WO2001027169A1 - Corps en materiau polymere comprenant des polymeres isotactiques lineaires - Google Patents

Corps en materiau polymere comprenant des polymeres isotactiques lineaires Download PDF

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Publication number
WO2001027169A1
WO2001027169A1 PCT/US2000/027135 US0027135W WO0127169A1 WO 2001027169 A1 WO2001027169 A1 WO 2001027169A1 US 0027135 W US0027135 W US 0027135W WO 0127169 A1 WO0127169 A1 WO 0127169A1
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WO
WIPO (PCT)
Prior art keywords
polymeric material
present
article
homopolymer
bodies
Prior art date
Application number
PCT/US2000/027135
Other languages
English (en)
Inventor
Bernhard Rieger
Mike Orroth
Gian De Belder
Original Assignee
The Procter & Gamble Company
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 The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU77468/00A priority Critical patent/AU7746800A/en
Priority to EP00967242A priority patent/EP1237955A1/fr
Priority to US10/089,344 priority patent/US6746780B1/en
Publication of WO2001027169A1 publication Critical patent/WO2001027169A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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

Definitions

  • the present invention relates to articles comprising bodies of polymeric material. Specifically, the present invention relates to bodies of elastic polymeric material.
  • Bodies of polymeric material and in particular of olefinic polymers are well known in the art and enjoy widespread usage throughout the industry. Typical areas of application of such body of polymeric material include for example medical applications, hygienic applications, automotive parts, sporting goods, and the like.
  • Bodies made from commonly used polyolefins such as PP, PE, PS PIB have a number of useful properties. They are bio- compatible and food compatible, chemically stabile, inert, non toxic materials. However, most of them are rigid and have poor mechanical properties including insufficient strength/tear resistance, insufficient stretchability/elasticity and the like.
  • the third approach proposed in the prior art to provide elastic properties to such bodies of polymeric material, which is more close to the present invention, is to exploit the formation of hetero-phases which reinforce the bulk material by forming a physical net.
  • the block-co- polymerization of two or more different monomers has been used leading to polymeric backbones comprising blocks with different Tg. This results in micro-phase separation in the bulk with formation of reinforcing crystalline domains of one co-polymer linked with each other by flexible chains of the second co-polymer.
  • the present invention provides an article comprising a first element and a second element separated from and joined to said first element, said first element being a body of polymeric material.
  • the article of the present invention is characterized in that said body of polymeric material comprises linear isotactic polymers having a structure of one or several C 2 to C 20 olefins, the isotacticity of said polymers, due to a statistic distribution of stereoscopic errors in the polymer chain, being within the range of 25% to 60% of [mmmm] pentad concentration with the proviso that an arbitrary or rather regular sequence of isotactic and atactic blocks is excluded, the polymer having a mean molecular weight Mw within the range of from 100000 to 800000 g/mol and a glass temperature T g of between -50 to +30 °C.
  • the present invention further provides a method for manufacturing a body from polymeric material comprising a step of processing said polymeric material selected from the group of to injection molding, extrusion blow molding, extrusion, casting, solution sedimentation, and combinations thereof.
  • the method of the present invention is characterized in that said polymeric material comprises linear or branched isotactic polymers having a structure of one or several C 2 to C 20 olefins, the isotacticity of said polymers, due to a statistic distribution of stereoscopic errors in the polymer chain, being within the range of 25% to 60% of [mmmm] pentad concentration with the proviso that an arbitrary or rather regular sequence of isotactic and atactic blocks is excluded, the polymer having a mean molecular weight Mw within the range of from 100000 to 800000 g/mol and a glass temperature T g of between -50 to +30 °C.
  • the present invention further provides a method for processing a body of polymeric material comprising a step selected from the group of thermoforming, laser forming, carving, and combinations thereof.
  • the method of the present invention is characterized in that said body of polymeric material comprises a linear or branched isotactic polymers having a structure of one or several C 2 to C 20 olefins, the isotacticity of said polymers, due to a statistic distribution of stereoscopic errors in the polymer chain, being within the range of 25% to 60% of [mmmm] pentad concentration with the proviso that an arbitrary or rather regular sequence of isotactic and atactic blocks is excluded, the polymer having a mean molecular weight Mw within the range of from 100000 to 800000 g/mol and a glass temperature T g of between -50 to +30 °C.
  • the present invention provides article comprising bodies of polymeric material comprising comprises a polyolefinic homopolymer having an isotacticity of less than 60% of [mmmm] pentad concentration.
  • the present invention provides body materials comprising a polyolefinic homopolymer.
  • polyolefinic homopolymer refers to those polyolefins which comprise only one phase of molecules all of which exhibiting a similar stereochemical configuration. For example, blends of atactic and isotactic polymers where the two phases have polymerized simultaneously are excluded when this term is used.
  • homopolymer includes copolymers where all molecules exhibit a similar stereochemical configuration.
  • the polyolefinic homopolymer of the present invention may comprise linear isotactic polymers having a structure of one or several C 3 to C 20 olefinic monomers, having an isotacticity of less than 60%, preferably less than 55%, more preferably less than 50%, and most preferably less than 45% of [mmmm] pentad concentration, and having an isotacticity of more 15%, preferably more than 20%, more preferably more than 25%, and most preferably more than of [mmmm] pentad concentration.
  • the polyolefinic homopolymer is polypropylene.
  • the isotacticity of the homopolymers may be reduced compared to the isotactic polypropylenes of the prior art due to a statistic distribution of stereoscopic errors in the polymer chain.
  • stereoscopic error refers to a stereoscopic sequence characterized by a [mrrm] pentad.
  • the central monomer has a stereo configuration opposed to the other four monomers in this pentad.
  • the pentad concentration is at least [p (l-p)] q p (1-p) with q being 0.8, more preferably q being 0.6, yet more preferably q being 0.4, yet more preferably q being 0.2, most preferably q being 0.1.
  • the [rmrm] pentad concentration is below 6%, more preferably below 5%, yet more preferably below 4%, yet more preferably below 3%, most preferably below 2.5%.
  • the [rrrr] pentad concentration is below 6%, more preferably below 5%, yet more preferably below 4%, yet more preferably below 3%, most preferably below 2.5%.
  • the homopolymer of the present invention may include sequences of atactic and isotactic blocks of polymer.
  • the mean molecular weight M w of the polymer is above 100000 g/mol, more preferably above 200000 g/mol, yet more preferably above 250000 g/mol, yet more preferably more than 300000 g/mol, most preferably more than 350000 g/mol.
  • the glass temperature T g is between -50 and +30 °C.
  • the glass temperature is below 10°C, more preferably below 5°C, yet more preferably below 0°C, most preferably below -6°C.
  • the melt temperature of the polymer is obtained after heating the sample 150°C and subsequently cooling the polymer to -50°C.
  • the polyolefinic polymers exhibit a semi-crystalline structure.
  • the structure contains elastic amorphous areas of nano-scale-size reinforced with self arranged crystalline domains of nano- crystals.
  • the formation of brittle macro-crystalline material from the polymer is achieved by introducing the defects into the polymeric backbone. Isolated monomer units with opposite stereo configuration have been used as the defects, i.e. single stereo errors.
  • Suitable polymers and a process for manufacturing such polymers are described in PCT patent application EP99/02379 incorporated herein by reference.
  • a catalyst combination suitable for the preparation of such polymers is described in PCT patent application EP99/02378 incorporated herein by reference.
  • the process of PCT patent application EP99/02378 is carried out by temperatures of less than 30°C, more preferably less than 25°C, yet more preferably less than 20°C, most preferably less than 15°C to increase the molecular weight of the resulting polymer.
  • the polymerization is preferably carried out in liquid monomer such as in liquid propene.
  • the catalyst is preferably used in combination with the boron activators mentioned in PCT patent application EP99/02378.
  • homopolymers for the bodies of the present invention since during manufacture of homopolymers the batch to batch variability is greatly reduced in comparison to multi phase polymers where the phases are polymerized in a single reaction.
  • the polymers used in manufacturing the body materials of the present invention have a distinctive rubber-elastic plateau in their tensile- strength curves.
  • the polymers used for the body of the present invention are bio-compatible may be burnt without toxic residues since they contain no heteroatoms such as chlorine. The further do not contain toxic monomer residues.
  • the body materials of the present invention have been found to be able exhibit superior softness.
  • the body material has a Shore hardness on the A scale of less than 30, more preferably, of less than 25, yet more preferably of less than 20, yet more preferably of less than 15, most preferably of less than 10.
  • the softness of the body material of the present invention can be increased by manufacturing the body by low density bodying and by reducing the isotacticity ([mmmm] pentad concentration).
  • the body material has been found to exhibit increased temperature stability compared to prior art body materials. This is partly due to the fact that for the bodies of the present invention a homopolymer is used and is partly due to the high molecular weight of the homopolymer.
  • the body material of the present invention has a melting point of at least 100°C, more preferably of at least 110°C, more preferably of at least 120°C, most preferably of at least 130°C.
  • the melt temperature of the polymer is obtained after heating the sample 150°C and subsequently cooling the polymer to -50°C. Higher melting point may be achieved my blending the homopolymer for example with conventional isotactic polymer such as polypropylene.
  • the body of the present invention have been found to be stretchable as well as elastic.
  • the stretcha bility of the body versus its elastic behavior can be adjusted by means of the tacticity of the homopolymer of the present invention.
  • the body material of the present invention has been found to be stretchable without tearing to at least 500% of its original length, more preferably 1000% of its original length, yet more preferably to at least 1500% of its original length, most preferably to at least 2000% of its original length.
  • the body material of the present invention preferably recovers within 10 minutes after being stretched and held for 1 minute to 500% of its original length back to less than 300% its original length, preferably less than 200% its original length, most preferably less than 150% of its original length.
  • the body of the present invention has been found to exhibit a low compressive set.
  • the body of the present invention recovers within 10 minutes after a compression to 50% of its original thickness for 1 minute to at least 60% of its original thickness, more preferably at least 70% of its original thickness, yet more preferably to at least 80% of its original thickness, yet more preferably to at least 90% of its original thickness, most preferably to at least 95% of its original thickness.
  • the compressibility of the body of the present invention can be adjusted by increasing the tacticity of the homopolymer or by blending the low tacticity homopolymer with conventional isotactic polymer such as polypropylene.
  • the body of the present invention has been found to exhibit a relative low tackiness at room temperature due to the high molecular weight of the polymer.
  • additives may be added to the homopolymer of the present invention to change the properties of the polymer such as is well known in the art.
  • the isotactic homopolymer is added at a level of at least 20% of the total weight of the polymeric body, more preferably at a level of at least 40%, yet more preferably at a level of at least 50%, most preferably at a level of at least 60%.
  • the low isotacticity homopolymer of the present invention is present in the polymeric body of the present invention at a level of at least 20%, more preferably at least 30%, yet more preferably at least 40%, most preferably at least 50% by total weight of the polymeric body.
  • the shrinkage of the molded is less than 10%, more preferably less than 8%, yet more preferably less than 6%, most preferably less than 4%.
  • the blending with the homopolymer of the present invention when making the body of the present invention allows processes such as extrusion to be performed at higher speeds since the required forces, pressure, or torques respectively are lowered.
  • the second element of the article of the present invention can preferably be made from the same homopolymer as the first element, either having the same low isotacticity or a different isotacticity depending on the intended use of the second element.
  • the configuration of the polymeric material of the second element can also be a body or it could be a foam, a fiber, a film, or the like. Making articles from different grades of the same material is beneficial when recycling material from a disposed article. If the same homopolymer is used for the different elements of the article, no separation step into the various materials is necessary before recycling of the material.
  • the article according to the present invention may be a hygienic article.
  • the term "hygienic article” as used herein refers to articles which are intended to be used in contact with or in proximity to the body of a living being. Such hygienic articles may be disposable or intended for multiple or prolonged use.
  • Such hygienic articles include but are not limited to catheters, tubing, drainage systems, syringes, grafts, prosthetics, body implants, instrumentation, support means, toothbrushes, bed covers, stents, gaskets, pump diaphragms, baby bottle nipples, pacifiers, and the like. Having regard to the specific advantages of the polymers used for the articles of the present invention, it will be readily apparent to the skilled practitioner to apply the bodies of polymeric material according to the present invention in the above and similar hygienic articles.
  • the article according to the present invention may be a household article.
  • the term "household article” as used herein refers to articles intended to be used when running a household.
  • the household articles of the present invention include but are not limited to garbage bins, storage containers, hoses, toys, kitchenware, clothing, shoes, furniture in particular garden furniture, sporting goods, bellows, and the like. Having regard to the specific advantages of the polymers used for the articles of the present invention, it will be readily apparent to the skilled practitioner to apply the bodies of polymeric material according to the present invention in the above and similar household articles.
  • the article according to the present invention may further be an automotive part including but not being limited to bumper fascia, air dams, side moldings, fender flares. Grills, body panels, ducts, tires, vibration dampers, flexible joints, window seals, interior parts, door gaskets, automotive boots, and the like.
  • the body of polymeric material according to the present invention may also be used as a construction element in an article.
  • the functionalities of the body of polymeric material includes but is not limited to supporting, carrying, fixing, protecting other elements of the article and the like.
  • Such articles include but are not limited to cover parts, complex constructions such as buildings (weather stripping, expansion joints, door gaskets and seals, water gaskets, window seals, hoses, ducts, tubes, wire and cable insulation, floor coverings, and the like), cars, household appliances, horticultural and agricultural constructions, and the like.

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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)

Abstract

La présente invention concerne des articles comprenant des corps constitués d'un matériau polymère dont la structure contient des zones élastiques amorphes de taille nanométrique, renforcées par des domaines cristallins de nanocristaux auto-assemblés.
PCT/US2000/027135 1999-10-08 2000-10-02 Corps en materiau polymere comprenant des polymeres isotactiques lineaires WO2001027169A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU77468/00A AU7746800A (en) 1999-10-08 2000-10-02 Bodies of polymeric material comprising linear, isotactic polymers
EP00967242A EP1237955A1 (fr) 1999-10-08 2000-10-02 Corps en materiau polymere comprenant des polymeres isotactiques lineaires
US10/089,344 US6746780B1 (en) 1999-10-08 2000-10-02 Bodies of polymeric material comprising linear, isotactic polymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP99120172.4 1999-10-08
EP99120172 1999-10-08

Publications (1)

Publication Number Publication Date
WO2001027169A1 true WO2001027169A1 (fr) 2001-04-19

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PCT/US2000/027135 WO2001027169A1 (fr) 1999-10-08 2000-10-02 Corps en materiau polymere comprenant des polymeres isotactiques lineaires

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EP (1) EP1237955A1 (fr)
AU (1) AU7746800A (fr)
WO (1) WO2001027169A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004062896A1 (fr) 2003-01-16 2004-07-29 Ian Orde Michael Jacobs Procedes, compositions et melanges permettant de former des articles avec une resistance aux craquelures generees par l'environnement amelioree

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0584609A2 (fr) * 1992-08-15 1994-03-02 Hoechst Aktiengesellschaft Procédé de préparation de polyoléfines
WO1996020225A2 (fr) * 1994-12-20 1996-07-04 Montell Technology Company B.V. Polypropylene issu d'un melange en reacteur, procede de preparation correspondant et procede de preparation de ligands metallocenes
WO1996026967A1 (fr) * 1995-03-01 1996-09-06 Minnesota Mining And Manufacturing Company Complexes de tris(pentafluorophenyl)borae et catalyseurs derives de ceux-ci
EP0943631A1 (fr) * 1998-03-20 1999-09-22 Basf Aktiengesellschaft Polymères à base de propylène
WO1999048775A1 (fr) * 1998-03-20 1999-09-30 Fort James Corporation Recipients utilisables au four a micro-ondes jetables, et procede de fabrication de ces recipients
WO1999052955A1 (fr) * 1998-04-09 1999-10-21 Bernhard Rieger Polymeres isotactiques lineaires, procede de preparation et utilisation de ceux-ci

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0584609A2 (fr) * 1992-08-15 1994-03-02 Hoechst Aktiengesellschaft Procédé de préparation de polyoléfines
WO1996020225A2 (fr) * 1994-12-20 1996-07-04 Montell Technology Company B.V. Polypropylene issu d'un melange en reacteur, procede de preparation correspondant et procede de preparation de ligands metallocenes
WO1996026967A1 (fr) * 1995-03-01 1996-09-06 Minnesota Mining And Manufacturing Company Complexes de tris(pentafluorophenyl)borae et catalyseurs derives de ceux-ci
EP0943631A1 (fr) * 1998-03-20 1999-09-22 Basf Aktiengesellschaft Polymères à base de propylène
WO1999048775A1 (fr) * 1998-03-20 1999-09-30 Fort James Corporation Recipients utilisables au four a micro-ondes jetables, et procede de fabrication de ces recipients
WO1999052955A1 (fr) * 1998-04-09 1999-10-21 Bernhard Rieger Polymeres isotactiques lineaires, procede de preparation et utilisation de ceux-ci

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DIETRICH ET AL: "Control of Stereoerror Formation with High-Activity Dual-Side Zirconocene Catalysts: A Novel Strategy To Design the Properties of Thermoplastic Elastic Polypropenes", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,US,AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, vol. 121, no. 18, 1999, pages 4348 - 4355, XP002110148, ISSN: 0002-7863 *
RIEGER B: "STEREOSPECIFIC PROPENE POLYMERIZATION WITH RAC-U1,2-BIS(N5-(90FLUOREN YL))-1-PHENYLETHANEZIRCONIUM DICHLORIDE/METHYLALUMOXANE", POLYMER BULLETIN,DE,SPRINGER VERLAG. HEIDELBERG, vol. 32, no. 1, 1 January 1994 (1994-01-01), pages 41 - 46, XP000420835, ISSN: 0170-0839 *
RIEGER ET AL: "Novel metallocene catalyzed polypropene homo- and brush-copolymers: control of new morphologies and beyond", POLYMERIC MATERIALS SCIENCE AND ENGINEERING,US,WASHINGTON, DC, vol. 80, 21 March 1999 (1999-03-21), pages 51 - 52, XP002110149, ISSN: 0743-0515 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004062896A1 (fr) 2003-01-16 2004-07-29 Ian Orde Michael Jacobs Procedes, compositions et melanges permettant de former des articles avec une resistance aux craquelures generees par l'environnement amelioree
EP2363276A2 (fr) 2003-01-16 2011-09-07 JACOBS, Ian Orde Michael Procédés de formation d'articles dotés d'une résistance de craquage de tension environnementale améliorée
US8518318B2 (en) 2003-01-16 2013-08-27 Viva Healthcare Packaging Limited Methods, compositions and blends for forming articles having improved environmental stress crack resistance
US9199421B2 (en) 2003-01-16 2015-12-01 Viva Healthcare Packaging Limited Methods, compositions and blends for forming articles having improved environmental stress crack resistance
US10035310B2 (en) 2003-01-16 2018-07-31 Viva Healthcare Packaging Limited Methods, compositions and blends for forming articles having improved environmental stress crack resistance

Also Published As

Publication number Publication date
AU7746800A (en) 2001-04-23
EP1237955A1 (fr) 2002-09-11

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