WO2010030216A1 - Poly(alkylène phtalate) acétylénique - Google Patents

Poly(alkylène phtalate) acétylénique Download PDF

Info

Publication number
WO2010030216A1
WO2010030216A1 PCT/SE2009/000102 SE2009000102W WO2010030216A1 WO 2010030216 A1 WO2010030216 A1 WO 2010030216A1 SE 2009000102 W SE2009000102 W SE 2009000102W WO 2010030216 A1 WO2010030216 A1 WO 2010030216A1
Authority
WO
WIPO (PCT)
Prior art keywords
acetylenic
poly
alkylene
alkynyl
phthalate
Prior art date
Application number
PCT/SE2009/000102
Other languages
English (en)
Inventor
Jan-Erik Rosenberg
Per Morin
Per Persson
Original Assignee
Nexam Chemical Ab
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 Nexam Chemical Ab filed Critical Nexam Chemical Ab
Publication of WO2010030216A1 publication Critical patent/WO2010030216A1/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
    • C08L67/06—Unsaturated polyesters
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/47—Polyesters chemically modified by esterification by unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention refers to a acetylenic poly(alkylene phthalate) and a composition comprising said poly(alkylene phthalate).
  • the acetylenic poly(alkylene phthalate) is obtained by incorporation of at least one acetylenic compound, having at least one carbon-carbon triple bond and at least one group reactive to hydroxyl and/or carboxyl groups, into said poly(alkylene phthalate).
  • the present invention refers to a composition comprising said acetylenic poly(alkylene phthalate) and a moulded article obtained from said acetylenic poly(alkylene phthalate) or said composition.
  • Acetylenic above and hereafter refers to any chemical compound, including monomers, oligomers and polymers, and/or any chemical group, which compound or group has at least one carbon-carbon triple bond.
  • Poly(alkylene phthalate)s such as the most commonly used poly(alkylene terephthalate)s, are thermoplastic polymers in the polyester family and are typically used in containers for beverages and food and feedstuffs and similar containers, thermoforming applications, synthetic fibres and engineering resins often in combination with for instance glass fibres.
  • Typical application areas of poly(alkylene phthalate)s furthermore include rod and slab, fibre optics, buffer tubes and cable liners.
  • Application areas of reinforced poly(alkylene phthalate) grades include automotive applications, such as electrical system parts, electrical and electronic connectors and sockets, switches, bobbins, motor housings and insulations, appliance housings and handles.
  • Poly(alkylene phthalate)s can be synthesised by esterification between a phthalic acid, such as o-phthalic acid or anhydride, isophthalic acid and/or terephthalic acid and an alkylene glycol, such as a methylene, ethylene, butylene, propylene and/or cyclohexyldimethylene glycol (cyclohexane dimethanol), yielding water as by-product, or by transesterification reaction between an alkylene glycol and for instance a dialkyl, such as a dimethyl or diethyl phthalate with alkanol, such as methanol or ethanol, as by-product. Polymerisation occurs immediately subsequent said esterification/transesterification through polycondensation of obtained ester.
  • a phthalic acid such as o-phthalic acid or anhydride
  • isophthalic acid and/or terephthalic acid and an alkylene glycol such as a methylene, ethylene, butylene
  • copolymers are produced and available, hi some cases, the modified properties of copolymers are more desirable for a particular application.
  • cyclohexane dimethanol can be added to the polymer backbone in place of for instance ethylene or butylene glycol. Since this building block is much larger than the ethylene or butylene glycol units it replaces, it does not fit in with the neighbouring chains the way for instance an ethylene glycol unit would, which effects crystallisation and reduces the melting temperature of yielded polymer.
  • poly(alkylene phthalate)s have excellent physical and chemical properties and for a long time have been widely used for resins, films and fibres, demands for improved and/or modified properties, such as changed E-module value, reduced shrinkage, changed impact strength and improved resistance towards thermo-oxidative, thermal, oxidative and mechanical degradation.
  • an acetylenic poly(alkylene phthalate) can be obtained by incorporation of at least one carbon-carbon triple bond for instance as endcapping group, as pendant group along the molecular backbone and/or as group being part of the molecular backbone.
  • Said acetylenic poly(alkylene phthalate) can suitably be obtained by subjecting at least one poly(alkylene phthalate) to reaction with at least one acetylenic compound having at least one carbon-carbon triple bond and at least one group reactive to hydroxyl and/or carboxyl groups or by co-condensing at least one phthalic acid or anhydride and/or a corresponding acid halide or alkyl ester, at least one alkylene glycol and at least one said acetylenic compound according to reactions discussed above, and that yielded acetylenic poly(alkylene phthalate) meets said demands for improved and/or modified properties.
  • Said acetylenic compound is preferably selected from acetylenic linear or branched aliphatic, cycloaliphatic or aromatic carboxylic acids or anhydrides, acetylenic linear or branched aliphatic, cycloaliphatic or aromatic alcohols and/or acetylenic phenolic compounds and/or other acetylenic compounds capable of bonding to carboxyl and/or hydroxyl groups.
  • Said acetylenic compound has at least one carbon-carbon triple bond, such as at least one alkynyl, alkynylaryl and/or arylalkynyl group, and at least one group reactive to hydroxyl and/or carboxyl groups, such as at least one carboxyl, hydroxyl and/or phenolic hydroxyl group and/or at least one halide group.
  • Embodiments of said acetylenic compound include aromatic compounds of Formula I through rv wherein the position in the aromatic ring of the acetylenic carbon-carbon triple bond is variable and wherein at least one substituent R is a hydroxyl, carboxyl, hydroxyalkyl, carboxyalkyl, hydroxyalkenyl or carboxyalkenyl group or a corresponding halide or ester group, each R is an alkyl, alkenyl, aryl, alkylaryl, alkenylaryl, arylalkyl or arylalkenyl group and each remaining substituent R and each substituent R individually is hydrogen or halo or a linear or branched, aliphatic or cycloaliphatic alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl or haloalkynyl group,
  • Embodiments of said acetylenic compound are found in the group consisting of aromatic as well as linear and branched, aliphatic and cycloaliphatic acetylenic carboxylic acids or anhydrides and alcohols having at least one carbon-carbon triple bond and at least one carboxyl or hydroxyl group or a corresponding halide or ester group.
  • Preferred embodiments of said acetylenic compound include alkynyl and arylalkynyl o-phthalic acids and anhydrides, alkynyl and arylalkynyl isophthalic acids, alkynyl and arylalkynyl terephthalic acids, alkynyl and arylalkynyl benzoic acids, alkynyl and arylalkynyl adipic acids, alkynyl and arylalkynyl azelaic acids, alkynyl and arylalkynyl sebacic acids, alkynyl and arylalkynyl furandicarboxylic acids and corresponding acid halides and alkyl esters as well as aliphatic and aromatic alkynyl and arylalkynyl glycols, alkynyl and arylalkynyl phenols, alkynyl and arylalkynyl
  • Said aryl is above and hereinafter preferably phenyl or naphthyl, said alkyl likewise preferably linear or branched, aliphatic or cycloaliphatic Ci-Cs or C 2 -C 8 alkyl, such as ethyl, propyl or butyl, said alkenyl likewise preferably aliphatic or cycloaliphatic, linear or branched C 2 -C 8 alkenyl, such as ethenyl, propenyl or butenyl, and said alkynyl likewise preferably aliphatic or cycloaliphatic, linear or branched C2-C 8 alkynyl, such as ethynyl, propynyl or butynyl.
  • acetylenic compound can be exemplified by acetylenedicarboxylic acid, ethynyl o-phthalic anhydride, phenylethynyl o-phthalic anhydride, naphthyl ethynyl o-phthalic anhydride, ethynyl isophthalic acid, phenylethynyl isophthalic acid, naphthyl ethynyl isophthalic acid, ethynyl terephthalic acid, phenylethynyl terephthalic acid, naphthyl ethynyl terephthalic acid, ethynyl benzoic acid, phenylethynyl benzoic acid, naphthyl ethynyl benzoic acid, ethynyl xylylene glycol, phenylethynyl xylylene glycol, phen
  • Said poly(alkylene phthalate) is in preferred embodiments of the present invention a poly(alkylene o-phthalate), a poly(alkylene isophthalate) and/or a poly(alkylene terephthalate), wherein said alkylene preferably is di, tri or polymethylene, ethylene, butylene, propylene and/or cyclohexyldimethylene.
  • the poly(alkylene phthalate) of the present invention is in its most preferred embodiments a poly(ethylene isophthalate), a poly(butylene isophthalate), a poly(propylene isophthalate), a poly(cyclohexyldimethylene isophthalate), a poly(ethylene terephthalate), a poly(butylene terephthalate), a poly(propylene terephthalate), a poly(cyclohexyldimethylene terephthalate) and/or a mixture thereof or therewith.
  • the acetylenic poly(alkylene phthalate) of the present invention is accordingly a corresponding acetylenic poly(alkylene phthalate) fitted with at least one carbon-carbon triple bond and comprising monomer units derived from at least one said acetylenic compound, at least one alkylene glycol and at least one phthalic acid or anhydride.
  • Said phthalic acid or anhydride, used as monomer in production of the acetylenic poly(alkylene phthalate) of the present invention is in said preferred embodiments accordingly an o-phthalic acid or anhydride, an isophthalic acid or a terephthalic acid or a corresponding acid halide or alkyl ester, such as a dimethyl or diethylester, and said alkylene glycol, also used as monomer, is likewise a mono, di, tri or polymethylene, ethylene, butylene, propylene and/or cyclohexyldimethylene glycol.
  • Said acetylenic compound is in preferred embodiments present in said acetylenic poly(alkylene phthalate) in an amount corresponding to at least 0.1 mole%, such as between 1 and 30 mole%, of the total molar amount of monomers, oligomers and/or polymers used in production of the acetylenic poly(alkylene phthalate) of the present invention.
  • the purpose of the present invention is to modify the mechanical properties of /?oly(alkylene phthalate)s and compositions comprising poly(alkylene phthalate)s.
  • these modifications of properties can be mentioned: higher softening temperature, higher E-modulus and improved ability to counteract creep strain.
  • acetylenic group of the acetylenic poly(alkylene phthalate) of the present invention can be arranged as an endcapping, in-chain and/or pendent group. This will, of course in it self give different properties to the polymer after curing.
  • Fibres suitable for use together with the acetylenic poly(alkylene phthalate) and/or the composition of the present invention can be exemplified by glass fibres, carbon fibres, steel fibres, aramide fibres, natural organic fibres, such as cellulose fibres, flax fibres, cotton fibres and silk.
  • glass fibres carbon fibres, steel fibres, aramide fibres, natural organic fibres, such as cellulose fibres, flax fibres, cotton fibres and silk.
  • most organic and inorganic fibres that are able to withstand the process temperatures may prove useful. It is also possible to use fullerenes for reinforcing as well as for changing other mechanical properties.
  • Fillers are typically used for increasing dimension stability even though a few other mechanical properties, such as density, rigidity and acoustic properties may be altered by means of fillers. Fillers may be organic like cellulose or inorganic, such as minerals like for instance mica, lime and talcum.
  • stabilisers to said acetylenic poly(alkylene phthalate) and/or said composition, such as compounds stabilising towards exposure to ultraviolet light, heat or other exposure that may cause for instance polymer chain breakdown.
  • the electrical properties of the acetylenic poly(alkylene phthalate) and/or the composition of the present invention may also be modified within the scope of the invention. This may be achieved by adding for instance an insulation modifier.
  • the most common modifier is carbon black which is used in smaller quantities to achieve antistatic properties. By adding more carbon black, the acetylenic poly(alkylene phthalate) and/or the composition may exhibit receive from dissipating properties to conducting and shielding properties.
  • carbon black also other known substances and compounds used for obtaining above or portions of thereof.
  • Metal fibres, carbon fibres and metal powder are only a few examples of such materials. Some of these materials also serve the purpose of reinforcing and filling agents.
  • Said acetylenic poly(alkylene phthalate) and/or said composition may also be expanded to change the density and thermal insulation property by adding a blowing, expanding or foaming agent. This may of course be used in combination with other additives.
  • acetylenic poly(alkylene phthalate) and/or the composition It is in some applications also advantageous to modify the surface properties of the acetylenic poly(alkylene phthalate) and/or the composition.
  • One such way is by adding anti-microbial agents for which the purpose is obvious.
  • Another way is by adding so called tackifiers increasing friction if and when needed.
  • the present invention refers to a composition
  • a composition comprising at least one acetylenic poly(alkylene phthalate) as disclosed above.
  • the composition can in various embodiments further comprise at least one additional polymer, such as at least one additional poly(alkylene phthalate), and/or at least one filler, reinforcement, pigment, plasticiser and/or any other additive known in the art.
  • Preferred embodiments of said acetylenic poly(alkylene phthalate) are as disclosed above.
  • Said acetylenic poly(alkylene phthalate) is suitably present in an amount of between 0.1 and 99.9, such as between 1 and 40 or between 1 and 25, % by weight of said composition.
  • the present invention refers to a moulded three-dimensional article obtained by moulding at least one acetylenic poly(alkylene phthalate) as disclosed above or at least one composition likewise disclosed above.
  • the acetylenic poly(alkylene phthalate) is for instance, upon and/or subsequent said moulding, crosslinked by heat, provided externally or in situ generated, induced crosslinking reaction of its acetylenic group(s).
  • Said crosslinking is suitably enhanced by the presence of an effective amount of at least one compound promoting crosslinking reactions of acetylenic polymers, such as a sulphur or an organic sulphur derivative as disclosed in for instance US patent no. 6,344,523 and/or a radical initiator.
  • Curing of the herein disclosed acetylenic poly(alkylene phthalate) and the herein disclosed composition are advantageously initiated by providing the mould, the inlet or the hotrunner with a choking valve or check valve arrangement creating heat in the polymer through friction caused during the injection phase.
  • the valve arrangement may be a solid arrangement whereas the generated heat is guided through the velocity of injection. There are numerous ways to guide the injection velocity.
  • PLC Programmable Logic Controller
  • Another way is to guide the process actively by using a temperature sensor in the mould and/or in the valve arrangement.
  • a pressure sensor advantageously arranged just before the valve arrangement, optionally with a second pressure sensor arranged after the valve arrangement, may serve the same purpose as it indicates the pressure drop and thereby the friction generated.
  • the temperature and pressure sensor(s) may also be used in combination.
  • the data generated from these sensor(s) are then used as process data for guiding the injection moulding cycle. This data may then be used for guiding the injection sequence through direct guiding or so-called statistical process guiding.
  • Statistical process guiding is especially advantageous where there is a risk for measurement lag, data delay or process guiding resonance in the process.
  • the check valve may also be provided with guided heating and/or cooling, either as a replacement for mechanically adjusting the orifice size, or as a complement thereto. Also this can be guided through PLC data only or by the aid of measuring data in the mould and/or around the valve as described above.
  • the mould is advantageously provided with one or more temperature sensors for the purpose of detecting the exothermic heat caused by the curing process. It is suitable to arrange several such sensors along the flow path of the polymer in order to detect variations in the curing in different portions of the article produced. These measurements are suitably used for statistical process guiding.
  • acetylenic poly(alkylene phthalate) and the herein disclosed composition are also well suited for use in a compression moulding process.
  • a predetermined amount of polymeric material can here be preheated to a temperature somewhat under the curing temperature and placed in an open mould. The mould is then closed so that the polymeric material is distributed in the mould as is the normal procedure in compression moulding.
  • the preheating, the mould temperature, the viscosity of the polymeric material and the compression pressure is adapted so that the friction and compression pressure will generate the heat needed to initiate the curing. It is also in a compression moulding process advantageous to provide the mould with one or more temperature and/or pressure sensors for the purpose of detecting the exothermic reaction during the curing.
  • the viscosity of the polymeric material during processing may be altered by means of rheology modifiers in order to obtain desired process parameters.
  • the temperature initiating curing is dependent on the structure of the acetylenic portion of said acetylenic poly(alkylene phthalate) and will have to be adapted to avoid material break down of the polymer chain on curing.
  • EB curing after the moulding process.
  • UV curing ultraviolet curing
  • This will also call for the need of for instance one or more photoinitiators.
  • EB curing In most applications only a surface curing can be achieved through means of UV curing since the thermoplastic polymer is not transparent, however EB curing will be possible to utilise even for opaque polymers.
  • the article produced is here after the moulding procedure placed in an oven for a period of time ranging from half an hour to a couple of days. This process is known as baking.
  • the article may be arranged on a jig during the curing process.
  • a surface curing can be performed through corona treatment or flash heating. It will through this process be possible to cure the surface of a produced article without softening the polymeric material.
  • acetylenic poly(alkylene phthalate) and composition are, due to the improved mechanical properties such as improved thermal stability and E-modulus allowing said acetylenic poly(alkylene phthalate) and/or said composition to be used at higher temperatures then possible with prior art polymers, well suited for manufacturing of a great number of articles.
  • Suitable and typical application areas will be found within, but not limited to, civilian and military transportation vehicles, such as cars, trucks, busses, motorcycles, trains, ships and aircrafts as well as recreational vehicles wherein for instance demands for weight reduction is an increasing demand.
  • Automotive, aeronautic and aerospace components suitably produced from the acetylenic poly(alkylene phthalate) and/or the composition of the present invention comprise, but are not limited to, for instance exterior body panels and glazing, such as back lights, door panels, fenders, panoramic roofs, roof modules, tailgates, heat shields, armours and spall linings.
  • Further suitable articles include exterior components, such as vent grilles, door handles, front grilles, mirror systems, roof racks, running boards, spoilers, tank flaps, wheel housings and wheel covers as well as traditional after market products. It is also possible to produce larger components for trucks, busses, ships and aircrafts.
  • Said acetylenic poly(alkylene phthalate) and/or said composition may furthermore be used in lighting, such as fog lamp lenses, reflectors and housings; headlamp bezels, housings, lenses and reflectors; lamp support brackets; projector lamp reflectors and holders; rear combination lamp housings, reflectors and lenses.
  • lighting such as fog lamp lenses, reflectors and housings; headlamp bezels, housings, lenses and reflectors; lamp support brackets; projector lamp reflectors and holders; rear combination lamp housings, reflectors and lenses.
  • These can be base coated, primed for painting, direct metallised and/or moulded in colour.
  • acetylenic poly(alkylene phthalate) and/or the composition of the present invention may also be used for other structural as well as interior components, such as composite headliners, energy absorption systems, front end modules, instrument panels, interior trimmings, load floors, pedestrian energy absorption systems and storage bins, as well as parts suitable for motorcycles, such as no-paint parts, tanks, fairing, chassis, frames, luggage containers and racks, as well as motorcycle rider safety items, such as helmets and all sorts of shields.
  • interior components such as composite headliners, energy absorption systems, front end modules, instrument panels, interior trimmings, load floors, pedestrian energy absorption systems and storage bins, as well as parts suitable for motorcycles, such as no-paint parts, tanks, fairing, chassis, frames, luggage containers and racks, as well as motorcycle rider safety items, such as helmets and all sorts of shields.
  • acetylenic poly(alkylene phthalate) and the composition herein disclosed may also be used in power train parts, such as air intake, automotive gears, wire coatings, brackets, sealings, electronic and electronic housings, fuel system components, pulleys, sensors, throttle bodies, transmissions and transmission parts, and valve rocker covers as well as other components in vehicle engine bays wherein heat may render prior art polymers insufficient.
  • power train parts such as air intake, automotive gears, wire coatings, brackets, sealings, electronic and electronic housings, fuel system components, pulleys, sensors, throttle bodies, transmissions and transmission parts, and valve rocker covers as well as other components in vehicle engine bays wherein heat may render prior art polymers insufficient.
  • acetylenic poly(alkylene phthalate) and/or the composition of the present invention include, but are not limited to, articles used in home entertainment, such as television apparatus and equipment, projectors and audio devices, as well as mobile entertainment and information carriers and communication devices.
  • Further application areas include communication devices such as antennas, satellite dishes, articles and devices for recreation, entertainment and sport activities wherein for instance the weight to strength ratio is important, such as light weight components in extreme sport equipment including body protection, parts to mountain bikes, heat shields and the like.
  • Further suitable applications include articles such as fishing rods and golf clubs.
  • the acetylenic poly(alkylene phthalate) and/or the composition according to the present invention will solve a number of problems linked to medium to long term storage under for instance elevated temperatures. Furthermore, creep strain in polymers, which today is a problem calling for over-dimensioning of carrying structures made of polymeric materials, can be eliminated or reduced by use of the acetylenic poly(alkylene phthalate) and/or the composition of the present invention. It is also advantageous to utilise the acetylenic poly(alkylene phthalate) and/or the composition herein disclosed in household, building and construction industry.
  • Said acetylenic poly(alkylene phthalate) and/or said composition can here be used for beams, girders, rails, panels, window frames and sub assemblies, roofing, flooring, doors and door frames, handles, knobs, cabinets, housings, kitchen appliances and central heating and energy recovery systems as well as for solar energy collectors and other parts of solar and wind energy and heating systems and equipment. Further application areas can be found among electrical components, equipment and installations, such as circuit breakers, films, flexible and rigid wire coatings, housings and discrete components.
  • acetylenic poly(alkylene phthalate) and/or composition are also suitably used in health care, including man and animal, and laboratory equipment such as cardiovascular and blood care equipment, oxygenators, filters, pumps, masks, sleep therapy equipment, drug delivery devices, inhales, syringes, injection devices, stopcocks and valves as well as orthopaedic equipment, external bone fixation, joint trials, mechanical instruments, surgical instruments, electrosurgical instruments, endomechanical instruments and access devices as well as sub components and spare parts to the above.
  • Said acetylenic poly(alkylene phthalate) and/or said composition can furthermore be used for supporting, diagnostic and monitoring equipment, such as hand instruments, equipment for imaging, ocular devices, dental devices, laboratory ware and vials as well as sterilisation trays.
  • diagnostic and monitoring equipment such as hand instruments, equipment for imaging, ocular devices, dental devices, laboratory ware and vials as well as sterilisation trays.
  • reaction vessel equipped with a heating device, mechanical stirring, nitrogen inlet, a cooler and a water trap.
  • the reaction mixture was heated to 210°C and kept at said temperature for 1.5 hour.
  • the reaction was performed in the presence of 0.5% by weight of an esterification catalyst (Fascat ® 4100) and under inert (N 2 ) atmosphere. Obtained reaction product was after said 1.5 hour allowed to cool to room temperature.
  • an esterification catalyst Fascat ® 4100
  • reaction vessel equipped with a heating device, mechanical stirring, nitrogen inlet, a cooler and a water trap.
  • the reaction mixture was heated to 210°C and kept at said temperature for 1.5 hour.
  • the reaction was performed in the presence of 0.5% by weight of an esterification catalyst (Fascat ® 4100) and under inert (N 2 ) atmosphere. Obtained reaction product was after said 1.5 hour allowed to cool to room temperature.
  • an esterification catalyst Fascat ® 4100
  • Example 1 The product obtained in Example 1 was mixed with a disulphide catalyst (benzyl disulphide). The amount of said disulphide was 20% by weight calculated on the concentration of acetylenic groups.
  • the crosslinking reaction was studied by DSC (Differential Scanning Calorimetry), using a heating gradient of 10°C / minute. The study revealed an exothermic reaction with onset at 240-250°C, evidencing a crosslinking of the carbon-carbon triple bonds.
  • FT-IR Fullier Transform Supported Infrared Analysis

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L’invention concerne un nouveau poly(alkylène phtalate) acétylénique et une composition qui comprend ledit poly(alkylène phtalate) acétylénique. Ledit poly(alkylène phtalate) acétylénique est muni par réaction d’au moins une triple liaison carbone-carbone acétylénique obtenue par réaction d'au moins un poly(alkylène phtalate) avec au moins un composé acétylénique ou par co-condensation d'au moins un acide ou anhydride phtalique ou d'un halogénure d’acide ou d'un ester alkylique correspondant, d'au moins un alkylène glycol et d'au moins un composé acétylénique. Ledit composé acétylénique contient au moins une triple liaison carbone-carbone et au moins un groupe réagissant avec les groupes hydroxyle et/ou carboxyle.
PCT/SE2009/000102 2008-09-09 2009-02-25 Poly(alkylène phtalate) acétylénique WO2010030216A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0801927-5 2008-09-09
SE0801927 2008-09-09

Publications (1)

Publication Number Publication Date
WO2010030216A1 true WO2010030216A1 (fr) 2010-03-18

Family

ID=42005329

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE2009/000102 WO2010030216A1 (fr) 2008-09-09 2009-02-25 Poly(alkylène phtalate) acétylénique

Country Status (1)

Country Link
WO (1) WO2010030216A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102844291A (zh) * 2010-04-16 2012-12-26 聂克斯姆化学有限公司 新型交联剂
US8492507B2 (en) 2008-09-23 2013-07-23 Nexam Chemical Ab Acetylenic polyamide
WO2014047015A1 (fr) * 2012-09-24 2014-03-27 Ticona Llc Polyester aromatique réticulable
US8822628B2 (en) 2012-09-24 2014-09-02 Ticona Llc Crosslinkable liquid crystalline polymer
US8853342B2 (en) 2012-09-24 2014-10-07 Ticona Llc Crosslinkable liquid crystalline polymer
WO2015110502A1 (fr) 2014-01-24 2015-07-30 Nexam Chemical Ab Combinaison d'agents de réticulation
JP2019516855A (ja) * 2016-04-24 2019-06-20 キューイーディー ラブズ インコーポレイテッドＱＥＤ Ｌａｂｓ Ｉｎｃ． 難燃性および／または向上した溶融滴下性のためのポリマー組成物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484411A (en) * 1964-02-10 1969-12-16 Union Carbide Corp Acetylenically unsaturated polymers
US4221895A (en) * 1978-04-18 1980-09-09 The Dow Chemical Company Thermally resistant thermosetting aromatic polymers containing pendant 1-alkynyl substituents
US4283551A (en) * 1979-09-13 1981-08-11 Gulf Oil Corporation Novel acetylene end-capped polyesters
US4638083A (en) * 1984-05-23 1987-01-20 The United States Of America As Represented By The Administrator Of The National Aeronautics & Space Administration Ethynyl terminated ester oligomers and polymers therefrom
EP0890595B1 (fr) * 1997-07-10 2000-02-02 Dainippon Ink And Chemicals, Inc. Polyesters auto-réticulants à haute température
US20060235189A1 (en) * 2003-02-05 2006-10-19 Basf Coatings Aktiengesellschaft, Polyesters comprising groups that can be activated by actinic radiation, corresponding method and use

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484411A (en) * 1964-02-10 1969-12-16 Union Carbide Corp Acetylenically unsaturated polymers
US4221895A (en) * 1978-04-18 1980-09-09 The Dow Chemical Company Thermally resistant thermosetting aromatic polymers containing pendant 1-alkynyl substituents
US4283551A (en) * 1979-09-13 1981-08-11 Gulf Oil Corporation Novel acetylene end-capped polyesters
US4638083A (en) * 1984-05-23 1987-01-20 The United States Of America As Represented By The Administrator Of The National Aeronautics & Space Administration Ethynyl terminated ester oligomers and polymers therefrom
EP0890595B1 (fr) * 1997-07-10 2000-02-02 Dainippon Ink And Chemicals, Inc. Polyesters auto-réticulants à haute température
US20060235189A1 (en) * 2003-02-05 2006-10-19 Basf Coatings Aktiengesellschaft, Polyesters comprising groups that can be activated by actinic radiation, corresponding method and use

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DIRLIKOV S. ET AL: "Poly(dipropargyl terephthalate). A candidate for thermosetting fibers", POLYMER PREPRINTS, vol. 33, no. 1, 1992, pages 483 - 484, XP003026314 *
FEIT B.-A. ET AL: "Acetylenic Polyesters", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 9, no. 7, 1965, pages 2379 - 2391, XP003026313 *
PATIL A.O. ET AL: "Photocrosslinkable polymers containing backbone triple bonds", POLYMER, vol. 22, no. 4, 1981, pages 434 - 435, XP024117120 *
QUINN, C.B.: "The Flammability properties of Copolyesters and Copolycarbonates Containing Acetylenes", JOURNAL OF POLYMER SCIENCE: POLYMER CHEMISTRY EDITION, vol. 15, 1977, pages 2587 - 2594, XP003026312 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8492507B2 (en) 2008-09-23 2013-07-23 Nexam Chemical Ab Acetylenic polyamide
CN102844291A (zh) * 2010-04-16 2012-12-26 聂克斯姆化学有限公司 新型交联剂
CN102844291B (zh) * 2010-04-16 2015-06-17 聂克斯姆化学有限公司 新型交联剂
WO2014047015A1 (fr) * 2012-09-24 2014-03-27 Ticona Llc Polyester aromatique réticulable
US8822628B2 (en) 2012-09-24 2014-09-02 Ticona Llc Crosslinkable liquid crystalline polymer
US8853342B2 (en) 2012-09-24 2014-10-07 Ticona Llc Crosslinkable liquid crystalline polymer
US9145519B2 (en) 2012-09-24 2015-09-29 Ticona Llc Crosslinkable aromatic polyester
WO2015110502A1 (fr) 2014-01-24 2015-07-30 Nexam Chemical Ab Combinaison d'agents de réticulation
JP2019516855A (ja) * 2016-04-24 2019-06-20 キューイーディー ラブズ インコーポレイテッドＱＥＤ Ｌａｂｓ Ｉｎｃ． 難燃性および／または向上した溶融滴下性のためのポリマー組成物

Similar Documents

Publication Publication Date Title
US8492507B2 (en) Acetylenic polyamide
WO2010030216A1 (fr) Poly(alkylène phtalate) acétylénique
WO2010087742A1 (fr) Polycarbonate acétylénique aromatique
CN102574385B (zh) 重叠注塑的耐热聚酰胺复合结构及其制备方法
US6762235B2 (en) Polybutylene terephthalate resin and compositions and molded articles comprising the resin
US20150315344A1 (en) Processable Semi-Crystalline Polymer Networks
KR20140135752A (ko) 내열성이 개선된 투명한 반-결정질 물품
AU2014364554A1 (en) Nucleated crystallization of poly(trimethylene-2,5-furandicarboxylate) (PTF) and articles made therefrom
EP1460106A1 (fr) Composition de resine thermoplastique
JP2009019134A (ja) レーザー溶着用ポリエステル樹脂組成物及びそれを用いた成形品
WO2010072760A1 (fr) Polyéthercétone aromatique acétylénique
WO2020235472A1 (fr) Composition de résine thermoplastique pour éléments de radar à ondes millimétriques, article moulé et procédé de production de composition de résine
JP2013531120A (ja) 高寸法安定性ポリエステル組成物
WO2010086385A9 (fr) Polycarbonate aromatique réticulable
US20130261254A1 (en) Reactive diluents, methods of reacting, and thermoset polymers derived therefrom
KR20120014888A (ko) 폴리에스테르 및 폴리아미드의 안정화된 블렌드
TWI644793B (zh) 包含低熔點聚酯樹脂的包裝托盤面板及其製備方法
EP2373721B1 (fr) Polyéthercétone aromatique acétylénique
WO2010071532A1 (fr) Résine phénol-aldéhyde acétylénique
US20120128911A1 (en) Solid state polymerizations of polyester
EP3218436B1 (fr) Composition de polyester et article préparé à partir de cette dernière
JP2009019135A (ja) レーザー溶着用ポリエステル樹脂組成物及びそれを用いた成形品
Salaeh et al. The utilization of glycerol and xylitol in bio-based vitrimer-like elastomer: Toward more environmentally friendly recyclable and thermally healable crosslinked rubber
JP5223254B2 (ja) レーザー溶着用ポリエステル樹脂組成物及びそれを用いた成形品
JP7424174B2 (ja) ミリ波レーダー部材用熱可塑性樹脂組成物及び成形体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09813299

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09813299

Country of ref document: EP

Kind code of ref document: A1