WO1996005253A1 - Reduction de la viscosite fondue de copolymere bloc cristallin liquide contenant du polycarbonate - Google Patents

Reduction de la viscosite fondue de copolymere bloc cristallin liquide contenant du polycarbonate Download PDF

Info

Publication number
WO1996005253A1
WO1996005253A1 PCT/US1995/010252 US9510252W WO9605253A1 WO 1996005253 A1 WO1996005253 A1 WO 1996005253A1 US 9510252 W US9510252 W US 9510252W WO 9605253 A1 WO9605253 A1 WO 9605253A1
Authority
WO
WIPO (PCT)
Prior art keywords
flexible
block copolymer
block
coil
liquid crystalline
Prior art date
Application number
PCT/US1995/010252
Other languages
English (en)
Original Assignee
Akzo Nobel Nv
Kim, Ki-Soo
Dashevsky, Sophia
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 Akzo Nobel Nv, Kim, Ki-Soo, Dashevsky, Sophia filed Critical Akzo Nobel Nv
Publication of WO1996005253A1 publication Critical patent/WO1996005253A1/fr

Links

Classifications

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

Definitions

  • liquid crystalline polymers LCPs
  • various resins including those of polycarbonate, to achieve certain desired characteristics including: improved flow; reinforcement; and blend toughness.
  • LCPs liquid crystalline polymers
  • thermotropic segmented liquid crystalline block copoly er containing rod blocks, with a flexible spacer therein, and flexible polyester coil blocks is described as a novel composition which is suitable for blending with certain flexible coil polymers in PCT WO 93/01238.
  • the flexible coil polymers to which this LCP can be added can be "selected from known polyester and polyamide polymer" (see page 4, lines 19-20).
  • the flexible coil block units of the LCO need to be "substantially similar to the matrix material" (see page 5, lines 13-14) . Therefore, this patent publication teaches away from blends of a polycarbonate, rather than either a polyamine or polyester, and this block copolymer additive.
  • the present invention relates to a process for reducing the melt viscosity of a polycarbonate resin which is being subjected to shearing in the melt which comprises adding to the polycarbonate resin an effective amount for such reduction of the melt viscosity of the resin of a thermotropic segmented liquid crystalline block copolymer containing rod blocks with a flexible spacer therein and flexible polyester coil blocks.
  • the present invention is applicable for use conventionally known polycarbonate resins.
  • the liquid crystalline copolymer additive which, when added to the forgoing type of polycarbonate resin, reduces the melt viscosity of the resulting blend, as compared to the neat polycarbonate resin, under the shearing conditions of melt processing.
  • the liquid crystalline polymer which is added is the type of liquid crystalline segmented block copolymer that is described in U.S. Ser. No. 53,838, filed April 28, 1993 and in PCT International Publication No. WO 93/01238, January 21, 1993 in which the respective blocks in the copolymer are "rod” and “flexible coil” blocks, respectively.
  • the liquid crystalline segmented block copolymer which is intended to be added to the polycarbonate resin can be envisioned to have the general formula:
  • Rod indicates the mesogenic block with x, normally from 2 to 15, indicating the number of mesogen repeats
  • "Coil” indicating the block comprising a flexible coil polyester segment, with y, normally from about 2 to about 25, indicating the number of repeat units in the flexible polyester block
  • p representing the repeat units of Rod and coil blocks.
  • the mole % rod in the total polymer can range from about 4% to about 80%.
  • the repeat unit p can range from about 1 to about very large numbers such as 50-500 for high molecular weight segmented block copolymers.
  • Polyethylene terephthalate or polybutylene terephthalate comprise the preferred coil segments.
  • the rod length which is responsible for liquid crystalline properties for the block copolymer additive and the % block in the matrix/block copolymer combination need to be appropriately balanced within the general ranges given above.
  • the amount of the liquid crystalline copolymer which can be added in accordance with the present invention will be up to about 10 %, by weight of the polycarbonate resin, preferably from about 0.1 % to about 5 %.
  • the type of mesogenic unit for the rod portion of the LCP can be appropriately selected from known mesogenic units (main chain thermotropic liquid crystal polymers) including those of the general structure:
  • mesogenic unit which can be employed has the structure -Ar-C(O) -NH-Ar-NH-C(0)-Ar-.
  • the commercial rod polymers based on oxybenzoate units, 4,4'-biphenylene terephthalate units, and oxynaphthalene carboxylate units (the latter two including copolymers with the oxybenzoate units) can be especially preferred.
  • a particularly preferred structure for the "Rod" or mesogenic unit is of the general type described by Ober et al. in Polymer Journal, Vol. 14, No. 1, pp. 9-17 (1982) and, in view of its presence in a block copolymer as contrasted to the Ober et al. homopolymer, has the structure:
  • n can range from 2 to 10, e.g., 4 and x can range, for example, from about 5 to about 15.
  • These mesogenic units can be characterized as aromatic ester mesogenic units containing a flexible alkylene spacer.
  • the "triad" structure comprising three linearly-aligned aromatic rings, the bis(p-carboxyphenyl) terephthalate moiety, and a flexible spacer of varying length (n) , which can be alkylene or alkylene with heteroatom (e.g., oxygen) interruption, is particularly preferred as depicted above.
  • the mesogenic units contain "diad” or “dyad” linkages, - OC(O)ArOC(O)ArC(O)-, at either end adjacent the connection points with the coil block segments.
  • the block copolymers described herein will have a molecular weight of no less than about 7,000 to about 8,000.
  • thermotropic LCP block e.g., triad with flexible spacer block and polyester block
  • structure (I) is not a true rigid-rod, it readily assumes an extended chain structure and forms nematic mesophases and consequently high modulus/strength structures.
  • the high strength chain extended block polymer molecules would be very finely dispersed in the PET matrix and would be expected to have potential as a high performance molecular composite material.
  • thermotropic liquid crystal block copolymer can be synthesized by the process shown in U.S. Serial No. 53,838, filed April 28, 1993.
  • oligomers of the mesogen are prepared in one reactor and oligomers of the selected polyester are prepared in a second reactor, each set of oligomers having appropriate complementary end groups for later reaction of each set of oligomers.
  • the previously formed oligomers are allowed to react to one another to form the desired block copolymer.
  • the sizes of the respective oligomers controls the lengths of the respective blocks. More preferably, it is synthesized by the one reactor process described and claimed in U.S. Patent No. 5,194,569, which is incorporated herein by reference.
  • an c., ⁇ -bis(hydroxybenzoyloxy) alkane is the preferred reagent for reaction with an aromatic acid chloride to form a functionalized liquid crystal oligomer containing the desired mesogenic unit or units and then reacting this oligomer with either a chosen polyester oligomer or the reagents for synthesizing such a polyester oligomer.
  • the most preferred synthesis procedure is described in U.S. Patent No.
  • thermotropic liquid crystalline block copolymer analogous to the preferred structures shown in PCT International Publication No. WO93/01238 containing five arylene groups in the mesogen with a butylene spacer and a polybutylene terephthalate (PBT) block.
  • PBT polybutylene terephthalate
  • TR-4 monomer 1,4- bis(p-hydroxybenzoyloxy) butane
  • TR diacid dichloride 4,4'- (terephthaloyldioxy)dibenzoyl dichloride
  • TR-4 monomer (2.97 g, 0,009 mole), TR diacid dichloride (5.31 g, 0.012 mole), BHBT oligomer (2.97 g, 0.00297 mole) and 70 ml of 1-chloronaphthalene solvent were placed in a 250 ml flask equipped with a stirrer and were heated at 170°C. under nitrogen for one hour. The temperature was then slowly increased to 250°C. and was kept at that temperature for twenty-two hours. To the resulting reaction medium was then added 0.1 g of 1,4- butanediol. After one hour the reaction was terminated. After cooling methanol (80 ml) was added, the product was collected by filtration.
  • the polymer was purified in boiling acetone five times and was vacuum dried at 110°C. overnight. The yield was about 94% by weight of the theoretical.
  • the polymer had an inherent viscosity of 0.45 dl/g in p-chlorophenol/tetra-chloroethane (6/4 wt/wt) at 25°C. , a melting point of 220°C. (by DSC), and a clearing temperature of greater than 350°C (by POM) .
  • This Example shows the melt flow index (MFI) properties of neat polycarbonate (PC) , and two samples containing thermotropic liquid crystalline (LC) block copolymers of the general type shown in PCT International Publication No. WO93/01238.
  • MFI melt flow index
  • Blends of the PC and the liquid crystalline block copolymers were prepared by dry blending at 175°C for four hours under nitrogen and melt blending in a CSI mixing extruder at 277°/270°C.
  • As-received PC (LEXAN LX 105 Brand) was extruded through the CSI extruder under the same conditions and was used as a control.
  • the melt indices of the PC containing the LC block copolymers are higher than that of the control PC:
  • TR-4/PBT the thermotropic liquid crystalline block copolymer of 0.5 dl/g inherent viscosity comprising a "triad" mesogenic block unit with C 4 alkylene spacer and a polybutylene terephthalate (PBT) flexible coil block as described as a preferred embodiment in PCT International Publication No. WO93/01238.
  • Pentad-4/PBT a copolymer of 0.45 dl/g inherent viscosity, as made in Example 1 which is analogous to the TR-4/PBT copolymer. It comprises a mesogen unit of the structure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

On peut réduire la viscosité fondue d'une résine de polycarbonate soumise au cisaillement dans le bain de fusion, en ajoutant dans cette dernière, pour assurer le maintien du poids molaire caractéristique, une dose efficace d'un copolymère bloc cristallin liquide segmenté contenant des blocs à tiges, contenant un bras écarteur flexible, et des blocs de polyester souples à spirales.
PCT/US1995/010252 1994-08-15 1995-08-11 Reduction de la viscosite fondue de copolymere bloc cristallin liquide contenant du polycarbonate WO1996005253A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29027994A 1994-08-15 1994-08-15
US08/290,279 1994-08-15

Publications (1)

Publication Number Publication Date
WO1996005253A1 true WO1996005253A1 (fr) 1996-02-22

Family

ID=23115287

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/010252 WO1996005253A1 (fr) 1994-08-15 1995-08-11 Reduction de la viscosite fondue de copolymere bloc cristallin liquide contenant du polycarbonate

Country Status (1)

Country Link
WO (1) WO1996005253A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7459494B2 (en) 2002-07-31 2008-12-02 The Procter & Gamble Company Phase change solvents for thermoplastic elastomers
US7468411B2 (en) 2002-07-31 2008-12-23 The Procter & Gamble Company Thermoplastic elastomer compositions containing a phase change solvent and selected processing oils
US7524984B2 (en) 2002-07-31 2009-04-28 The Procter & Gamble Company Phase change solvents
US7563838B2 (en) 2002-07-31 2009-07-21 The Procter & Gamble Company Phase change solvents for thermoplastic polymers
CN112940449A (zh) * 2019-12-11 2021-06-11 波音公司 用于增材制造的可加工聚合物、方法和装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4438236A (en) * 1979-11-30 1984-03-20 Imperial Chemical Industries Plc Compositions of melt-processable polymers having improved processability
EP0265791A2 (fr) * 1986-10-31 1988-05-04 General Electric Company Compositions de résine de polycarbonate et de copolyestercarbonate à module d'élasticité élevé
US5258486A (en) * 1992-07-31 1993-11-02 Akzo Nv Synthesis of block liquid crystal copolymer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4438236A (en) * 1979-11-30 1984-03-20 Imperial Chemical Industries Plc Compositions of melt-processable polymers having improved processability
EP0265791A2 (fr) * 1986-10-31 1988-05-04 General Electric Company Compositions de résine de polycarbonate et de copolyestercarbonate à module d'élasticité élevé
US5258486A (en) * 1992-07-31 1993-11-02 Akzo Nv Synthesis of block liquid crystal copolymer

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7459494B2 (en) 2002-07-31 2008-12-02 The Procter & Gamble Company Phase change solvents for thermoplastic elastomers
US7468411B2 (en) 2002-07-31 2008-12-23 The Procter & Gamble Company Thermoplastic elastomer compositions containing a phase change solvent and selected processing oils
US7524984B2 (en) 2002-07-31 2009-04-28 The Procter & Gamble Company Phase change solvents
US7563838B2 (en) 2002-07-31 2009-07-21 The Procter & Gamble Company Phase change solvents for thermoplastic polymers
CN112940449A (zh) * 2019-12-11 2021-06-11 波音公司 用于增材制造的可加工聚合物、方法和装置

Similar Documents

Publication Publication Date Title
US5541240A (en) Method for making blends of liquid crystalline and isotropic polymers
EP0044175B2 (fr) Composition à base de polycarbonate et de polyester entièrement aromatique
US4792587A (en) Resin composition which exhibits anisotropism when melted
JPH02113063A (ja) フリーフローポリアミド成形材料及びブレンド
CA1261515A (fr) Melange de polyester entierement aromatique et de poly(ester-amide) pouvant donner une phase fondue anisotrope
EP0169947B1 (fr) Mélange à l'état fondu de polyesters entièrement aromatiques non thermotropiques et thermotropiques
US5346970A (en) Blend of polyethylene terephthalate matrix and thermotropic liquid crystal block copolymer
CA2069492A1 (fr) Polyesters aromatiques et methode de preparation
US4952334A (en) Compatible blends of main chain and side chain thermotropic liquid crystal polymers
WO1996005253A1 (fr) Reduction de la viscosite fondue de copolymere bloc cristallin liquide contenant du polycarbonate
US5391689A (en) Aromatic polyester and polyester resin composition
KR930009411B1 (ko) 액정 중합체
US5679288A (en) Blend of polyphosphate flame retardant and liquid crystalline additive
US5508338A (en) Compatibilized blend of polycarbonate, polyester and liquid crystalline additive
US5142017A (en) Aromatic polyester and a process for producing the same
JPH10502404A (ja) 液晶コポリ（エステル−イミド）およびその製造方法
CA2145457A1 (fr) Polyesters a chaine rigide et methode de preparation
JPH0718065A (ja) サーモトロピック液晶芳香族ポリエステル類
Song et al. Synthesis and characterization of a series of wholly aromatic copolyesters containing 2‐(α‐phenylisopropyl) hydroquinone moiety
US5418299A (en) Blend of flexible coil polymer and themotropic liquid crystalline oligomer
US5157103A (en) Copolymer of liquid crystal triad aromatic ester mesogenic unit with flexible spacer and polyester
WO1994020552A1 (fr) Traitement ameliore de polymeres a tres haute masse moleculaire
JPH0655883B2 (ja) 非サ−モトロピツクおよびサ−モトロピツク全芳香族ポリエステルの溶融ブレンド
Kimura et al. Novel network morphology of poly (p‐oxybenzoyl)
WO1994010243A1 (fr) Polymerisation a l'etat solide d'un melange de polyester

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA 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

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