US3895090A - Method for direct spinning of polyethylene-1,2-diphenoxyethane-p,p{40 -dicarboxylate fibers - Google Patents

Method for direct spinning of polyethylene-1,2-diphenoxyethane-p,p{40 -dicarboxylate fibers Download PDF

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Publication number
US3895090A
US3895090A US810775A US81077569A US3895090A US 3895090 A US3895090 A US 3895090A US 810775 A US810775 A US 810775A US 81077569 A US81077569 A US 81077569A US 3895090 A US3895090 A US 3895090A
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United States
Prior art keywords
fibers
dicarboxylate
polyethylene
diphenoxyethane
polymer
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Expired - Lifetime
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US810775A
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English (en)
Inventor
Hidehiko Kobayashi
Masatsugu Yoshino
Kazuya Neki
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Chemical Industry Co Ltd
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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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters

Definitions

  • ABSTRACT Commercially useful polyethylene-1,2- diphenoxyethane-p,p-dicarboxylate fibers are obtained by the direct spinning of a melt of polyethylene-l,2-diphenoxyethane-p,p'-dicarboxylate with a commercially feasibletake-up speed of 1800-3500 m/min by maintaining an intrinsic viscosity and a residual carboxyl group of said polymer within the range of 0.4-1.3 and less than 20 equivalents/10 g., respectively, and when the monofilament denier is as thin as 1.5 0.3, the take-up speed can be reduced to a value of 1000-1800 m/min.
  • the present invention consists in a novel direct spinning method of polyethylene-1,2- diphenoxyethane-p,p-dicarboxylate fibers which comprises taking up the filament yarns spun with a common spinning machine from polyethylene- 1,2- diphenoxyethane-p,p-dicarboxylate which satisfies specified conditions.
  • the polymers used in the practice of the present invention must be a polyethylene-1,Z-diphenoxyethanep,p-dicarboxylate containing at least 70 mol.% of repetition unit of -m-C-O-CH -CH whose intrinsic viscosity [1 of polymer is more than 0.4 and less than 1.3, (inclusive) and containing less than 20 eq./10 g. (inclusive) of residual carboxyl group in the polymer.
  • An intrinsic viscosity [1 of the polymer less than 0.4 and more than 1.3, is not preferable because breakage of filaments frequently occurs in such cases.
  • the intrinsic viscosities are values as measured in a solvent consisting of a 2:1 mixture by weight of tetrachloroethene and phenol at 35C.
  • the residual carboxyl radicals herein referred to are values measured by a method which resorts to titration with a solution of causticsoda and benzyl alcohol by using, as a solvent, benzyl alcohol, and, as an indicator, phenol red. [See H. H. Pohl (Annal. Chem., 26, 1614 (1954)].
  • the yield strengths herein referred to are values determined from stress-strain curves in case where samples 20 cm long are stretched at an elongation speed of per minute.
  • the above-mentioned polymer can be produced by subjecting l,2-bis-(paracarbomethoxy .phenoxyethane or its ester-forming derivatives and ethylene glycol to ester-exchange reaction in the presence of a catalyst to form bisglycol of 1,2-bis- (paracarbomethoxy)-phenoxyethane and then subjecting the latter to condensation polymerization in the presence of a polymerization catalyst, at an elevated temperature and under a reduced pressure while eliminating excessive glycol produced in the condensation.
  • the constitution material suitable to the method of the present invention and consisting essentially of polyethylene-1 ,2-diphenoxyethane-p,-p-dicarboxylate may contain upto 30 mol of another glycol such as diethylene glycol, tetramethylene glycol, hexamethylene glycol or the like. Further, the molecule may contain up to 30 mol of another acid.
  • .Illustrative copolymerizable acids suitable to the present method include hexahydroterephthalic acid, terephthalic acid, isophthalic acid, bibenzoic acid, adipic acid, sebacic acid, azelaic acid, naphthalic acid, 2,5-dimethyl terephthalic acid.
  • fibers having a yield strength of more than 1.0 g/d, an initial modulus of elasticity of more than 70 g/d, a breaking strength of morethan 3.0 g/d and a residual elongation of less than 80% can be obtained by taking up the fiber filaments produced by melt-extrusion at a speed of more than 1800 m/min. but a take-up speed greater than 3500 m/min. is not preferable because it brings about frequent breakages of filaments.
  • the lower limit of taking-up can be reduced nearly down to a common spinning speed in the spinning of fine filaments.
  • monofilament denier is in the range of less than 0.5 and greater than 0.2 (inclusive)
  • the fibers obtained in the method of the present invention have properties superior to those of the filaments obtained by a conventional direct spinning method but it is possible to .provide a production method of practically very useful fibers furnished with even much more superior properties if considerations are given to various conditions such as those regarding the polymer, spinneret, the temperature of atmosphere surroundingthe course of extruded filaments upto a take-up point, method for taking up filaments and proper limitations thereof. Description will be directed firstly to the condition regarding the polymer.
  • ester-exchange catalyst and polymerization catalyst useful in the production of polymer can be utilized so long as residual carboxyl radical in the polymer becomes less than eq./10 g. (inclusive) by the proper selection of other polymerization conditions such as polymerization time and temperature but when a combination system consisting of a specified ester exchange catalyst and polymerization catalyst is used in the production of polymer, and fibers are produced therefrom by a high speed spinning process, resultant fibers have particularly excellent properties such as greater yield strength, greater breaking strength, lower residual elongation, etc..
  • ester exchange catalyst and polymerization catalyst combinations of a barium compound invention.
  • Useful compounds for ester exchange catalyst include elementary metal,.carbonate, oxide, hydroxide, acetate and borate of barium orcalciurn.
  • Asvantimony compounds useful for polymerization catalyst salts of antimony with inorganic or organic acid, double salts such as potassium, antimony tartrate salts of antimonic acid, (e.g. ammonium pyroantimonate), oxides, glcoside, catechol complex salts, etc. are illustrated.
  • organic tin compounds expressed by ageneral formula of R,,,S,,X 'are suitable.
  • Sn is tin atom
  • m is an integer of l-4
  • Vx is a valency of X atom
  • 4-m/vx is an integer of 0-3
  • R is an aliphatic group having 1 l8 carbon atoms, acyclic radical having 3-6 rings, or an aromatic group
  • the above-mentioned ester-exchange catalyst is used in an amount'of 0.005 0.5% (inclusive) be weight, preferably 0.0l0.3% (inclusive) by weight relative to the produced polymer.
  • the above-mentioned polymerization catalyst is used in an amount of 0.005-0.5% (inclusive) by weight, preferably 0.0l-0.5% (inclusive) by weight relative to the produced polymer.
  • the crystallization velocity of the resultant polymer is particularly fast.
  • Half crystallization time as measured by changing the temperature of polymers melted at 290C for 10 minutes immediately to 220C and maintaining the polymers at this temperature by using aDifferential Scanning Calorimeter made by Perkin Elmer C0, is within 2 minutes. This fast crystallization velocity is believed to give advantageous infiuence uponstretching, orientation and crystallization at the time of high speed taking-up.
  • the hole diameter of spinneret used in the spinning of the present invention is greater than 0.25 mmd) and smaller than 0.9 mmdJ (inclusive). When it is within this range, the stability is extremely good at the time of spinning. When the hole length of spinneret is greater than 1.5 mm and smaller than 10 mm (inclusive), most uniform fibers can be obtained. When it is smaller than 1.5 mm,
  • take-up is a device which determines the running speed of extruded filament yarns after cooled and solidified. It is not limited only to a device for winding up filament yarns on bobbins which are used together with a common driving mechanism. It also includes the entire apparatus containing a device which runs the filament yarns at a substantially high speed such as an air jet device, etc.
  • the material which affords friction comprises a pin which does not rotate or a revolving roller.
  • a revolving material it is necessary to make the peripheral speed of revolving material slower or faster than the speed of filament yarns.
  • EXAMPLE 1 Polyethylenel ,2-diphenoxyethane-p,p dicarboxylate having an intrinsic viscosity of polymer of 0.65 and an amount of residual carboxyl group of polymer of 1 6eq./l0"' g., produced by the polymerization using 0.03 part of manganese acetate as an ester exchange catalyst and 0.01 part of germanium dioxide as a polymerization catalyst, was extruded through a spinneret having a diameter of each hole of 0.35 mmd and a length of 2 mm at a spinning temperature of 290C and subjected to spinning under varied spinning conditions. Results obtained are indicated in Table I.
  • the intrinsicyiscosity and'the residual carboxyl group of the polymer were 84 and 13 ,eq JIIO g., respectively.
  • Resultant polymer was extruded from a spinneret having a diameter of each hole of 0.45 mm, 10
  • EXAMPLE 3 Polyethylene-l ,Z-diphenoxy p,p'dicarboxylate having an intrinsic viscosity of polymer of 0.73 and a residual carboxyl radical of polymer of 14 eq./10 g., produced by the polymerization using manganese acetate as an ester exchange catalyst and ethanegermanium dioxide as 'a.polymerization'catalyst, was
  • the resultant mixture was heated at 280C, under a reduced pressure below 1 mm Hg, in a polymerizationivessel", in the presence of a polymerization catalyst, 0.03 part of TiO as a delustering'agent and 0.1 'part of 'triphenyl phosphite as a stabilizer, and formed ethylene glycol was eliminated.
  • the intrinsic viscosities of the polymer and the amounts of residual carboxyl group in'th'e polymer producedi n the presence of various ester'exchang'e catalysts and polymerization catalysts are shovvn in the'following Table IV.
  • EXAMPLE 5 The polymer used in Example 1 was melt-extruded from a spinneret having holes of 2 mm length and various diameters; at a spinning temperature of 290C.
  • Fibers whose monofilament denier was 2 were ob tained at a take-up speed of 3000 m/min.
  • the spinning conditions in this case are shown in the following Table V, in term of number of times of breakages of fibers in case of continuous spinning carried out for 8 hours.
  • the physical properties of fibers obtained in the spinning carried out under the same conditions and by the use of a spinneret having holes of various lengths and diameters, are shown in Table VI, expresssed in term of deviations from the arithmetic mean values in the The polymer used in Example 1 was melt-extruded from a spinneret having a diameter of each hole of 0.35 mmd and a length of 2 mm, at a temperature of 290C.
  • the temperature at the zone apart from the spinneret by 5 to 90 cm was miiintained 'at' a pre-determined point by installing a Heating or cooling tube of l m length immediately" below the spinneret.
  • a cooling wind of -l 0C was directly blown to the spinneret from a compressor.
  • the physical properties of fibers whose moiifilament denier was 2 and which above-mentioned cases, are shown in' 'Table VII.
  • EXAMPLE 7 90 parts of 1,2-bis-p-carbomethoxyphenoxyethane and 7.5 parts of ethylene glycol were heated at 220C, for 4 hours, in the presence of 0.04 part of barium acetate as an ester exchange catalyst, and formed methanol was eliminated. Thereafter, the resultant mixture was heated at 280C, under a reduced pressure below 1 mm Hg, in a polymerization vessel, in the presence of a mixture of 0.03 part of dibutyl tin oxide as a polymerization catalyst and 0.03 part of TiO as a delustering agent and 0.1 part of triphenyl phosphite as a stabilizer, and formed ethylene glycol was eliminated.
  • the polymer thus obtained had an intrinsic viscosity of polymer of 0.73 and a residual carboxyl radical of polymer of 12 eq./l g..
  • the polymer was melt-extruded from a spinneret having a diameter of each hole of 0.5 mm and a length of 3 mm, at a spinning temperature of 295C, and resultant filaments were taken up at a take-up speed of 3000 m/min., while passing through-a heating tube of l m length installed below the spinneret and maintained at 160C.
  • the fibers thus obtained whose monofilaments denier was 2 denier had a yield strength of 2.4 g/d, a tenacity of 4.2 g/d, an elongation,of 38%, and a Youngs modulus of 118 g/d, and were. excellent in uniformity.
  • said polymer having an intrinsic viscosity of between about 0.4 and 1.3, and containing less than about 20.0 eq./l0 g. of residual carboxyl group in the polymer, and taking up the resultant extruded fibers at a velocity ranging from about 1800 to 3500 m/min.
  • a process according to claim 1 wherein the fibers so produced have a yield strength of at least 1.0 g/d., an initial modulus of elasticity of at least g/d., a breaking strength of at least 3.0 g/d., and a residual elongation of less than 5.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
US810775A 1968-04-09 1969-03-26 Method for direct spinning of polyethylene-1,2-diphenoxyethane-p,p{40 -dicarboxylate fibers Expired - Lifetime US3895090A (en)

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US (1) US3895090A (enrdf_load_stackoverflow)
DE (1) DE1918057A1 (enrdf_load_stackoverflow)
FR (1) FR2009817A1 (enrdf_load_stackoverflow)
GB (1) GB1231337A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4069657A (en) * 1975-07-18 1978-01-24 E. I. Du Pont De Nemours And Company Yarn texturing process
US5242645A (en) * 1989-11-15 1993-09-07 Toray Industries, Inc. Rubber-reinforcing polyester fiber and process for preparation thereof
US5509996A (en) * 1988-07-12 1996-04-23 Geophysical Engineering Company Method of evaporating and cooling liquid

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2604689A (en) * 1952-06-18 1952-07-29 Du Pont Melt spinning process and fiber
US2604667A (en) * 1950-08-23 1952-07-29 Du Pont Yarn process
US2957747A (en) * 1958-07-22 1960-10-25 Du Pont Process for producing crimpable polyamide filaments
US3048467A (en) * 1957-06-10 1962-08-07 Union Carbide Corp Textile fibers of polyolefins
US3161710A (en) * 1961-07-27 1964-12-15 Du Pont Polymerization process for polyester films
US3215486A (en) * 1962-04-17 1965-11-02 Toyo Spinning Co Ltd Fixation of polypropylene fibers impregnated with dyestuffs and other treating agents
US3361859A (en) * 1960-04-29 1968-01-02 Du Pont Melt-spinning process
US3475381A (en) * 1967-03-23 1969-10-28 Fmc Corp Preparation of polyethylene terephthalate by direct esterification in the presence of a metal citrate as a direct esterification catalytic additive
US3513110A (en) * 1965-07-26 1970-05-19 Celanese Corp Open-celled low density filamentary material
US3624031A (en) * 1967-12-27 1971-11-30 Asahi Chemical Ind Process for producing a polyethylene-1,2-diphenoxyethane-4,4{40 -dicarboxylate
US3642697A (en) * 1968-06-03 1972-02-15 Asahi Chemical Ind Preparation of polyethylene 1 2-diphenoxyethane -4 4'-dicarboxylate using strontium calcium and barium compounds as an ester interchange catalyst and antimony compound as a polymerization catalyst
US3654225A (en) * 1968-06-01 1972-04-04 Asahi Chemical Ind Process for the preparation of polyethylene 1 2 - diphenoxyethane-4 4'-dicarboxylate using a manganese compound as an ester interchange catalyst and amorphous germanium dioxide as a condensation catalyst

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2604667A (en) * 1950-08-23 1952-07-29 Du Pont Yarn process
US2604689A (en) * 1952-06-18 1952-07-29 Du Pont Melt spinning process and fiber
US3048467A (en) * 1957-06-10 1962-08-07 Union Carbide Corp Textile fibers of polyolefins
US2957747A (en) * 1958-07-22 1960-10-25 Du Pont Process for producing crimpable polyamide filaments
US3361859A (en) * 1960-04-29 1968-01-02 Du Pont Melt-spinning process
US3161710A (en) * 1961-07-27 1964-12-15 Du Pont Polymerization process for polyester films
US3215486A (en) * 1962-04-17 1965-11-02 Toyo Spinning Co Ltd Fixation of polypropylene fibers impregnated with dyestuffs and other treating agents
US3513110A (en) * 1965-07-26 1970-05-19 Celanese Corp Open-celled low density filamentary material
US3475381A (en) * 1967-03-23 1969-10-28 Fmc Corp Preparation of polyethylene terephthalate by direct esterification in the presence of a metal citrate as a direct esterification catalytic additive
US3624031A (en) * 1967-12-27 1971-11-30 Asahi Chemical Ind Process for producing a polyethylene-1,2-diphenoxyethane-4,4{40 -dicarboxylate
US3654225A (en) * 1968-06-01 1972-04-04 Asahi Chemical Ind Process for the preparation of polyethylene 1 2 - diphenoxyethane-4 4'-dicarboxylate using a manganese compound as an ester interchange catalyst and amorphous germanium dioxide as a condensation catalyst
US3642697A (en) * 1968-06-03 1972-02-15 Asahi Chemical Ind Preparation of polyethylene 1 2-diphenoxyethane -4 4'-dicarboxylate using strontium calcium and barium compounds as an ester interchange catalyst and antimony compound as a polymerization catalyst

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4069657A (en) * 1975-07-18 1978-01-24 E. I. Du Pont De Nemours And Company Yarn texturing process
US5509996A (en) * 1988-07-12 1996-04-23 Geophysical Engineering Company Method of evaporating and cooling liquid
US5242645A (en) * 1989-11-15 1993-09-07 Toray Industries, Inc. Rubber-reinforcing polyester fiber and process for preparation thereof

Also Published As

Publication number Publication date
GB1231337A (enrdf_load_stackoverflow) 1971-05-12
FR2009817A1 (enrdf_load_stackoverflow) 1970-02-13
DE1918057A1 (de) 1970-05-21

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