+

WO1999055782A1 - Melanges polymeres obtenus a partir de polycetone et de polyamide - Google Patents

Melanges polymeres obtenus a partir de polycetone et de polyamide Download PDF

Info

Publication number
WO1999055782A1
WO1999055782A1 PCT/GB1999/001144 GB9901144W WO9955782A1 WO 1999055782 A1 WO1999055782 A1 WO 1999055782A1 GB 9901144 W GB9901144 W GB 9901144W WO 9955782 A1 WO9955782 A1 WO 9955782A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer composition
blend
polyamide
polyketone
less
Prior art date
Application number
PCT/GB1999/001144
Other languages
English (en)
Inventor
James Graham Bonner
Alan Gray
Original Assignee
Bp Chemicals Limited
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 Bp Chemicals Limited filed Critical Bp Chemicals Limited
Publication of WO1999055782A1 publication Critical patent/WO1999055782A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a polymer blend composition
  • a polymer blend composition comprising a polyketone and a polyamide.
  • polyketones are defined as linear polymers having an alternating structure of (a) units derived from carbon monoxide and (b) units derived from one or more olefinically unsaturated compounds.
  • EP 0339745 relates to a polyketone polymer composition
  • a polyketone polymer composition comprising a blend of a linear alternating polymer of carbon monoxide and at least one ethylenically unsaturated compound with a polyamide.
  • the method of producing the blend is said not to be material as long as a relatively uniform distribution of the polyamide through the polyketone is obtained. It is preferred for the blend to have intimate mixing of the polymers, i.e. microscopic distribution of polyamide through the polyketone, the size of the dispersed phase being no more than about 10 microns.
  • the polyketone polymer/polyamide polymer blend of EP 0339745 is a non-miscible blend with the polyamide existing as a discrete phase in a
  • a polymer composition comprising a polymer blend and optionally conventional additives the blend consisting of a linear polyketone having an alternating structure of (a) units derived from carbon monoxide and (b) units derived from one or more olefinically unsaturated compounds and a polyamide wherein the blend is a miscible blend having a single phase.
  • An advantage of the polymer composition of the present invention is that the polymer blend has improved mechanical properties (e.g. tensile stiffness and Izod impact strength).
  • a miscible blend of polyketone and polyamide having a single phase may be formed by selecting the viscosities of the polyketone and the polyamide such . that the viscosity of the polyamide is not significantly lower than that of the polyketone but may be significantly higher than that of the polyketone.
  • a miscible blend of a polyketone and a polyamide has a single glass transition temperature intermediate the glass transition temperatures of the individual components of the blend.
  • Melt flow rate may be used as a measure of the viscosities of the polyketone and polyamide components of the blend.
  • MFR Melt flow rate
  • the ratio of the melt flow rate of the polyketone to the melt flow rate of the polyamide should typically be less than 13, preferably less than 12, more preferably less than 10, most preferably less than 7.5, typically less than 5, for example less than 2.
  • melt flow rates of miscible blends of polyketones and polyamides are less than would be predicted from the melt flow rates of the individual components of the blend.
  • MFR blend ⁇ WjMFRi + w MFR 2 where w ⁇ and w 2 are the weight fractions of the polyketone and polyamide components of the blend respectively and MRFi and MFR 2 are the melt flow rates of the polyketone and polyamide components of the blend respectively.
  • w 2 is less than 0.1
  • the MFRbiend is preferably 25 to 75% less, more preferably 25 to 70% less, most preferably at least 25 to 65% less than the sum of WiMFRi and w 2 MFR 2 .
  • the MFRbiend is preferably 50 to 90% less, more preferably 60 to 85% less, most preferably 60 to 80% less than the sum of WiMFRi and w 2 MFR 2 .
  • the MFRbicd is preferably 60 to 95% less, more preferably 70% to 90% less, most preferably 80 to 85% less than the sum of WiMFRi and w MFR 2 .
  • the MFRbiend is preferably 80 to 125% less, more preferably 90 to 110% less, most preferably 95% to 100% less than the sum of WiMFRi and w 2 MFR 2 .
  • the present invention solves the problems defined above by selecting the polyketone and polyamide so that the miscibility of the individual components of the blend is maintained.
  • polyketones are defined as linear polymers having an alternating structure of (a) units derived from carbon monoxide and (b) units derived from one or more olefinically unsaturated compounds.
  • Suitable olefinic units are those derived from C 2 to C 12 alpha-olefins or substituted derivatives thereof or styrene or alkyl substituted derivatives of styrene.
  • olefin or olefins are selected from C to C ⁇ straight chain alpha-olefins (hereinafter termed normal alpha-olefins) and it is particularly preferred that the olefin units are either derived from ethylene or most preferred of all from a mixture of ethylene and one or more C 3 to C 6 normal alpha- olefin(s) especially propylene or butylene. In these most preferable materials it is further preferred that the molar ratio of ethylene derived units to C 3 to C ⁇ normal alpha-olefin derived units is greater than or equal to 1 most preferably between 2 and 30.
  • the polyketone will be a copolymer of ethylene/propylene/CO or ethylene/butylene/CO where the amount of units derived from propylene or butylene is in the range 0.5-10 mole % e.g. 6 mole % of the polymer.
  • the polyketone will suitably have a number average molecular weight of between 10,000 and 500,000 preferably between 15,000 and 300,000, more preferably between 20,000 and 200,000, for example, 25,000 to 250,000.
  • polyamide is meant a condensation product which contains recurring amide groups as integral parts of a polymeric chain. These polyamides are well known in the art.
  • the polyamide component of the blend may be a homopolymer of an aminomonocarboxylic acid, typically having up to 16 carbon atoms inclusive, for example, Nylon 12 or Nylon 6.
  • the polyamide component of the blend may be a copolymer of a primary diamine and a dicarboxylic acid.
  • the primary diamine is preferably a terminal primary diamine having up to 16 carbon atoms inclusive and at least two carbon atoms between the primary amino groups which are located on terminal carbon atoms of the diamine structure.
  • the diamines suitably contain aromatic moieties linking the amino groups as illustrated by phenylenediamine, 4,4'-diaminobiphenyl and di(4-aminophenyl)ether, or the linking group is cycloaliphatic as in the case of di(4-aminocyclohexyl)methane or 1,4- diaminocyclooctane.
  • the preferred diamines are acyclic terminal primary diamines of the formula H 2 N(CH 2 ) classroomNH 2 wherein n is an integer from 2 to 16 inclusive.
  • Such polymethylenediamines include trimethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine and hexadecamethylenediamine.
  • the dicarboxylic acid suitably has up to 16 carbon atoms inclusive as illustrated by aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid.
  • aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid.
  • the preferred dicarboxylic acids are aliphatic dicarboxylic acids, particularly those of the formula
  • dicarboxylic acids are oxalic acid, pimelic acid, sebacic acid, suberic acid, azelaic acid, undecanedioic acid, and adipic acid.
  • the molecular weight of the polyamide is preferably at least 5,000, most preferably in the range 10,000 to 250,000.
  • the polyamide may be present in the blend in amounts of up to 50% by weight, preferably up to 40% by weight, more preferably up to 30% by weight, most preferably up to 20% by weight, typically in the range 5 to 15% by weight, based on the total amount of the blend.
  • the polymer compositions of the present invention may contain conventional polymer additives such as anti-oxidants, melt stabilisers, UV stabilisers, heat stabilisers, toughening agents, impact modifiers, flame retardants, and mould release agents.
  • conventional polymer additives such as anti-oxidants, melt stabilisers, UV stabilisers, heat stabilisers, toughening agents, impact modifiers, flame retardants, and mould release agents.
  • the amount of the polyamide is expressed in terms of percent by weight, it is meant, unless otherwise indicated, percent by weight based on the total weight of the polymer blend, excluding further components.
  • the polymer composition of the present invention can be prepared using conventional techniques and equipment for batch or continuous blending such as a two-roll mill, a Banbury mixer, or a single/twin screw compounding extruder.
  • the scope of the present invention extends to articles (for example, containers, pipe, and tubing), films, sheet, coatings, liners, fibres and monofilaments comprising the polymer compositions as defined hereinbefore.
  • a polymer-based container wherein the polymer comprises a polymer composition as defined herein before.
  • examples of such containers include bottles, cups, bowls and trays.
  • Such a container may be made at least in part from a monolayer of the composition of the present invention. Alternatively it could be of a multi-layer construction at least one layer of which is a composition according to the present invention.
  • compositions into either containers, films or other applications are standard in the art, for example extrusion, coextrusion, injection moulding, blow-moulding and thermoforming.
  • Preferred methods of fabricating the compositions are those where orientation of the polymer is likely e.g. extrusion (film extrusion), blow-moulding and thermoforming.
  • PA1 and PA4 low viscosity Nylon 12 polymers, supplied by Huls
  • PA3 a low viscosity Nylon 6 polymer, supplied by BIP Chemicals Limited.
  • PA2 a high viscosity Nylon 12 polymer, supplied by Huls;
  • the polyamides PA1, PA2, PA3 and PA4 were cryo-ground before use.
  • Ethylene/propylene/CO copolymers PKl, PK2, PK3, PK4, and PK5
  • PK6 ethylene/butylene/CO copolymer
  • Blends were prepared using a Prism 16mm co-rotating twin screw extruder.
  • the two materials (polyamide and polyketone) were premixed before being fed to the extruder.
  • the feed, barrel and die sections of the extruder were set to the following temperatures:
  • Blend Characterisation 210, 225, and 235°C respectively when using PKl or PK5; 195, 205 and 220°C respectively when using PK2; and 190, 215 and 230 °C respectively when using PK3 or PK6. 195, 215 and 225°C respectively when using PK4.
  • a screw speed of 150 rpm was used when blending PKl, PK2, or PK4 and 200 rpm when blending PK3, PK5 or PK6.
  • a torque of 30-50%o was used throughout production runs. Blend Characterisation
  • DSC Differential scanning calorimetry
  • SEM Scanning electron microscopy
  • Samples were prepared by cryo polishing a surface on a pellet of material.
  • a Battenfeld BA 230 injection moulding machine was used to prepare specimens of the polymer compositions for tensile and Izod impact testing.
  • a flat temperature profile of 230°C was employed across the barrel zones. The temperature at the nozzle was 235°C while the mould temperature was 40°C.
  • An injection pressure of 120 bar and a cooling time of 20 seconds were used.
  • the uniaxial tensile tests were conducted using an Instron Series IX automated materials testing system at a temperature of 23°C and at 50% relative humidity.
  • the tensile testing and Izod impact were performed in accordance with ISO/R527 and ISO 180 respectively. Examples
  • Polyketone/polyamide blends containing 9 to 40% w/w polyamide were prepared using a Prism 16mm co-rotating twin screw extruder as described above. In addition, samples of the polyamides and polyketones were separately processed under the above conditions. Melting points and glass transitions (Tg) were measured by differential scanning calorimetry (DSC) and dynamic thermal analysis respectively. Scanning electron microscopy (SEM) was used to observe polymer phase structure.
  • the blends of polyketone and polyamide had glass transition temperatures intermediate those of the individual components of the blends.
  • Table 1 shows that the blends of polyketone and polyamide have glass transitions temperatures intermediate those of the individual components of the . blends.
  • Table 3 shows that the blend of Example 6 has improved processability when compared with PK3.
  • the polyketone could not be stranded through the water cooling bath of the extruder as a coherent strand.
  • the melt extrudate could be stranded, cooled and pellitised easily.
  • the blend of Example 6 has improved elongational melt strength when compared with PK3.
  • Improved elongation melt strength has significant advantages in certain applications, for example, blow moulding or fibre drawing.
  • Table 4 provides information relating to the polymer compositions (polyamide loadings, melt flow rates and phase structure).
  • Table 5 shows the mechanical properties of blends of PK5 (PK 5 has a melting point of 223°C and a melt flow rate of 32g/10 minutes under a load of 1.2kg) with PA4 (PA4 has a melting point of 180°C and a melt flow rate of 70g/10 minutes under a load of 1.2 kg).
  • the data shows improvements in modulus and impact strength of the blends when compared with PK5.
  • Table 6 shows the ratio of MFR of the polyketones : MFR of the polyamides
  • Example 1 PK1/PA1 223 42 (89.2 a ) 32 single phase
  • Example 2 PK1/PA3 224 65 (88.7 a ) 32 single phase a. predicted MFR
  • Comparative PK2/PA1 205 14 two phase Ex H (0.5-1.0 ⁇ m a )
  • Example 5 PK2/PA2 206 2.3 single phase a. particle size of the nylon dispersed phase TABLE 3 PROCESSABILITY OFPOLYKETONE/NYLON 12 BLEND
  • Example 11 PK6/10%wPA4 29 2 single phase
  • Example 12 pK6/15%wPA4 19 2 single phase

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

L'invention concerne une composition polymère comprenant un mélange polymère et éventuellement des additifs classiques, ledit mélange étant constitué d'une polycétone linéaire à structure alternée (a) de motifs dérivés du monoxyde de carbone et (b) de motifs dérivés de un ou plusieurs composés oléfiniquement insaturés et d'un polyamide. Le mélange miscible est formé en sélectionnant les viscosités de la polycétone et du polyamide de manière que la viscosité du polyamide ne soit pas largement inférieure à celle de la polycétone, mais éventuellement sensiblement supérieure à celle de la polycétone.
PCT/GB1999/001144 1998-04-29 1999-04-14 Melanges polymeres obtenus a partir de polycetone et de polyamide WO1999055782A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9809208.3A GB9809208D0 (en) 1998-04-29 1998-04-29 Polymer blends
GB9809208.3 1998-04-29

Publications (1)

Publication Number Publication Date
WO1999055782A1 true WO1999055782A1 (fr) 1999-11-04

Family

ID=10831223

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/001144 WO1999055782A1 (fr) 1998-04-29 1999-04-14 Melanges polymeres obtenus a partir de polycetone et de polyamide

Country Status (2)

Country Link
GB (1) GB9809208D0 (fr)
WO (1) WO1999055782A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106700525A (zh) * 2016-12-27 2017-05-24 上海长伟锦磁工程塑料有限公司 一种高冲击无卤阻燃pok/pa合金材料
CN111748199A (zh) * 2019-03-26 2020-10-09 现代摩比斯株式会社 用于蜗轮的组合物及使用其制造的蜗轮
CN113388246A (zh) * 2021-05-27 2021-09-14 广州辰东新材料有限公司 一种长碳链聚酰胺、聚酮和聚苯硫醚合金材料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0339745A2 (fr) * 1988-04-29 1989-11-02 Shell Internationale Researchmaatschappij B.V. Compositions de polycétones
US5266392A (en) * 1991-09-16 1993-11-30 Exxon Chemical Patents Inc. Plastomer compatibilized polyethylene/polypropylene blends

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0339745A2 (fr) * 1988-04-29 1989-11-02 Shell Internationale Researchmaatschappij B.V. Compositions de polycétones
US5266392A (en) * 1991-09-16 1993-11-30 Exxon Chemical Patents Inc. Plastomer compatibilized polyethylene/polypropylene blends

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106700525A (zh) * 2016-12-27 2017-05-24 上海长伟锦磁工程塑料有限公司 一种高冲击无卤阻燃pok/pa合金材料
CN106700525B (zh) * 2016-12-27 2018-12-18 上海长伟锦磁工程塑料有限公司 一种高冲击无卤阻燃pok/pa合金材料
CN111748199A (zh) * 2019-03-26 2020-10-09 现代摩比斯株式会社 用于蜗轮的组合物及使用其制造的蜗轮
CN113388246A (zh) * 2021-05-27 2021-09-14 广州辰东新材料有限公司 一种长碳链聚酰胺、聚酮和聚苯硫醚合金材料及其制备方法
CN113388246B (zh) * 2021-05-27 2022-10-25 广州辰东新材料有限公司 一种长碳链聚酰胺、聚酮和聚苯硫醚合金材料及其制备方法

Also Published As

Publication number Publication date
GB9809208D0 (en) 1998-07-01

Similar Documents

Publication Publication Date Title
EP2606083B1 (fr) Compositions, procédés et articles produits par élaboration d'un mélange de polyamides avec des polymères oléfine-anhydride maléique
US8420221B2 (en) Semiaromatic moulding compositions and uses of these
EP2670805B1 (fr) Composition thermoplastique obtenue par mélange à chaud
US12139610B2 (en) Thermoplastic polymer composition having improved mechanical properties
US5436294A (en) Polyphthalamide blends
JPH06504304A (ja) ポリアミド組成物
KR20090107556A (ko) 폴리아미드 및 폴리(락트산) 기재 복합체 물질, 이의 제조 방법 및 용도
JPH08509771A (ja) 無機充填剤配合コポリアミド組成物
CN1329448C (zh) 聚酰胺模塑材料、可由其生产的模塑制品及其用途
EP1198520B1 (fr) Procede et composition pour reduire la formation de depots de moulage pendant le moulage de polyamides
EP1325081A2 (fr) Melanges de polyamide translucide
US20140066568A1 (en) Polyamide resin blends
KR102452073B1 (ko) 유리섬유 보강 폴리아마이드 수지 조성물, 이의 제조방법 및 이를 포함하는 성형품
WO1999055782A1 (fr) Melanges polymeres obtenus a partir de polycetone et de polyamide
EP0812869A2 (fr) Composition de polyphthalamide
JPH04108855A (ja) プラスチック組成物およびその用途
WO2024024330A1 (fr) Composition de résine, et article moulé
GB2318120A (en) Crystalline aromatic polyamide resin composition
CN111117234A (zh) 一种冲击强度改善的增强聚酰胺56组合物及其应用
JP7644020B2 (ja) 強化用繊維を含み、高弾性率安定性を有するコポリアミド組成物およびその使用
KR20250042785A (ko) 수지 조성물, 및, 성형품
JP2000186202A (ja) ポリアミド樹脂組成物
JP2023129250A (ja) ポリアミド樹脂組成物、ポリアミド樹脂成形体およびその製造方法
KR20240004688A (ko) 폴리아미드 및 유리 섬유 기반 조성물 및 위생 및 물 관리 분야에서의 이의 용도
JPH0726021B2 (ja) ポリアミド組成物

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 CY DE DK ES FI 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
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