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 PDFInfo
- 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
Links
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 title claims abstract description 15
- 229920000515 polycarbonate Polymers 0.000 title description 11
- 239000004417 polycarbonate Substances 0.000 title description 11
- 239000000155 melt Substances 0.000 claims abstract description 13
- 229920000728 polyester Polymers 0.000 claims abstract description 13
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 12
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 12
- 125000006850 spacer group Chemical group 0.000 claims abstract description 6
- 238000010008 shearing Methods 0.000 claims abstract description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- -1 polybutylene terephthalate Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 12
- 229920000106 Liquid crystal polymer Polymers 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- WPWSKDAAFNCELW-UHFFFAOYSA-N 4-(4-hydroxybenzoyl)oxybutyl 4-hydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCCCCOC(=O)C1=CC=C(O)C=C1 WPWSKDAAFNCELW-UHFFFAOYSA-N 0.000 description 1
- QOBMQTZOKFYGNH-UHFFFAOYSA-N 4-(4-hydroxybutoxycarbonyl)benzoic acid Chemical compound OCCCCOC(=O)C1=CC=C(C(O)=O)C=C1 QOBMQTZOKFYGNH-UHFFFAOYSA-N 0.000 description 1
- UZSSRHAULVYOBH-UHFFFAOYSA-N 4-[4-(4-carboxyphenoxy)carbonylbenzoyl]oxybenzoic acid Chemical group C1=CC(C(=O)O)=CC=C1OC(=O)C1=CC=C(C(=O)OC=2C=CC(=CC=2)C(O)=O)C=C1 UZSSRHAULVYOBH-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 229920004142 LEXAN™ Polymers 0.000 description 1
- 239000004418 Lexan Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KRBOHJMLLYJDBX-UHFFFAOYSA-N bis(4-carbonochloridoylphenyl) benzene-1,4-dicarboxylate Chemical compound C1=CC(C(=O)Cl)=CC=C1OC(=O)C1=CC=C(C(=O)OC=2C=CC(=CC=2)C(Cl)=O)C=C1 KRBOHJMLLYJDBX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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
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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)
- 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.
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)
| 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)
| 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 |
-
1995
- 1995-08-11 WO PCT/US1995/010252 patent/WO1996005253A1/fr active Application Filing
Patent Citations (3)
| 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)
| 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 |
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