DK170896B1 - Polyolefin Compositions and Products Made Therefrom - Google Patents

Polyolefin Compositions and Products Made Therefrom Download PDF

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Publication number
DK170896B1
DK170896B1 DK150387A DK150387A DK170896B1 DK 170896 B1 DK170896 B1 DK 170896B1 DK 150387 A DK150387 A DK 150387A DK 150387 A DK150387 A DK 150387A DK 170896 B1 DK170896 B1 DK 170896B1
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weight
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polymer
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ethylene
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DK150387A
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DK150387A (en
DK150387D0 (en
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Vincent Crenna
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Norsolor Sa
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

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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)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Dental Preparations (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Polyolefin composition comprising, as first constituent (A) at least one highly isotactic propylene polymer and, as second constituent (B), at least one linear copolymer with a density of between 0.914 and 0.945, of ethylene and of at least one alpha -olefin containing from 3 to 12 carbon atoms. It comprises, per 100 parts by weight, from 30 to 40 parts by weight of the polymer (A), from 40 to 67 parts by weight of the polymer (B) and additionally from 3 to 25 parts by weight of at least one terpolymer (C) which has a density of between 0.865 and 0.912, containing from 70 to 94 mol% of ethylene, from 4 to 20 mol% of propylene and from 2 to 10 mol% of at least one alpha -olefin containing from 4 to 12 carbon atoms. Application to conversion into industrial articles.

Description

i DK 170896 B1in DK 170896 B1

Fra EP-patentpublikation nr. 0 102 857 kendes forbindelser omfattende 10-40 vægtprocent isotaktlsk polypropylen og 60-90 vægtprocent af en ethylencopolymer med en a-olefin med mindst 4 carbonatomer, af en tæthed på mellem 5 0,905 og 0,940 og et flydetal på mellem 0,2 og 3 dg/min.From EP Patent Publication No. 0 102 857, compounds comprising 10-40 wt.% Isotactic polypropylene and 60-90 wt.% Of an ethylene copolymer having an α-olefin having at least 4 carbon atoms are known, having a density of between 0.905 and 0.940 and a float number of between 0.2 and 3 dg / min.

Disse forbindelser tillader fremstilling af monoorienterede tråde med forbedrede egenskaber, især forbedret sejhed, der især anvendes i emballageindustrien i form af vævede poser.These compounds allow the production of mono-oriented yarns with improved properties, especially improved toughness, especially used in the packaging industry in the form of woven bags.

I modsætning til denne kendte teknik, hvis formål 10 det er at forbedre sejheden i monoorienterede tråde, er det den foreliggende opfindelses formål væsentligt at forbedre slagbestandigheden, navnlig ved lav temperatur, af ter-moplastiske sammensætninger på isotaktisk polypropylenbasis og af ethylen/a-olefincopolymerer. Dette formål opnås ifølge 15 den foreliggende opfindelse med en polyolefinsammensætning, der som første komponent (A) omfatter mindst en kraftigt isotaktisk pr opy lenpolymer, og som anden komponent (B) mindst en lineær copolymer, der har en densitet på mellem 0,914 og 0,945, af ethylen og af mindst en α-olefin med 3-12 carbona-20 tomer, hvilken sammensætning er ejendommelig ved, at den ud af 100 vægtandele omfatter 30-40 vægtandele af polymer (A), 40-67 vægtandele af polymer (B) og desuden 3-25 vægtandele af mindst en terpolymer (C), som har en densitet på mellem 0,865 og 0,912, og omfatter 70-94 molprocent ethylen, 4-20 molpro-25 cent propylen og 2-10 molprocent af mindst en α-olefin med 4-12 carbonatomer.Contrary to this prior art, the object of which is to improve the toughness of mono-oriented threads, the object of the present invention is to significantly improve the impact resistance, especially at low temperature, of isotactic polypropylene-based thermoplastic compositions and of ethylene / α-olefin copolymers. . This object is achieved according to the present invention with a polyolefin composition comprising as first component (A) at least one strongly isotactic polyethylene polymer and, as second component (B), at least one linear copolymer having a density of between 0.914 and 0.945. of ethylene and of at least one α-olefin of 3-12 carbon atoms, the composition of which comprises, out of 100 parts by weight, 30-40 parts by weight of polymer (A), 40-67 parts by weight of polymer (B) and in addition, 3-25 weight percent of at least one terpolymer (C) having a density of between 0.865 and 0.912, comprising 70-94 mole percent ethylene, 4-20 mole percent propylene and 2-10 mole percent of at least one α olefin with 4-12 carbon atoms.

Således er den foreliggende opfindelse baseret på den erkendelse, at termpolymeren (C), som har en densitet, der er beliggende mellem den termoplastiske copolymer (B) og 30 kautsjukcopolymererne, på grund af dens mellemtilstand mellem krystallinske og amorfe faser udviser en særlig evne til at forstærke komponenterne (A) og (B), og det selv om den anvendes i ringe mængdeforhold. Det bør desuden bemærkes, at tilsætningen af denne terpolymer til sammensætningerne, sådan 35 som de, der kendes fra EP-patent nr. 102.857, er ufordelagtige til opnåelse af monoorienterede tråde.Thus, the present invention is based on the recognition that, because of its intermediate state between crystalline and amorphous phases, the thermal polymer (C), which has a density located between the thermoplastic copolymer (B) and the rubber polymer copolymers, exhibits a particular ability to to reinforce components (A) and (B), even though it is used in poor proportions. In addition, it should be noted that the addition of this terpolymer to the compositions, such as those known from EP Patent No. 102,857, is disadvantageous in obtaining mono-oriented strands.

Ved propylenpolymeren (A) som første komponent skal DK 170896 B1 2 forstås en polymer, der omfatter mindst 80 molprocent af enheder, der stammer fra propylen, og i påkommende tilfælde højst 20 molprocent enheder, der stammer fra ethylen eller en a-olefin med 4-12 carbonatomer. I polymerernes (B) og (C) 5 definitioner bør bemærkes, at disse kan omfatte enheder af en eller flere α-olefiner i sådanne molforhold, som opfylder betingelserne hvad angår nævnte polymerers densitet. Sammenhængene i afhængighed af a-olefincomonomerens natur mellem disse molforhold og den resulterende copolymers densitet er 10 velkendt af fagfolk.By the propylene polymer (A) as the first component, DK 170896 B1 2 is understood to mean a polymer comprising at least 80 mole percent of units derived from propylene and, where applicable, a maximum of 20 mole percent of units derived from ethylene or an α-olefin having 4 -12 carbon atoms. In definitions of polymers (B) and (C) 5 it should be noted that these may comprise units of one or more α-olefins in such molar ratios which meet the conditions of density of said polymers. The relationships depending on the nature of the α-olefin comonomer between these molar ratios and the density of the resulting copolymer are well known to those skilled in the art.

Ved de påtænkte anvendelser for sammensætningerne ifølge opfindelsen kan normflydetallene for komponenterne (A), (B) og (C) vælges indenfor relativt store værdi intervaller. F.eks. kan normflydetallet målt ifølge ASTM normen D 15 1238-73 ved 230°C under 2,16 kg for polymeren (A) være beliggende mellem 0,4 og 60 dg/min., fortrinsvis mellem 1 og 20 dg/min. Normflydetallet målt ved 190eC under 2,16 kg for polymeren (B) kan være beliggende mellem 0,3 og 100 dg/min., fortrinsvis mellem 0,8 og 60 dg/min. Normflydetallet målt ved 20 190eC under 2,16 kg for polymeren (C) kan være beliggende mellem 0,8 og 20 dg/min.In the intended applications of the compositions of the invention, the norm flow numbers of components (A), (B) and (C) can be selected within relatively large value ranges. For example. For example, the norm flow rate measured according to ASTM standard D 15 1238-73 at 230 ° C below 2.16 kg for the polymer (A) may be between 0.4 and 60 dg / min, preferably between 1 and 20 dg / min. The standard flow rate measured at 190 ° C under 2.16 kg for the polymer (B) may be between 0.3 and 100 dg / min, preferably between 0.8 and 60 dg / min. The standard flow rate measured at 20 190 ° C under 2.16 kg for the polymer (C) can be between 0.8 and 20 dg / min.

Sammensætningerne ifølge opfindelsen kan desuden omfatte sædvanlige mængder antioxidanter og/eller stabilisatorer mod UV-stråling samt i givet fald op til 100 vægtandele 25 for 100 andele polyolefin-sammensætning, af mineralbestandde-le, såsom talkum, glimmer, kridt, glaskugler, aluminium-hydroxyder eller organiske bestanddele, såsom savsmuld. Disse bestanddele kan indarbejdes med sædvanlige midler, såsom en inderblander.The compositions of the invention may additionally comprise usual amounts of antioxidants and / or UV radiation stabilizers as well as up to 100 parts by weight 25 for 100 parts of polyolefin composition, of mineral constituents such as talc, mica, chalk, glass beads, aluminum hydroxides. or organic constituents such as sawdust. These components can be incorporated with conventional means such as an inner mixer.

30 Opfindelsen angår ligeledes et industrielt emne, der er ejendommeligt ved, at det er dannet ved omdannelse af en sammensætning ifølge krav 1 ved sprøjtestøbning eller ved blæseekstrudering af et hult legeme eller ved blæseekstru-dering af en folie.The invention also relates to an industrial article, characterized in that it is formed by the conversion of a composition according to claim 1 by injection molding or by blow extrusion of a hollow body or by blow extrusion of a foil.

35 Opfindelsen illustreres nærmere i de følgende eksempler.The invention is further illustrated in the following examples.

DK 170896 B1 3DK 170896 B1 3

Eksempel 1-4Examples 1-4

Der betragtes sammensætninger, som af 100 vægtandele indeholder: - 30 vægtandele af en propylenhomopolymer (Ax) med densitet 5 0,900 og normflydetal bestemt ifølge ASTM norm D 1238-73 lig med 6 dg/min.Compositions considered as containing 100 parts by weight contain: - 30 parts by weight of a propylene homopolymer (Ax) of density 5,900 and standard flow rate determined according to ASTM standard D 1238-73 equal to 6 dg / min.

- x vægtandele af en ethylen-buten-1 copolymer (Bj) med densiteten 0,920 og normflydetal bestemt ifølge ASTM norm D 1238-73 lig emd 20 dg/min., og 10 - y vægtandele af en ethylen-propylen-buten-1 terpolymer (Οχ) med densiteten 0,906 og normflydetal bestemt ifølge ASTM norm D 1238-73 lig med 1 dg/min. bestående af 91,6 molprocent ethylen, 5,2 molprocent propylen og 3,2 molprocent buten-1.- x parts by weight of an ethylene-butene-1 copolymer (Bj) of density 0.920 and standard flow rate determined according to ASTM standard D 1238-73 equal to 20 dg / min, and 10 - y parts by weight of an ethylene-propylene-butene-1 terpolymer (Οχ) with the density 0.906 and norm flow rate determined according to ASTM norm D 1238-73 equal to 1 dg / min. consisting of 91.6 mole percent ethylene, 5.2 mole percent propylene and 3.2 mole percent butene-1.

Disse sammensætninger omdannes ved sprøjtestøbning 15 til stænger, hvis slagfasthed RC måles ved -40®C, bestemt ifølge ASTM norm D 256-81 og udtrykt i kJ/m2.These compositions are converted by injection molding 15 into rods whose impact resistance RC is measured at -40 ° C, determined according to ASTM standard D 256-81 and expressed in kJ / m2.

Tabel I herunder opsummerer resultaterne af disse målinger som funktion af andelen x af polymeren (B) og af andelen y af terpolymeren (C). Som det uden vanskelighed vil 20 forstås, er eksempel 1 komparativt.Table I below summarizes the results of these measurements as a function of the proportion x of the polymer (B) and of the proportion y of the terpolymer (C). As will be readily understood, Example 1 is comparative.

Tabel ITable I

Eksempel 1234 x 70 65 60 50 y 0 5 10 20 25 RC 7 11 14 22Example 1234 x 70 65 60 50 y 0 5 10 20 25 RC 7 11 14 22

Eksempel 5-7Examples 5-7

Sammensætningerne indeholder pr. 100 vægtandele:The compositions contain per. 100 parts by weight:

- 40 vægtandele af en propylenhomopolymer (A2) ved et flydetal bestemt ved 230°C under 2,16 kg ifølge ASTM norm D- 40 parts by weight of a propylene homopolymer (A2) at a flow rate determined at 230 ° C under 2.16 kg according to ASTM standard D

30 1238-73 og lig med 3 dg/min.30 1238-73 and equal to 3 dg / min.

- x vægtandele af en ethylen-buten-1 copolymer (B2) med densiteten 0,919 og et normflydetal lig med 1 dg/min og - y vægtandele af en ethylen-propylen/buten-1 terpolymer (C2) med densiteten 0,874 og et normflydetal på 2 dg/min. og 35 omfattende 80 molprocent ethylen, 12 molprocent propylen og 8 molprocent buten-1 tilvejebringes ved tørblanding og omdannes dernæst til film DK 170896 B1 4 af en tykkelse på 50pm ved blæseekstrudering under følgende betingelser: - extruder: KIEFEL B60 - ydelse: 105 kg i timen 5 - materialetemperatur: 213°C.- x parts by weight of an ethylene-butene-1 copolymer (B2) with a density of 0.919 and a standard flow rate equal to 1 dg / min; and - y by weight of an ethylene-propylene / butene-1 terpolymer (C2) of density 0.874 and a standard flow number of 2 dg / min. and 35 comprising 80 mole percent ethylene, 12 mole percent propylene and 8 mole percent butene-1 are obtained by dry mixing and then converted to film DK 170896 B1 4 by a thickness of 50pm by blow extrusion under the following conditions: - extruder: KIEFEL B60 - yield: 105 kg in hour 5 - material temperature: 213 ° C.

Ved de således opnåede folier måltes i Jouleenheder slagstyrken RI ved 23°C bestemt ifølge NFT norm 51118 og ved hjælp af en slagstift efter NFT norm 54116. Resultaterne af disse målinger er vist i nedenstående tabel II. Som 10 det uden vanskelighed vil forstås, er eksempel 5 komparativt.In the foils thus obtained, in Joule units the impact strength RI was measured at 23 ° C according to NFT standard 51118 and by means of a impact pin according to NFT standard 54116. The results of these measurements are shown in Table II below. As will be readily understood, Example 5 is comparative.

Tabel IITable II

Eksempel 567 x 60 55 50 y 0 5 10 15 RI 0,76 1,13 1,13Example 567 x 60 55 50 y 0 5 10 15 RI 0.76 1.13 1.13

Claims (5)

1. Polyolefinsammensætninger, der som første bestanddel (A) omfatter mindst en kraftigt isotaktisk propylenpolymer og som anden bestanddel (B) mindst en lineær copolymer, der har en 5 densitet på mellem 0,914 og 0,945, af ethylen og af mindst en α-olefin med 3-12 carbonatomer, kendetegnet ved, at de af 100 vægtandele omfatter 30-40 vægtandele af polymer (A), 40-67 vægtandele af polymer (B) og herudover 3-25 vægtandele af mindst en terpolymer (C), har en densitet på 10 mellem 0,865 og 0,912 og omfattende 70-94 molprocent ethylen, 4-20 molprocent propylen og 2-10 molprocent af mindst en a-olefin med 4-12 carbonatomer.Polyolefin compositions comprising, as a first component (A), at least one highly isotactic propylene polymer and, as a second component (B), at least one linear copolymer having a density of between 0.914 and 0.945, of ethylene and of at least one α-olefin having 3-12 carbon atoms, characterized in that those of 100 parts by weight include 30-40 parts by weight of polymer (A), 40-67 parts by weight of polymer (B) and in addition 3-25 parts by weight of at least one terpolymer (C), have a density of 10 between 0.865 and 0.912 and comprising 70-94 mole percent ethylene, 4-20 mole percent propylene and 2-10 mole percent of at least one α-olefin having 4-12 carbon atoms. 2. Sammensætning ifølge krav 1, kendetegnet ved, at bestanddelens (A) normf lydetal målt ved 230° C og under 15 2,16 kg er beliggende mellem 0,4 og 60 dg/min.Composition according to claim 1, characterized in that the standard sound number of the component (A) measured at 230 ° C and below 2.16 kg is between 0.4 and 60 dg / min. 3. Sammensætning ifølge krav 1 eller 2, kendetegnet ved, at bestanddelens (B) normflydetal målt ved 190°C og under 2,16 kg er beliggende mellem 0,3 og 100 dg/min.Composition according to claim 1 or 2, characterized in that the standard flow rate of the component (B) measured at 190 ° C and below 2.16 kg is between 0.3 and 100 dg / min. 4. Sammensætning ifølge krav 1, 2 eller 3, kendeteg-20 net ved, at bestanddelens (C) normflydetal målt ved 190°C og under 2,16 kg er beliggende mellem 0,8 og 20 dg/min.Composition according to claim 1, 2 or 3, characterized in that the standard flow rate of the component (C) measured at 190 ° C and below 2.16 kg is between 0.8 and 20 dg / min. 5. Industrielt emne, kendetegnet ved, at det er dannet ved omdannelse af en sammensætning ifølge krav 1 ved sprøjtestøbning eller ved blæseekstrudering af et hult legeme 25 eller ved blæseekstrudering af en folie.Industrial blank, characterized in that it is formed by the conversion of a composition according to claim 1 by injection molding or by blow extrusion of a hollow body 25 or by blow extrusion of a foil.
DK150387A 1986-03-28 1987-03-25 Polyolefin Compositions and Products Made Therefrom DK170896B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8604499A FR2596402B1 (en) 1986-03-28 1986-03-28 TERNARY POLYOLEFINIC COMPOSITIONS AND A PROCESS FOR THEIR TRANSFORMATION INTO INDUSTRIAL ARTICLES
FR8604499 1986-03-28

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DK150387D0 DK150387D0 (en) 1987-03-25
DK150387A DK150387A (en) 1987-09-29
DK170896B1 true DK170896B1 (en) 1996-03-04

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EP (1) EP0254599B1 (en)
JP (1) JP2577377B2 (en)
KR (1) KR950013149B1 (en)
CN (1) CN1011510B (en)
AT (1) ATE76420T1 (en)
BR (1) BR8701415A (en)
CA (1) CA1269468A (en)
DE (1) DE3779205D1 (en)
DK (1) DK170896B1 (en)
ES (1) ES2032842T3 (en)
FI (1) FI91532C (en)
FR (1) FR2596402B1 (en)
GR (1) GR3005388T3 (en)
IN (1) IN167497B (en)
NO (1) NO172942C (en)

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US5250631A (en) * 1990-06-13 1993-10-05 Shell Oil Company Polymer compositions
EP3947554B1 (en) 2019-03-29 2023-05-03 Borealis AG Compatibilization of recycled polyethylene-polypropylene blends

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632674A (en) * 1967-11-02 1972-01-04 Itsuho Aishima Blend of ethylene polymer crystalline polypropylene polymer and crystalline ethylene-propylene block copolymer
FR2529563B1 (en) * 1982-06-30 1986-01-24 Charbonnages Ste Chimique COMPOSITIONS OF POLYPROPYLENE AND ETHYLENE / A-OLEFIN COPOLYMERS AND THEIR APPLICATION IN THE MANUFACTURE OF SINGLE-ORIENTED YARNS
CA1243257A (en) * 1983-10-18 1988-10-18 Masakazu Ito Multi-layer film or sheet material
JPS61213237A (en) * 1985-03-20 1986-09-22 Dainichi Nippon Cables Ltd Flame-retardant resin composition

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IN167497B (en) 1990-11-10
DK150387A (en) 1987-09-29
FI91532C (en) 1994-07-11
JPS62240341A (en) 1987-10-21
NO172942C (en) 1993-09-29
FR2596402B1 (en) 1988-05-20
DE3779205D1 (en) 1992-06-25
FI871371A (en) 1987-09-29
NO871291D0 (en) 1987-03-27
GR3005388T3 (en) 1993-05-24
CA1269468A (en) 1990-05-22
CN87102429A (en) 1987-10-07
NO172942B (en) 1993-06-21
EP0254599B1 (en) 1992-05-20
KR950013149B1 (en) 1995-10-25
FI91532B (en) 1994-03-31
KR870008943A (en) 1987-10-22
FI871371A0 (en) 1987-03-27
NO871291L (en) 1987-09-29
BR8701415A (en) 1987-12-29
JP2577377B2 (en) 1997-01-29
CN1011510B (en) 1991-02-06
ATE76420T1 (en) 1992-06-15
ES2032842T3 (en) 1993-03-01
EP0254599A1 (en) 1988-01-27
FR2596402A1 (en) 1987-10-02
DK150387D0 (en) 1987-03-25

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