WO1995012636A1 - Compositions d'alliage de polyester thermoplastique stabilisees - Google Patents

Compositions d'alliage de polyester thermoplastique stabilisees Download PDF

Info

Publication number
WO1995012636A1
WO1995012636A1 PCT/US1994/012034 US9412034W WO9512636A1 WO 1995012636 A1 WO1995012636 A1 WO 1995012636A1 US 9412034 W US9412034 W US 9412034W WO 9512636 A1 WO9512636 A1 WO 9512636A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
composition according
group
composition
units derived
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1994/012034
Other languages
English (en)
Inventor
Stephen L. Tondre
Alan Yeung
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Raychem Corp
Original Assignee
Raychem Corp
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 Raychem Corp filed Critical Raychem Corp
Publication of WO1995012636A1 publication Critical patent/WO1995012636A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • H01B3/421—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • This invention relates to a polymeric blend which exhibits improved thermal stability, and an electrical conductor coated with the polymeric blend.
  • Polyesters of many kinds are known. They include, for example, poly(ethylene terephthalate) (PET), poly(butyleneterephthalate) (PBT), and the recently developed so-called polyester alloys, which comprise (1) a grafted polyester obtained by reacting a polyester with a polymeric grafting agent, and (2) a second polymer which has a chemical structure similar to the grafting agent .
  • the presence of the polymeric side chains results in improved compatibility between the polyester and the second polymer, so that they can form an intimate mixture having remarkably good physical properties.
  • There may be a chemical reaction between the grafting agent and the second polymer so that part or all of the second polymer becomes part of the grafted polyester.
  • Particular polyester alloys are disclosed in PCT (International) Application No.
  • compositions comprising polyesters including both conventional polyesters and polyester alloys
  • compositions in the form of coatings on wires are that they suffer from a lack of stability, in particular a loss of elongation on aging, particularly at elevated temperatures. This loss of elongation is particularly apparent when the composition includes a flame retardant, particularly a bromine- containing flame retardant.
  • a stabilizing compound which contains at least one thioether linkage and at least one long chain alkyl group, particularly such a compound containing a carboxylic ester group.
  • this invention provides a thermoplastic composition which comprises
  • polymeric side chains which are grafted to the backbone and which comprise units derived from addition polymerization of a monomer containing ethylenic unsaturation
  • this invention provides an insulated wire or cable comprising at least one insulating layer of a composition according to the first preferred aspect of the invention.
  • the layer is preferably made by melt extruding the composition around the wire or cable.
  • the layer can be the sole insulation around a single conductor, or one of two or more contiguous insulating layers around a single conductor, or can be all or part of a jacket around a plurality of insulated conductors.
  • the thickness of the layer can be for example 2-50 mils, preferably 4-30 mils, especially 6-20 mils.
  • this invention provides a method of making an insulated wire or cable which comprises melt extruding a composition according to the first preferred aspect of the invention around a conductor.
  • polyalkylene terephthalate is used herein to denote a polymer in which at least 80%, preferably substantially 100%, of the repeating units are alkylene erephthalate groups. (Percentages are by weight throughout this specification.) Preferably all the alkylene groups are the same. Preferably each of the alkylene groups contains 2 to 6 carbon atoms .
  • the invention is particularly useful when the polyalkylene terephthalate is polybutylene terephthalate (PBT), i.e. a polyester in which at least 80%, preferably 100%, of the repeating units are butylene terephthalate units, and the invention will be described chiefly by reference to PBT. It is to be understood, however, that such description is also applicable, with modifications which will be apparent to those skilled in the art having regard to their own knowledge and the contents of this specification.
  • PBT polybutylene terephthalate
  • the polymeric side chains in the grafted polyester preferably contain (a) at least 50%, particularly at least 60%, of units derived from ethylene;
  • the graft copolymer preferably contains a% of the polyalkylene terephthalate backbone and b% of the polymeric side chains, where a is 99.5 to 20, particularly 97 to 60, and b is 0.5 to 80, particularly 3 to 40, and a + b is 100.
  • the addition polymer (B) preferably comprises a polymer containing at least 50%, particularly at least 60%, of units derived from ethylene, and 0.5 to
  • the addition polymer (B) preferably comprises a styrene/diene block copolymer, preferably one having the formula
  • S is a polystyrene block
  • D is a hydrogenated polyisoprene block or a hydrogenated polybutadiene block, and k is an integer
  • copolymer in which the polystyrene content is less than 50%.
  • copolymers can be grafted with maleic acid to form graft copolymers containing 0.1 - 10, e.g. 0.2 - 5, % of units derived from maleic anhydride.
  • the addition polymer (B) can be a single polymer or a mixture of polymers.
  • the composition preferably contains x% of the graft copolymer (A) and y% of the addition polymer (B) , where x is 55 to 95, y is 45 to 5, and x + y is 100.
  • composition can also contain other polymeric ingredients, for example up to 25% of a thermoplastic elastomer, particularly a copolyester ester or a copolyether ester, for example the polymers sold under the trade names Hytrel (du Pont) and Arnitel (Akzo) .
  • a thermoplastic elastomer particularly a copolyester ester or a copolyether ester, for example the polymers sold under the trade names Hytrel (du Pont) and Arnitel (Akzo) .
  • the polymeric ingredients of the compositions of the invention are preferably made by melt blending (i) polyalkylene terephthalate, (ii) a polymeric grafting agent which contains reactive groups which can graft to the polyalkylene terephthalate and which comprises repeating units derived from addition polymerization of a monomer containing ethylenic unsaturation, and (iii) an addition polymer which comprises units derived from addition polymerization of a monomer containing ethylenic unsaturation.
  • the grafting agent and the addition polymer contain groups which will react with each other, and especially when a melt blending process as described above is used, part or even all of the addition polymer may be present as a reaction product with the grafting agent and/or the grafted polyester.
  • polymeric material may be a partially grafted, flexible thermoplastic composition formed by melt blending
  • a polymeric grafting agent which is a copolymer of at least 50% by weight of ethylene, 0.5-15% by weight of at least one reactive moiety selected from the group consisting of (i) an unsaturated epoxide of 4-11 carbon atoms, (ii) an unsaturated isocyanate of 2-11 carbon atoms, (iii) an alkoxy or alkyl silane wherein the alkyl group is from 1-12 carbon atoms, (iv) an alkyl halide, (v) an alkyl alpha-halo ketone or aldehyde, and (vi) oxazoline, and 0-49% by weight of a moiety selected from at least one of an alkyl acrylate, alkyl methacrylate, vinyl ether, carbon monoxide, and sulfur dioxide, where the alkyl and ether groups above are of 1-12 carbon atoms;
  • thermoplastic elastomer selected from the group consisting of a copolyester ester and a copolyether ester
  • S-(D-S) n structure where n is a whole number, S is a polystyrene block, D is a hydrogenated isoprenic block or hydrogenated butadienic block, with a content in styrene less than 50% by weight optionally grafted with maleic anhydride;
  • the stabilizing compounds used in this invention contain a thioether (-S-) linkage and a long chain alkyl group.
  • Preferred stabilizing compounds contain at least one carboxyl group in addition to the long chain alkyl group and the -S- group and preferably have the formula RC0 2 R', wherein each of R and R 1 , which may be the same or different, comprises an alkyl group containing 8 to 22 carbon atoms and at least one of R and R' contains an -S- group.
  • each of R and R' consists essentially of carbon, oxygen, hydrogen and sulfur.
  • Particularly preferred stabilizing compounds have one of the two formulae set out below:
  • each of m and p, which may be the same or different, is 1, 2 or 3; and each of n and q, which may be the same or different, is from 8 to 22 inclusive.
  • each of m and p which may be the same or different, is 1, 2 or 3, and n is from 8 to 22, inclusive.
  • stabilizing compounds as defined above are distearyl thiodipropionate (often referred to herein as DSTDP) , which is the most preferred compound and has the formula
  • dilauryl thiodipropionate and dimyristyl thiodipropionate, which are also preferred, ditridecyl thiodipropionate, mixed esters (lauryl and stearyl) of thiodipropionic acid, and pentaerythritol tetrakis (3- (dodecylthio)propionate) .
  • compositions of the invention can also include one or more flame retardants.
  • the flame retardants can be free of halogen atoms or can contain halogen atoms .
  • Suitable flame retardants are for example the known brominated and chlorinated flame retardants, including brominated aromatic and aliphatic compounds, such as decabromodiphenyl ether, ethylene bis tetrabromophthalimide, and the brominated flame retardant available from Great Lakes Chemical under the trade name Saytex BT8010.
  • the amount of halogen- containing flame retardant present will generally be at least 3%, preferably at least 5%, e.g., 5-30% or 5-25%, by weight of the composition.
  • the halogen-containing flame retardant can be used in conjunction with an inorganic flame retardant, for example antimony trioxide.
  • an inorganic flame retardant for example antimony trioxide.
  • Polyester compositions with bromine-containing flame retardants have been described, for example in copending, commonly assigned U.S. Patent Application Serial No. 07/537,558, filed on June 13, 1990 by Lunk et al and commonly assigned, U.S. Patent No. 4,332,855 (Zingheim et al) , the disclosures of which are incorporated herein by reference for all purposes .
  • ETP is a polyester alloy available from du Pont under the trade name ETP-1383 and which is described in a trade brochure for that alloy as "an intimately alloyed, permanent blend of poly(butyleneterephthalate) PBT and polyacrylic elastomers" and "intimately mixed alloys of PBT and polyacrylic elastomers"
  • PBT is polybutylene terephthalate available from Celanese under the trade name Celanex 1600A
  • EEA is an ethylene/ethyl acrylate copolymer available from du Pont under the trade name Alathon A710
  • DSTDP is distearyl thiodipropionate
  • BT93 is ethylene bis tetrabromophthalimide available from Great Lakes Chemical under the trade name Saytex BT-93
  • Sb 2 0 3 is antimony trioxide.
  • compositions were prepared by mixing the ingredients and amounts thereof in Table I in a twin screw extruder, and the compositions were then extruded over tin-coated copper 20 AWG wire, using a 1 inch (2.54 cm) extruder, to give insulating layers about 8 mil thick.
  • the ingredients were mixed at about 180 - 220°C, and extruded over the wire at about 250 * C. Samples of the insulation, about 3 inch long, were stripped from the wire, and the elongation measured initially and after aging in a circulating air oven at 180 * C for 168 hours, or at 200°C for 30 hours, or at 220 * C for 5 hours. The percentage of the original elongation which was retained after such aging was then calculated.
  • Table I in which Examples 6 and 8 are Examples of the invention and the other Examples are comparative Examples. TABLE: i

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Un mélange d'alliage de PBT comprenant une dose efficace d'un composé de stabilisation contient au moins une liaison thioéther et au moins un groupe alkyle à chaîne longue, et plus particulièrement un tel composé contenant un groupe ester carboxylique. Cette composition est particulièrement utilisée en tant que matériau d'isolation de fils.
PCT/US1994/012034 1993-11-04 1994-10-21 Compositions d'alliage de polyester thermoplastique stabilisees Ceased WO1995012636A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14724793A 1993-11-04 1993-11-04
US08/147,247 1993-11-04

Publications (1)

Publication Number Publication Date
WO1995012636A1 true WO1995012636A1 (fr) 1995-05-11

Family

ID=22520829

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/012034 Ceased WO1995012636A1 (fr) 1993-11-04 1994-10-21 Compositions d'alliage de polyester thermoplastique stabilisees

Country Status (1)

Country Link
WO (1) WO1995012636A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999030330A1 (fr) * 1997-12-08 1999-06-17 Acome Societe Cooperative De Travailleurs Fil electrique ayant un isolant mince a base de polybutyleneterephtalate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3758549A (en) * 1971-10-12 1973-09-11 Ciba Geigy Corp Poly alkanol esters of alkylthio-alkanoic acids
US3928279A (en) * 1973-03-26 1975-12-23 Teijin Ltd Glass fiber-containing aromatic polyester composition
JPS60202147A (ja) * 1984-03-27 1985-10-12 Toray Ind Inc ポリエステル樹脂組成物
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3758549A (en) * 1971-10-12 1973-09-11 Ciba Geigy Corp Poly alkanol esters of alkylthio-alkanoic acids
US3928279A (en) * 1973-03-26 1975-12-23 Teijin Ltd Glass fiber-containing aromatic polyester composition
JPS60202147A (ja) * 1984-03-27 1985-10-12 Toray Ind Inc ポリエステル樹脂組成物
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 85-293378 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999030330A1 (fr) * 1997-12-08 1999-06-17 Acome Societe Cooperative De Travailleurs Fil electrique ayant un isolant mince a base de polybutyleneterephtalate

Similar Documents

Publication Publication Date Title
JP4388721B2 (ja) ポリフェニレンスルフィドアロイ組成物
EP0194808B1 (fr) Composition de résine de polyester pour former un objet résistant au choc
AU661069B2 (en) Thermoplastic polybutylene terephthalate compositions for wire coating applications
US5824412A (en) Thermoplastic polybutylene terephthalate compositions for wire coating applications
EP0290588B1 (fr) Compositions thermoplastiques partiellement greffees
JPS632289B2 (fr)
EP0182629B1 (fr) Fil et câble électrique
US4780506A (en) Impact resistant polyethylene terephthalate/polycarbonate blends
EP0119311B1 (fr) Compositions de copolyester-carbonates
WO1995012636A1 (fr) Compositions d'alliage de polyester thermoplastique stabilisees
US5908887A (en) Polyester compositions
US6805956B2 (en) Process for coating a wire or cable with polyphenylene sulfide alloy and resulting coated wire
GB1603910A (en) Polymeric compositions
EP0185103A1 (fr) Compositions de polyester thermoplastiques flexibles
JPS61168644A (ja) 難燃性樹脂組成物
USH766H (en) Polyarylate compositions
JPH059298A (ja) ポリカプロラクトンをグラフト化したポリオレフイン共重合体、およびその製造方法
JPH0427269B2 (fr)
US4587298A (en) Composition comprising a copolyester-carbonate and a polymeric impact modifier
KR20010001126A (ko) 저발연성 및 저독성 난연 열가소성 수지 조성물
JP3070982B2 (ja) 耐衝撃性ポリエステル系樹脂組成物
EP0032587A2 (fr) Polymères réticulables par la chaleur et procédé pour leur fabrication
EP0230703A1 (fr) Compositions à mouler de polytéréphtalate de butylène à résistance au choc modifiée
EP0322405A2 (fr) Fil et câble électrique
JPS6264852A (ja) 難燃性樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP

AL Designated countries for regional patents

Kind code of ref document: A1

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

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase