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WO1991010707A1 - Procede pour former un poly[co(4-oxybenzoate/paraphenylene-isophtalate)] et produit resultant - Google Patents

Procede pour former un poly[co(4-oxybenzoate/paraphenylene-isophtalate)] et produit resultant Download PDF

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Publication number
WO1991010707A1
WO1991010707A1 PCT/US1990/006753 US9006753W WO9110707A1 WO 1991010707 A1 WO1991010707 A1 WO 1991010707A1 US 9006753 W US9006753 W US 9006753W WO 9110707 A1 WO9110707 A1 WO 9110707A1
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Prior art keywords
oxybenzoate
poly
phenyleneisophthalate
preformed
melt
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PCT/US1990/006753
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English (en)
Inventor
Larry F. Charbonneau
Balaram Gupta
H. Clay Linstid
Linda C. Sawyer
James P. Shepherd
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CNA Holdings LLC
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Hoechst Celanese Corp
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Publication of WO1991010707A1 publication Critical patent/WO1991010707A1/fr
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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
    • 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

Definitions

  • Poly[co(4-oxybenzoate/phenyleneisophthalate)] is a previously known polymer which is disclosed in U.S. Patent No. 3,637,595.
  • such polymer is recognized to be difficult to form on a uniform and reliable basis.
  • Such difficulty can be traced to its inherent structural morphology wherein the polymer when melted forms a biphasic melt.
  • Some regions within the melt form an ordered anisotropic melt phase at a given temperature range and other regions form a nonordered isotropic melt phase.
  • the nonuniformity of the product of the prior art also commonly has led to formation of three-dimensional molded articles having widely varying properties. See, (1) "Anomalous
  • 4,414,365 discloses a bulk polymerization process for forming an aromatic polyester of a specified formula which may exhibit anisotropic melt properties in the presence of a preformed polymer which is a polyalkylene terephthalate, polyphenylene sulfide, aromatic
  • U.S. Patent No. 4,778,858 discloses a process for preparing a polymer blend composition wherein one forms polyethylene terephthalate in a melt process in the presence of at least one liquid crystalline polymer and subsequently subjects the blend to solid state
  • 88/00605 discloses the formation of a specified liquid crystalline polymer in the presence of a preformed poly(aryl ether ketone), poly(aryl ether) or
  • inventions to provide a novel polymeric composition of matter which is capable of undergoing melt processing to form a three-dimensional article which exhibits a heat deflection temperature of at least 200°C. and a Notched Izod impact strength of at least 1.0 ft.- lb./in.
  • the polymeric sections were heated from room temperature at a rate of 20°C./minute to a maximum temperature of 420°C. followed by rapid quenching. The results were video taped and
  • micrographs were obtained from the video tape at room temperature (A), 285°C. (B), 345°C. (C), and 395°C.
  • poly[co(4-oxybenzoate/phenyleneisophthalate] contained 35 mole percent of p-oxybenzoyl units, 32.5 mole percent of 1,4-dioxyphenylene units, and 32.5 mole percent of isophthaloyl units in each instance .
  • the preformed poly[co(4-oxybenzoate/6-oxynaphthoate)] contained 73 mole percent of recurring 4-oxybenzoyl units and 27 mole percent of recurring 6-oxynaphthoyl units.
  • Figs. 1A, 1B, 1C and 1D illustrate typical sections of poly[co(4-oxybenzoate/
  • crystalline domains are apparent in the temperature range of 285 (Fig. 1B) to 345°C. (Fig. 1C). At 345°C. liquid crystalline domains are present in an isotropic melt. At 395°C. (Fig. 1D) the melt becomes mostly isotropic and is completely isotropic at 410°C.
  • Fig. 2 illustrates typical sections of the product of the present invention wherein approximately 1 percent by weight of preformed poly[co(4- oxybenzoate/6-oxynaphthoate)] was intimately admixed with the poly[co(4-oxybenzoate/phenyleneisophthalate)] at the time of its formation.
  • the preformed poly[co(4- oxybenzoate/6-oxynaphthoate)] was intimately admixed with an equal part by weight of poly[co4-oxybenzoate/ oxybenzoate/phenyleneisophthalate)] at the time of its introduction into the reactor.
  • Such intimate admixture was achieved by preliminarily forming the poly[co(4- oxybenzoate/ phenyleneisophthalate)] in the presence of the preformed poly[co(4-oxybenzoate/6-oxynaphthoate)] to form a masterbatch. Approximately two parts by weight of this masterbatch were added to approximately 98 parts by weight of the monomers. A finer
  • Fig. 3 illustrates typical sections of the product of the present invention similar to that illustrated in Fig. 2 with the exception that
  • Fig. 4 illustrates typical sections of the preformed poly[co(4-oxybenzoate/6-oxynaphthoate)].
  • Fig. 5 illustrates typical sections of the product of the present invention similar to that illustrated in Figs. 2 and 3 with the exception that approximately 10 parts by weight of the masterbatch were added to approximately 90 parts by weight of the monomers, and approximately 5 percent by weight of the preformed poly[co(4-oxybenzoate/6-oxynaphthoate)] was intimately admixed with the poly[co(4-oxybenzoate/ phenyleneisophthalate)] at the time of its formation.
  • a further refinement of the microstructure than illustrated in Fig. 3 is apparent. There is a liquid crystalline texture over the temperature range of 285 to 395°C. (Figs. 5B, 5C, and 5D) which closely
  • Appropriate monomers capable of forming poly[co(4-oxybenzoate/phenyleneisophthalate)] via a melt acidolysis reaction are provided in a stirred heated reaction zone together with a suitable amount of the molten preformed polymer which is capable of forming an anisotropic single phase melt as described hereafter.
  • Typical reactants used to form the poly[co(4- oxybenzoate/phenyleneisophthalate)] are phydroxybenzoic acid, hydroquinone and isophthalic acid.
  • Other ester- and amide-forming comonomers e.g., terephthalic acid, chloroterephthalic acid,
  • dicarboxylic acid 4,4'-biphenol, 4,4'-dihydroxy diphenyl ether, 4,4'-dihydroxy diphenyl sulfone, resorcinol, meta and/or para-hydroxy analine, 4- hydroxy-4'-carboxydiphenyl ether, 2,6- dihydroxynaphthalene, etc., and mixtures of the
  • the aromatic rings of the monomers optionally may include substitution of at least some of the hydrogen atoms present upon an aromatic ring selected from the group consisting of an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, halogen (e.g., fluorine, chlorine and bromine), phenyl (including substituted phenyl), and mixtures thereof.
  • halogen e.g., fluorine, chlorine and bromine
  • phenyl including substituted phenyl
  • the reactants In order for the reactants to undergo the melt-acidolysis reaction it is essential that the reactive hydroxyl groups present thereon first be modified.
  • the p-hydroxybenzoic acid and hydroquinone reactants may be initially provided in a modified form whereby the usual hydroxyl groups of the monomers are esterified (i.e., they are provided as lower acyl esters).
  • Such lower acyl groups commonly have from about two to about four carbon atoms.
  • the acetate esters of the organic monomer reactants are provided. Accordingly, particularly preferred reactants are p-acetoxybenzoic acid,
  • isophthalic acid, and hydroquinone diacetate The acetylation can be carried out in a separate vessel outside the reactor, or such acetylation preliminarily may be carried out in the same reactor through the addition of acetic anhydride prior to the commencement of the polymerization.
  • Conventional esterification catalysts such as potassium acetate, may be utilized.
  • the preformed polymer which is capable of forming an anisotropic single phase melt is provided in the reaction zone in a well-dispersed form in a
  • Such preformed polymer preferably exhibits the single phase anisotropic melt at a temperature within the range of 280 to 340°C. It also preferably is capable of undergoing melt processing at a temperature as high as 340°C. in the absence of significant polymer
  • the anisotropic character of the polymer melt may be confirmed by conventional polarized light techniques whereby crossed-polarizers are utilized. More specifically, the anisotropic or ordered nature of the melt phase may conveniently be confirmed by the use of a Leitz polarizing microscope at a magnification of 400 to 750X with the sample on a Leitz hot stage and under a nitrogen atmosphere. The amount of light transmitted changes when the sample is forced to flow; however, the sample is optically anisotropic even in the static state. On the contrary, typical melt- processable polymers do not transmit light in the melt to any substantial degree when examined under quiescent conditions and are isotropic in nature.
  • melt rheology The single phase nature of the melt may be confirmed by thermal optical microscopy, x-ray crystallography, electron microscopy, polarized light microscopy, differential scanning calorimetry, melt rheology, and other known techniques.
  • Representative classes of polymers from which the preformed polymer may be selected include
  • anisotropic melt-forming wholly aromatic polyesters anisotropic melt-forming aliphatic-aromatic polyesters, anisotropic melt-forming poly(ester-amides),
  • anisotropic melt-forming poly(ester-carbonates), and mixtures of these are preferable.
  • the preformed polymer which is capable of forming an anisotropic single phase melt is a wholly aromatic polyester. Also, in a preferred embodiment the
  • preformed polymer comprises not less than about 10 mole percent of recurring units which include a naphthalene moiety (e.g., a 6-oxy-2-naphthoyl moiety, 2,6- dioxynaphthalene moiety, and a 2,6- dicarboxynaphthalene moiety).
  • the preformed polymer which is utilized preferably exhibits an inherent viscosity of at least 2.0 dl./g. (e.g., 2.0 to 10.0 dl./g/) when dissolved in a concentration of 0.1 percent by weight in equal parts by volume of
  • the preformed polymers which are capable of forming an anisotropic single phase melt may be selected by those skilled in polymer technology from those known in the art. Preferred polymers which may serve in this role are disclosed in U.S. Patent Nos. 4,161,470; 4,184,996; 4,256,624; 4,330,457; 4,371,660; and 4,473,682, which are herein incorporated by reference.
  • the preformed polymer which is capable of forming an anisotropic single phase melt is poly[co(4- oxybenzoate/6-oxynaphthoate)].
  • This wholly aromatic polyester is the subject matter of U.S. Patent No.
  • aromatic rings are substantially free of ring substitution.
  • the poly[co(4- oxybenzoate/ 6-oxynaphthoate)] comprises approximately 20 to 40 mole percent of moiety I and approximately 60 to 80 mole percent of moiety II.
  • the poly[co(4-oxybenzoate/6- oxynaphthoate)] consists essentially of approximately 27 mole percent of recurring 6-oxy-2-naphthoyl moieties and approximately 73 mole percent of recurring
  • such polymer consists essentially of approximately 20 mole percent of recurring 6-oxy-2- naphthoyl moieties and approximately 80 mole percent of recurring 4-oxybenzoyl moieties.
  • 6-oxynaphthoate is capable of forming an anisotropic single phase melt at a temperature below approximately 340°C, and most preferably at a temperature below approximately 325°C. It also is particularly preferred that such preformed polymer exhibit an inherent viscosity of at least 4.0 dl./g. (e.g., approximately 5.0 to 7.5 dl./g.) when dissolved in a concentration of 0.1 percent by weight in equal parts by volume of pentafluorophenol and hexafluoroisopropanol at 25°C.
  • the preformed polymer is formed in the presence of an approximately 0.25 to 4 percent molar excess of an aromatic
  • the preferred aromatic dicarboxylic acid is terephthalic acid and the resulting polymer is substantially incapable of further chain growth upon heating.
  • preformed polymer which is capable of forming an anisotropic single phase melt is preblended and intimately admixed with a quantity of preformed poly[co(4-oxybenzoate/
  • preblending may be accomplished by physical blending of the molten polymers or by preparing the poly[co(4- oxybenzoate/ phenyleneisophthalate)] in the presence of the preformed polymer which is capable of forming an anisotropic single phase melt. Particularly good results have been achieved when the preformed polymer which is capable of forming an anisotropic single phase melt is preblended with a substantially equal amount by weight of preformed poly[co(4-oxybenzoate/
  • melt-acidolysis polymerization in the stirred heated reaction zone it is preferred that a maximum temperature of no more than approximately 350°C. be achieved, and most preferably a maximum temperature of no more than approximately
  • the process of the present invention has been found to be capable of forming poly[co(4-oxybenzoate/ phenyleneisophthalate)] on a more reliable, more reproducible, and a more stable basis than the prior art. Processing difficulties normally associated with the biphasic nature of such polymer are substantially eliminated.
  • the resulting product advantageously is found to exhibit anisotropic melt properties over a broader temperature range than when poly[co(4- oxybenzoate/phenyleneisophthalate)] is formed in accordance with the prior art. Also, the resulting novel composition of matter is capable of reliably undergoing melt processing to form quality three- dimensional articles.
  • the product of the present invention may optionally incorporate approximately 1 to 50 percent by weight (preferably approximately 10 to 30 percent by weight), based upon the total weight of the polymers, of a solid filler and/or reinforcing agent.
  • filler materials include calcium
  • silicate silica
  • clays silica
  • talc silica
  • mica silicate, silica, clays, talc, mica
  • Representative reinforcing fibers include glass fibers, graphitic carbon fibers,
  • amorphous carbon fibers synthetic polymeric fibers, alumina fibers, aluminum silicate fibers, aluminum oxide fibers, titanium fibers, magnesium fibers, rock wool fibers, steel fibers, tungsten fibers,
  • wollastonite fibers having an aspect ratio greater than 3 to 1, cotton, wood, cellulose fibers, etc.
  • quality three- dimensional articles are formed upon melt processing which exhibit a heat deflection temperature at 264 psi of at least 200°C. (most preferably at least 220°C), and a Notched Izod impact strength of at least 1.0 ft.- lb./in. (most preferably at least 1.5 ft.-lb./in).
  • a cylindrical two liter round-bottomed glass reactor was provided which was equipped with a nitrogen inlet, a thermocouple, Vigreux column attached to a condenser and receiver, and a C-shaped 316 stainless steel mechanical stirrer.
  • the reactor was immersed in a sand bath and provided with means to accurately control the temperature.
  • 290.1 grams (2.1 moles) of p-hydroxybenzoic acid 218.0 grams (1.98 moles including 0.5 percent molar excess) of hydroquinone, and 324.0 grams (1.95 moles) of isophthalic acid which upon polymerization were capable of forming poly[co(4-oxybenzoate/
  • the preformed polymer contained 73 mole percent of recurring 4-oxybenzoate units and 27 mole percent of recurring 6-oxynaphthoate units and exhibited an inherent viscosity of 7.0 dl./g. when dissolved in a concentration of 0.1 percent by weight in equal parts by volume of pentafluorophenol and hexafluoroisopropanol at 25°C.
  • Such preformed polymer was present in the reactor in a concentration of 2.9 percent by weight based upon the total concentration of the three monomers which initially were present in the reaction zone. Additionally, 0.63 grams (75.5 parts per million) of potassium acetate catalyst were added to the reactor. The reactor was under a constant purge of nitrogen at a rate of approximately 30 to 40
  • the reactor was next evacuated to approximately 1 to 2 mbar two times with the reduced pressure being broken with nitrogen each time.
  • Acetic anhydride next was introduced into the reactor through an addition funnel in a quantity of 637.4 grams (6.15 moles including a 2.5 mole percent excess). Such acetic anhydride was of 98.5 mole percent purity and was added for the purpose of
  • the acetic acid began distilling-off when the reactor was at 150°C. and at the end of heating stage No. 8 approximately 98 percent of the theoretical amount (687 ml.) had evolved.
  • poly[co(4-oxybenzoate/6-oxynaphthoate)] was intimately admixed.
  • the polymer admixture was cut and ground into chips to yield 713.2 grams of product (95.8 percent of theoretical).
  • the resulting product was found to exhibit an inherent viscosity of 0.81 dl./g. when dissolved in a concentration of 0.1 percent by weight in equal parts by volume of pentafluorophenol and hexafluoroiso- propanol at 25°C.
  • the product also was found to exhibit the following properties as determined by standard differential scanning calorimetry at
  • Heat of Crystallization (Hc) -8.9 joules/gram.
  • the melt viscosity of the product at 330°C. was 344 poise at a shear rate of 100 sec. -1 , and 112 poise at a shear rate of 1000 sec. -1 .
  • the product when melted exhibited a homogeneous fine uniform microstructure by thermal-optical microscopy and this texture was
  • Example 1 was substantially repeated with the exceptions indicated. More specifically, the molar ratios of the three monomers required to form the poly[co(4-oxybenzoate/ phenyleneisophthalate)] were varied except in Example 2, and in some instances the polymerization heating schedule was varied. In
  • Examples 5 to 8 Heating Stage Nos. 7 through 9 were carried out at 340°C. instead of 325°C.
  • Heating Stage Nos. 7 through 9 were carried out at a temperature of 330°C instead of 325°C.
  • the molar ratios of the monomers and the concentration of the preformed polymer which is capable of forming an anisotropic single phase melt are reported in Table I where Monomer A is p-hydroxybenzoic acid, Monomer B is hydroquinone, and Monomer C is isophthalic acid.
  • the preformed poly[co(4-oxybenzoate/6-oxynaphthoate)] is designated the "Preformed Polymer" and the
  • melt viscosity measurements were made at 325°C. instead of 330°C.
  • melt viscosity measurements were made at 340°C. instead of 330°C.
  • melt viscosity measurements were made at 350°C. instead of 330°C.
  • Example 2 was repeated two times in the absence of the preformed poly[co(4-oxybenzoate/6-oxynaphthoate)]. The identical runs were designated “Comparative X” and “Comparative Y”. The properties of the resulting products are not readily reproducible and are reported in Table I.
  • Example 1 was substantially repeated with the exceptions indicated. More specifically, the preformed polymer contained 77 mole percent of recurring 4- oxybenzoate units and 23 mole percent of recurring 6- oxynaphthoate units and exhibited an inherent viscosity of 6.8 dl./g. when dissolved in a concentration of 0.1 percent by weight in equal parts by volume of
  • Examples 21 and 22 the molar ratios of the three monomers required to form the poly[co(4- oxybenzoate/phenyleneisophthalate)] were varied, and Heating Stage Nos. 7 to 9 were carried out at 330°C. instead of 325°C.
  • the molar ratios of the monomers and the concentration of the preformed polymer which is capable of forming an anisotropic single phase melt are reported in Table III where Monomer A is p- hydroxybenzoic acid, Monomer B is hydroquinone, and Monomer C is isophthalic acid.
  • poly[co(4-oxybenzoate/6-oxynaphthoate)] is designated the "Preformed Polymer” and its concentration is expressed in weight percent based upon the total concentration of monomers initially present in the reactor. Properties of the resulting product also are reported in Table III. Glass fiber-reinforced test specimens were injection molded as described with respect to Examples 2 to 16. The properties of the resulting test specimens are reported in Table IV.
  • Example 1 was substantially repeated with the exceptions indicated. More specifically, the preformed polymer contained 80 mole percent of recurring 4- oxybenzoate units and 20 mole percent of recurring 6- oxynaphthoate units and Heating Stage Nos. 7 to 9 were carried out at 330°C. instead of 225°C. The preformed polymer was not sufficiently soluble to carry out the standard inherent viscosity determination.
  • the preformed polymer was not sufficiently soluble to carry out the standard inherent viscosity determination.
  • Preformed Polymer and its concentration is expressed in weight percent based upon the total concentration of monomers initially present in the reactor. Properties of the resulting product also are reported in Table V. Glass fiber-reinforced test specimens were injection molded as described with respect to Examples 2 to 16. When the glass fiber reinforced products of Examples 23 and 24 were combined, a Notched Izod impact strength of 1.27 ft.-lb./in., and a heat defection temperature of 217°C. were observed. When the glass fiber reinforced products of Examples 25 and 26 were combined, a
  • preformed poly[co(4-oxybenzoate/phenyleneisophthalate)] was formed of monomers which were supplied in the same relative molar concentrations as described in Example 1.
  • the poly[co (4-oxybenzoate/6-oxynaphthoate)] contained 73 mole percent of recurring 4-oxybenzoate units and 27 mole percent of recurring 6-oxynaphthoate units.
  • the poly[co(4-oxybenzoate/6- oxynaphthoate)] contained 77 mole percent of recurring 4-oxybenzoate units and 23 mole percent of recurring 6-oxynaphthoate units.
  • the poly[co(4-oxybenzoate/6-oxynaphthoate)] contained 80 mole percent of recurring 4-oxybenzoate units and 20 mole percent of recurring 6-oxynaphthoate units.
  • Heating Stage Nos. 7 to 9 were carried out at 330°C. for Examples 27 to 32, and at 340°C. for Examples 33 to 34.
  • the resulting products were found via thermo- optical microscopic studies to exhibit an excellent uniform microstructure which was of an even finer nature than that achieved in the preceding examples wherein the preformed polymer when introduced into the reactor was not in the form of a master blend.
  • the product of Examples 27 to 30 is illustrated in Figs. 5A, 5B, 5C, and 5D.
  • test results were as follows:
  • concentration of recurring terephthaloyl units 0.066 grams of potassium acetate and 672.7 grams of acetic anhydride were added to the reactor. 88.1 grams of equal parts by weight of an intimate admixture of preformed poly[co(4-oxybenzoate/6-oxynaphthoate)] and preformed poly[co(4-oxybenzoate/phenyleneisophthalate)] were added to the reactor.
  • phenyleneisophthalate was formed of monomers which poly[co(4-oxybenzoate/phenyleneisophthalate) was formed of monomers which were supplied in the same relative molar concentrations as described in Example 1.
  • Example I was substantially repeated two times with the exceptions indicated wherein a different preformed polymer which is capable of forming an anisotropic single phase melt was substituted for the poly[co(4-oxybenzoate/6-oxynaphthoate)].
  • preformed polymer was a poly(ester-amide) formed in accordance with the teachings of U.S. Patent No.
  • Example 1 was substantially repeated with the exceptions indicated wherein a different preformed polymer which is capable of forming an anisotropic single phase melt was substituted for the poly[co(4- oxybenzoate/6-oxynaphthoate)].
  • Such preformed polymer which was capable of forming an anisotropic single phase melt was a wholly aromatic polyester formed in accordance with U.S. Patent No. 4,256,624, and
  • terephthaloyl units and 1,4-dioxyphenylene units.
  • the molar ratios of these units were 60:20:20 respectively, and the wholly aromatic polyester exhibited an inherent viscosity of 2.8 dl./g. when dissolved in a concentration of 0.1 percent by weight in equal parts by volume of pentafluorophenol and hexafluoroisopropanol at 25°C.
  • the molar ratios of these units were 50:25:25 respectively, and the wholly aromatic polyester
  • Example 1 was substantially repeated with the exceptions indicated wherein a different preformed polymer which is capable of forming an anisotropic single phase melt was substituted for the poly[co(4- oxybenzoate/6-oxynaphthoate)].
  • Such preformed polymer was a wholly aromatic polyester formed in accordance with U.S. Patent No. 4,473,682, and contained recurring 4-oxybenzoyl units, 6-oxy-2-naphthoyl units,
  • Example 46 into the reactor were placed 274.01 grams (1.995 moles) of p-hydroxybenzoic acid, 205.95 grams (1.8639 moles including a 0.2 mole percent excess) of hydroquinone, 306.04 grams (1.8525 moles) of isophthalic acid, 42 grams of the preformed wholly aromatic polyester, 0.06 gram of potassium acetate catalyst, and 608.1 grams of acetic anhydride.
  • the preformed wholly aromatic polyester was provided in a concentration of 5.3 percent by weight based on the total concentration of the monomers present.
  • poly[co(4-oxybenzoate/phenyleneiso- phthalate)] were supplied in the same relative molar concentrations as described in Example 1.
  • the preformed wholly aromatic polyester capable of forming an anisotropic single phase melt was provided in a concentration of 5.4 percent by weight based on the total concentrations of the monomers present.
  • Example 1 was substantially repeated with the exceptions indicated wherein a different preformed polymer which is capable of forming an anisotropic single phase melt was substituted for the poly[co(4- oxybenzoate/6-oxynaphthoate)].
  • Such preformed polymer was a wholly aromatic polyester which contained
  • Example 52 the preformed wholly aromatic polyester capable of forming an anisotropic single phase melt was provided in a concentration 5.5 percent by weight based on the total concentration of the monomers present.
  • Example 1 was substantially repeated with the exceptions indicated wherein the poly[co(4-oxybenzoate/ 6-oxynaphthoate)] was introduced in two different relatively low concentrations while intimately admixed with an equal part by weight of preformed poly[co(4- oxybenzoate/phenyleneisophthalate)].
  • Such intimate admixtures were prepared by preliminarily forming the poly[co(4-oxybenzoate/phenyleneisophthalate)] in the presence of the preformed wholly aromatic polyester in a manner similar to that previously described to form a masterbatch.
  • the monomers used when preparing the preformed poly[co(4-oxybenzoate/phenyleneisophthalate)] were supplied in the same molar concentrations as described in Example 1.
  • poly[co(4-oxybenzoate/6-oxynaphthoate)] was provided in a concentration of 0.95 percent by weight based on the total concentration of the monomers present.
  • concentration 0.95 percent by weight based on the total concentration of the monomers present.
  • the nature of the product is illustrated in Figs. 2A, 2B, 2C, and 2D.
  • Example 1 was substantially repeated with the exceptions indicated wherein the preformed poly[co(4- oxybenzoate/ 6-oxynaphthoate)] was prepared in
  • the prepolymer was substantially incapable of undergoing additional chain growth upon heating since the polymer chains were caused to
  • Example 58 In Example 58 into the reactor were charged 688.9 grams (4.9875 moles) of p-hydroxybenzoic acid,
  • poly[co(4-oxybenzoate/6-oxynaphthoate)] was provided in a concentration of 4.9 percent by weight based on the total concentration of monomers present.
  • Example 59 the poly[co(4-oxybenzoate/ 6-oxynaphthoate)] was introduced while intimately admixed with an equal part by weight of preformed poly[co(4-o ⁇ ybenzoate/ phenyleneisophthalate)].
  • Such intimate admixture was prepared by preliminarily forming the poly[co(4-oxybenzoate/phenyleneisophthalate)] in the presence of the preformed
  • Example 59 into the reactor were charged 652.7 grams (4.725 moles) of p-hydroxybenzoic acid, 486.1 grams (4.4145 moles including 0.2 mole percent excess) of hydroquinone, 728.9 grams (4.3815 moles) of isophthalic acid, 187.4 grams of the masterbatch, 0.56 gram of potassium acetate, and 1441.5 grams of acetic anhydride.
  • the poly[co(4-oxybenzoate/6-oxynaphthoate)] was provided in a concentration of 5.0 percent by weight based on the total concentration of monomers present.

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Abstract

On forme un poly[co(4-oxybenzoate/phénylèneisophtalate)] au moyen de la polymérisation par fusion-acidolyse de monomères appropriés dans des conditions qui atténuent sensiblement les difficultés de traitement rencontrées jusqu'à présent et liées de manière intrinsèque à la nature biphasique irrégulière d'un tel polymère à l'intérieur duquel certaines régions forment une phase de fusion anisotrope ordonnée et d'autres régions forment une phase de fusion isotrope non ordonnée. Le procédé amélioré de l'invention revendiquée s'effectue dans un réacteur chauffé et brassé auquel on a ajouté une faible concentration appropriée d'un polymère préformé capable de former un bain de fusion à phase unique anisotrope. La polymérisation recherchée s'effectue sur une base stable, sûre et facilement reproductible. On obtient une nouvelle composition de matière polymère relativement peut coûteuse présentant une phase de fusion anisotrope sur une plus vaste plage de températures et subissant de manière fiable le traitement par la fusion pour former des articles de qualité moulés en trois dimensions, et ce, en raison de la morphologie structurelle modifiée de cette nouvelle composition de matière polymère résultant d'une diminution de son caractère biphasique.
PCT/US1990/006753 1990-01-16 1990-11-16 Procede pour former un poly[co(4-oxybenzoate/paraphenylene-isophtalate)] et produit resultant Ceased WO1991010707A1 (fr)

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CN116334784A (zh) * 2023-03-24 2023-06-27 扬州奕杉新材料科技有限公司 一种防水功能纤维材料及其制备方法与应用

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US4414365A (en) * 1981-03-16 1983-11-08 Sumitomo Chemical Company, Limited Process for producing an aromatic polyester composition
US4563508A (en) * 1984-05-18 1986-01-07 Dart Industries, Inc. Injection moldable aromatic polyesters compositions and method of preparation
WO1988000605A1 (fr) * 1986-07-21 1988-01-28 Amoco Corporation Melanges contenant des polyesters cristallins liquides

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US4414365A (en) * 1981-03-16 1983-11-08 Sumitomo Chemical Company, Limited Process for producing an aromatic polyester composition
US4563508A (en) * 1984-05-18 1986-01-07 Dart Industries, Inc. Injection moldable aromatic polyesters compositions and method of preparation
WO1988000605A1 (fr) * 1986-07-21 1988-01-28 Amoco Corporation Melanges contenant des polyesters cristallins liquides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116334784A (zh) * 2023-03-24 2023-06-27 扬州奕杉新材料科技有限公司 一种防水功能纤维材料及其制备方法与应用
CN116334784B (zh) * 2023-03-24 2023-10-03 扬州奕杉新材料科技有限公司 一种防水功能纤维材料及其制备方法与应用

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