+

WO1991013119A1 - Polyester thermoplastique ayant des caracteristiques d'impact ameliorees. - Google Patents

Polyester thermoplastique ayant des caracteristiques d'impact ameliorees. Download PDF

Info

Publication number
WO1991013119A1
WO1991013119A1 PCT/GB1991/000271 GB9100271W WO9113119A1 WO 1991013119 A1 WO1991013119 A1 WO 1991013119A1 GB 9100271 W GB9100271 W GB 9100271W WO 9113119 A1 WO9113119 A1 WO 9113119A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
ethylene
blend
polyester
epoxy
Prior art date
Application number
PCT/GB1991/000271
Other languages
English (en)
Inventor
Jacques Paul Eugene Joseph Horrion
Vincent Bernard Benoît Ghislain GALLEZ
Silvestro Cartasegna
Original Assignee
Exxon Chemical Limited
Exxon Chemical Patents Inc.
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
Priority claimed from GB909003908A external-priority patent/GB9003908D0/en
Priority claimed from GB909008124A external-priority patent/GB9008124D0/en
Application filed by Exxon Chemical Limited, Exxon Chemical Patents Inc. filed Critical Exxon Chemical Limited
Publication of WO1991013119A1 publication Critical patent/WO1991013119A1/fr

Links

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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates

Definitions

  • the present invention relates to a blend of a thermoplastic polyester and an agent which improves the impact properties, in particular the low temperature impact properties, of the polyester, a process for producing the blend and a process for improving the impact properties of a polyester.
  • thermoplastic polyesters such as thermoplastic polyesters, polycarbonates and polyamides
  • polycarbonates are particularly susceptible to surface problems when moulded, and tend to suffer from surface delamination effects immediately after injection moulding. Notches and cracks in the article are places of weakness and it only requires a relatively small impact to break the material at this point.
  • the moulding of such resins e.g. by extrusion or injection, results in imperfections at the corners and surfaces of the moulded articles. There is therefore interest in providing an improved resin which is not so susceptible to impacts, especially at low temperature.
  • Elastomers such as ethylene/alpha olefin copolymer rubbers and their terpolymer counterparts which contain a small proportion, say 1-10 weight percent of polyenes such as dienes, exemplified by ethylene propylene rubber (EPR) and ethylene propylene diene terpolymer (EPDM) , provide good impact properties and may therefore be dispersed within an engineering resin to toughen it, provided that good compatibility is achieved between the elastomer and the resin matrix, i.e. there is good adhesion between rne matrix phase and the dispersed elastomer.
  • EPR ethylene propylene rubber
  • EPDM ethylene propylene diene terpolymer
  • Unmodified ethylene/alpha olefin copolymer and terpolymer rubbers such as EPR or EPDM are substantially non-polar, whereas engineering resins tend to have a high polarity. Consequently, adhesion between unmodified elastomer and engineering resins is poor.
  • a functional group such as maleic anhydride (MANH) in the elastomer, commonly as a graft of the anhydride onto EPR or EPDM, is a well known way to toughen polya ide/elastomer blends. Graft copoiymers between the maleic anhydride and the polyamide are formed during blending. Good adhesion is achieved via the maleic anhydride between the polyamide and the elastomer.
  • Thermoplastic polyesters do not have a particularly high reactivity with MANH. They are more reactive to epoxy groups but it has not proved possible to form a suitable terpolymer of an epoxy-containing monomer with ethylene and propylene monomers. Moreover, only very limited success has been achieved when attempting to graft epoxy-containing monomers onto pre-formed EPR or EPDM. Difficulties are encountered with this approach because the epoxy-containing monomer tends to homopolymerise. Grafting efficiency is therefore poor, and furthermore the homopoly er of the epoxy-containing monomer is difficult to eliminate from the product.
  • PET polyethylenetere- phthalate
  • PBT polybutyleneterephthalate
  • polycarbonates do not have a particularly high reactivity with MANH. They are more reactive to epoxy groups but it has not proved possible to form a suitable terpolymer of an epoxy-containing monomer with ethylene and propylene monomers. Moreover, only very limited success has been achieved when attempting to graft epoxy-containing mono
  • EP-A-89042 discloses a thermoplastic polycarbonate based blend which includes rubber modified copolymer and an epoxy-group containing olefin copolymer or terpolymer for improving impact behaviour at room temperature.
  • the rubber modified copolymer has to comprise a graft copolymer of a rubber and a copolymer of at least two components, which are typically aromatic vinyl compounds such as styrene and vinyl cyanides or esters.
  • the only specific materials described and tested comprise rubber modified styrene-acryeonitrile.
  • non-aromatic copoiymers There is no specific disclosure of non-aromatic copoiymers. Furthermore, no guidance is given on how to obtain improved low temperature impact strength.
  • US-A-4172859 discloses a multi-phase thermoplastic composition comprising polyester, polycarbonate and a random copolymer, which has improved impact strength at room temperature.
  • the random copolymer may include many possible repeating units, including ethylene and epoxy units but is a single component and there is no separate polyolefin rubber component. Furthermore, the problem of low temperature impact resistance is not addressed.
  • EP-A-300051 which relates to a blend of a thermoplastic polycarbonate with an epoxy-modified olefin copolymer.
  • EP-A-180648 describes a thermoplastic composition which includes a polyester and a polycarbonate together with (1) unmodified, apparently amorphous alpha-olefin copolymer and (2) an ethylene/glycidyl methacrylate copolymer or an ethylene/glycidyl methacrylate/vinyl acetate terpolymer. This is said to achieve improved impact strength at room temperature.
  • EP-A-72455 discloses a thermoplastic polyester- based blend which includes an unmodified, apparently amorphous ethylene/alpha-olefin rubber component and an ethylene/glycidyl ester copolymer or an ethylene/glycidyl ester/vinyl acetate terpolymer. Such a blend is said to have improved low temperature impact strength.
  • J89-26380 discloses a polyester- based thermoplastic composition which includes (l) an unmodified ethylene/alpha-olefin/nonconjuga ed diene terpolymer and (2) an alpha-olefin/glycidyl ester copolymer having improved low temperature .impact strength.
  • polyester and/or polycarbonate blends having improved ductility or reduced brittleness combined with improved impact strength especially at low temperature.
  • a polyester blend comprising an impact modifier which comprises: (A) an elastomeric component; and
  • (B) a component being one or more of ethylene/epoxy copoiymers and ethylene/epoxy polymers containing units derived from other monomers said elastomeric component (A) being cross-linked to said component (B) or being a partially crystalline polymer blend containing at least one semi-crystalline component and at least one low crystalline to amorphous component, both components of said partially crystalline polymer blend being ethylene based elastomeric polymers of monomers selected from ethylene and alpha-olefin, diolefin and vinyl polar monomers copolymerisable therewith.
  • component (B) a component being one or more of ethylene/epoxy copoiymers and ethylene/epoxy polymers containing units derived from other monomers.
  • Component (A) achieves a stronger bonding/interaction with component (B) , and this leads to increased impact resistance and ductility (reduced brittleness) , particularly at low temperature, of the blend.
  • component (A)' By “functionalised” it is meant that the chemical reactivity of component (A)' with the epoxy groups of component (B) has been increased. This may be achieved by incorporating in component (A) functional groups which are reactiv- to epoxy groups.
  • component (A) functional groups which are reactiv- to epoxy groups.
  • partially crystalline polymer blends is meant blends of two or more ethylene-containing elastomers wherein at least one of such elastomers is sufficiently crystalline to interact with component (B) and at least one of which is sufficiently low in crystallinity to provide the impact improvement.
  • the low crystalline component should preferably have a crystallinity less than about 55 wt %.
  • Suitable as the partially crystalline polymer are any homo-, co-, terpoly ers based on ethylene and having an E-modulus less than 150 kPA (kilo-Pascals) . Included are ethylene with " alpha-olefins; dj.olefins; vinyl esters, acids/anhydrides, amides, etc.
  • the amorphous, low crystallinity polymers are suitably the EP/EPDM type, optionally with other alpha-olefins such as 1- butene and 1-hexane.
  • polyesters suitable for use herein may be any of the linear or branched saturated polyesters known to those skilled in this art.
  • the polyesters will comprise linear saturated polyesters derived from C ⁇ C. g alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, etc., including cycloaliphatic glycols, such as 1,4- cyclohexanedimethanol, and mixtures of any of these glycols with one or more aromatic dicarboxylic acids.
  • the polyesters will comprise polyf ⁇ -C 8 alkylene terephthalates) prepared by known techniques, such as the transesterification of esters of terephthalic acid alone or mixtures of esters of terephthalic acid and isophthalic acid, with the glycol or mixture of glycols and subsequent polymerization, by heating the glycols with the free acids or which halide derivatives thereof, and similar processes.
  • polyf ⁇ -C 8 alkylene terephthalates prepared by known techniques, such as the transesterification of esters of terephthalic acid alone or mixtures of esters of terephthalic acid and isophthalic acid, with the glycol or mixture of glycols and subsequent polymerization, by heating the glycols with the free acids or which halide derivatives thereof, and similar processes.
  • a suitable poly(1,4-butylene terephthalate) resin is commercially available from General Electric Company under the trade designation VALOX 315; and poly(ethylene terephthalate) resins are also extremely well known
  • Thermoplastic polyesters which are preferred in the blend of the present invention include PET (polyethylene terephthalate) , PBT (polybutylene terephthalate) and polycyclohexane terephthalate and thermoplastic polycarbonates.
  • Thermoplastic polycarbonates which may be used in the blend of the present invention include those possessing recurring structural units of the formula:
  • A is a divalent aromatic radical.
  • Polycarbonates which are widely used in engineering plastics applications have the typical general formula:
  • R 1 and R 2 are, independently, hydrogen, alkyl or phenyl
  • X 1 and X 2 are independently hydrogen, halogen (e.g. chlorine or bromine), alkyl, alkenyl or alkaryl (optionally substituted)
  • p and r represent the total number of substituents (other than hydrogen) on the rings and are, independently, integers from 0 to 4
  • n represents the total number of monomer units in the polymer and typically is an integer of at least 30.
  • the alkyl and alkenyl groups preferably have from 1 to 10, more frequently 1 to 6, carbon atoms inclusive.
  • Aryl is preferably phenyl.
  • Polycarbonate homopolymers and copoiymers commonly used in engineering plastics applications and which may be used in the present invention typically have a molecular weight (number average) of from 8000 to 200000 or even higher, but preferably from 10000.to 80000, and an intrinsic viscosity of from about 0.3 to 1.0 decilitres per gram as measured in methylene chloride at 25 ⁇ C.
  • the polycarbonate resins are, for example, prepared from dihydric phenols, including 2,2-bis(4- hydroxypheny1) propane (bisphenol A), bis-(4- hydroxypheny1)methane, 2,2-bis(4-hydroxy-3- methylpheny1)propane, 4,4'-bis(4-hydroxypheny1)heptane, 2,2-(3,5,3• ,5'-tetrachloro-4,4'-dihydroxypropane, 2,2- (3,5,3' ,5*-tetrabromo-4-dihydroxydiphenyl)propane, and 3,3'-dichloro-4,4'-dihydroxy-diphenyl)methane.
  • dihydric phenols including 2,2-bis(4- hydroxypheny1) propane (bisphenol A), bis-(4- hydroxypheny1)methane, 2,2-bis(4-hydroxy-3- methylpheny1)propane, 4,4'-bis(4-hydroxypheny1)heptane, 2,2-(
  • dihydric phenols which are also suitable for producing polycarbonates are disclosed in US-A- 2,999,835, 3,028,365, 3,334,154 and 4,131,575.
  • the aromatic polycarbonates can be prepared using known processes, such as, for example, by reacting a dihydric phenol with a carbonate precursor, e.g. phosgene, in accordance with the techniques set forth in the above cited patents and in US-A-4,018,750 and 4,123,436, or by transesterification processes such as those disclosed in US-A-3,153,008.
  • polyester as used herein are aromatic polyestercarbonates derived from a mixture of a dihydric phenol, a dicarboxylic acid or acid chloride and phosgene, for example, as disclosed in US-A-3,169,131 as well as branched polycarbonates such-as disclosed in US- A-4,001,184.
  • polycarbonate as used herein is also intended to include blends of two or more aromatic polycarbonates, including any of those which have been described. There may also be utilized a blend comprising one or more of the above polyesters.
  • the epoxy-containing polymer (B) may be one or more of ethylene/epoxy copoiymers and ethylene/epoxy polymers containing units derived from other monomers.
  • (B) may be a copolymer of ethylene and an epoxy monomer or a terpolymer of ethylene/epoxy monomer with ethylenically unsaturated polar monomers such as vinyl esters, vinyl alcohols and acrylamides.
  • the ethylene content for such terpolymers should preferably exceed 35 wt % to allow for ethylene segment interaction with elastomeric co-components.
  • the epoxy monomer may be, for example, a glycidyl ether or ester, an alicyclic epoxide or an epoxy compound of the general formula:
  • R 1 , R 2 , R 3 and R 4 may independently be hydrogen, a saturated organic radical e.g. alkyl or an unsaturated organic radical e.g. alkenyl, with the proviso that at least one of R.
  • R 1 , R 2 , R 3 and R 4 may independently be hydrogen, a saturated organic radical e.g. alkyl or an unsaturated organic radical e.g. alkenyl, with the proviso that at least one of R.
  • a simple example of such an epoxy compound is:
  • R is an organic radical, for example alkylene.
  • the epoxy-containing monomer is glycidyl acrylate or glycidyl methacrylate.
  • a preferred epoxy- containing polymer is a copolymer of ethylene and glycidyl methacrylate (GMA) , containing from 7 to 17, preferably from 10 to 14, weight percent of GMA.
  • the epoxy-containing copolymer may be a terpolymer containing a vinyl polar monomer, for example an ester of acrylic or methacrylic acid, such as methyl, ethyl, propyl or butyl acrylate or methacrylate.
  • the vinyl ester may for example be incorporated in the copolymer in an amount up to 25 percent by weight depending on the nature of (A) .
  • the epoxy-containing copolymer may be a terpolymer containing acrylamides, e.g. methacrylamide.
  • ethylene content should be sufficient to provide for interaction with the elastomer.
  • a content of for example greater than 35 wt % is preferred.
  • the basic components (A) which may be used in the present invention cover a broad range.
  • the basic components (Al) of blends according to the invention are ethylene/alpha olefin copolymer rubbers, optionally including polyene units as in corresponding terpolymer rubbers which include an additional polyene monomer such as non-conjugated diene.
  • alpha-olefins suitable for use may be branched or straight chained, cyclic, and aromatic substituted or unsubstituted, and are preferably ⁇ -C ⁇ alpha-olefins.
  • Mixed olefins can be used (e.g., mixed butenes) .
  • X substituents are aryl of 6 to 10 carbon atoms (e.g.
  • cycloalkyl of 3 to 12 carbon atoms e.g. cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl and the like
  • alkaryl of 7 to 15 carbon atoms e.g. tolyl, xylyl, ethylphenyl, diethylphenyl, ethylnapthyl and the like.
  • alpha-olefins substituted by one or more such X substituents wherein the substituents(s) are attached to a non-terminal carbon atom, with the proviso that the carbon atom so substituted is not in the 1- or 2-carbon position in the olefin, in addition to alkyl-substituted bicyclic and bridged alpha-olefins of which C 1 -C 9 alkyl substituted norbornenes are preferred (e.g. 5-methyl-2- norbornene, 5-ethyl-2-norbornene, 5-(2'-ethylhexyl)-2- norbornene and the like) .
  • alpha-olefins are propylene, 1-butene, 1-pentene, 1- hexene, 1-octene and 1-dodecene.
  • the ethylene is generally contained in component (Al) in an amount of from 40 to 90 wt%, more preferably from 45 to 85 wt%.
  • the polymer may optionally contain a third type of polymer chain monomer which is an easily polymerizable polyene such as a non-conjugated diene.
  • Non-conjugated dienes suitable for the purposes of the present invention can be straight chain, hydrocarbon di-olefins or cycloalkenyl-substituted alkenes, having from 6 to 15 carbon atoms, for example:
  • single ring alicyclic dienes such as 1,3- cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclo-octadiene and 1,5-cyclododecadiene;
  • multi-ring alicyclic fused and bridged ring dienes such as tetrahydroindene, methyl- tetrahydroindene, dicyclopentadiene, bicyclo-(2.2.1)- hepta-2,5-diene, alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2- norbornene (MNB) , 5-propenyl-2-norbornene, 5- isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2- norbornene, 5-cyclohexylidene-2-norbornene and 5-vinyl- 2-norbornene;
  • MNB 5-methylene-2- norbornene
  • V cycloalkenyl-substituted alkenes, such as allyl cyclohexene, vinyl cyclooctene, allyl cyclodecene and vinyl cyclododecene.
  • the preferred dienes are dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene.
  • Particularly preferred diolefins are 5-ethylidene-2- norbornene (ENB) and 1,4-hexadiene.
  • the non-conjugated diene is preferably present in the polymer in an amount of from 0.5 to 15 wt% more preferably from 1 to 10 wt%, e.g. 5 wt%.
  • component (Al) in accordance with the invention are ethylene/propylene monomer copolymer rubber (EPM) and ethylene/propylene/diene terpolymer rubber (EPDM), which terms are used herein in accordance with their ASTM designations.
  • EPM ethylene/propylene monomer copolymer rubber
  • EPDM ethylene/propylene/diene terpolymer rubber
  • functionalisation of component (A) may be achieved by incorporating a functional group which is reactive to epoxy groups in component (A) .
  • the functional group may be copolymerised with the other monomeric components, or it may be grafted onto the pre-formed polymer. Preferably the functional group is grafted on the pre-formed polymer.
  • a pre-formed polymer may be an ethylene/alpha olefin co- or ter-polymer rubber as described hereinbefore.
  • the pre-formed base for the graft may be an ethylene/vinyl ester copolymer.
  • the vinyl ester monomer may be an ester of acrylic or methacrylic acid as described above in relation to Component (B) .
  • the functional group reactive to epoxy is preferably an unsaturated mono- or di-carboxylic acid or its anhydride such as maleic acid/anhydride, itaconic acid/anhydride, acrylic acid or ethacrylic acid.
  • the basic polymer is (Al)
  • the dicarboxylic acid or anhydride functional groups are preferred; when it is (A2) , then the mono-carboxylic acid functional groups are preferred.
  • the polymer is an EPR on which has been grafted MANH.
  • the polymer (Al) or (A2) contains from 0.1 to 2 percent, preferably 0.2 to 1 percent, by weight of grafted groups such as MANH.
  • the degree of functionality depends on the concentration of epoxy groups in the polymer (B) , since there must be sufficient epoxy groups present after reaction with the functional groups of (Al) and/or (A2) to give the necessary interaction with the polyester phase.
  • the epoxy component (B) and the elastomeric component (A) may form a single phase or, more usually, will form a core-shell structure in which the component (B) forms a shell around a core of component (A) .
  • modifier dispersed in the polyester commonly forms particles, the majority (i.e. at least 50%, preferably at least 80%, more preferably at least 90%) of which comprise a core of component (A) and a shell of component (B) .
  • the core-shell particles are preferably below 5 micrometres, more preferably less than 1 micrometre, in diameter for optimised impact property improvement.
  • the bond between component (B) and elastomer (A) may be covalent (when elastomer (A) carries functional groups reactive with epoxy groups or when a mixture of components A and B are cross-linked e.g. using peroxide) or may be achieved by Van der Waals interaction between the polyolefinic backbone of the epoxy component (B) and the crystalline regions of the partially crystalline elastomer (A) . In all cases, the interaction of (A) with (B) will be significantly stronger than when component (A) is unfunctionalised and wholly amorphous.
  • component (B) react with terminal acid or ester groups of the polyester to provide covalent bonds therewith.
  • component (B) provides a strong bond between the polyester and the elastomer (A) .
  • the functionality (type or concentration) of the copoiymers (Al) and (A2) should be such that the graft copolymer formed on reaction with component (B) will contain unreacted epoxy groups.
  • the polyester then interacts with these unreacted epoxy groups to form a graft copolymer as described hereinbefore.
  • component (A) and component (B) and between component (B) and the polyester ensures that the polyester benefits from the elastomeric properties of the modifier
  • component (A) is partially crystalline.
  • component (A) may be semi- crystalline or a mixture of amorphous and semi- crystalline. It is particularly preferred that component (A) be composed of an amorphous and a semi- crystalline component.
  • Such a partially crystalline component (A) appears to be co-crystallised with component (B) .
  • the impact improvement is increased with decreasing crystallinity of the modifier component.
  • the disadvantages of partially crystalline elastomer can be offset by addition of a low crystallinity/amorphous component. This gives a strong van der Waals interaction between components (A) and (B) , the interaction being stronger than that between a solely amorphous component (A) and component (B) , thus leading to improved impact strength and ductility.
  • the weight ratio of (A) to (B) is preferably from 1:1 to 20:1, more preferably 2:1 to 10:1, for example 3:1.
  • the weight ratio of polyester to modifier in the blend of the invention is preferably from 99:1 to 60:40, more preferably from 90:10 to 70:30 and is typically about 80:20.
  • a process for preparing a polyester blend as hereinbefore defined comprises blending a polyester with ah impact improving agent comprising a component (A) as defined above and a component (B) as defined above.
  • the impact improving agent may be formed in the polyester in situ.
  • a process for producing a thermoplastic polyester blend according to the invention comprising mixing components (A) and (B) as defined above with a polyester.
  • the blend is formed in a two step process in which the modifier components are first blended together; the polyester is melted and the modifier is mixed into the melted polyester to form a homogeneous (ie. uniform) mixture.
  • an impact strength improving agent comprising
  • (B) a component being one or more of ethylene/epoxy copoiymers and ethylene/epoxy polymers containing units derived from other monomers said elastomeric component (A) being cross-linked to said component (B) or being a partially crystalline polymer blend containing at least one semi-crystalline component and at least one low crystalline to amorphous component, both components of said partially crystalline polymer blend being ethylene based , elastomeric polymers of monomers selected from ethylene and alpha-olefin, diolefin and vinyl polar monomers copolymerisable therewith.
  • an impact strength improving agent comprising:
  • the weight ratio of semi-crystalline to amorphous component is preferably from 1:15 to 3:5, more preferably 1:10 to 1:3, especially 1:6.5.
  • the components (A) and (B) employed as impact improvers in the blends of the invention may be used in any combination of (Al) and/or (A2) with (Bl) and/or (B2) .
  • the components are matched for optimum ⁇ compatibility.
  • the components (A) with vinyl ester content are preferably matched with components (B) with vinyl ester content; and components (A) without vinyl ester content are preferably matched with components (B) without vinyl ester content.
  • Particularly preferred combinations are (Al) and (Bl) or (A2) and (B2) .
  • the polyester blends may contain further additives such as dyes, pigments, fillers and reinforcing substances. Suitable dyes and pigments are well known in the art. Suitable fillers and reinforcing agents are e.g. glass fibres, talc, kaolin, clay and diatomaceous earth.
  • the polyester blends may be moulded in the same way as polyester and/or polycarbonate may be moulded e.g. by melt extrusion or compression to form sheets or shaped articles. According to another aspect of the prevent invention there is provided a moulded article comprising a polyester blend as described above.
  • PBT 1 Polybutyleneterephthalate: POCAN 1505 (Bayer) , having melt flow rate (MFR) at 230 ⁇ C/10kg of 44 g/10 min.
  • PBT 2 VALOX 325 (General Electric) .
  • PBT 3 VALOX 312 (General Electric) .
  • PBT 4 ORGATER (Atochem) .
  • EP-Ma2 ethylene/propylene rubber grafted with 0.7 weight percent MANH.
  • MFR (230*C/10 kg) 8 g/10 min EXXELOR VA 1801 (Exxon Chemical) .
  • MI 190'C/2.16kg
  • MI 3.3 g/10 min
  • IGETABOND E 3.3 g/10 min
  • Modifier blends were prepared by mixing the EP-Ma with PE-GMA at 200°C in a laboratory two roll mill operated at 18 RPM for 5 to 7 minutes.
  • Example 1 The samples were tested for the tangent flexural modulus (MPa) , their room temperature notched izod impact strength (RTNIIS) [ISO R180], and their notched izod impact strength at 0°C, -10*C and - 20"C respectively in the same manner as Example 1.
  • MPa tangent flexural modulus
  • RTNIIS room temperature notched izod impact strength
  • ISO R180 room temperature notched izod impact strength
  • Example 3 Peroxide Partial Cross-linking 1. Preparation of graft copoiymers of Components (A) and (B) in the presence of peroxide
  • Ethylene propylene rubber (EP, Vistalon V606 of Exxon) and polyethylene glycidyl methacrylate (PE GMA, "Igetabond E” of Sumitomo) were blended together in the mixing chamber of a Haake internal mixer at 160*C at a blade speed of 40 rpm. After stablization of the torque, an amount of peroxide (LUPERSOL 130) was added, and the mixing continued for another 15 minutes.
  • EP Vistalon V606 of Exxon
  • PE GMA polyethylene glycidyl methacrylate
  • Table 3 gives the composition of four graft copoiymers according to the invention prepared in the above manner (B20 and B21) , together with a comparative composition excluding peroxide (C19):-
  • Blends of compositions B20 and B21 and Cll with PBT were prepared in the same way as Example 1. The thus prepared blends were then subjected to testing to determine the tangent flexural modulus and the Notched Izod Impact value at both 25 ⁇ C and -20*C in the same way as Example 1. The results are given in the following Table 4.
  • Table 5 clearly shows the low temperature Impact strength improvement that occurs on partially cross-linking the elastomeric and epoxy components.
  • An amorphous ethylene propylene rubber, a semi- crystalline EPR or EPDM and a EGMA were blended together in a mixing chamber of a HAAKE internal mixer at 160 ⁇ C at a blade speed of 40 rpm. After stabilization of the torque, the blend is used.
  • Blends of compositions PI to P9 with PBT were prepared. The thus prepared blends were then subjected to testing to determine the tangent flexural modulus and the notched Izod Impact value at -20 * C in the same way
  • the morphology of the blends shows particles of size smaller than 2 microns.
  • Table 8 shows blends incorporating glass-fiber filler (GF 429 Y2 (O.C) ) .

Landscapes

  • 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

On décrit un mélange de polyester comportant un agent de modification des caractéristiques d'impact et comprenant: (A) un constituant élastomère; et (B) un constituant formé d'un ou plusieurs copolymères éthylène/époxy et polymère éthylène/époxy contenant des unités dérivées d'autres monomères. Ledit constituant élastomère (A) est relié par réticulation audit constituant (B) ou est un mélange partiellement cristallin contenant au moins un constituant semi-cristallin et au moins un constituant faiblement cristallin/amorphe. Les deux constituants dudit mélange polymère partiellement cristallin sont constitués de polymères élastomères à base d'éthylène de monomères choisis parmi des monomères polaires d'éthylène et alpha-oléfine, dioléfine et vinyle, qui sont copolymérisables avec eux. Un mélange du type décrit possède une résistance à l'impact et une ductilité accrues.
PCT/GB1991/000271 1990-02-21 1991-02-21 Polyester thermoplastique ayant des caracteristiques d'impact ameliorees. WO1991013119A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9003908.2 1990-02-21
GB909003908A GB9003908D0 (en) 1990-02-21 1990-02-21 Impact modified thermoplastic polyester
GB909008124A GB9008124D0 (en) 1990-04-10 1990-04-10 Impact modified thermoplastic polycarbonate
GB9008124.1 1990-04-10

Publications (1)

Publication Number Publication Date
WO1991013119A1 true WO1991013119A1 (fr) 1991-09-05

Family

ID=26296701

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1991/000271 WO1991013119A1 (fr) 1990-02-21 1991-02-21 Polyester thermoplastique ayant des caracteristiques d'impact ameliorees.

Country Status (1)

Country Link
WO (1) WO1991013119A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993008234A1 (fr) * 1991-10-24 1993-04-29 E.I. Du Pont De Nemours And Company Compositions thermoplastiques a base de terephtalate de polybutylene destines aux revetements de cables
WO1994024210A1 (fr) * 1993-04-08 1994-10-27 The Dow Chemical Company Compositions polymeres melangees presentant une brillance limitee
US5824412A (en) * 1991-10-24 1998-10-20 E. I. Du Pont De Nemours And Company Thermoplastic polybutylene terephthalate compositions for wire coating applications
WO2005111143A1 (fr) * 2004-05-19 2005-11-24 Exxonmobil Chemical Patents Inc. Modificateurs pour alliages thermoplastiques et alliages fabriques au moyen de ces modificateurs

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5817151A (ja) * 1981-07-24 1983-02-01 Toray Ind Inc ポリエステル樹脂組成物
EP0072455A1 (fr) * 1981-07-24 1983-02-23 Toray Industries, Inc. Composition résineuse de polyester et procédé pour sa préparation
EP0234035A1 (fr) * 1985-12-23 1987-09-02 General Electric Company Composition de résines
EP0269275A2 (fr) * 1986-10-29 1988-06-01 Mitsui Petrochemical Industries, Ltd. Composition élastomère thermoplastique
EP0309800A2 (fr) * 1987-10-01 1989-04-05 COPOLYMER RUBBER & CHEMICAL CORPORATION Polyesters ayant une haute résistance au choc
US4833194A (en) * 1987-11-13 1989-05-23 R.J.F. International Corporation Elastomeric thermoplastic compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5817151A (ja) * 1981-07-24 1983-02-01 Toray Ind Inc ポリエステル樹脂組成物
EP0072455A1 (fr) * 1981-07-24 1983-02-23 Toray Industries, Inc. Composition résineuse de polyester et procédé pour sa préparation
EP0234035A1 (fr) * 1985-12-23 1987-09-02 General Electric Company Composition de résines
EP0269275A2 (fr) * 1986-10-29 1988-06-01 Mitsui Petrochemical Industries, Ltd. Composition élastomère thermoplastique
EP0309800A2 (fr) * 1987-10-01 1989-04-05 COPOLYMER RUBBER & CHEMICAL CORPORATION Polyesters ayant une haute résistance au choc
US4833194A (en) * 1987-11-13 1989-05-23 R.J.F. International Corporation Elastomeric thermoplastic compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Database WPIL, no. 83-24143k, Derwent Publications Ltd., (London, GB); & JP-A-58017151 (TORAY), 1 February 1983 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993008234A1 (fr) * 1991-10-24 1993-04-29 E.I. Du Pont De Nemours And Company Compositions thermoplastiques a base de terephtalate de polybutylene destines aux revetements de cables
US5824412A (en) * 1991-10-24 1998-10-20 E. I. Du Pont De Nemours And Company Thermoplastic polybutylene terephthalate compositions for wire coating applications
WO1994024210A1 (fr) * 1993-04-08 1994-10-27 The Dow Chemical Company Compositions polymeres melangees presentant une brillance limitee
WO2005111143A1 (fr) * 2004-05-19 2005-11-24 Exxonmobil Chemical Patents Inc. Modificateurs pour alliages thermoplastiques et alliages fabriques au moyen de ces modificateurs
US8349949B2 (en) 2004-05-19 2013-01-08 Exxonmobil Chemical Patents Inc. Modifiers for thermoplastic alloys and alloys produced using such modifiers

Similar Documents

Publication Publication Date Title
EP0518703B1 (fr) Compositions de résine de polyester sulfoné
US5091478A (en) Partially grafted thermoplastic compositions
EP0111179B1 (fr) Masses à mouler à base de polyester thermoplastique et de polyéthylène à basse densité
US6699946B1 (en) Polyphenylene sulphide-based compositions with improved impact strength and process for preparing them
EP0389055B1 (fr) Compositions de résine de polyester aromatique
EP0275141B1 (fr) Modificateur de la résistance au choc contenant des groupes époxy pour résines thermoplastiques
EP0119533B1 (fr) Composition de polycarbonate
US5175204A (en) Thermoplastic resin composition and method for preparing the same
EP0290588B1 (fr) Compositions thermoplastiques partiellement greffees
EP0519098B1 (fr) Mélange de polycarbonate aromatique à faible brillance
US4895897A (en) Aromatic carbonate compositions modified with oxazoline functionalized polystyrene reacted with an ethylene elastomer containing reactive polar groups
US4699935A (en) Inorganic filler-containing polyolefin resin compositions
US4638033A (en) Resinous composition of a carbonate resin and a grafted derivative of ethylene-propylene-diene terpolymer exhibiting improved resistance to organic solvents
EP0131188A1 (fr) Composition de polycarbonate
JPH0579700B2 (fr)
WO1991013119A1 (fr) Polyester thermoplastique ayant des caracteristiques d'impact ameliorees.
US6025420A (en) Compositions for tough and easy melt processible polycarbonate/polyolefin blend resin
EP0272857A2 (fr) Compositions de polycarbonate
KR920006369B1 (ko) 개선된 열가소성 폴리에스테르 수지 및 그의 제조방법
US4647619A (en) Impact modified polybutylene terephthalate resin molding compositions
EP0299064A1 (fr) Modificateurs d'impact olefiniques pour des resines de polyester plastique et melanges avec celles-ci.
JP2723552B2 (ja) 改善された衝撃強さをもつポリエステル
EP0234035A1 (fr) Composition de résines
US4897447A (en) Thermoplastic compositions and impact modifiers for same
JP2659975B2 (ja) 熱可塑性樹脂の耐衝撃及びニットライン強度を改善するための改良剤、ならびにそれを含む樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载