EP0764195A1 - Poly(esteramides) cristallins liquide thermotropiques - Google Patents

Poly(esteramides) cristallins liquide thermotropiques

Info

Publication number
EP0764195A1
EP0764195A1 EP95919897A EP95919897A EP0764195A1 EP 0764195 A1 EP0764195 A1 EP 0764195A1 EP 95919897 A EP95919897 A EP 95919897A EP 95919897 A EP95919897 A EP 95919897A EP 0764195 A1 EP0764195 A1 EP 0764195A1
Authority
EP
European Patent Office
Prior art keywords
monomer repeat
repeat unit
fiber
liquid crystalline
esteramide
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.)
Withdrawn
Application number
EP95919897A
Other languages
German (de)
English (en)
Inventor
Balaram Gupta
Matthew J. Bylicki
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.)
CNA Holdings LLC
Original Assignee
Hoechst Celanese 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 Hoechst Celanese Corp filed Critical Hoechst Celanese Corp
Publication of EP0764195A1 publication Critical patent/EP0764195A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides

Definitions

  • This invention relates generally to thermotropic liquid crystalline polymers, and more specifically to liquid crystalline poly(esteramides) that have a high heat distortion temperature.
  • Thermotropic liquid crystalline polymers are well known in the art. They have excellent properties that make them useful in the manufacture of molded parts.
  • the strength of molded parts at elevated temperatures, as measured by the heat distortion temperature, is ultimately limited by the melting temperature of the polymers. Nevertheless, molded parts made from some polymers retain their physical integrity at temperatures close to the melting temperature. This may be characterized as the difference between the melting temperature of the polymer and the heat distortion temperature.
  • NDA 1,3-bis(trimethacrylate)-styrene resin
  • HQ 1 ,4-hydroquinone
  • TA terephthalic acid
  • HBA 4- hydroxybenzoic acid
  • BP 4,4'-biphenol
  • Thermotropic liquid crystalline poly(esteramides) that consist essentially of monomer repeat units I, II, III, IV, V and optional VI have an excellent combination of properties, where:
  • R and R' are alike or different and are selected from the group consisting of H, alkyl groups having 1 to 4 carbon atoms, fluoroalkyl groups having 1 to 4 carbon atoms, phenyl, and mixtures thereof.
  • Some of the hydrogen atoms on the aromatic rings of monomer repeat units I, II, III, IV, V and VI optionally may be replaced with one or more substituents selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, fluoroalkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, Cl, Br, F, I, aromatic groups having up to 7 carbon atoms and mixtures thereof.
  • alkyl groups having 1 to 4 carbon atoms include linear and branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl and tert-butyl.
  • Fluoroalkyl groups having 1 to 4 carbon atoms include linear and branched fluoroalkyl groups in which some or all of the hydrogen atoms have been replaced with fluorine.
  • Alkoxy groups having 1 to 4 carbon atoms can be linear or branched, such as methoxy, ethoxy, n-propoxy or isopropoxy.
  • Aromatic groups having up to 7 carbon atoms include phenyl and methyl substituted phenyl groups.
  • the liquid crystalline poly(esteramides) contain on a mole basis about 5% to about 80%) of monomer repeat unit I, about 5% to about 35%> of monomer repeat unit II, about 3%> to about 20%) of monomer repeat unit III, about 5% to about 35%) of monomer repeat unit IV, about 2%> to about 30%> of monomer repeat unit V, and 0 to about 10%> of monomer repeat unit VI.
  • These polymers show an exceptionally high heat distortion temperature compared with their melting temperature as measured by differential scanning calorimetry. They also show excellent impact resistance, as measured by their high notched Izod impact strength values.
  • monomer unit V is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • the aromatic rings of monomer units I, II, III, IV, V and VI are not substituted.
  • Monomer unit VI may be present in amounts up to about 10%>; its presence in the polymer is not necessary.
  • Preferred polymer compositions contain on a mole basis about 20% to about 60% of monomer repeat unit I, about 10% to about 30%> of monomer repeat unit II, about 5% to about 15%) of monomer repeat unit III, about 10% to about 30%o of monomer repeat unit IV, and about 5%> to about 20% of monomer repeat unit V.
  • the preferred poly(esteramides) may optionally also include up to about 10% of monomer repeat unit VI.
  • More preferred poly(esteramides) on a mole basis are composed of about 30%) to about 50%) of monomer repeat unit I, about 15%) to about 25%) of monomer repeat unit II, about 5% to about 15%» of monomer repeat unit III, about 20%> to about 30%> of monomer repeat unit IV, and about 5%> to about 10%> of monomer repeat unit V; monomer repeat unit VI is not present.
  • An especially preferred composition on a mole basis consists essentially of about 40%) of monomer unit I, about 20%> of monomer unit II, about 10%) of monomer unit III, about 25%) of monomer unit IV, and about 5%> of monomer unit V.
  • Polymers having the compositions described above melt to form liquid crystalline melt phases.
  • the polymers described above generally have melting temperatures as measured by differential scanning calorimetry in the range of about 275 °C to about
  • compositions generally melt in the range of about 300°C to about
  • liquid crystalline poly(esteramides) can be made by any of the methods already used in the art for making aromatic polyesters and poly(esteramides). These methods include: interfacial polymerization; the reaction of preformed phenyl esters of the aromatic acid groups with the phenolic groups of other monomers to yield polyester linkages and by-product phenol; and melt acidolysis polymerization, which is the preferred method. All of these polymerization methods involve the condensation of • reactive derivatives of the monomers rather than the free monomers, since the aromatic phenols and acids do not polymerize well.
  • melt acidolysis polymerization the phenolic reactants are acetylated to yield aromatic acetate groups, and these are then heated in the melt with the aromatic acids to yield acetic acid and polyester linkages.
  • This method is described in numerous patents, including U. S. Patent No. 4,473,682.
  • the melt acidolysis method is most conveniently carried out by acetylating the phenolic groups in situ and then heating the acetylated monomers to a high enough temperature to induce polymerization.
  • the melt acidolysis method is also useful for aromatic amines, which are generally charged to the reaction as N-acetyl derivatives rather than being acetylated in situ.
  • the preferred aromatic amine, 4-aminophenol is generally charged to the polymerization reaction as N-acetyl-4- aminophenol (also referred to as 4-hydroxyacetanilide or acetaminophen).
  • N-acetyl-4- aminophenol also referred to as 4-hydroxyacetanilide or acetaminophen.
  • Examples of methods of synthesizing aromatic poly(esteramides) by this method can be found in numerous references, such as U. S. Patent Nos. 5,204,443, 4,330,457, 4,966,956, 4,355,132, 4,339,375, 4,351,917 and 4,351,918.
  • the phenolic groups are acetylated in situ by including an approximately stoichiometric amount of acetic anhydride relative to the phenolic groups.
  • acetic anhydride typically included in the "stoichiometric" reactions. It has surprisingly been found that the reaction is improved when a large excess of acetic anhydride is included in the reaction. Thus if an additional excess of about 20% acetic anhydride is included above the typical 2.5%> excess, so that a total of 23%) excess acetic anhydride is used, then the reaction rate increases and the polymeric product has a higher molecular weight, as shown by the increased inherent viscosity.
  • excess acetic anhydride is generally beneficial when the amount of excess acetic anhydride (above the 2.5%> excess that is normally used in "stoichiometric" reactions) is in the range of about 5% to about 50%, preferably in the range of about 10% to about 30%>, and most preferably is about 20% (i.e. about 23% above true stoichiometry).
  • the polymerization reaction is carried out until the polymer reaches a useful molecular weight, as indicated by the inherent viscosity measured at 25 °C of a 0.1 %> solution on a weight/volume basis in a mixture of equal volumes of pentafluorophenol and hexafluoroisopropanol.
  • the inherent viscosity of the polymer generally is at least about 2 dl/g, preferably is at least about 3 dl/g, and ideally is at least about 5 dl/g.
  • the polymers of this invention are useful in the manufacture of shaped articles, such as fibers, films (e.g. extruded sheets or films) and molded articles. They are particularly useful for making molded articles in which a high heat distortion temperature or high impact resistance is desired. These polymers have an unusually high heat distortion temperature (HDT) in comparison with the crystalline melting temperature (Tm). This is desirable because molded articles with a high HDT can be made from these polymers at lower temperatures than from other polymers that have the same HDT. Therefore, the deleterious effects that are associated with processing the polymer at a high temperature in the molten phase, such as decomposition of the polymer, fillers, or other additives, are less likely to occur.
  • HDT heat distortion temperature
  • Tm crystalline melting temperature
  • Tm-HDT melting temperature and HDT
  • the polymers of this invention are generally blended with fillers and other additives at levels up to about 70%> by weight in order to achieve optimum properties.
  • Fillers and additives that may be useful include one or more fillers or reinforcing agents selected from the following list, which is not a complete or exhaustive list: glass fiber, calcium silicate, silica, clays, talc, mica, polytetrafluoroethylene, graphite, alumina, sodium aluminum carbonate, barium ferrite, woUastonite, carbon fiber, polymeric fiber, aluminum silicate fiber, titanium fiber, rock wool fiber, steel fiber, tungsten fiber and woUastonite fiber.
  • Other kinds of additives that may be used in addition to reinforcing fillers and reinforcing fibers include oxidation stabilizers, heat stabilizers, light stabilizers, lubricants, mold release agents, dyes, pigments, and plasticizers.
  • the polymers may also be melt spun into fibers having high strength and high modulus. After heat treatment, the fibers have tensile strengths up to about 20-25 gpd and modulus values up to about 500 gpd.
  • the reactor was evacuated to approximately 1 to 2 mbar followed by breaking the vacuum with nitrogen.
  • the vacuum-nitrogen purging process was repeated twice and 1004.1 grams (9.74 moles, 2.5 mole %> excess, 99 mol %> purity) of acetic anhydride was introduced into the reactor through an addition funnel.
  • the reactor was then heated in stages using a MicRIcon® controller. The temperature at each stage was increased to the final temperature of that stage during the elapsed time. Steps 1, 12 and 13 are isothermal.
  • the program follows:
  • the acetic acid began distilling off when the reactor was at 150°C. About 99% of the theoretical amount (1165 ml) had evolved at the end of segment 13.
  • the nitrogen purge was then turned off and the reactor was evacuated to about 2 mbar.
  • the torque on the stirrer that was needed to maintain constant stirring speed started to rise.
  • the reaction was terminated when the voltage to the stirrer increased by 12 mvolts above the initial value. This time was usually about 60 minutes to 100 minutes.
  • the reactor was cooled and broken to obtain the polymer. The polymer was then cut and ground into 11 chips. The yield was 1180 grams (87%>).
  • the inherent viscosity (IN.) of each sample was measured at 25 °C as a 0.1%) solution (wt./volume) in equal parts by volume of pentafluorophenol and hexafluoroisopropanol.
  • the melting temperature (T m ), heat of melting ( ⁇ H m ), crystallization temperature on cooling from the molten state (T c ), and heat of crystallization ( ⁇ H C ) were measured by differential scanning calorimetry (DSC; 20°C/min heating rate).
  • the melt viscosity of the polymer was measured in a capillary viscometer at shear rates of 100 sec "1 and 1000 sec" 1 . These properties are reported in Table 2.
  • the molten polymer of Example 10(a) was extruded at about 340°C through a single hole spinneret (0.005 inch diameter and 0.007 inch length) at a rate of 0.15 g/min.
  • the extruded filament was drawn down at a speed of 700 meters/minute and quenched in air at ambient conditions (about 25 °C and 65%> relative humidity).
  • the tensile properties of the as-spun fiber were measured using ASTM test method D3822: tenacity, 6 gdp; elongation, 1.8%; modulus, 423 gpd.
  • the as-spun fiber was then heat treated to obtain improved fiber properties as follows.
  • Fiber in an unstressed state was heated from room temperature to 150°C over a period of 60 minutes.
  • the fiber was held at 150°C for 60 minutes, then heated to 230°C over 60 minutes, held at 230°C for 3 hours, heated to 270°C over 60 minutes, and held at 270°C for 16 hours.
  • the properties of the heat treated fibers were measured using ASTM test method D3822: tenacity, 16.3 gpd; elongation, 2.8%), modulus, 499 gpd.
  • Example 8(b) was spun at about 329 °C to yield a fiber (single filament) having an as-spun tenacity of 6.2 gpd; elongation, 1.6%; modulus, 440 gpd. After heat treatment, the fiber had tenacity, 22 gpd; elongation, 4.2%>; modulus, 463 gpd.
  • a polymer having the same composition as Example 9 and an IN. - of 3.8 dl/g was spun at 340 °C through a single hole spinneret to yield a fiber having as- spun tenacity, 7.9 gpd; elongation, 2%; modulus, 450 gpd. After heat treatment, the fiber had tenacity, 23 gpd; elongation, 4.1%>; modulus, 500 gpd.
  • Examples C-1 to C-10 are comparative examples Table2. PHYSICALPROPERTIES

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une nouvelle classe de poly(estéramides) cristallins liquides thermotropiques se composant principalement d'unités monomères obtenues à partir d'environ 5 à 80 % de moles d'acide 4-hydroxybenzoïque, d'environ 5 à 35 % de moles d'acide 2,6-naphthalènedicarboxylique, d'environ 3 à 20 % de moles d'acide téréphthalique, d'environ 2 à 30 % de moles de 1,4-hydroquinone, d'environ 2 à 30 % de moles de 4-aminophénol et éventuellement d'un maximum d'environ 10 % de moles de 4,4'-diphénol. Ces poly(estéramides) se caractérisent par des températures de distorsion thermique exceptionnellement élevées par rapport à leurs températures de fusion.
EP95919897A 1994-06-06 1995-05-22 Poly(esteramides) cristallins liquide thermotropiques Withdrawn EP0764195A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US25409994A 1994-06-06 1994-06-06
US254099 1994-06-06
PCT/US1995/006364 WO1995033803A1 (fr) 1994-06-06 1995-05-22 Poly(esteramides) cristallins liquide thermotropiques

Publications (1)

Publication Number Publication Date
EP0764195A1 true EP0764195A1 (fr) 1997-03-26

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Family Applications (1)

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EP95919897A Withdrawn EP0764195A1 (fr) 1994-06-06 1995-05-22 Poly(esteramides) cristallins liquide thermotropiques

Country Status (3)

Country Link
EP (1) EP0764195A1 (fr)
JP (1) JPH10501277A (fr)
WO (1) WO1995033803A1 (fr)

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US5798432A (en) * 1996-03-22 1998-08-25 Hoechst Celanese Corp. Method of making thermotropic liquid crystalline polymers containing hydroquinone
US5731401A (en) * 1996-09-30 1998-03-24 Hoechst Celanese Corp. Process for the preparation of thermotropic aromatic polyesters directly from dialkyl aromatic esters
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US6171802B1 (en) 1998-06-10 2001-01-09 Kent State University Detection and amplification of ligands
CA2523124A1 (fr) 2003-03-20 2004-10-07 Gary D. Niehaus Dispositif d'analyse autonome pour detection rapide d'agents de risque biologique
WO2005116141A1 (fr) * 2004-05-26 2005-12-08 Polyplastics Co., Ltd. Composition de résine thermoplastique
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EP1871818B1 (fr) * 2005-04-19 2009-01-14 E.I. Du Pont De Nemours And Company Composition polymere cristalline liquide
US7947492B2 (en) 2008-08-20 2011-05-24 Northeastern Ohio Universities College Of Medicine Device improving the detection of a ligand
JP2009280831A (ja) * 2009-08-31 2009-12-03 Sumitomo Chemical Co Ltd 液晶性ポリエステル溶液組成物
WO2013032975A1 (fr) 2011-08-29 2013-03-07 Ticona Llc Polymère cristallin liquide thermotrope à viscosité à faible cisaillement améliorée
US8778221B2 (en) 2011-08-29 2014-07-15 Ticona Llc Aromatic amide compound
WO2013032977A1 (fr) 2011-08-29 2013-03-07 Ticona Llc Composition de polymère à cristaux liquides résistante à la chaleur ayant une faible température de fusion
US8852730B2 (en) 2011-08-29 2014-10-07 Ticona Llc Melt-extruded substrate for use in thermoformed articles
CN103764741B (zh) 2011-08-29 2015-09-23 提克纳有限责任公司 低熔体粘度液晶聚合物的熔融聚合
WO2013032967A1 (fr) 2011-08-29 2013-03-07 Ticona Llc Pièces coulées au moule formées à partir d'un polymère cristallin liquide
CN103764793B (zh) 2011-08-29 2016-09-14 提克纳有限责任公司 高流动液晶聚合物组合物
JP2014525498A (ja) 2011-08-29 2014-09-29 ティコナ・エルエルシー 高流動性液晶ポリマー組成物
TWI577092B (zh) 2011-11-15 2017-04-01 堤康那責任有限公司 微間距電連接器及用於其中之熱塑性組合物
US20130123420A1 (en) * 2011-11-15 2013-05-16 Ticona Llc Liquid Crystalline Polymer Composition for High Voltage Electronic Components
US8646994B2 (en) * 2011-11-15 2014-02-11 Ticona Llc Compact camera module
US8906259B2 (en) 2011-11-15 2014-12-09 Ticona Llc Naphthenic-rich liquid crystalline polymer composition with improved flammability performance
KR101996106B1 (ko) * 2011-11-15 2019-07-03 티코나 엘엘씨 치수 공차가 작은 성형 부품에 사용하기 위한 저-나프텐 액정 중합체 조성물
US8932483B2 (en) 2011-11-15 2015-01-13 Ticona Llc Low naphthenic liquid crystalline polymer composition
US20140134419A1 (en) * 2012-11-09 2014-05-15 Ticona Llc Liquid crystalline polymer composition for melt-extruded sheets
US8853344B2 (en) 2012-11-09 2014-10-07 Ticona Llc Liquid crystalline polymer composition for films

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Also Published As

Publication number Publication date
JPH10501277A (ja) 1998-02-03
WO1995033803A1 (fr) 1995-12-14

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