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WO1991006592A1 - Copolymere greffe de polylactone sur un squelette de polymere - Google Patents

Copolymere greffe de polylactone sur un squelette de polymere Download PDF

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Publication number
WO1991006592A1
WO1991006592A1 PCT/US1990/005922 US9005922W WO9106592A1 WO 1991006592 A1 WO1991006592 A1 WO 1991006592A1 US 9005922 W US9005922 W US 9005922W WO 9106592 A1 WO9106592 A1 WO 9106592A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
polylactone
anhydride
backbone
polymer
Prior art date
Application number
PCT/US1990/005922
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English (en)
Inventor
Jacques Horrion
Donald Norman Schulz
Pawan Kumar Agarwal
Trazollah Ouhadi
Donald Bruce Siano
Original Assignee
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
Application filed by Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Publication of WO1991006592A1 publication Critical patent/WO1991006592A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences

Definitions

  • the present invention relates to a graf t copolymer of a pol ylactone and a polymer backbone , which is preferably a polyol ef in of rubbery character ( ie . of low E-modulus) , and a process for its preparation . It also relates to a blend of a resi n and the graf t copolymer , which blend has an improved impact strength.
  • EP-A-0181587 relates to anti-static or
  • thermoplastic polymer blends in which a first polymer containing an electrically conductive substance forms a continuous phase, and a second polymer, of higher Belt viscosity than the first, is blended in this first polymer.
  • the first polymer may be polycaprolactone and the second polymer may be a maleic-acid-anhydride- modified polyethylene or maleic-acid-anhydride-modified- ethylene-propylene-diene ter polymer. Copolymers may form at the interface between the two polymer phases.
  • the lactone used is pivalolactone.
  • the highly crystalline nature of the polymer obtained from pivalolactone provides a graft copolymer which can be moulded into a shaped article eg. by compression or injection moulding.
  • the present invention relates to a novel graft copolymer comprising a polylactone and a polymer backbone which copolymer is useful as an impact strength modifier in an engineering resin.
  • the present invention provides a polymer comprising continuous phase amorphous or semi-crystalline polymer backbone which incorporates or on which are grafted
  • repeat unit chain length is used to mean the length, exclusive of any optional branching, of the repeat unit in the polylactone chain and corresponds to the atoms in the monomer lactone ring.
  • the polymer backbone in the copolymers of the invention may be grafted with unsaturated dicarboxylic acid anhydride groups, in which case the copolymers of the present invention may be schematically represented as follows:
  • the polymer backbone may incorpor ate the anhydride groups as part of the polymer chain (rather than being grafted thereto). Such incorporation may be accomplished by including the anhydride as a comonomer during the polymer backbone production process.
  • Such copolymers of the invention may be schematically represented as follows:
  • the important feature is that the elastomeric polymer and the polylactone are grafted together, rather than the manner in which such graft is achieved.
  • backbone and “backbone polymer” as used hereafter in this description refer to the backbone on which the anhydride groups have been grafted or in which the anhydride groups have been incorporated.
  • amorphous or semi-crystalline polymer backbone or "backbone
  • elasto-neric polymer refers to the backbone without any anhydride functional ising groups since this should be elastomeric. Thus this term refers to the polymers before any anhydride-functional ising groups are grafted thereto, or to the polymer without incorporated anhydride groups which otherwise is produced from the same other (co)aonomers and under the same conditions as the backbone polymer which does have such anhydride-functionalising comonomer incorporated in the molecular chain.
  • the backbone elastomeric polymer preferably has "soft rubbery" characteristics, it has been found that graft copolymers of the invention which have particularly useful properties as impact modifiers for engineering resins are those wherein the backbone elastomeric polymer is elastomeric and soft-rubbery in nature, as characterised by having eg. an E-Modulus (ASTM D638) of from 1 to 400 MPa preferably from 10 to 150 MPa.
  • ASTM D638 E-Modulus
  • Preferred polymers for use as the backbone elastomeric polymer are homopolymers of monoethylenically unsaturated monomers, such as those of C 2 -C 12 alpha-mono olefins, and copolymers of any two or more thereof.
  • Such backbone homo- or copolymers may be for example (provided they have the required amorphous or semi-crystalline
  • Especially preferred polymers are those homo- or co-polymers comprising ethylene units.
  • Particular preferred backbone elastomeric polymers include:
  • Homopolyethylene eg. low density polyethylene, linear-low density polyethylene.
  • Ethylene/C 3 -C 12 alpha-mono olefin/non conjugated diene terpolymer For example a terpolymer of ethylene/propylene, 1-butene and/or 1-pentene/ and a diene such as: 5-ethylene-2-norbornene (ENB); 1,4-hexadiene;
  • HNB 5-methylene-2-norbornene
  • 1,6-octadiene 1,6-octadiene
  • vinylester is a member of the group consisting of acrylate- or methacrylate-esters having from 4 to 22 carbon atoms and nitriles having from 2 to 6 carbon atoms eg:
  • the backbone polymer preferably soft-rubbery
  • the polylactone is grafted with the polylactone.
  • Such grafting is via anhydride groups which effectively modify the basic backbone elastomeric polymer.
  • modification may be achieved by incorporating the anhydride function during polymerisation of the backbone elastomeric polymer, or by grafting the anhydride
  • the anhydride functionality derives from an unsaturated dicarboxylic acid anhydride entity such as maleic anhydride, citraconic anhydride, itaconic anhydride, himic anhydride (ie. 5-norbornene endo 2,3 dicarboxy anhydride) , tetrahydrophthallic anhydride, nadic anhydride, nadic methyl anhydride, dodecenylsuccinic anhydride and their derivatives; of these, maleic anhydride is the preferred source of anhydride functionality.
  • an unsaturated dicarboxylic acid anhydride entity such as maleic anhydride, citraconic anhydride, itaconic anhydride, himic anhydride (ie. 5-norbornene endo 2,3 dicarboxy anhydride) , tetrahydrophthallic anhydride, nadic anhydride, nadic methyl anhydride, dodecenylsuccinic anhydride and their derivative
  • the amount of anhydride present in the backbone polymer is preferably from 0.01 to 10 wt % based on the backbone elastomeric polymer. If the proportion of anhydride function is below 0.01 wt % then the amount of polylactone which can be incorporated into the copolymer by grafting is low. If the proportion is above 10 wt % then the amount of polylactone which can be grafted, or the proportion of free anhydride groups remaining, is high.
  • the polylactone component of the graft copolymer provides a means of improving the miscibility or mechanical
  • the discontinuous phase polylactone component provides anchoring of the graft copolymer into the matrix of the engineering resin, and thus if the anhydride level in or on the backbone polymer is too low, the maximum possible polylactone level in the copolymer is low and hence the desired improvement in mechanical and impact properties of the graft copolymer/engineer ing resin blend cannot be achieved: the inter facial adhesion between the phases will be insufficient. If the amount of polylactone grafted onto the backbone is too great, then even though the anchoring may be improved, the impact improvement of the engineering resin is not proportionately observed.
  • the amount of anhydride is more preferably from 0.1 to 3 wt %, most preferably from 0.2 to 0.7 wt %.
  • Production of the backbone polymer which is one component of the gra ft copolymers of the invention may be by methods wel l under stood in the art.
  • the backbone polymer which is one component of the gra ft copolymers of the invention.
  • anhydr ide may be grafted onto the already formed base backbone elastomer ic polymer in solution or in the melt phase , with or without a radical initiator such as a
  • anhydride functional ity may simply be incorporated into the polymerisation system as a monomer under free radical polymerisation conditions .
  • the polylactone to be grafted onto the backbone (via the anhydride groups) is a polymer of a lactone in which the lactone ring contains 5 to 7 carbon atoms.
  • polyvalerolactone may be used, it is preferred to use polycaprolactone since this has been found to give optimised results.
  • the graft copolymers according to the invention may contain crosslinks between the backbone polymer chains. Such crosslinks occur when the backbone contains or carries free anhydride groups after all available polylactone polymer units have been grafted to the backbone. In this case crosslinking might occur directly between the anhydride groups of adjacent backbone polymer chains. Alternatively crosslinking can occur via a polylactone entity, when such polylactone contains more than one hydroxy group.
  • the graft copolymer is particularly effective at increasing the impact strength of resins. It is therefore preferred that the polylactone to be grafted onto the backbone possesses only one hydroxy group capable of reacting with the anhydride grafted on or incorporated in the backbone.
  • the graft copolymer may be desired for the graft copolymer to contain crosslinks between the backbone
  • crosslinking may be achieved by having anhydride groups present in excess and/or by having the polylactone component of the copolymer contain more than one hydroxyl group.
  • dicarboxylic acid anhydride to moles of polylactone is greater than 1.
  • this ratio be close to 1 eg. 1:1 to 1.5:1.
  • the present invention also provides a process for producing the novel graft copolymer, which process comprises melt mixing an amorphous or semi-crystalline polymer backbone which incorporates or on which are grafted dicarboxylic acid anhydride groups, and a polylactone in which the repeat unit chain length contains 5 to 7 carbon atoms the proportions of backbone polymer and polylactone being such that in the resulting graft copolymer, the backbone polymer portion constitutes a continuous phase and the polylactone
  • the dicarboxylic acid anhydride containing, eg. maleated, backbone polymer is melted in a mixer eg. internal or extruder mixer and the polylactone is added to this melt and mixed for a time from 1 to 30 minutes.
  • the resulting graft copolymer may be mixed with an engineering resin, such as polycarbonate or
  • SAN styreneacrylonitrile
  • PBT polybutene terephthalate
  • PET polyethyleneterephthalate
  • ABS polyamide
  • styrenemaleicanhydr ide copolymer acrylonitrile/butadiene/ styrene copolymer
  • ABS polyacetal
  • Typical weight ratios of resin to graft copolymer are from 98:2 to 60:40 depending on the particular resin and copolymer used, and on the degree of improvement which is required.
  • the copolymer is of a form where the backbone polymer constitutes a continuous phase, whilst the polylactone component constitutes a discontinuous phase. It is believed that the polylactone chains grafted to the backbone almost coalesce with other polylactone chains to form distinct discrete phases or globules; and that it is the anchoring of these polylactone phases into the matrix of the engineering resin which leads to the fixing of the rubbery backbone polymer in the mixture, ie. the improved inter facial adhesion between otherwise incompatible polymer species.
  • the manner in which the graft copolymer interacts with the matrix resin will depend on the relative amounts of backbone polymer and polylactone component, and to some extent on the molecular weights of these two copolymer components.
  • the degree of grafting of the polylactone onto the backbone will depend of course on the concentration of anhydride units in or on the backbone polymer and on the amount of polylactone employed in the grafting, as explained hereinbefore.
  • the polylactone component comprises from 2 to 50 wt %, more preferably from 5 to 35 wt % , especially from 7 to 30 wt % and particularly from 10 to 25 wt %. These ranges have been found to give optimised phase relationships in the copolymer.
  • the preferred proportion of the modified backbone polymer comprises from 50 to 98 wt %, more
  • the molecular weight of the backbone polymer can be selected for optimum results depending on the polymer type. It is preferred that the backbone polymer types based on ethylene/propylene copolymer have a number average molecular weight in the range of 20000 to 1000000, more preferably 30000 to 100000.
  • the polylactone component of the graft copolymer preferably has a number average molecular weight in the range of 5000 to 100000, more preferably 15000 to 60000. Too low a molecular weight leads to poor anchoring effect (phase adhesion); and too high a molecular weight leads to too low a concentration of polylactone chains, ie. reactive groups for the preparation of the graft copolymer.
  • VISTALON is a registered Trade Mark of Exxon Corporation.
  • the polycaprolactone had been produced from caprolactone monomer using an
  • PCL monohydroxyl terminated polycaprolactone
  • the graft copolymer (EP-g-PCL) (4% by weight) prepared in Example 2 was mixed with polycarbonate (96% by we ight) in a sing le screw Brabender extruder at 20-32 RPM and 230°C to form a blend .
  • the polycarbonate was LEXAN 141 ( trade mark) resin of Dupont of melt flow rate 9. 5 g/10 min (ASTM D1238 , condition 0) .
  • the blend was molded into spiral molds and into test pieces using a Boy-15 injection molder at 240°C The spiral molds were used to gauge relative flow; and the test pieces were subjected to an impact strength test at least 24 hours after molding. The notched impact strengths of the test pieces were measured according to ASTM D256 at four temperatures.
  • Styrene/acrylonitrile copolymer Styrene/acrylonitrile copolymer, SAN, (Tyril 1000B resin of the Dow Chemical Company of melt flow rate 7.5 g/10min according to ASTM 01238) was dried overnight at 75°C in an air oven.
  • 20 Parts by weight of the graft copolymer prepared in Example 3 was extruded with 80 parts by weight of the SAN in a single screw Braebender extruder at 20-32 RPM at 230°C to form a blend.
  • the blend was molded into test pieces using a Boy-15 injection molder at 240 c. Notched izod strength testing of the pieces was carried out according to ASTM D256 at least 24 hours after molding. Table 2 shows the results.
  • the SAN resin of Example 6 was dried in a circulating oven, weighed into jars and put back into the oven to await mixing.
  • the EP-PCL graft copolymer prepared in Example 4 was weighed into a plastic bag and kept separately.
  • the peroxide initiator (dicumylpe ide (diCup, Supplied by Hercules Inc.) was weighed into a paper cup and kept
  • the graft rubber (20 parts) and peroxide (0.1 part) were mixed and poured into the hopper of the extruder and then added to the SAN (80 parts) under N 2 in a single screw Brabender extruder at ca. 220°C at 18 RPM.
  • the torque reading was about 800 psi (5.5 MPa). Each mixture took about 20 minutes to extrude. Later the blends were ground, placed in an 80°C oven and injection molded on a Boy-15 at 220°C, 650 psi (4.5 MPa). Izod impact testing was run according to ASTM D256 at several different temperatures on samples which were 24 hours old.
  • the -40°C impact strength of the blend containing the graft copolymer was 160% higher than that of the control without the graft copolymer. Examples 8-20
  • ethyl ene/propylene copolymer rubber grafted with 0.7 wt % maleic anhydride having a melt flow rate (230°C/10 kg) of 7.8; and EXXELOR VA 1803 of Exxon Chemical Belgium, being a low ethylene content ethylene/propylene copolymer rubber grafted with 0.5 wt % maleic anhydride, having a melt flow rate (230°C/2.16 kg) of 3.
  • the polycaprolactones employed were CAPA 630, 640, 650 of INTEROX SA having number average molecular weights of 30000, 40000 and 500.00 respectively.
  • Example 17 Also present in Example 17 was an amine catalyst, DABCO, more specifically 1,4 diazobicyclo 2,2,2 octane.
  • the pellets produced by the extruder, being graft copolymer according to the invention, were heated in air at 50 °C for 24 hours and then compression molded into test pieces at 150 °C/10 tonnes for 5 minutes in a Daniels 100T press. The test pieces were then subjected to various physical property measurements as follows:
  • copolymer compositions and properties are shown in Table 3. From this it may be seen that the melt flow rate and tensile strength of the graft copolymer increase with increasing polycaprolactone content, but the elongation at break decreases. Furthermore, by comparison of Examples 12 and 17 it may be seen that the copolymer prepared in the presence of the added catalyst has a lower melt flow rate than the otherwise identical copolymer prepared without added catalyst. At the same time, the tensile strength is substantially unchanged and the elongation at break is only marginally changed. This thus represents a means by which the melt flow rate of the copolymer may be controlled, so as to match it with the melt flow rate of the engineering resin into which it is to be incorporated as impact strength modifier. Matching of melt flow rates greatly facilitates the mixing procedures employed to obtain the final blend.

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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

On peut améliorer la résistance à la flexion par choc de résines industrielles en les mélangeant à un copolymère greffé, lequel comprend une phase continue d'un squelette de polymère amorphe ou semi-cristallin, lequel incorpore ou dans lequel sont greffés des groupes anhydrides d'acide dicarboxylique non saturé, ainsi qu'une polylactone à phase discontinue dont la longueur de chaîne à unités à répétition contient 5 à 7 atomes de carbone, la polylactone étant fixée au squelette par l'intérmédiaire des groupes anhydrides.
PCT/US1990/005922 1989-10-24 1990-10-15 Copolymere greffe de polylactone sur un squelette de polymere WO1991006592A1 (fr)

Applications Claiming Priority (2)

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US42612889A 1989-10-24 1989-10-24
US426,128 1989-10-24

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WO1991006592A1 true WO1991006592A1 (fr) 1991-05-16

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897513A (en) * 1971-07-26 1975-07-29 Du Pont Pivalolactone random graft copolymers
US4029718A (en) * 1972-06-30 1977-06-14 E. I. Du Pont De Nemours And Company Pivalolactone random graft copolymers
US4281087A (en) * 1978-05-31 1981-07-28 Philippe Teyssie Lactone copolymers, process for their preparation and compositions containing them
US4282338A (en) * 1979-04-04 1981-08-04 Anic S.P.A. Process for the preparation of grafted polymers of α-substituted-β-propiolactone on amorphous base polymers
EP0181587A2 (fr) * 1984-11-07 1986-05-21 Zipperling Kessler & Co (GmbH & Co) Mélanges polymères thermoplastiques antistatiques ou électriquement semi-conducteurs, procédé pour leur fabrication et leur mise en oeuvre
EP0260799A2 (fr) * 1986-08-21 1988-03-23 Nippon Oil And Fats Company, Limited Compositions de peinture pour couche de fond

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897513A (en) * 1971-07-26 1975-07-29 Du Pont Pivalolactone random graft copolymers
US4029718A (en) * 1972-06-30 1977-06-14 E. I. Du Pont De Nemours And Company Pivalolactone random graft copolymers
US4281087A (en) * 1978-05-31 1981-07-28 Philippe Teyssie Lactone copolymers, process for their preparation and compositions containing them
US4282338A (en) * 1979-04-04 1981-08-04 Anic S.P.A. Process for the preparation of grafted polymers of α-substituted-β-propiolactone on amorphous base polymers
EP0181587A2 (fr) * 1984-11-07 1986-05-21 Zipperling Kessler & Co (GmbH & Co) Mélanges polymères thermoplastiques antistatiques ou électriquement semi-conducteurs, procédé pour leur fabrication et leur mise en oeuvre
EP0260799A2 (fr) * 1986-08-21 1988-03-23 Nippon Oil And Fats Company, Limited Compositions de peinture pour couche de fond

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