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WO1993001238A1 - Melange d'un polymere en pelote souple et d'un copolymere bloc segmente a cristaux liquides thermotropes - Google Patents

Melange d'un polymere en pelote souple et d'un copolymere bloc segmente a cristaux liquides thermotropes Download PDF

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Publication number
WO1993001238A1
WO1993001238A1 PCT/US1992/005670 US9205670W WO9301238A1 WO 1993001238 A1 WO1993001238 A1 WO 1993001238A1 US 9205670 W US9205670 W US 9205670W WO 9301238 A1 WO9301238 A1 WO 9301238A1
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WO
WIPO (PCT)
Prior art keywords
pbt
lcp
blend
flexible coil
blends
Prior art date
Application number
PCT/US1992/005670
Other languages
English (en)
Inventor
Richard J. Farris
Byung-Wook Jo
Original Assignee
University Of Massachusetts At Amherst
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 University Of Massachusetts At Amherst filed Critical University Of Massachusetts At Amherst
Priority to JP5502375A priority Critical patent/JPH06508879A/ja
Priority to EP19920915938 priority patent/EP0593664A4/en
Publication of WO1993001238A1 publication Critical patent/WO1993001238A1/fr

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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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences

Definitions

  • LCPs main chain thermotropic liquid crystal polymers
  • LC phase When processed in the mesophase state, LCPs generally provide many advantages over random coil polymers because most LCPs have an intrinsically low melt viscosity in the nematic melt and a tendency toward easy orientation in the flow direction. Furthermore, it is well known that oriented LCPs relax very slowly and therefore the orientation developed in a processed melt may be retained after solidification. Under controlled processing conditions droplets of the LC phase can be induced to form elongated or even fibrillar domains in which the molecular chains are highly aligned yielding self-reinforcement.
  • TLCP with a flexible coil-like polymer may achieve the characteristics of TLCP, but at a lower cost.
  • the TLCP which is initially dispersed as spheres or droplets in the matrix can be elongated in adequate flow-fields to give
  • poly(ethylene terephthalate), poly (butylene terephthalate), polycarbonate, polyamide and polyethers as matrix materials are: Shin et al., Polymer. Eng. and Sci., Vol. 30, No. 1, 13-21, which describes blends of poly (ethylene terephthalate) and a very high molecular weight LCP with a long flexible spacer, and M. Pracella, Makromol. Chem. 187, 2387-2400, which shows blends of poly(butylene terephthalate) with a polymer containing a triad aromatic ester mesogenic unit containing a decamethylene flexible spacer unit.
  • crystalline "copolyester” based on 60 mole % parahydroxy benzoic acid (PHB) and 40 mole % PET; work by Misra and co- workers on blends of PET with an LCP copolymer of PET and PHB; and the general work (footnotes 47-68) which relates to the miscibility behavior of blends containing an LCP including work involving liquid crystalline copolyesters of PET and PHB with other, flexible-chain polymers. All of this work has involved use of a LC copolymer additive which was essentially random in nature.
  • the most promising way to get good dispersion would be to prepare block or graft copolymers which contain both rigid and flexible moieties.
  • the flexible blocks which are attached to the rigid blocks can increase the entropy of mixing to result in uniform dispersion and good adhesion of the rigid blocks in a flexible polymer matrix, (when the aggregation energy of rigid blocks is correspondingly low).
  • block/matrix blends such as poly(p-phenylene terephthalamide) /nylon and poly(p-benzamide) /nylon block copolymers blended into a nylon matrix showed improved properties over the normal blends with
  • block copolymers of rigid and flexible polymers are considered by the present inventors to have great potential in self-reinforced composites.
  • dilute solutions must be employed in order to obtain good dispersion because the rod-like molecules aggregate above a certain critical concentration.
  • a TLCP in-situ composite would be expected to have the same merits as lyotropic LCP systems, but would have the advantages of melt processability and well dispersed mixing.
  • the present invention in its broadest embodiment, relates to a blend which comprises a flexible coil polymer matrix and a thermotropic liquid crystal block, as contrasted to random, copolymer comprising segmented mesogenic and segmented flexible coil blocks.
  • the flexible coil blocks are substantially similar to the flexible coil polymer of the matrix.
  • the present invention in a more narrow, but preferred, embodiment relates to a blend of a polyester, such as
  • PBT polybutylene terephthalate
  • polyester such as PBT
  • the polyester matrix is substantially similar in structure to the polyester resin forming one component of the liquid crystal
  • polyalkylene moieties in the polyester in the matrix and segmented block copolymer are identical, for example,
  • liquid crystalline segmented block copolymer which is intended to be added to the selected flexible coil polymer matrix can be envisioned to have the general formula:
  • Rod indicates the mesogenic block with x, normally from 2 to 50, indicating the number of mesogen repeats
  • "Coil” indicating the block comprising the flexible coil polymer
  • y normally from about 2 to about 50, indicating the number of repeat units of the flexible coil polymer
  • 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.
  • block copolymer additive which is the subject of U.S. Serial No. , filed on even date herewith
  • % block in the matrix/block copolymer combination need to be appropriately balanced within the general ranges given above so that there is liquid crystalline properties imparted to the additive so that appropriate phase separation, with creation of domains of rod and coil, is created with a concomitant reinforcement of the entire blend.
  • the flexible coil polymer matrix for the instant blend invention can be selected from known polyester and polyamide polymers such as poly(ethylene terephthalate), poly(butylene terephthalate) nylon-6,6, nylon 6, amorphous nylons, and polyester thermoplastic elastomers based on PBT and
  • the type of mesogenic unit for the rod portion of the LC copolymer can be appropriately selected from known mesogenic units (main chain thermotropic liquid crystal polymers) including those of the general structure:
  • X can be (CH 2 ) n , where n is an integer of from 2 to 10, m can range from about 2 to about 50, and Y and Z can each be -C(O)O- or -C(O)NH- or can be a single bond between two carbon atoms, and A can be p- phenylene, 1,4-, 2,6-, or 1,5-naphthylene, monosubstituted phenylene with methyl, chloro, or phenyl substitution;
  • -ArCH CHAr-, where Ar is a phenyl ring, -AR-C(O)OAr-,
  • the commercial rod polymers based on oxybenzoate units, 4,4'-biphenylene terephthalate units, and oxynaphthalene carboxylate units can be especially preferred.
  • the flexible coil block in the block copolymer segment described above should be substantially similar to the matrix material by being either substantially the same in regard to the repeat units of the matrix or by having some of the same repeat units. Thus, if a PET matrix is chosen a PET block segment in the copolymer would be selected.
  • thermotropic LCP block 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 a PBT matrix and would be expected to have potential as a high performance molecular composite material.
  • the LCP segmented block copolymer (triad mesogenic unit with flexible spacer and polyester segment) can be
  • low oligomers of the triad oligomer can be prepared by the following reaction:
  • Ar is paraphenylene
  • a can be 2-50
  • b can be 2-50
  • n is the length of the spacer, e.g., 2-10, 2 or 4 most preferably
  • T' is (para)-OCArCO-.
  • low oligomers of the polyester e.g., preferably either ethylene terephthalate or butylene terephthalate
  • the polyester e.g., preferably either ethylene terephthalate or butylene terephthalate
  • the end-groups of the triad oligomer and the polyester oligomers can be selected as either acyl chloride or hydroxyl, respectively (or the converse), depending on the chosen preselected stoichiometry.
  • the oligomers can be allowed to react with each other to produce the desired block copolymer
  • the same block copolymer may be prepared from acyl chloride end-groups on the triad oligomer and hydroxyl end-groups on the polyester oligomer in the two step sequence shown below:
  • both the length of the blocks and the composition of the copolymer may be controlled.
  • the sizes of the oligomers can be controlled by the stoichiometric ratios of the triad monomer to
  • Triad-4" poly(butylene terephthalate) (PBT) copolymer (B) with an average block size of five triad-4 terephthalate and eight butylene terephthalate units in the corresponding blocks.
  • PBT poly(butylene terephthalate)
  • B poly(butylene terephthalate) copolymer
  • the LCP copolymer used was a block polymer made in
  • Example 1 (hereinafter termed "LCP-b-PBT (5/8)"), which consisted of blocks of a triad aromatic ester mesogenic unit containing an alkylene spacer (C 4 alkylene) of the type described by Lenz et al. in Polym. J., Vol. 14, p. 9 (1982).
  • the chemical structure of the LC block polymers was as shown below:
  • the tetramethylene [(CH 2 ) 4 ] groups between the rigid mesogen blocks and the PBT block may increase the compatibility and
  • PBT 225 - - - - - - 33 000 a Melt transition temperature from DSC thermogram.
  • Blends of LCP-b-PBT with PBT in various compositions were prepared by solution blending. Dilute (less than 5 wt%) solutions of PBT and LCP-b-PBT in trifluoroacetic acid at room temperature were mixed together in appropriate portions and were co-precipitated in methanol, then were washed with 5% NaHC0 3 solution, water and methanol followed by drying at 130°C under vacuum overnight. The concentration of LCP-b-PBT was varied over the range of 5-50 wt%.
  • the extrudate was elongated by a take-up machine below the die.
  • the draw ratio (DR) was determined by measuring the reduction in fiber diameter by either laser diffraction or optical microscopy. It is understood that the term “draw ratio” as used herein is to be construed as relating to "drawn as spun”, also termed “jet draw” or "jet stretch”.
  • Tensile properties were measured at 10 or 20 mm/min cross-head speed on an Instron Mechanical Tester at ambient conditions in the laboratory. Each tensile property was averaged over six tests.
  • Morphology was characterized using a JEOL [JSM-35C] scanning electron microscope with an accelerating voltage of 25 kv.
  • Fracture surfaces were prepared by snapping the materials after cooling in liquid nitrogen. To observe the deformation of dispersed LCP-b-PBT particles in the blend, the strands stretched by the tensile tester were also examined. These samples were mounted on aluminum stubs and sputtered with gold using an SPI Sputter Coater for enhanced conductivity. A Perkin-Elmer model DSC-7 was used for thermal
  • thermograms of the LCP-b-PBT and the pure PBT were taken.
  • the parameters determined from the thermograms are given in Table 1, above.
  • the crystal to nematic transition for the LCP-b-PBT and isotropic melt for the PBT were 210°C and 225°C, respectively.
  • the cooling cycle thermogram showed a considerable super-cooling of the mesophase to solid crystal transition.
  • T m melting transition
  • the pure LCP-b-PBT fiber fracture surfaces were also imaged by SEM.
  • the fiber was extruded through a die of a capillary rheometer.
  • extruded strand of pure LCP-b-PBT with draw ratios over 1 could not be obtained because of the fibers brittle behavior.
  • IV 0.51
  • the spherical particle shape was understandable since the semirigid-rod geometry of the TR-4 segments caused them to align side by side in elongated LCP-b-PBT domains.
  • Fibers of LCP-b-PBT/PBT blend and pure PBT were spun at
  • LCP-b-PBT draw ratio ultimate strength MPa. initial modulus (GPa) content extrusion .temp. extrus ion temp.
  • the following Table shows the tensile strength (MPa) of LCP-b-PBT/PBT (20/80 w/w) blends versus draw ratio when extruded at 245°C and 255°C.
  • the LCP-b-PBT domains were 0.05 ⁇ m to 0.1 ⁇ m in size and uniformly well dispersed over the PBT matrix.
  • the LCP-b-PBT was not totally miscible with the matrix, but the adhesion between the two materials was excellent.
  • the initial moduli for 20% LCP-b-PBT fibers extruded at 245°C and 255°C were 13.0 GPa and 14.2 GPa amounting to an increase of 6 to 7 times that for pure PBT.

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

Abstract

L'invention décrit de nouveaux copolymères en blocs segmentés comprenant des blocs mésogéniques (ou ''en barre''), ainsi que des blocs de polymère en pelote souple, spécialement conçus pour se mélanger avec une matrice de polymère en pelote souple sensiblement similaire, afin d'améliorer les propriétés mécaniques de ladite matrice. Par exemple, on a préparé des mélanges de téréphtalate de polybutylène (PBT) avec un copolymère en bloc à cristaux liquides contenant un térétphtalate de polytétraméthylène 4,4'-téréphtaloyldioxydibenzoate-b-polybutylène (LCP-b-PBT) par précipitation provoquée par un solvant commun, par séchage et par filature à chaud à travers une filière capillaire, afin de produire un monofilament. Dans tous les mélanges, les régions de LCP-b-PBT ont présenté une dimension inférieure à 0,1 νm ainsi qu'une dispersion ultrafine et uniforme. Même si les mélanges n'ont été que modérément allongés pour être transformés en fibrilles, l'adhérence interfaciale entre le LCP-b-PBT et le PBT pur s'est avérée excellente.
PCT/US1992/005670 1991-07-08 1992-07-07 Melange d'un polymere en pelote souple et d'un copolymere bloc segmente a cristaux liquides thermotropes WO1993001238A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP5502375A JPH06508879A (ja) 1991-07-08 1992-07-07 柔軟なコイルポリマーとサーモトロピック液晶セグメント化ブロックコポリマーの配合物
EP19920915938 EP0593664A4 (en) 1991-07-08 1992-07-07 Blend of flexible coil polymer and thermotropic liquid crystal segmented block copolymer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US72660091A 1991-07-08 1991-07-08
US726,600 1991-07-08

Publications (1)

Publication Number Publication Date
WO1993001238A1 true WO1993001238A1 (fr) 1993-01-21

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Application Number Title Priority Date Filing Date
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Country Status (4)

Country Link
EP (1) EP0593664A4 (fr)
JP (1) JPH06508879A (fr)
CA (1) CA2113114A1 (fr)
WO (1) WO1993001238A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996009349A1 (fr) * 1994-09-20 1996-03-28 Akzo Nobel N.V. Melange de polycarbonate et de polyester rendus compatibles par un additif liquide cristallin

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4228218A (en) * 1977-11-04 1980-10-14 Motowo Takayanagi Polymer composite material
US4792587A (en) * 1986-03-24 1988-12-20 Polyplastics Co., Ltd. Resin composition which exhibits anisotropism when melted

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4228218A (en) * 1977-11-04 1980-10-14 Motowo Takayanagi Polymer composite material
US4792587A (en) * 1986-03-24 1988-12-20 Polyplastics Co., Ltd. Resin composition which exhibits anisotropism when melted

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Polymer Engineering and Science, January 1990, Vol. 30 (SHIN), "Speculation on Interfacial Adhesion and Mechanical Properties of Blends of PET and Thermotropic polyester with Flexible Spacer Groups", pages 13-21, see the entire document. *
See also references of EP0593664A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996009349A1 (fr) * 1994-09-20 1996-03-28 Akzo Nobel N.V. Melange de polycarbonate et de polyester rendus compatibles par un additif liquide cristallin
US5508338A (en) * 1994-09-20 1996-04-16 Akzo Nobel Nv Compatibilized blend of polycarbonate, polyester and liquid crystalline additive

Also Published As

Publication number Publication date
EP0593664A4 (en) 1994-06-15
CA2113114A1 (fr) 1993-01-21
EP0593664A1 (fr) 1994-04-27
JPH06508879A (ja) 1994-10-06

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