanligvis bidra til å redusere aldrings-bestandigheten og stivheten til materialer basert på polyvinylklorid hvori de er innlemmet. For extruding polyvinyl chloride profiles, such as profiles for frames for outdoor use, it is well known to use materials comprising reinforcing polymers, usually elastomeric in nature, such as for example alkyl acrylate polymers or alternatively ethylene/vinyl acetate copolymers. These materials are obtained either by external mixing of polyvinyl chloride with reinforcing polymers of the above-mentioned type, or by using polyvinyl chloride that has been modified "in situ" by polymerization with grafting of vinyl chloride onto such reinforcing polymers. Regardless of the method of incorporation of the reinforcing polymers, materials based on polyvinyl chloride which are particularly recommended for extrusion of profiles for frames for outdoor use usually comprise from approximately 6 to 10 parts by weight of reinforcing polymer per 100 parts by weight of the total polymeric constituents in the material, and also a few percent of fatty acid-coated calcium carbonate with a fine particle size. With such materials it is usually possible to satisfy the quality requirements for window frames set in certain countries, such as for example the German quality requirement RAL which specifies an impact resistance by a single U-shaped incision on a pressed small plate of 4 mm thick (according to DIN standard 53453) of more than 20 kJ/m<2> and an impact strength at a double V-shaped notch (according to DIN standard 53753) of more than 40 kJ/m<2>. Nevertheless, the reinforcing polymers will usually help to reduce the aging resistance and stiffness of the polyvinyl chloride-based materials in which they are incorporated.
Formålet med foreliggende oppfinnelse er å oppnå slagfaste materialer basert på vinylklorid-polymerer som er sterkere og som følgelig muliggjør at det kan oppnås minst like god ytelse med hensyn til slagfasthet med et lavere samlet innhold av forsterkende polymerer. The purpose of the present invention is to achieve impact-resistant materials based on vinyl chloride polymers which are stronger and which consequently make it possible to achieve at least as good performance in terms of impact resistance with a lower overall content of reinforcing polymers.
Med dette formål vedrører foreliggende oppfinnelse slagfaste materialer basert på vinylklorid-polymerer, som erkarakterisert vedat de omfatter, som vinylklorid-polymerer: (a) fra 40 til 60 deler av pode-kopolymer av vinylklorid med lett tverrbundet polybutylakrylat og med en tverrbindingsgrad på mindre enn 1%, som inneholder fra 2 To this end, the present invention relates to impact-resistant materials based on vinyl chloride polymers, which are characterized in that they comprise, as vinyl chloride polymers: (a) from 40 to 60 parts of graft copolymer of vinyl chloride with lightly cross-linked polybutyl acrylate and with a degree of cross-linking of less than 1%, which contains from 2
til 10 vekt% av lett tverrbundet polybutylakrylat, to 10% by weight of lightly cross-linked polybutyl acrylate,
(b) fra 10 til 50 deler av pode-kopolymer av vinylklorid med en etylen/vinylacetat-kopolymer, som inneholder fra 0,5 til 7 vekt% av etylen/vinylacetat-kopolymer som inneholder fra 50 til 80 vekt% etylen og har en grenseviskositet, målt ved 20°C i m-xylen, på mellom (b) from 10 to 50 parts of graft copolymer of vinyl chloride with an ethylene/vinyl acetate copolymer, containing from 0.5 to 7% by weight of ethylene/vinyl acetate copolymer containing from 50 to 80% by weight of ethylene and having a intrinsic viscosity, measured at 20°C in m-xylene, of between
0,05 og 0,10 l/g, (c) fra 10 til 50 deler av umodifisert vinylklorid-polymer pr. 100 vektdeler av totale vinylklorid-polymerer, og, 0.05 and 0.10 l/g, (c) from 10 to 50 parts of unmodified vinyl chloride polymer per 100 parts by weight of total vinyl chloride polymers, and,
som et forsterkende fyllstoff: as a reinforcing filler:
(d) fra 4 til 10 deler av kalsiumkarbonat i fettsyre-belagte partikler med gjennomsnittlig diameter på mindre enn 1fim pr. 100 vektdeler av vinylklorid-polymerer. (d) from 4 to 10 parts of calcium carbonate in fatty acid-coated particles having an average diameter of less than 1 µm per 100 parts by weight of vinyl chloride polymers.
Pode-kopolymerene av vinylklorid med lett tverrbundet polybutylakrylat, heretter angitt med uttrykket "polymerer (a)", og også pode-kopolymerene av vinylklorid med en etylen/vinylacetat-kopolymer, heretter angitt med uttrykket "polymerer (b)", er polymerer som er kjente som sådanne. The graft copolymers of vinyl chloride with lightly crosslinked polybutyl acrylate, hereinafter referred to as "polymers (a)", and also the graft copolymers of vinyl chloride with an ethylene/vinyl acetate copolymer, hereinafter referred to as "polymers (b)", are polymers which are known as such.
Lett. tverrbundet polybutylakrylat er ment å bety polybutylakrylat som har en tverrbindingsgrad på mindre enn 1%. Tverrbindingen oppnås ved å anvende, ved polymeriseringen av butylakrylat, en liten mengde av en komonomer som har flere etylenisk umettede bindinger, så som for eksempel diallylftalat eller diallylmaleat. En fordelaktig metode for fremstilling av polymerene (a) , som består i å pode vinylklorid i vandig suspensjon på en tverrbundet polybutylakrylat-lateks, er beskrevet i patentpublikasjonen DE-B-1.090.857, som innlemmes heri ved referanse. Easy. cross-linked polybutyl acrylate is intended to mean polybutyl acrylate having a degree of cross-linking of less than 1%. The cross-linking is achieved by using, in the polymerization of butyl acrylate, a small amount of a comonomer having several ethylenically unsaturated bonds, such as, for example, diallyl phthalate or diallyl maleate. An advantageous method for producing the polymers (a), which consists in grafting vinyl chloride in aqueous suspension onto a crosslinked polybutyl acrylate latex, is described in patent publication DE-B-1,090,857, which is incorporated herein by reference.
Foretrukne polymerer (a) inneholder tilnærmet fra 4 til 8 vekt% av lett tverrbundet polybutylakrylat. Preferred polymers (a) contain approximately from 4 to 8% by weight of lightly crosslinked polybutyl acrylate.
Etylen/vinylacetat-kopolymer er ment å bety kopolymerer som inneholder fra 50 til 80 vekt% etylen, og hvor resten består av vinylacetat. En fordelaktig metode for fremstilling av polymerene (b), som består i å fordispergere etylen/vinylacetat-kopolymeren i vinylklorid i nærvær av vann før vinylkloridet utsettes for polymerisering i vandig suspensjon, er beskrevet i patentsøknaden EP-A-0.074.139, som også innlemmes heri ved referanse. Ethylene/vinyl acetate copolymer is intended to mean copolymers containing from 50 to 80% by weight of ethylene, and where the balance consists of vinyl acetate. An advantageous method for the preparation of the polymers (b), which consists in predispersing the ethylene/vinyl acetate copolymer in vinyl chloride in the presence of water before subjecting the vinyl chloride to polymerization in aqueous suspension, is described in patent application EP-A-0,074,139, which also incorporated herein by reference.
Foretrukne polymerer (b) inneholder tilnærmet fra 1,5 til 5 vekt% av etylen/vinylacetat-kopolymer. Preferred polymers (b) contain approximately from 1.5 to 5% by weight of ethylene/vinyl acetate copolymer.
Umodifisert vinylklorid-polymer, heretter angitt med uttrykket "polymer (c)", er ment å bety vinylklorid-polymerer som ikke inneholder en forsterkende polymer. Foretrukne polymerer (c) består av vinylklorid-homopolymerer. Som eksempel på slike homopolymerer kan nevnes vinylklorid-homopolymerer oppnådd ved polymerisering i vandig suspensjon som har en K-verdi (målt ved 25°C i cykloheksanon i mengdeforholdet 5 g/l) som varierer fra 60 til 70, og mer spesielt fra 64 til 70, og også vinylklorid-homopolymerer oppnådd ved polymerisering i vandig emulsjon som har en K-verdi varierende fra 68 til 80, og enda mer spesielt fra 72 til 76. De mest spesielt foretrukne polymerer (c) er vinylklorid-homopolymerer oppnådd ved polymerisering i vandig emulsjon med en K-verdi (målt under de ovennevnte forhold) varierende fra 72 til 76. Unmodified vinyl chloride polymer, hereinafter referred to as "polymer (c)", is intended to mean vinyl chloride polymers that do not contain a reinforcing polymer. Preferred polymers (c) consist of vinyl chloride homopolymers. Examples of such homopolymers include vinyl chloride homopolymers obtained by polymerisation in aqueous suspension which have a K value (measured at 25°C in cyclohexanone in a quantity ratio of 5 g/l) which varies from 60 to 70, and more particularly from 64 to 70, and also vinyl chloride homopolymers obtained by polymerization in aqueous emulsion having a K value varying from 68 to 80, and even more particularly from 72 to 76. The most particularly preferred polymers (c) are vinyl chloride homopolymers obtained by polymerization in aqueous emulsion with a K value (measured under the above conditions) varying from 72 to 76.
Kalsiumkarbonat i fettsyre-belagte partikler er ment å bety kalsium-karbonat i partikler belagt med en fettsyre inneholdende fra10 til 24karbonatomer, og blandinger derav. Fettsyrene inneholder fortrinnsvis fra 12 til 22 karbonatomer. Disse fettsyrer består for det meste av blandinger av stearin-og palmitinsyre. Calcium carbonate in fatty acid-coated particles is intended to mean calcium carbonate in particles coated with a fatty acid containing from 10 to 24 carbon atoms, and mixtures thereof. The fatty acids preferably contain from 12 to 22 carbon atoms. These fatty acids mostly consist of mixtures of stearic and palmitic acid.
Det er dessuten foretrukket med naturlige eller utfelte kalsium-karbonater i partikler med gjennomsnittlig diameter mellom 0,05 og 2^m, og mer spesielt mellom 0,05 og 0,1^m. Et overraskende aspekt ved materialene i henhold til oppfinnelsen ligger i det faktum at, med likt samlet innhold av forsterkningsmidler, har de en meget betraktelig større slagfasthet ved et enkelt U-formet innsnitt og ved et dobbelt V-formet innsnitt enn slike materialer som utelukkende inneholder polybutylakrylat som forsterkningsmiddel. Materialene i henhold til oppfinnelsen er dessuten lettere å utnytte og de har en sveiseevne (målt på basis av den statiske strekkfasthet til sveiste sammensetninger) som er relativt ufølsom overfor variasjoner i sveisetemperaturen. It is also preferred to use natural or precipitated calcium carbonates in particles with an average diameter between 0.05 and 2 µm, and more particularly between 0.05 and 0.1 µm. A surprising aspect of the materials according to the invention lies in the fact that, with the same total content of reinforcing agents, they have a very considerably greater impact resistance with a single U-shaped incision and with a double V-shaped incision than such materials which exclusively contain polybutyl acrylate as a reinforcing agent. The materials according to the invention are also easier to use and they have a welding ability (measured on the basis of the static tensile strength of welded compositions) which is relatively insensitive to variations in the welding temperature.
Foretrukne materialer i henhold til oppfinnelsen omfatter, som vinylklorid-polymerer: (a) fra 45 til 55 deler av pode-kopolymer av vinylklorid med Preferred materials according to the invention comprise, as vinyl chloride polymers: (a) from 45 to 55 parts of graft copolymer of vinyl chloride with
lett tverrbundet polybutylakrylat, lightly cross-linked polybutyl acrylate,
(b) fra 20 til 40 deler av pode-kopolymer av vinylklorid med (b) from 20 to 40 parts of graft copolymer of vinyl chloride with
en etylen/vinylacetat-kopolymer, an ethylene/vinyl acetate copolymer,
(c) fra 20 til 40 deler av umodifisert vinylklorid-polymer pr. 100 vektdeler av vinylklorid-polymerer, og, som et forsterkende fyllstoff, (d) fra 5 til 8 deler av kalsiumkarbonat pr. 100 vektdeler av vinylklorid-polymerer. (c) from 20 to 40 parts of unmodified vinyl chloride polymer per 100 parts by weight of vinyl chloride polymers, and, as a reinforcing filler, (d) from 5 to 8 parts of calcium carbonate per 100 parts by weight of vinyl chloride polymers.
I henhold til et annet foretrukket aspekt ved oppfinnelsen er summen av innholdene av lett tverrbundet polybutylakrylat og etylen/vinylacetat-kopolymer i materialene mindre enn 6 deler og dessuten større enn 2 deler pr. 100 vektdeler.av de totale vinylklorid-polymerer. Spesielt foretrukne materialer er slike hvori innholdet av lett tverrbundet polybutylakrylat utgjør minst 2 deler og innholdet av etylen/vinylacetat-kopolymer minst 0,25 deler, og summen av innholdene av lett tverrbundet polybutylakrylat og etylen/vinylacetat-kopolymer ikke overskrider 4,5 vektdeler pr. 100 vektdeler av de totale vinylklorid-polymerer. According to another preferred aspect of the invention, the sum of the contents of lightly cross-linked polybutyl acrylate and ethylene/vinyl acetate copolymer in the materials is less than 6 parts and, moreover, greater than 2 parts per 100 parts by weight of the total vinyl chloride polymers. Particularly preferred materials are those in which the content of lightly cross-linked polybutyl acrylate is at least 2 parts and the content of ethylene/vinyl acetate copolymer at least 0.25 parts, and the sum of the contents of lightly cross-linked polybutyl acrylate and ethylene/vinyl acetate copolymer does not exceed 4.5 parts by weight . 100 parts by weight of the total vinyl chloride polymers.
Bortsett fra de karakteristiske vinylklorid-polymerer og de forsterkende fyllstoffer som er beskrevet ovenfor, kan materialene i henhold til oppfinnelsen inneholde alle vanlige ingredienser som anvendes i materialer basert på vinylklorid-polymerer, så som varme-stabilisatorer, midler for å lette anvendbarheten, smøremidler, pigmenter og lignende. Materialene i henhold til oppfinnelsen kan anvendes i form av pulvere eller granuler, og de sistnevnte er foretrukket. Apart from the characteristic vinyl chloride polymers and the reinforcing fillers described above, the materials according to the invention may contain all the usual ingredients used in materials based on vinyl chloride polymers, such as heat stabilizers, agents to facilitate applicability, lubricants, pigments and the like. The materials according to the invention can be used in the form of powders or granules, and the latter are preferred.
Materialene i henhold til oppfinnelsen er spesielt egnet for profil-ekstrudering, og enda mer spesielt profiler for rammer til anvendelse utendørs. Anvendelsen av materialene i henhold til oppfinnelsen til profil-ekstrudering, og enda mer spesielt slike for rammer til anvendelse utendørs, utgjør et annet aspekt ved foreliggende oppfinnelse. The materials according to the invention are particularly suitable for profile extrusion, and even more particularly profiles for frames for outdoor use. The use of the materials according to the invention for profile extrusion, and even more particularly such for frames for outdoor use, constitutes another aspect of the present invention.
Eksemplene som følger er ment å belyse oppfinnelsen. The examples that follow are intended to illustrate the invention.
Eksempel 1 illustrerer et materiale i henhold til oppfinnelsen som omfatter totalt 3,5 deler av forsterkende polymerer, nemlig 3 deler av lett tverrbundet polybutylakrylat (tilstede i form av en pode-kopolymer av vinylklorid med et lett tverrbundet polybutylakrylat) og 0,5 deler av etylen/vinylacetat-kopolymer (til stede i form av en pode-kopolymer av vinylklorid med et lett tverrbundet polybutylakrylat) og 0,5 deler av etylen/vinylacetat-kopolymer (til stede i form av en kopolymer av vinylklorid podet på en etylen/vinylacetat-kopolymer). Example 1 illustrates a material according to the invention which comprises a total of 3.5 parts of reinforcing polymers, namely 3 parts of lightly cross-linked polybutyl acrylate (present in the form of a graft copolymer of vinyl chloride with a lightly cross-linked polybutyl acrylate) and 0.5 parts of ethylene/vinyl acetate copolymer (present in the form of a graft copolymer of vinyl chloride with a lightly cross-linked polybutyl acrylate) and 0.5 parts of ethylene/vinyl acetate copolymer (present in the form of a copolymer of vinyl chloride grafted onto an ethylene/vinyl acetate -copolymer).
Eksemplene 2 og 3, angitt for sammenligning, omfatter utelukkende, som forsterkende polymer, henholdsvis 3 og 3,9 deler av lett tverrbundet polybutylakrylat (til stede i form av en kopolymer av vinylklorid podet på et lett tverrbundet polybutylakrylat). Examples 2 and 3, given for comparison, comprise exclusively, as reinforcing polymer, 3 and 3.9 parts respectively of lightly cross-linked polybutyl acrylate (present in the form of a copolymer of vinyl chloride grafted onto a lightly cross-linked polybutyl acrylate).
Eksempel 4 illustrerer et materiale i henhold til oppfinnelsen som omfatter totalt 4 deler av forsterkende polymerer, nemlig 3,6 deler av lett tverrbundet polybutylakrylat (til stede i form av en pode-kopolymer av vinylklorid med et lett tverrbundet polybutylakrylat) og 0,4 deler av etylen/vinylacetat-kopolymer (til stede i form av en kopolymer av vinylklorid podet på en etylen/vinylacetat-kopolymer) . Example 4 illustrates a material according to the invention comprising a total of 4 parts of reinforcing polymers, namely 3.6 parts of lightly cross-linked polybutyl acrylate (present in the form of a graft copolymer of vinyl chloride with a lightly cross-linked polybutyl acrylate) and 0.4 parts of ethylene/vinyl acetate copolymer (present in the form of a copolymer of vinyl chloride grafted onto an ethylene/vinyl acetate copolymer).
Vinylklorid-polymerene som anvendes i eksemplene er som følger: Polymer (a): kopolymer oppnådd ved polymerisering i vandig suspensjon av vinylklorid i nærvær av en lett tverrbundet polybutylakrylat-lateks (tverrbindingsgrad The vinyl chloride polymers used in the examples are as follows: Polymer (a): copolymer obtained by polymerization i aqueous suspension of vinyl chloride in the presence of a lightly cross-linked polybutyl acrylate latex (degree of cross-linking
<1%) inneholdende 94 vektdeler av polyvinylklorid pr. 6 <1%) containing 94 parts by weight of polyvinyl chloride per 6
vektdeler av lett tverrbundet polybutylakrylat. Polymer (b): kopolymer med K-verdi lik henholdsvis 68 parts by weight of lightly cross-linked polybutyl acrylate. Polymer (b): copolymer with K-value equal to 68 respectively
(eksemplene 1 til 3) og 64 (eksempel 4) (ved 25°C i cykloheksan i andelen 5 g/l), oppnådd ved polymerisering av vinylklorid i vandig suspensjon med en etylen/vinylacetat-kopolymer inneholdende 60 vekt% etylen, med en grenseviskositet, målt ved 20°C i m-xylen, som er på 0,08 g/l, inneholdende 98 vektdeler polyvinylklorid pr. 2 vektdeler etylen/vinylacetat-kopolymer . (Examples 1 to 3) and 64 (Example 4) (at 25°C in cyclohexane in the proportion of 5 g/l), obtained by polymerization of vinyl chloride in aqueous suspension with an ethylene/vinyl acetate copolymer containing 60% by weight of ethylene, with a limit viscosity, measured at 20°C in m-xylene, which is 0.08 g/l, containing 98 parts by weight of polyvinyl chloride per 2 parts by weight ethylene/vinyl acetate copolymer.
Polymer (c): vinylklorid-homopolymer oppnådd i vandig emulsjon med en K-verdi (målt ved 25°C i cykloheksanon i andelen 5 g/l) som er lik 73 (PVC-E), eller i vandig suspensjon med en K-verdi (samme forhold) som er lik 64 Polymer (c): vinyl chloride homopolymer obtained in aqueous emulsion with a K-value (measured at 25°C in cyclohexanone in the proportion of 5 g/l) equal to 73 (PVC-E), or in aqueous suspension with a K- value (same ratio) which is equal to 64
(PVC-S) . (PVC-S) .
Det forsterkende fyllstoff (d) består av utfelt kalsiumkarbonat i stearinsyre-belagte partikler som har en gjennomsnittlig diameter på 0,08fim. The reinforcing filler (d) consists of precipitated calcium carbonate in stearic acid-coated particles having an average diameter of 0.08 µm.
Materialene fremstilt og vurdert er som følger, og innholdene er uttrykt ved vekt: The materials produced and evaluated are as follows, and the contents are expressed by weight:
Før-blandinger ble fremstilt i en langsom blander, og så gelatinert i en indre mølle i tilnærmet 2,5 minutter, og tatt ut ved 160°C og innført i en valsemølle. Temperaturene til for- og bak-valsene var henholdsvis 150 og 145°C. En strimmel derav ble tatt bort, avkjølt i en vannbeholder og så overført til en granulator. Premixes were prepared in a slow mixer, then gelatinized in an internal mill for approximately 2.5 minutes, and removed at 160°C and introduced into a roller mill. The temperatures of the front and rear rollers were 150 and 145°C respectively. A strip of it was taken away, cooled in a water container and then transferred to a granulator.
Fra de derved oppnådd granuler ble småplater presset under de forhold som er spesifisert i DIN-standard 7748 for bedømmelse av Charpy-slagfastheten ved et enkelt U-formet innsnitt i henhold til DIN-standard 53453 (teststykker 50 x 6 x 4 mm). From the granules thus obtained, small plates were pressed under the conditions specified in DIN standard 7748 for evaluation of the Charpy impact resistance by a single U-shaped incision according to DIN standard 53453 (test pieces 50 x 6 x 4 mm).
Videre ble profiler ekstruder på en dobbelt-konisk-skruemaskin med en utførsel på 12 0 kg/time med den følgende temperatur-profil: Furthermore, profiles were extruded on a double-conical screw machine with an output of 120 kg/hour with the following temperature profile:
sylinder 190°C-170°C-150°C cylinder 190°C-170°C-150°C
adapter 160°C adapter 160°C
hullplate 165°C perforated plate 165°C
hode 165°C head 165°C
dyse 185°C skrue-kondisjonering 160°C nozzle 185°C screw conditioning 160°C
Charpy-slagfastheten ved et dobbelt V-formet innsnitt ble vurdert i henhold til DIN-standard 53753 (innsnitt-radius 0,1 mm) på test-stykker som var 3 mm tykke og tatt fra den ytre overflate av profilene. The Charpy impact resistance of a double V-shaped incision was assessed according to DIN standard 53753 (incision radius 0.1 mm) on test pieces 3 mm thick and taken from the outer surface of the profiles.
På identiske teststykker ble Charpy-slagfastheten ved et enkelt V-formet innsnitt vurdert i henhold til BS-standard 2782, metode 359 (for modifisert PVC). On identical test pieces, the Charpy impact strength at a single V-shaped incision was assessed according to BS Standard 2782, Method 359 (for modified PVC).
Profiler ble også sveiset under de følgende betingelser: Varme-speil-temperatur : 265 og 245°C Bevegelse av profilet mot speilet : 5,7 mm Bevegelse av profilet under sammensetning : 1,4 mm For-oppvarmings-periode for profilene under Profiles were also welded under the following conditions: Heat-mirror temperature : 265 and 245°C Movement of the profile towards the mirror : 5.7 mm Movement of the profile during assembly : 1.4 mm Pre-heating period for the profiles during
flytting mot speilet : 15 sek. For-oppvarmings-periode for profilene ved støtte moving towards the mirror: 15 sec. Pre-heating period for the profiles at support
mot speilet : 20 sek. Tid for anbringelse av profilene mot hverandre against the mirror : 20 sec. Time for placing the profiles against each other
under sammensetning : 4 0 sek. Lengde på armene fra den indre vinkel ved de during composition : 4 0 sec. Length of the arms from the internal angle at de
sveisede hjørne-sammenføyninger : 32 cm Overlappingene som ble dannet under sveising ble welded corner joints : 32 cm The overlaps formed during welding were
ikke freset bort. not milled away.
Kvaliteten på sveisningene ble vurdert ved måling av den kvasi-statiske strekkfasthet for de sveisede hjørner etter varme-kondisjonering av profilene i 12 timer ved 23° i det isotermiske rom hvori vurderingen ble foretatt, og detaljerte betingelser for denne er anført nedenfor: En av armene for det støpte hjørne er utstyrt med mot- kiler tilpasset til formen på'profilet og anbrakt vertikalt mot den stive bærer i testmaskinen. Mot-kilene er slik at de unngår å bli klemt fast til falsene. Den horisontale arm er ved toppen. The quality of the welds was assessed by measuring the quasi-static tensile strength of the welded corners after heat-conditioning the profiles for 12 hours at 23° in the isothermal room in which the assessment was carried out, and detailed conditions for this are listed below: One of the arms for the molded corner is equipped with counter- wedges adapted to the shape of the profile and placed vertically against the rigid carrier in the testing machine. The counter wedges are such that they avoid being clamped to the rebates. The horizontal arm is at the top.
Utsiden av hjørnet er fastklemt ved anvendelse av et The outside of the corner is clamped using a
trykkstempel. pressure stamp.
Sidene av hjørnet er fastklemt ved anvendelse av to andre The sides of the corner are clamped using two others
trykkstempler. printing stamps.
Testmaskinen skyver den horisontale arm i hjørnet vertikalt oppover ved hjelp av et trykkstempel med et rundt hode. The testing machine pushes the horizontal arm in the corner vertically upwards by means of a pressure piston with a round head.
Skyvnings-hastighet : 50 mm/min. Pushing speed: 50 mm/min.
Avstand fra den indre vinkel i det sveisede hjørne til skyvningsaksen: 3 0 cm. Distance from the inner angle in the welded corner to the push axis: 30 cm.
Topp-belastningen blir notert ved brudd i hjørnet. Treghetsmomentet til profilene vurderes ved anvendelse av en måling tatt med video-kamera og beregning med passende The peak load is noted in the case of a break in the corner. The moment of inertia of the profiles is assessed using a measurement taken with a video camera and calculation with appropriate
programvare. software.
Strekkfasthetene sigma beregnes ved anvendelse av den følgende formel: The tensile strengths sigma are calculated using the following formula:
hvor P : brudd-belastning where P : breaking load
d: avstand fra det indre hjørne til skyvningspunktet d: distance from the inner corner to the thrust point
for trykkstempler (= 3 0 cm) for pressure stamps (= 3 0 cm)
v: avstanden fra den nøytrale fiber i profilen til den lengst bortstående fiber utsatt for trekking under testen v: the distance from the neutral fiber in the profile to the farthest fiber exposed to pulling during the test
I: treghetsmoment i forhold til aksen svarende til I: moment of inertia relative to the axis corresponding to
enkel bøyning av profilen simple bending of the profile
Resultatene av vurderingen av Charpy-slagfasthetene, innbefattet standard-awik målt på 10 teststykker, og sveis-barheten på basis av den statiske strekkfasthet til de sveisede sammensetninger, er anført i den etterfølgende tabell. The results of the assessment of the Charpy impact strengths, including standard deviation measured on 10 test pieces, and the weldability based on the static tensile strength of the welded compositions, are listed in the following table.
Sammenligning av resultatene for eksemplene 1 og 4 i henhold til oppfinnelsen med resultatene for sammen-ligningseksemplene 2 og 3, som har like samlede innhold av forsterkningsmidler, viser merkbar overlegenhet for materialene i henhold til oppfinnelsen med hensyn til Charpy-slagf astheter ved et enkelt U-formet innsnitt, ved et enkelt V-formet innsnitt og ved et dobbelt V-formet innsnitt, og også med hensyn til sveisbarhet, som i virkeligheten er upåvirkelig overfor variasjon i sveisetemperatur, i motsetning for ved materialene vurdert for sammenligningsformål. Comparison of the results for examples 1 and 4 according to the invention with the results for comparative examples 2 and 3, which have the same total content of reinforcing agents, shows a noticeable superiority of the materials according to the invention with regard to Charpy impact strengths at a single U -shaped notch, in the case of a single V-shaped notch and in the case of a double V-shaped notch, and also with regard to weldability, which is in fact unaffected by variation in welding temperature, unlike in the case of the materials considered for comparison purposes.
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE9100099A BE1004374A3 (en) | 1991-02-01 | 1991-02-01 | Compositions resistant to impact polymer vinyl chloride and use. |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO920421D0 NO920421D0 (en) | 1992-01-31 |
| NO920421L NO920421L (en) | 1992-08-03 |
| NO303545B1 true NO303545B1 (en) | 1998-07-27 |
Family
ID=3885321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO920421A NO303545B1 (en) | 1991-02-01 | 1992-01-31 | Impact resistant materials based on vinyl chloride polymers and their use in profile extrusion |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0502560B1 (en) |
| JP (1) | JPH04311753A (en) |
| KR (1) | KR920016529A (en) |
| AT (1) | ATE140470T1 (en) |
| BE (1) | BE1004374A3 (en) |
| BR (1) | BR9200334A (en) |
| CA (1) | CA2060451A1 (en) |
| DE (1) | DE69212181T2 (en) |
| DK (1) | DK0502560T3 (en) |
| ES (1) | ES2092008T3 (en) |
| NO (1) | NO303545B1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4233052A1 (en) * | 1992-10-01 | 1994-04-07 | Wacker Chemie Gmbh | Process for the production of vinyl chloride polymer compositions with continuously adjustable material properties |
| BE1008919A3 (en) * | 1994-11-25 | 1996-10-01 | Solvay | Graft copolymers of vinyl chloride with a high impact resistance, method for production and use copolymers for extrusion profiles. |
| JPH1180475A (en) * | 1997-09-10 | 1999-03-26 | Sekisui Chem Co Ltd | Vinyl-chloride conduit-component material |
| KR100384382B1 (en) * | 1998-02-05 | 2003-08-21 | 주식회사 엘지화학 | Preparation method of impact resistant vinyl chloride-based resin |
| JP2003306589A (en) * | 2002-04-12 | 2003-10-31 | Sekisui Chem Co Ltd | Polyvinyl chloride resin composition |
| KR100568412B1 (en) * | 2003-11-14 | 2006-04-05 | 주식회사 엘지화학 | PVC-PCC Nanocomposites Resin Composition with Superior Impact Strengths and Method for Preparing the Same |
| KR100828726B1 (en) * | 2006-06-29 | 2008-05-09 | 주식회사 엘지화학 | Nano composite composition comprising vinylchloride based copolymer and method of producing the same |
| MX2015010338A (en) * | 2013-02-11 | 2016-09-19 | Vestolit Gmbh & Co Kg | Plasticizer-free article made of pvc graft copolymers. |
| JP7130935B2 (en) * | 2017-10-13 | 2022-09-06 | 信越化学工業株式会社 | Polyvinyl chloride resin molded product and its manufacturing method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2231695A1 (en) * | 1973-05-28 | 1974-12-27 | Solvay | Filled vinyl chloride polymer compsn - with good mechanical properties, contains vinyl chloride-alpha-olefin copolymer and calcium carbonate filler |
| DE2534049C3 (en) * | 1975-07-30 | 1980-10-23 | Wacker-Chemie Gmbh, 8000 Muenchen | Impact-resistant molding compounds based on polyvinyl chloride |
-
1991
- 1991-02-01 BE BE9100099A patent/BE1004374A3/en not_active IP Right Cessation
-
1992
- 1992-01-22 ES ES92200167T patent/ES2092008T3/en not_active Expired - Lifetime
- 1992-01-22 EP EP92200167A patent/EP0502560B1/en not_active Expired - Lifetime
- 1992-01-22 AT AT92200167T patent/ATE140470T1/en not_active IP Right Cessation
- 1992-01-22 DK DK92200167.2T patent/DK0502560T3/en active
- 1992-01-22 DE DE69212181T patent/DE69212181T2/en not_active Expired - Fee Related
- 1992-01-31 NO NO920421A patent/NO303545B1/en unknown
- 1992-01-31 JP JP4016865A patent/JPH04311753A/en active Pending
- 1992-01-31 BR BR929200334A patent/BR9200334A/en not_active Application Discontinuation
- 1992-01-31 CA CA002060451A patent/CA2060451A1/en not_active Abandoned
- 1992-02-01 KR KR1019920001622A patent/KR920016529A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| BR9200334A (en) | 1992-10-13 |
| EP0502560A1 (en) | 1992-09-09 |
| CA2060451A1 (en) | 1992-08-02 |
| KR920016529A (en) | 1992-09-25 |
| DK0502560T3 (en) | 1996-12-02 |
| DE69212181D1 (en) | 1996-08-22 |
| ES2092008T3 (en) | 1996-11-16 |
| EP0502560B1 (en) | 1996-07-17 |
| DE69212181T2 (en) | 1997-02-20 |
| JPH04311753A (en) | 1992-11-04 |
| BE1004374A3 (en) | 1992-11-10 |
| ATE140470T1 (en) | 1996-08-15 |
| NO920421D0 (en) | 1992-01-31 |
| NO920421L (en) | 1992-08-03 |
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