EP0000084A1 - Verwendung von alpha-Polyolefinzusammensetzungen zum Extrudieren - Google Patents

Verwendung von alpha-Polyolefinzusammensetzungen zum Extrudieren Download PDF

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Publication number
EP0000084A1
EP0000084A1 EP78200028A EP78200028A EP0000084A1 EP 0000084 A1 EP0000084 A1 EP 0000084A1 EP 78200028 A EP78200028 A EP 78200028A EP 78200028 A EP78200028 A EP 78200028A EP 0000084 A1 EP0000084 A1 EP 0000084A1
Authority
EP
European Patent Office
Prior art keywords
compositions
process according
extrusion
alpha
extruded
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.)
Granted
Application number
EP78200028A
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English (en)
French (fr)
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EP0000084B1 (de
Inventor
Joseph Alard
Jean-Louis Derroitte
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.)
Solvay SA
Original Assignee
Solvay SA
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Publication date
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Application filed by Solvay SA filed Critical Solvay SA
Publication of EP0000084A1 publication Critical patent/EP0000084A1/de
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Classifications

    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3

Definitions

  • the present invention relates to a process for the extrusion of compositions based on polymers of alpha-olefins. It relates more particularly to a process for the manufacture of objects, by extrusion followed by water cooling, of compositions based on propylene polymers.
  • the polymers of alpha-olefins in particular the polymers of lower alpha-monoolefins such as ethylene and propylene are thermoplastic polymers suitable for processing by extrusion.
  • An important outlet for this transformation process lies in the production of films, sheets, tubes and filaments.
  • propylene polymers a large volume of these extruded polymers is intended for the manufacture of fibers and films. These can for example be used as such as packaging films, can be cut into strips for weaving, or can be fibrillated for various textile applications.
  • the extruded filaments generally pass, at the outlet of the die, into a quench tank containing water.
  • the extruded sheets can be cooled by spraying water after calendering.
  • Extruded tubes are often cooled by immersion in a water bath.
  • films we know that they can be manufactured by the methods known as "blown film” and "flat die”. According to the latter, the film from the die is cooled by cylinders with internal circulation of fluid ("chill roll") or by water bath. The sudden cooling obtained by this latter method makes it preferable for obtaining clear films. This method is very appreciated for the manufacture of textiles so-called “techniques" (weaving, cordage, stringing, etc.), for which the film must be cut into strips.
  • the films and filaments generally undergo stretching in order to increase their resistance. Furthermore, the films can be cut into strips before stretching.
  • compositions based on alpha-olefin polymers make it possible to manufacture objects by extrusion followed by cooling with water, without the latter being entrained, even for high extrusion speeds, and without harming the other essential properties of the extruded objects.
  • the alpha-olefin polymers used in the compositions which can be used according to the invention are polymers containing at least 50 mol% and preferably at least 75 mol% of terminal unsaturated olefins the molecule of which contains from 2 to 18 and preferably from 2 to 6 carbon atoms such as ethylene, propylene, butene- !, pentene-1, methylbutenes-1, hexene-1, 3- and 4-methylpentenes-1 and vinylcyclo- hexane. They are more particularly polymers containing tertiary carbon atoms such as highly isotactic crystalline polymers of butene-1, 4-methylpentene-1, and very particularly, propylene.
  • They may also be copolymers of these alpha-olefins with one another and / or with diolefins comprising from 4 to 18 carbon atoms, such as non-conjugated aliphatic diolefins such as, for example, 1,4-hexadiene or such that alicyclic diolefins having an endocyclic bridge such as dicyclopentadiene for example.
  • these may be block copolymers which consist of successions of chain segments of variable lengths, each segment consisting of a homopolymer of an alpha-olefin or of a random copolymer comprising an alpha-olefin and at least one comonomer chosen from alpha-olefins and diolefins.
  • compositions which can be used according to the invention can also be based on mixtures of two or more polymers as described above.
  • the polymers which can be used can be prepared according to known methods of polymerization of alpha-olefins at low pressure.
  • highly isotactic crystalline homopolymers of propylene can be prepared in the presence of stereospecific catalytic systems based on organometallic compounds and titanium chlorides being at a valence lower than its maximum valence.
  • compositions which can be used according to the invention comprise at least one constituent (a) which is any phenolic antioxidant.
  • This antioxidant can advantageously be chosen from the group of alkylated mono-, poly- and thiobis-phenols.
  • alkylated monophenols By way of examples of alkylated monophenols, mention may be made of 2,6-di-tert-butyl-p-cresol and (3,5-di-tert-butyl-4-hydroxyphenyl) propionate of n-octa-decyl .
  • alkylated polyphenols mention may be made of methylene tetrakis (3,5-di-tert-butyl-4-hydroxy) methane dihydrocinnamate, 2,2'-methylene bis (4-methyl-6- terephthalate) tert-butylphenol), 2,6-bis- (2'-hydroxy-3-tert-butyl-5'-methylbenzyl) -4-methylphenol and tris- (3,5-di-tert-butyl isocyanurate) -4-hydroxy) benzyl.
  • compositions which can be used according to the invention can also comprise a mixture of the phenolic antioxidants listed above.
  • compositions which can be used according to the invention comprise at least one component (b) which is an organic phosphite.
  • This organic phosphite is advantageously chosen from the phosphites and thiophosphites of general formulas (RO) 3 P and (RS) 3 P in which the radicals R, which are identical or different, represent an alkyl, aryl, alkylaryl, cycloalkyl or alkoxyalkyl radical and among cyclic phosphites derived from pentaerythritol.
  • Preferred phosphites as constituents (b) are, on the one hand, the trialkylphosphites such as the triethyl-, tributyl- and trinonylphosphites for example and, on the other hand, the dialkylpentaerythritol diphosphites, such as the distearylpentaerythritol diphosphite for example. Mixtures of these phosphites can also be advantageously used.
  • compositions extruded according to the invention finally comprise at least one component (c) which is a carbonate of an alkaline earth metal.
  • All the alkaline earth metal carbonates are suitable as constituents (c). Mention may be made, for example, of magnesium, calcium, strontium and barium carbonates. However, it is preferred to use calcium carbonate, and in particular calcium carbonates which are in the form of particles with an average diameter of less than 10 microns.
  • the so-called "precipitated" calcium carbonates that is to say the calcium carbonates obtained by carbonation of a lime milk, are very suitable.
  • Constituents (a) and (b) are incorporated in the extruded compositions according to the invention in the usual stabilizing amounts.
  • these amounts are generally between 0.005 and 10% by weight of the polymer entering into the composition and preferably between 0.01 and 5 X. More particularly, these amounts are of the order of 0.05 to 0.5%.
  • Component (c) is incorporated into the compositions in an amount of 0.1 to 50 ⁇ (per thousand) by weight of the polymer approximately, preferably in an amount of 0.1 to 10 ⁇ .
  • the average diameter of its particles is a fraction of a micron. More particularly, the particles have an average diameter of between 0.05 and 0.8 microns. It has been found in fact that if the size of the particles of component (c) is greater, this results, in the case of the extrusion of films cut into strips, of rapid wear of the cutting blades.
  • compositions which can be used according to the invention can contain other usual additives such as, for example, other antioxidants such as thioesters generally derived thiodipropionic acid, other polymers, agents that facilitate processing, reinforcing agents, pigments, fillers, lubricants, anti-static agents, etc.
  • Components (a), (b) and (c) can be incorporated into the polymer in any manner known per se, for example by dry mixing or by impregnating the polymer in powder or granules by means of a solution of the components in a suitable solvent, alone or as a standard charge with other ingredients, or by mixing a solution or a suspension of the polymer with a solution of the constituents.
  • the incorporation can be carried out for example, either in a mixer or a grinder where the solvent is evaporated, or by kneading on cylinders heated or by extrusion of a mixture of the polymer and the other constituents.
  • compositions according to the invention can be carried out according to all the conventional techniques known to those skilled in the art.
  • the characteristics of the apparatus will obviously be chosen as a function of the transformation which it is desired to subject to the composition to be extruded and of the type of object which it is intended to shape.
  • the cooling or quenching treatment by means of water it is carried out at a temperature which depends on the nature of the extruded object and on the properties which it is intended to confer on the latter.
  • the temperature of the quench bath of the primary film is generally between approximately 20 and approximately 50 ° vs.
  • the method according to the invention therefore provides an elegant solution to the problem of entraining water, by extruded compositions, when the latter are cooled with water.
  • the use, in the extrusion process which is the subject of the invention, of the compositions described above makes it possible, surprisingly, to ensure an excellent compromise between the elimination of water entrainment even at high extrusion speed, the initial coloring and the anti-corrosion efficiency, a compromise which is not achieved with the compositions of the prior art.
  • compositions according to the invention containing calcium carbonate "precipitated" into particles of average diameter of the order of a fraction of a micron do not soil the die of the extruder; during the extrusion of films which are cut into strips, they do not cause premature wear of cutting knives.
  • This granulated composition is then extruded in the form of a film approximately 100 microns thick.
  • This film is cooled by passing through a water bath at room temperature (25 ° C) and then cut into strips which are stretched, at a stretching rate of about 1/6 in a stretching oven brought to a temperature from 150 - 180 ° C.
  • This composition is transformed into strips as indicated in Example 1. These strips show the same properties as those found for the strips of Example 1.
  • An extrudable composition is prepared as in Example 3, except that SOCAL Ul is replaced by 0.5 part by weight of calcium stearate.
  • SOCAL Ul is replaced by 0.5 part by weight of calcium stearate.

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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)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
EP78200028A 1977-06-07 1978-06-01 Verwendung von alpha-Polyolefinzusammensetzungen zum Extrudieren Expired EP0000084B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR777717978A FR2393829A1 (fr) 1977-06-07 1977-06-07 Procede pour l'extrusion de compositions a base de polymeres d'alpha-olefines
FR7717978 1977-06-07

Publications (2)

Publication Number Publication Date
EP0000084A1 true EP0000084A1 (de) 1978-12-20
EP0000084B1 EP0000084B1 (de) 1986-11-20

Family

ID=9192004

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78200028A Expired EP0000084B1 (de) 1977-06-07 1978-06-01 Verwendung von alpha-Polyolefinzusammensetzungen zum Extrudieren

Country Status (10)

Country Link
US (1) US4190624A (de)
EP (1) EP0000084B1 (de)
JP (1) JPS543149A (de)
AT (1) AT385044B (de)
BR (1) BR7803570A (de)
CA (1) CA1112013A (de)
DE (1) DE2862482D1 (de)
ES (1) ES470543A1 (de)
FR (1) FR2393829A1 (de)
IT (1) IT1094840B (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2550231A1 (fr) * 1983-08-02 1985-02-08 Labofina Sa Procede de fabrication de fibres de polypropylene
EP0212486A3 (en) * 1985-08-19 1988-01-20 Hoechst Aktiengesellschaft Polyolefin moulding composition
EP0330019A3 (de) * 1988-02-19 1992-05-20 Hoechst Aktiengesellschaft Rohstoff und daraus hergestellte Folie mit verbesserten elektrischen Eigenschaften
GB2336366A (en) * 1998-04-14 1999-10-20 Ecc Int Ltd Filled polyethylene compositions

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1173616A (en) * 1980-12-22 1984-09-04 George Kletecka Hindered phenolic antioxidants and diazacycloalkane uv stabilizers in polymeric films
US4540538A (en) * 1981-10-08 1985-09-10 Union Carbide Corporation Anti-block compounds for extrusion of transition metal catalyzed resins
JPS5930840A (ja) * 1982-08-12 1984-02-18 Chisso Corp 水処理槽用ポリオレフイン樹脂組成物
GB8621094D0 (en) * 1986-09-01 1986-10-08 Ici Plc Loading of polymer additives
US5102611A (en) * 1990-05-18 1992-04-07 Phillips Petroleum Company Process for making smooth plastic tubing
GB9127028D0 (en) * 1991-12-20 1992-02-19 Scott & Fyfe Ltd A method of producing a polyolefinic film by a water quench process
ZA9510604B (en) * 1994-12-20 1996-07-03 Kimberly Clark Co Low gauge films and film/nonwoven laminates
TW330217B (en) 1994-12-20 1998-04-21 Kimberly Clark Co Low gauge films and film/nonwoven laminates
US6179939B1 (en) 1997-05-12 2001-01-30 Kimberly-Clark Worldwide, Inc. Methods of making stretched filled microporous films
US6909028B1 (en) 1997-09-15 2005-06-21 Kimberly-Clark Worldwide, Inc. Stable breathable elastic garments
US6045900A (en) * 1997-09-15 2000-04-04 Kimberly-Clark Worldwide, Inc. Breathable filled film laminate
US6238767B1 (en) 1997-09-15 2001-05-29 Kimberly-Clark Worldwide, Inc. Laminate having improved barrier properties

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3012003A (en) * 1956-11-13 1961-12-05 Collier Carbon & Chemical Co Stabilization of polyolefines with alkaline stabilizers
FR1296276A (fr) * 1960-07-29 1962-06-15 Shell Int Research Compositions polymères de polyoléfines à basse pression
FR1345203A (fr) * 1961-11-17 1963-12-06 Shell Int Research Compositions de polymères oléfiniques et procédé pour les préparer
US3254041A (en) * 1961-12-28 1966-05-31 Exxon Research Engineering Co Stable slurry of calcium carbonate and calcium stearate, and methods of making and using it
CH581162A5 (en) * 1973-06-29 1976-10-29 Sandoz Ag Preventing organic phosphate flame retardants migration in polyolefins - by addn. of oil absorbent inorganic cpd.
US3998781A (en) * 1975-04-14 1976-12-21 Chemetron Corporation Polyolefin composition and method for minimizing migration of U.V. absorber therein

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL206015A (de) * 1955-04-04 1900-01-01
CA644406A (en) * 1955-09-02 1962-07-10 S. Kenyon Allen Polymer stabilization
US2991264A (en) * 1957-05-01 1961-07-04 Du Pont Method of partially crystallizing an alpha-olefin polymer
US2941254A (en) * 1959-05-20 1960-06-21 Du Pont Process of forming polyethylene film and product
US3039993A (en) * 1960-05-10 1962-06-19 Weston Chemical Corp Polyethylene stabilizers
US3560432A (en) * 1967-03-17 1971-02-02 Ici Ltd Stabilisation of polymers
GB1250917A (de) * 1967-12-30 1971-10-27
US3922249A (en) * 1973-04-12 1975-11-25 Phillips Petroleum Co Stabilized antistatic compositions useful with olefin polymers
CA1078991A (en) * 1975-02-20 1980-06-03 Hans J. Lorenz Stabilization systems from triarylphosphites and phenols
JPS5930737B2 (ja) * 1975-10-18 1984-07-28 三井化学株式会社 ポリオレフイン組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3012003A (en) * 1956-11-13 1961-12-05 Collier Carbon & Chemical Co Stabilization of polyolefines with alkaline stabilizers
FR1296276A (fr) * 1960-07-29 1962-06-15 Shell Int Research Compositions polymères de polyoléfines à basse pression
FR1345203A (fr) * 1961-11-17 1963-12-06 Shell Int Research Compositions de polymères oléfiniques et procédé pour les préparer
US3254041A (en) * 1961-12-28 1966-05-31 Exxon Research Engineering Co Stable slurry of calcium carbonate and calcium stearate, and methods of making and using it
CH581162A5 (en) * 1973-06-29 1976-10-29 Sandoz Ag Preventing organic phosphate flame retardants migration in polyolefins - by addn. of oil absorbent inorganic cpd.
US3998781A (en) * 1975-04-14 1976-12-21 Chemetron Corporation Polyolefin composition and method for minimizing migration of U.V. absorber therein

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2550231A1 (fr) * 1983-08-02 1985-02-08 Labofina Sa Procede de fabrication de fibres de polypropylene
EP0212486A3 (en) * 1985-08-19 1988-01-20 Hoechst Aktiengesellschaft Polyolefin moulding composition
AU582670B2 (en) * 1985-08-19 1989-04-06 Hoechst Aktiengesellschaft Polyolefin molding composition
EP0330019A3 (de) * 1988-02-19 1992-05-20 Hoechst Aktiengesellschaft Rohstoff und daraus hergestellte Folie mit verbesserten elektrischen Eigenschaften
GB2336366A (en) * 1998-04-14 1999-10-20 Ecc Int Ltd Filled polyethylene compositions

Also Published As

Publication number Publication date
DE2862482D1 (en) 1987-01-08
FR2393829A1 (fr) 1979-01-05
JPS6150096B2 (de) 1986-11-01
US4190624A (en) 1980-02-26
FR2393829B1 (de) 1980-01-18
IT7824300A0 (it) 1978-06-07
CA1112013A (fr) 1981-11-10
BR7803570A (pt) 1979-03-13
IT1094840B (it) 1985-08-10
AT385044B (de) 1988-02-10
ATA411078A (de) 1982-06-15
ES470543A1 (es) 1980-01-01
JPS543149A (en) 1979-01-11
EP0000084B1 (de) 1986-11-20

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