EP0785965A1 - Particules de polyolefine moussees aux prealable produites par extrusion - Google Patents

Particules de polyolefine moussees aux prealable produites par extrusion

Info

Publication number
EP0785965A1
EP0785965A1 EP95935911A EP95935911A EP0785965A1 EP 0785965 A1 EP0785965 A1 EP 0785965A1 EP 95935911 A EP95935911 A EP 95935911A EP 95935911 A EP95935911 A EP 95935911A EP 0785965 A1 EP0785965 A1 EP 0785965A1
Authority
EP
European Patent Office
Prior art keywords
polyolefin
particles
extrusion
blowing agent
temperature
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.)
Withdrawn
Application number
EP95935911A
Other languages
German (de)
English (en)
Inventor
Joachim Fischer
Franz-Josef Dietzen
Gerd Ehrmann
Isidoor De Grave
Jens Rieger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0785965A1 publication Critical patent/EP0785965A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene

Definitions

  • Pre-expanded polyolefin particles made by extrusion
  • the invention relates to prefoamed polyolefin particles produced by extrusion and subsequent granulation.
  • Pre-expanded polyolefin particles in particular based on a copolymer of propylene with small amounts of ethylene, are being used to an increasing extent for the production of foam molded parts in the automotive, packaging and leisure sectors.
  • the foam particles are usually produced by suspending finely divided polyolefin granules in water, impregnating them with a volatile blowing agent under pressure at temperatures close to the softening temperature of the polyolefin, relaxing and thereby foaming (see EP-A 53333).
  • the polyolefin has a special crystal structure, which is characterized in that it has a peak characteristic of the polyolefin and a high-temperature peak (so-called “double peak”) in a DSC curve.
  • EP-A 588 321 describes a particularly elegant and simple method for producing prefoamed polypropylene particles.
  • Polypropylene is melted in an extruder, a blowing agent is injected into this melt and mixed homogeneously at 125 to 250.degree. The homogeneous mass is pressed out through a round nozzle, foams up and is cut into foam particles.
  • the polypropylene used should have a melt strength of 5 to 40 cN and a branched structure.
  • the foam particles produced in this way have a very narrow processing range in the production of molded parts and do not weld sufficiently well to one another. For this reason, the molded parts have relatively poor mechanical properties; especially elongation at break and tensile strength leave something to be desired.
  • the invention was therefore based on the object of providing pre-foamed polyolefin particles which had been produced from a conventional, ie not melt-strengthened, polyolefin by extrusion and subsequent granulation and which can be welded to molded parts with good mechanical properties without problems. It was found that this is the case if the polyolefin in the foam particles has a crystal structure with a double peak, the distance between the two tips being at least 5 ° C., preferably more than 8 ° C.
  • polyolefins are crystalline olefin polymers whose X-ray crystallinity is above 25% at 25 ° C.
  • Low, medium and high density polyethylenes between 0.88 to 0.965 g / cm 3 polypropylene and ethylene and propylene copolymers which contain at least 50 mol% of ethylene or propylene units are suitable for the process.
  • Suitable comonomers are, for example, ⁇ -alkenes having up to 12 carbon atoms, such as ethylene, propylene, butene, pentene, hexene, octene, and also vinyl esters, such as vinyl acetate, esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid with alcohols which have 1 to 8 Contain carbon atoms, copolymers of ethylene and acrylic acid or their derivatives, and ionomers. Mixtures of different olefin polymers can also be used.
  • Ethylene-propylene copolymers and copolymers of ethylene and / or propylene with a C 4 - bis are preferably used
  • propylene copolymers are copolymers of propylene with 0.5 to 6% by weight of ethylene or 0.5 to 15% by weight of butene (1).
  • Particularly preferred ethylene copolymers are copolymers of ethylene with 1 to 18% by weight of butene (1), hexene (1) or octene (1).
  • a C 4 - to C 8 - ⁇ -01e-fin such as butene-1, pentene-1, hexene-1, heptene-1 or octene-1.
  • the copolymers should have a G modulus of 100 to 900, preferably 150 to 750 N / mm 2 .
  • the copolymers are prepared in a known manner by copolymerizing the monomers using transition metal catalysts.
  • the copolymers are generally linear, uncrosslinked and not melt-solidified.
  • the crystallite point, determined by the DSC method is generally zwi ⁇ rule 95 and 170 C C.
  • the heat of fusion is generally from 30 to 130 J / g, preferred wise between 35 and 120 J / g.
  • Copolymers with a melt index MFI (230; 2.16) (according to DIN 53 735) of 0.1 to 50, in particular 0.5 to 20 [g / 10 min] are preferably used.
  • the foam particles according to the invention are produced by impregnating polyolefin particles with a blowing agent in an extruder at a low temperature, homogenizing and dwelling the mass at higher temperatures and finally pressing out with foaming.
  • the polyolefin particles are impregnated with a volatile blowing agent.
  • Fine semolina with particle sizes of 0.01 to 10 mm, such as is obtained directly in the polymerization, or granules with particle sizes of 0.1 to 10 mm, as is obtained in the extrusion of the polyolefin, can be used.
  • Suitable blowing agents are organic compounds with boiling points between 0 and 150 ° C., for example n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane or cyclohexane, heptanes, octanes,
  • Halogenated hydrocarbons and their mixtures The amount of blowing agent depends on the desired bulk density of the foam particles. It is preferably 5 to 40, in particular 8 to 30 parts by weight, based on 100 parts by weight of polyolefin. At this point it is also possible to add conventional additives in effective amounts, such as dyes, pigments, nucleating agents, stabilizers, flame retardants, lubricants and antistatic agents.
  • the polyolefin particles are impregnated with the blowing agent preferably in the only slightly sheared feed zone of an extruder. It is essential that the swelling takes place at a relatively low temperature, ie the temperature must be 50 to 180, preferably 100 to 150 ° C. below the crystalline melting point of the polyolefin and at least 10 ° C. below the boiling point of the blowing agent, so that the latter does not evaporate.
  • the temperature By applying an excess pressure of maximum 10 bar, low-boiling blowing agents, such as butanes, can also be metered in at room temperature.
  • the polyolefin particles are fed to zone A, for example via a cell-wheel lock.
  • the temperature in the zone A is preferably zwi ⁇ 's 10 and 40 C C, especially at room temperature.
  • the residence time in this zone is preferably 0.1 to 5 minutes.
  • the polyolefin is soaked with the blowing agent to such an extent that its viscosity is greatly reduced.
  • zone B The described lowering of the viscosity makes it possible to carry out the homogenization in zone B at temperatures which are 2 to 50 ° C., preferably 5 to 40 ° C. below the crystallite melting point of the pure polyolefin lie. This is a further advantage over the method according to EP-A 588 321, where extrusion takes place at considerably higher temperatures.
  • This homogenization with simultaneous temperature increase is preferably carried out in a second zone (homogenization zone) of the extruder already used in stage A.
  • zine B in order to regulate the cell diameter, small amounts (for example 0.1 to 5% by weight) of carbon dioxide or nitrogen can be metered in.
  • the mass is then kept for a time, preferably 1 to 60 minutes, at a temperature which is 2 to 50 ° C. below the crystalline melting point of the polyolefin.
  • This is expediently carried out in a residence time zone C downstream of zone B, for example a static mixer (Sulzer mixer) or a low-shear extruder (single-screw extruder).
  • the resulting foam particles are ellipsoid to spherical.
  • the average diameter is 2 to 20 mm.
  • Their debris weight can be set within wide limits between 0.01 and 0.2 g ⁇ cm "-, preferably between 0.01 and 0.15 g • cm -1 .
  • the number of cells is generally 0.1 to 1000 cells per mm 2 .
  • Shaped parts with good mechanical properties can be produced in a conventional manner from the pre-expanded particles according to the invention by welding.
  • a dwell time zone C consisting of 4 Sulzer mixers (DN * • »80 mm) was connected to the gear pump. These were kept at 130 ° C. After a dwell time of 45 min, the polymer containing blowing agent was pressed out of a round nozzle with a diameter of 2 mm and was blown by means of a granulator from
  • the foam particles obtained had a diameter of 10 mm. Their bulk density was .22 g • L ⁇ -.
  • the DSC curve shows two maxima at 146 ° C and 160 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Des particules de polyoléfine moussées au préalable sont produites par extrusion puis par granulation et ont une structure cristalline avec une double crête.
EP95935911A 1994-10-15 1995-10-06 Particules de polyolefine moussees aux prealable produites par extrusion Withdrawn EP0785965A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4436980 1994-10-15
DE4436980A DE4436980A1 (de) 1994-10-15 1994-10-15 Durch Extrusion hergestellte, vorgeschäumte Polyolefinteilchen
PCT/EP1995/003946 WO1996011971A1 (fr) 1994-10-15 1995-10-06 Particules de polyolefine moussees aux prealable produites par extrusion

Publications (1)

Publication Number Publication Date
EP0785965A1 true EP0785965A1 (fr) 1997-07-30

Family

ID=6530924

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95935911A Withdrawn EP0785965A1 (fr) 1994-10-15 1995-10-06 Particules de polyolefine moussees aux prealable produites par extrusion

Country Status (5)

Country Link
US (1) US5744505A (fr)
EP (1) EP0785965A1 (fr)
JP (1) JPH10507224A (fr)
DE (1) DE4436980A1 (fr)
WO (1) WO1996011971A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19739113A1 (de) * 1997-09-06 1999-03-11 Gefinex Polymerschaeume Gmbh Vorexpandierte polyolefinische Schaumpartikel
DE19740058C2 (de) * 1997-09-12 2001-10-31 Mannesmann Vdo Ag Verfahren zum Herstellen eines Schwimmers, kraftstoffbeständiger Schwimmer sowie Verwendung von miteinander verpreßten, durch Extrusion hergestellten Partikeln
JP3692760B2 (ja) * 1998-01-30 2005-09-07 株式会社カネカ ポリプロピレン系樹脂型内発泡成形体の製造方法
JP3950557B2 (ja) 1998-07-30 2007-08-01 株式会社カネカ ポリプロピレン系樹脂予備発泡粒子およびそれからの型内発泡成形体の製造方法
JP3581025B2 (ja) * 1998-08-03 2004-10-27 住友化学工業株式会社 無架橋ポリプロピレン系樹脂発泡シートの製造方法及び無架橋ポリプロピレン系樹脂発泡シート
JP5296279B2 (ja) 1999-12-28 2013-09-25 株式会社カネカ 発泡性ポリスチレン系樹脂粒子およびそれを用いた発泡体
FR2856950B1 (fr) * 2003-07-04 2007-03-02 Rhodia Polyamide Intermediates Procede de preparation de perle a base de polymere expanse
TW200708541A (en) * 2005-08-31 2007-03-01 Chi Lin Technology Co Ltd Method of making polyester foam particles
CN108329590A (zh) * 2018-02-08 2018-07-27 贵州省材料产业技术研究院 一种双峰结晶聚丙烯复合材料及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0123144B1 (fr) * 1983-03-25 1987-10-07 Japan Styrene Paper Corporation Perles prémoussées en résine de polypropylène
JPS60110734A (ja) * 1983-11-21 1985-06-17 Japan Styrene Paper Co Ltd 無架橋ポリプロピレン系樹脂予備発泡粒子
CA1280549C (fr) * 1986-05-27 1991-02-19 Kyoichi Nakamura Particules pre-expansees de resine propylene
JP2878527B2 (ja) * 1992-06-22 1999-04-05 鐘淵化学工業株式会社 ポリエチレン系樹脂予備発泡粒子
IT1255364B (it) * 1992-09-15 1995-10-31 Himont Inc Processo per la preparazione di manufatti in polipropilene espanso mediante produzione di granuli pre-espansi e termoformatura per sinterizzazione degli stessi
DE4420590A1 (de) * 1994-06-13 1995-12-14 Basf Ag Polyolefin-Partikelschaum

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9611971A1 *

Also Published As

Publication number Publication date
DE4436980A1 (de) 1996-04-18
MX9702620A (es) 1997-07-31
US5744505A (en) 1998-04-28
WO1996011971A1 (fr) 1996-04-25
JPH10507224A (ja) 1998-07-14

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