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WO1991008263A1 - Composition de melange polymere - Google Patents

Composition de melange polymere Download PDF

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Publication number
WO1991008263A1
WO1991008263A1 PCT/GB1990/001808 GB9001808W WO9108263A1 WO 1991008263 A1 WO1991008263 A1 WO 1991008263A1 GB 9001808 W GB9001808 W GB 9001808W WO 9108263 A1 WO9108263 A1 WO 9108263A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymeric composition
polyester
polymer
polyolefin
weight
Prior art date
Application number
PCT/GB1990/001808
Other languages
English (en)
Inventor
Pauline Emma Crook
Iain Mcpherson Forrest
Original Assignee
Imperial Chemical Industries Plc
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 Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Publication of WO1991008263A1 publication Critical patent/WO1991008263A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • This invention relates to a polymer blend composition and in particular to a blend of a polyester and two types of olefinic polymer; a polyolefin and a functionalised olefinic polymeric material.
  • Aromatic polyesters i.e. polyesters made from aromatic acids such as terephthalic acid, referred to herein simply as 'polyesters', are widely used materials. They are relatively impermeable to gasses and common organic solvents and can form strong tough moulded products. Despite their advantages, they do suffer from certain drawbacks which restrict their use. Injection moulded products made from polyesters often have regions, particularly at corners in the moulded product, that are much less tough than might be expected. This makes injection moulded polyester products liable to failure by brittle fracture especially at corners. In containers, such as paint containers, this is an obvious major disadvantage.
  • polyethylene terephthalate is used in the manufacture of bottles by injection stretch blow moulding, in which a preform the plastic is made by injection moulding, put in a blowing mould and stretched and then blown to produce the moulded product.
  • the low melt viscosity of typical polyester resins means that the preform needs to be stretched to strengthen it prior to blowing.
  • the effect of the initial axial stretching and the subsequent circumferential stretching in the blowing step is to bi-axially orient the polyester, thus markedly strengthening and toughening it so that the product is strong and tough and is not liable to brittle fracture in ordinary use, even in the storage of carbonated drinks.
  • teh present invention provides a polymeric composition which is an intimate blend of from 70 to 98Z by weight of at least one polyester and from 2 to 30Z by weight of the combination of at least one polyolefin and at least one functionalised olefinic polymer wherein the weight ratio of polyolefin to functionalised olefinic polymer is from 1:3 to 3:1.
  • the polyester used in the invention is a polyester derived from an aromatic acid.
  • the polyester will be a poly(alkylene)- phthalate polyester.
  • acid residues will be derived from, at least predominantly, terephthalic acid although, as is described below, a proportion of isophthalic acid residues may be included in the polymer.
  • the alkylene group will usually be ethylene, thus forming PET (as hoomopolymer or copolymer - see below), but other residues such as butylene groups can also be used.
  • the main functional requirement for the polyester is that it can, as part of the composition of the invention, be fabricated into the desired end products.
  • the requirements for the polyester are that it should be capable of being fabricated into a container, or the like, under conditions which provide the polyester in a form which is essentially amorphous.
  • a polyester such as a polyethylene terephthalate homopolymer this can be achieved in an injection moulding process using cold moulds, i.e. at a temperature of less than 30°C and preferably less than 10°C.
  • the use of a polyester having a higher molecular weight e.g. as measured by intrinsic viscisity (see below) can be beneficial.
  • polyester can be one having a lower crystallisation rate than polyethylene terephthalate homopolymer.
  • inhibition of crystallisation of PET can be provided by using additives which inhibit crystallisation or, more conveniently, by including comonomers, such as isophthalic acid as about 22 of the acid monomers, which disrupt chain packing and decrease crystallisation rates.
  • the polyester which forms the matrix of the moulded article
  • the intrinsic viscosity (IV) of the polyester when it is a polymer or copolymer of ethylene terephthalate, (measured as described below) is from 0.3 to 1, particularly, between 0.4 and 0.8.
  • IV intrinsic viscosity
  • the IV of the PET is optimally from 0.5 to 0.75, particularly about 0.6; the use of lower IV material adversely affects the toughness of the product and the use of higher IV material can give process difficulties from the high melt viscosity of the polymer.
  • the IV is optimally at least about 0.7 and can be up to 1.0.
  • the IV is optimally at least about 0.5 and can be up to 1.0, which represents about the highest IV available for PET polymers commercially available; higher values could be used were they available.
  • the polyolefin used in the composition of the invention is a crystalline polymer ethylene or propylene, especially crystalline forms of polyethylene (PE) such as high density polyethylene (HDPE) or linear low density polyethylene (LLDPE) or crystalline polypropylene (PP) such as isotactic polypropylene, or a copolymer of ethylene and propylene (EP), or a copolymer of ethylene and/or propylene with a minor proportion, that is up to 15Z by weight, of another ethylenically unsaturated monomer.
  • PE polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • PP crystalline polypropylene
  • EP copolymer of ethylene and propylene
  • the polyolefin has a melt flow index (MFI) of from 0.3 to 50 (measured as described below).
  • the polyolefin may be polypropylene or a copolymer of propylene and ethylene containing, for example, between 5 and 15Z by weight of ethylene.
  • the use of such a copolymer can give products having higher impact strength than otherwise similar products made using a crystalline polypropylene homopolymer. Blends of more than one such polyolefin polymer may be used.
  • the functionalised olefinic polymer is a polymer of ethylene and/or propylene which has been graft polymerised with di-carboxylic acid or, and especially, anhydride, particularly maleic anhydride residues.
  • the ⁇ raft residues are or include anhydride, especially maleic anhydride, residues which are retained at least partly unhydrolyzed in the resulting graft co-polymer.
  • a functionalised olefin polymer including grafted maleic anhydride residues is referred to herein as being maleinised.
  • the functionalised olefinic polymer appears to improve both the impact strength of the composition and compatibility between the polyester matrix and the polyolefin polymers in the composition.
  • the (preformed) olefin polymer is typically one having rubbery characteristics, in particular a tensile modulus of less than 3,000 kg/cm 2 (ca. 294 MPa), such as an ethylene propylene rubber.
  • the material grafted onto the olefinic polymer will typically be an ethylenically unsaturated monomer including the desired functional group.
  • a particularly convenient way of carrying out such a grafting step is by extrusion compounding the rubber with the monomer under melt conditions in the presence of a free radical generating peroxide catalyst.
  • the concentration of combined anhydride containing monomer will usually be from the range 0.05 to 5Z and most desirably 0.1 to 2.0Z, by weight of the olefin polymer.
  • composition of the invention will usually be pre-blended prior to manufacture into end products.
  • Unfilled blends made as described in more detail below are substantially colourless (white) translucent or pearlescent materials. Microscopic examination of these blends shows a matrix of the polyester with the polyolefin and functionalised olefin polymer as separate dispersed phases in the matrix.
  • the dispersed phases are present as approximately spherical particles having ⁇ 7 polyolefin phase enables the pigment to be supplied to the blend as a masterbatch in a suitable polyolefin such as polypropylene. This represents a particularly convenient way of pigmenting polyesters.
  • Suitable pigments include titanium dioxide.
  • Other non blend materials such as fillers, which can be reinforcing fibrous fillers such as glas mineral, carbon or polymeric e.g. aramid, fibres, or non-fibrous fille including inorganic fillers such as calcium carbonate or silica, can b included.
  • the amounts of these materials used will usually be conventional.
  • the total amount will typicall be from 5 to 50 parts by weight per 100 parts by weight of the resin blend (phr).
  • the blend include no materials of a type or a concentration which will cause the polyest to crystallise significantly under the moulding conditions used.
  • composition of the invention is preferably used in the form of a pre-formed intimate blend of the components, prepared by melt blending It is highly desirable that intensive mixing is applied during blendin to ensure uniform distribution of the disperse phase polymers. This c suitably be done by using a twin screw extruder.
  • intensive mixing device is important as less intensive techniques may not give an adequately intimate blend. In particular, the use of a single screw extruder may not be satisfactory.
  • compositions of the present invention can provide good barrier properties in the form of an intimate blend of the components of the composition.
  • the compositions are suitable for providing barrier properties in the form of a single layer. This is clearly an advantag over the provision of barrier properties using multilayers, each of different composition, because apart from the ease of fabrication the eventual moulded or extruded products can be recovered as scrap withou the need to separate differing materials.
  • the compositions of the invention provide articles which are much less pro 6 an average particle size (diameter) of from 2 to 4 ⁇ m, usually 2.5 to
  • the invention includes in a particular and very desirable subsidiary aspect a polymeric composition which is an intimate blend of from 75 to 90Z by weight of polyester and from 10 to 35Z by weight of the combination of a polypropylene and a graft maleinised ethylene/propylene copolymer wherein the weight ratio of polypropylene to graft maleinised ethylene/propylene copolymer is from 3:2 to 2:3.
  • the amount of the functionalised olefin polymer is not excessive so as to avoid adverse effects on the processing characteristics of the final composition arising from uncontrolled changes in melt viscosity.
  • the amount of the functionalised olefin polymer will normally be kept to the minimum necessary to give the desired properties such as good impact strength.
  • the composition may contain various- other additives, particularly antioxidants and/or stabilisers, pigments and fillers.
  • the inclusion of pigments illustrates a further advantage of the invention.
  • the present compositions have a high level of acceptability of typical pigment for plastics, without causing a deterioration in the impact strength of the blends.
  • This desirable behaviour of the composition with respect to pigments is believed to arise because when the components are homogenised in the presence of the pigments, the pigments mostly end up dispersed in the polyolefin component (rather than the polyester component) of the blend.
  • the relative absence of evidence of deiamination indicates that the blend is substantially compatible. This property of the blend provides compositions which have applications other than as single layer barrier materials.
  • compositions of the invention are important use for the compositions of the invention in paint containers, particularly for paints employing an organic solvent.
  • this application requires a composition which can provide a good level of white opacity e.g. by including pigments such as titanium dioxide.
  • Other end uses for the compositions of the invention include bottle tops, particularly as made by injection moulding, blow (injection or extrusion) moulded bottles and thermoformable sheet and products made from it by thermoforming the sheet. It is notable that blends of the invention can be used in extrusion blow moulding even for some grades of polyester that are by themselves not suitable for this fabrication method.
  • Intrinsic Viscosty (IV) - (of polyesters) was measured on a 1Z solution in o.-chlorophenol at 23°C.
  • Melt Flow Index (MFI) - (of polyolefins) was measured according to ISO 1133 at 230°C with a load of 2.16 kg (21.18 N) .
  • Tensile strength to yield point (TS) - was measured by the method of ISO 527 on injection moulded tensile test samples.
  • Izod Impact Strength (Izod) - was measured by the method of ISO 180 on injection moulded test samples having a 0.25 mm (tip radius) milled notch. Tests were carried out on dry samples at ambient temperature (23°C) and on samples at -30°C. Results are given in kJ.m -2 .
  • the polymer blends used in the Examples were made by drying the components of the blends in particle form to a moisture content of not more than 0.01Z, dry blending the components and then mixing and extruding the blend using a Pfleiderer ZSK-30 twin screw extruder at a melt temperature of 295°C and a screw speed of 285 rpm (4.75 Hz). The extruded strands were water cooled, cut into pellets and dried.
  • Table 1 shows the composition of the blends.
  • Test specimens were injection moulded using a Demag Hamilton moulding apparatus at a barrel temperature maintained in the range 280 to 295°C. A chiller was used to keep the mould temperature within the range 10 to 15°C. Test data on injection moulded samples are set out in Table 2 below.
  • Bottles were extrusion blow moulded using blends of the invention. Table 1 below sets out the compositions of the blends. Small bottles, 14 cm long and 275 ml capacity were extrusion blow moulded on a pilot extrusion blow moulding apparatus. The solvent barrier resistance of these bottles was tested by filling samples with different solvents, closing them by sticking aluminium foil over the mouth of each bottle using epoxy resin and assessing the weight loss on storage. The results of these tests are set out in Table 3 below. It will be noted that the PET grade (Melinar BS 90N) used in this Example is not suitable on its own for extrusion blow moulding.
  • Blend compositions of the invention wereestruded as 53 cm wide sheet using an Egon 1.25 inch (31.75 mm) sheet extrusion apparatus with a barrel temperature of 260°C. This sheet was then fed to a standard thermoforming machine to make food trays of 19x12x4 cm at a mould temperature of 23°C. The polyester in trays made in this way was amorphous. Increasing the. temperature of the mould enabled the manufacture of trays in which the polyester was
  • compositions of blends used in the Examples are Compositions of blends used in the Examples.

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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)

Abstract

Les mélanges ternaires de polyester, de polyoléfine et de polymère d'oléfine fonctionnalisée sont des matériaux durs et résistants présentant de faibles signes d'incompatibilité. Avec ces matériaux, on peut fabriquer des produits manufacturés au moyen de plusieurs techniques parmi lesquelles on trouve le moulage par injection, le moulage par extrusion-soufflage, le moulage par injection-soufflage et le thermoformage (d'une feuille extrudée).
PCT/GB1990/001808 1989-11-24 1990-11-23 Composition de melange polymere WO1991008263A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8926632.4 1989-11-24
GB898926632A GB8926632D0 (en) 1989-11-24 1989-11-24 Polymer blend composition

Publications (1)

Publication Number Publication Date
WO1991008263A1 true WO1991008263A1 (fr) 1991-06-13

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Application Number Title Priority Date Filing Date
PCT/GB1990/001808 WO1991008263A1 (fr) 1989-11-24 1990-11-23 Composition de melange polymere

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AU (1) AU6750890A (fr)
GB (1) GB8926632D0 (fr)
WO (1) WO1991008263A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0518703A3 (en) * 1991-06-14 1993-01-13 Polyplastics Co. Ltd. Sulfonated polyester resin compositions
WO1993002140A1 (fr) * 1991-07-22 1993-02-04 Exxon Chemical Patents Inc. Polymeres greffes destinees a etre utilises dans des melanges thermoplastiques industriels
FR2816627A1 (fr) * 2000-11-16 2002-05-17 Catherine Dumouchel Piece en materiau thermoplastique recycle, procede de fabrication correspondant et palette comprenant au moins un profile de ce type
EP3442874A4 (fr) * 2016-04-11 2020-01-08 Dak Americas LLC Récipients et films en polyester présentant une perméabilité aux gaz réduite

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0177151A2 (fr) * 1984-08-31 1986-04-09 Sumitomo Chemical Company, Limited Composition d'une résine thermoplastique
EP0307802A2 (fr) * 1987-09-09 1989-03-22 Nippon Petrochemicals Company, Limited Composition thermoplastique et procédé pour sa préparation
EP0337214A2 (fr) * 1988-03-31 1989-10-18 Sumitomo Chemical Company, Limited Composition de résine de polypropylène modifié

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0177151A2 (fr) * 1984-08-31 1986-04-09 Sumitomo Chemical Company, Limited Composition d'une résine thermoplastique
EP0307802A2 (fr) * 1987-09-09 1989-03-22 Nippon Petrochemicals Company, Limited Composition thermoplastique et procédé pour sa préparation
EP0337214A2 (fr) * 1988-03-31 1989-10-18 Sumitomo Chemical Company, Limited Composition de résine de polypropylène modifié

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0518703A3 (en) * 1991-06-14 1993-01-13 Polyplastics Co. Ltd. Sulfonated polyester resin compositions
US5300572A (en) * 1991-06-14 1994-04-05 Polyplastics Co., Ltd. Moldable polyester resin compositions and molded articles formed of the same
WO1993002140A1 (fr) * 1991-07-22 1993-02-04 Exxon Chemical Patents Inc. Polymeres greffes destinees a etre utilises dans des melanges thermoplastiques industriels
US5244971A (en) * 1991-07-22 1993-09-14 Exxon Chemical Patents Inc. Graft polymers for use in engineering thermoplastic blends
FR2816627A1 (fr) * 2000-11-16 2002-05-17 Catherine Dumouchel Piece en materiau thermoplastique recycle, procede de fabrication correspondant et palette comprenant au moins un profile de ce type
EP1207178A1 (fr) 2000-11-16 2002-05-22 Cybele Environnement Pièce en matériau thermoplastique recyclé, procédé de fabrication correspondant et palette comprenant au moins un profilé de ce type
US6780500B2 (en) 2000-11-16 2004-08-24 Catherine Dumouchel Part made of recycled thermoplastic material, a corresponding method of manufacture, and a pallet comprising at least one bar of this type
EP3442874A4 (fr) * 2016-04-11 2020-01-08 Dak Americas LLC Récipients et films en polyester présentant une perméabilité aux gaz réduite
US11186713B2 (en) 2016-04-11 2021-11-30 Dak Americas Llc Polyester containers and films with reduced gas permeability

Also Published As

Publication number Publication date
GB8926632D0 (en) 1990-01-17
AU6750890A (en) 1991-06-26

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