KR800001163B1 - Process for preparing (co)polyazomethines - Google Patents

Abstract

Fiber or films of (Co)polyazomethines consisted of I and II, wherein unit I and II are present in supstantially equimolar amounts; Z1 and Z2, which may be the same or different are selected from the hydrogen atom or a methyl or ethyl radical; and R1 and R2 are radicals selected from the group of single and fused 6-membered carbocylic ring system.

Description

(Co) preparation method of polyazomethine

The accompanying drawings are the transmission and background transmission curves of light obtained for the solid and molten state of two different kinds of polyazomethine.

The present invention relates to a process for the preparation of melt-proseable aromatic and substituted polyazomethyl and copolyazomethine exhibiting polymer melting temperatures up to 37 ° C., intrinsic viscosity of at least 0.2, and optical anisotropy in the molten state. The present invention also provides useful culture fibers spun from these polymers without the need for post-stretching.

Many spun fibers substantially increase the orientation and strength and also increase the counting rate when heated to temperatures above 100 ° C. and below the melting point in relaxed or strained conditions. Other shaped bodies such as films and bars can be made from polymers.

Dopes (or solutions) of synthetic polyamides are known as optically anisotropic for the dope of US Pat. No. 3,671,542 to Kwolek, for example. Liquid crystal crystal development is described in the polyolefin literature according to the art. Polyazomethines [or poly (shape bases)] are extensively described in the literature. (“Encyclopedia of Polymer Science and Technology.Vol. 10, 659-670 (1960), Interscience Publishers, New York, G.F.D Alelio and patent documents, ie US Pat. Nos. 3,526,611 and 3,418,281)

Polyazomethines that can be molded at high temperatures and pressures are described in US Pat. No. 3,418,281 and UK Pat. No. 1,080,526. This polymer is known to have excellent thermal stability and toughness. Films of polyazomethine that are molded in diluents or molded at high temperatures and pressures are described in Becker et al. T 918005 (1974.1.1) United States Official Gadget. However, the above mentioned documents do not suggest that any aromatic polyazomethine can form an anisotropic melt directly melt-spun into filaments.

The polyazomethine and copolyazomethine of the present invention are composed mainly of repeating structural units selected from the following groups.

In the above structural formula

Units I and R are present in equimolar amounts,

Z ₁ , Z ₂ and Z ₃ are the same or different and are hydrogen or methyl or ethyl group,

R ₁ , R ₂ and R ₃ are (1) single and bonded 6-membered ring carbocycle rings (if necessary aliphatic ring-cyclic carbon can be substituted with nitrogen atom, where the chain extension bond of ring is attached to single ring When in 1,4-position to each other and in parallel and opposite directions when attached to different rings). Or (2) a polycyclic ring, preferably a carbocycle ring (each ring is connected by a chemical bond or by a bridging unit having a valence of 14 or less, preferably 4 or less, and the chain extension bond of each ring is in the 1,4-position And R ₁ is a chemical bond.

As a description of said (1),

ego,

As explanation of (2)

to be.

The rings described above may contain one or more substituents such as lower alkyl and chloro of 1 to 4 carbon atoms. In addition, up to 40 mole percent, preferably up to 25 mole percent, based on the total amount of I, II and III units, was replaced by polyazomethine forming units not consistent with those described above and hindered the anisotropic melt forming ability of the polymer. Poly (azomethine) which is not (co) is also included in the present invention. These units are not limited to the following.

As described above, the (co) polyazomethine may contain an equimolar amount of units (I) and (II), or a mixture of units (III) or units (I), (II) and (III) and unit (I) , II or II) One or more polymers may be present, for example

Preferred (co) polyazomethines of the present invention consist in particular of units (I) and (II). Such polymers include those in which R ₁ is chloro-, bromo-, methoxy, fluoro-, methyl-, hydroxy- and nitro-1,4-phenylene, 4,4'-biphenylene, 3,3'- Dimethyl-4,4'-biphenylene, 1,4-phenylene, 4.4'-methylenediphenylene, 4,4'-dimethylenediphenylene, 4,4'-trimetalenediphenylene, 4, 4'-tetramethylenediphenylene; 2,6-naphthalene, 1,5-naphthalene; 2,6-dichloro-1,4-phenylene; Trans-1,4-cyclohexylene; Trans-2-methyl-1,4-cyclohexylene; Trans-4,4'-methylenedicyclohexylene, 3,3'-dimethyl-4,4'-tetramethylenedioxydiphenylene;4,4'-azoxydiphenylene;3,3'-dimethyl-4,4'-azodiphenylene; And R ₂ is 1,4-phenylene; Chloro-1,4-phenylene; Methyl-1,4-phenylene; 4,4'-biphenylene;4,4'-oxydiphenylene;4,4'-ethylenediphenylene;4,4'-methylenediphenylene;4,4'-ethylenedioxydiphenylene;2,5-pyridinediyl;1,5-naphthalene;2,6-naphthalene;1,4-naphthalene;2,5-dichloro-1,4-phenylene;2,5-dibromo-1,4-phenylene;2,5-dimethoxy-1,4-phenylene;2-bromo-1,4-phenylene;2-methoxy-1,4-phenylene; And 2-hydroxy-1,4-phenylene group.

Most preferably at least 25% of the total number of rings in units (I) and (II) are ring substituted by groups consisting of chloro and methyl because of the stability including good processability and / or processability.

When only unit (III) is present or together with units (I) and (II) R ₃ is 1,4-phenylene, methyl-1,4-phenylene, 4,4′-oxydiphenylene, 2, Preference is given to being selected from 6-naphthalene, 1,5-naphthalene or chloro-1,4-phenylene. If the polymer consists of unit (III) or a mixture of units (I), (II) and (III), it is preferred that at least 25% of the rings in these total units be ring-substituted into groups consisting of chloro and methyl.

Preferred polymers are made of (1) methylene-1,4-phenylenediamine and terephthal aldehyde due to their good processability, so that their fibers are particularly tough and (2) methyl-1,4-phenylenediamine, 1 Prepared with, 4-phenylenediamine and terephthalaldehyde and (3) bis (4-aminophenyl) ethane and chloroterephthalaldehyde can obtain crystalline fibers with excellent hydrolytic stability.

The (co) polyazomethine of the present invention forms an anisotropic molten state and dissolves below 375 ° C., preferably below 350 ° C. to provide processability to fibers and other types of materials. Depending on the structure, rapid decomposition of the (co) polyazomethine occurs at high temperatures. The melt contains parallel connected polymer chains which are produced as spinning fibers in the spinning process.

The (co) polyazomethine of the present invention is capable of melt spinning. By "melt radioactive" is meant a polymer that can be melt spun and remain molten for the time required for the spin filament. Other (co) polyazomethines do not melt. It also instantly softens or spills at high temperatures to bend into an infusible material due to rapid polymerization. The melt-spun polymer of the present invention may be present in the molten state for at least 5 minutes.

The (co) polyazomethine of the present invention is functionally equivalent to the diamine of the following formula (I) and the dialdehyde or diketone of the following formula (II) and / or the aminoaldehyde or aminoketone of the following formula (III) or such a reactant Prepared by reaction with equivalent derivatives.

In the above structural formula

R ₁ , R ₂ , R ₃ , Z ₁ , Z ₂ , and Z ₃ are as defined above.

Diamines useful for preparing the polymers of the present invention correspond to the following structural formula.

In the above formula

R ₁ is as mentioned above.

That is, they are 1,4-phenylenediamine-chloro-1,4-phenylenediamine, bromo-1,4-phenylenediamine-fluoro-1,4-phenylenediamine, methyl-1,4-phenylene Diamine, methoxy-1,4-phenylenediamine, nitro-1,4-phenylenediamine, 2,6-dichloro-1,4-phenylenediamine, 4,4'-diaminobiphenyl, 3,3 ′ -Dimethyl-4,4′-diaminobiphenyl, bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 2 , 6-naphthalenediamine, trans-1,4-cyclohexanediamine, 2-methyl-trans-1,4-cyclohexanediamine, bis (trans-4-amino-cyclohexyl) methane, hydrazine and the like. Diamines are used in the form of neutrals (ie lithium carbonate) salts (ie, such as dihydrochloride salts) in the reaction.

Dialdehydes and diketones useful in preparing the polymers of the invention correspond to the following structural formulas.

In the above formula

R ₂ and Z ₁ and Z ₂ are as mentioned above. That is, they are 1,4-diacetylbenzene, 4,4'-diacetylbiphenyl; Terephthalaldehyde, chloroterephthalaldehyde; Methyl terephthalaldehyde; 2,5-dipotmilpyridine; 4,4'-diformylbiphenyl;2,6-diformylnaphthalene; 1,5-diformylnaphthalene 1,4-diformylnaphthalene; Bis (4-prylphenyl) methane; Bis (4-formylphenyl) ethane; Bis (4-formylphenyl) ether; 1,2-bis (4-formylphenoxy) ethane; 2,5-dichloroterephthalaldehyde, 2,5-dibromoterephthalaldehyde, 2,5-dimethoxyterephthalaldehyde; 2-bromoterephthalaldehyde; 2-methoxyterephthalaldehyde; 2-hydroxyterephthalaldehyde and the like.

The aminoaldehydes and aminoketones useful for preparing the polymers of the invention correspond to the following structural formulas.

From above

Z ₃ and R ₃ are as described above.

These are 4-amino-3-chlorobenzaldehyde; 4-amino-3-fluorobenzaldehyde; 4-amino-3-methylbenzaldehyde; 4-amino-3-chloroacetophenone; 4-amino-3-fluoroacetophenone, 4-amino-3-methylacetophenone, and the like. It can be seen that mixing of the reactants produces no anisotropic melt. Mixing of reactants that produce polymers with melting points above 375 ° C. should be avoided, and products of such high melting points are difficult to prepare (ie spin into useful fibers).

The different blends of reactants indicate that the polymer is temporarily softened and then polymerized further into a non-solid, regardless of anisotropy. Such a polymer is far from the background of the present invention. This polymer is limited in its use because it cannot be melt spun. However, if end caps or continuous transitions are used in the preparation of such polymers, the product obtained is an end cap polymer that exhibits anisotropy in the melt. The present invention relates to only anisotropic melts wherein the end caps are added during the polymerization to form (co) polyazomethines, whether or not the polymers are end caps.

The (co) polymer of the present invention has a sufficient molecular weight that exhibits fiber forming properties in the polymer. Some (co) polymers do not dissolve in the solvents used to measure intrinsic viscosity. Good fibers and films are obtained from these (co) polymers as well as those obtained from polymers having an intrinsic viscosity of at least 0.2 (preferably at least 0.1) according to all the measurement methods described below. The melting point of the polymer is somewhat dependent on the intrinsic viscosity, ie, the polymer having a low intrinsic viscosity, which generally melts at lower temperatures than the same polymer having a higher intrinsic viscosity.

[Polymerization Condition]

Polyazomethine and copolyazomethine are prepared by thermal polymerization from suitable monomers, preferably by polymerization under anhydrous conditions in an inert atmosphere. For example, the same amount of reactive diamine and dialdehyde (or derivative thereof, such as diacetal) are mixed in the reaction vessel. The contents in the vessel are stirred and heated and the contents are kept under nitrogen. When polymerizing the reaction, the off-product (ie water or alcohol) is removed. When the polymerization proceeds at a desired point, the polymer is taken out and purified. When melted, the polymer is optionally produced by direct transfer to a suitable container, such as a fiber spinning device. The reactants are dissolved in a solvent (eg benzene) which forms an azeotrope with the adduct and assists in removing the adduct. After completion of the polymerization, the precipitated product is filtered off, the soluble product is separated and the residual solvent is evaporated.

The (co) polymer of the present invention is also produced by a low temperature solution polymerization method using a polar solvent. One convenient method is polarity selected from the group of N, N-dimethylacetamide (DMAC), N-methylpyrrolidone-2 (NMP), hexamethylphosphoamide (HMPA) or mixtures thereof, for example diamines. It dissolves by containing lithium chloride in the amide solvent. Dialdehyde is added and the reaction mixture is stirred. The reaction proceeds for several hours to several days. The reaction mixture is mixed with a nonsolvent (e.g. water) and then accumulated, thoroughly washed (e.g. water, ether, methanol), deaerated and processed.

In order to easily perform the following processing, it is preferable to use an end capping agent or a chain stopper during these polymerizations. Useful terminators include aniryl, 4-carboxybenzaldehyde, 4-aminoacetanilide, 4-amino-3-methylbenzoic acid, benzaldehyde and benzoyl chloride. Although benzoyl chloride is satisfactorily used, reagents that generally cause photoacids (weakening polymers) should be avoided. Their stoppers assist in inhibiting or minimizing the increase in the molecular weight of the polymer during melt spinning. For example, during spinning, if the molecular weight is higher due to the polymer, spinning may yield or stop poor quality fibers. When performing heat treatment in fiber formation, it is necessary to grow some chains, and thus, chain stops which completely prohibit polymerization should be avoided.

If desired, the end cap can be achieved without the injection of other reagents. For example, one of the reactants is used in excess (above stoichiometric amounts) and a closed system or other mechanism is used to prevent the rapid loss of excess reactants, which acts as endcaps. This method is described in the literature as another polymer. [“Fibres from Synthetic Polymevs” -R. Hill, Elsevier Publishing Co, Amsterdam, 1953 (pp. 106, 107)] A thermally stable antioxidant can be added to the reaction mixture to make it useful for subsequent processing.

[Anisotropic Melt]

Anisotropy in the molten state of the polyazomethine and copolyazomethine of the present invention adjusts the degree of orientation, strength, and initial elastic modulus of the fibers produced from the agglomerate, and increases tension by heat treatment mainly in the relaxed or strained state. Impart tension to some of these fibers.

The optical anisotropy of the (co) polyazomethine melt can be determined by known methods which are somewhat improved. Since the conduction of light is theoretically zero for isotropic materials, it is well known that translucent light-emitting anisotropic materials cause light to conduct interference deviations to the optical system. See S.A. Jabrin and R.S. Stein, J. Phys., 77, (1973).

In the former way an anisotropic melt takes place immediately. The thermo-optic test (TOT) described below uses this apparatus to identify these melts. This mechanism is similar to that described in the literature. [I. Krishenbaum, R. B. Isaacson, and W.C. Feist, Polymcr Lettens, 2, 897-901 (1964).

[Production of Molded Products]

The (co) polyazomethines of the present invention are formed into useful shaped articles such as fibers, films, bars or other molds by compression or by spinning, by molding or by extruding their anisotropic melts. The skilled artisan readily determines the optimum process temperature within the anisotropic melt range for each sample to obtain the desired properties for the molded article. Care should be taken to avoid pyrolysis or the formation of isotropic melts (ie by heating to excessive high temperatures).

The highly oriented and strong fibers of the present invention are made from the above-mentioned (co) polyazomethine. In the fabrication of the present invention, the amount of molten polymer obtained from the melt or from the melt of the (co) polymer forming component or from the block of the filling or the block of the (co) polymer is processed through melt spinning and quenched through a spinneret. Ie air kept at room temperature). As used herein, “spun fibers” refers to fibers that are not stretched, elongated or heat cooled after extrusion and general winding. Indeed, the “spun” fibers of anisotropic melts cannot be stretched to the usual rigid angle, ie 100% or more.

Fibers are typically made from single or porous spinning nozzles. The temperature maintained in the melt zone and spinneret in the melt chamber, of course, varies as the polymer is spun. Heating is preferably used in the spinneret and a short melting zone above the spinneret, which keeps it below the intrinsic viscosity and emits more easily. Filtering screens and discs are used in the spinneret pack. Air or nitrogen is used as a quench medium when the fibers leave the spinneret. The spinning fiber is wound at a displacement speed of 90 m / min to 1200 m / min or more. The radial draws vary with spinneret size, extrusion ratio and winding speed. If desired, processing is used for spinning fibers.

The film is produced by conventional melt compression methods, for example, the ratio is produced by conventional methods.

[Fibers, Films, Bars: Properties, Heat Treatment, Usability]

The spinning fibers of the present invention are highly oriented, for example, exhibiting low values of about 45 ° or less of these X-ray orientation angles. In addition, the spun fiber exhibits properties that differ from the desired balance of tension. For example, many spinning fibers are characterized by a tensile strength of at least about 4 gpd and an initial modulus of at least 400 gpd (often at least 500 gpd).

The fibers of the present invention are useful for fiber reinforced plasticity and other industries.

In using these fibers, the fibers are exposed to the base medium or at elevated temperatures, for example, the reinforcement resins often cure with a base catalyst, the rubber compounds generally contain organic amines and the cure is often hot for the time periods in which they appear. It implies The fibers of the present invention are generally resistant even in adverse conditions. It can be seen that the fibers have good strength retention after exposure to morphine, sodium hydroxide, rubber or heat aging.

) 또는 평평한 상태의 섬유 열처리는 통살적으로 고분자량의 고유점도가 증가하에 된다. 열처리로 고유점도가 증가하는 섬유는 강력이 증가함을 알 수 있다. 따라서 열처리의 온도 및 시간을 선택하여서 고유점도의 증가를 이룬다.The spin fiber of the present invention is subjected to a heat treatment method to form the heat-treated fiber of the present invention having an extremely high balance of tensile properties in which the spin fiber is usefully produced as a tire reinforcing material. Surprisingly, fiber-Frax mainly relaxes, ie, scans or flexes at temperatures above 100 ° C and below the fiber melting point (preferably within 20 ° C of the melting point).

) Or the heat treatment of the fiber in a flat state is usually under high molecular weight intrinsic viscosity. It can be seen that the fibers having increased intrinsic viscosity by heat treatment have increased strength. Therefore, the intrinsic viscosity is increased by selecting the temperature and time of the heat treatment.

The heating temperature is preferably maintained at a temperature at which the fusing between the filaments substantially occurs. For practical purposes, heating is carried out for as short a time as possible to consistently obtain increased strength. Depending on the polymer, the heating time is about 5 seconds, generally from 1/2 hour to 24 hours or more. Typically, heating above 8 hours does not produce an improved product. The heat treatment must be carried out around an inert atmosphere that does not adversely affect the fiber, and nitrogen is suitable for this purpose. Fibers having a strength of at least 10 gpd are preferred and the heat treatment of the plurality of spun fibers of the present invention is a balance of strength. The increase in the degree of orientation measured by the X-ray orientation angle is also a heat treated fiber. Preferably, the heat treated fibers of the present invention have a modulus of at least 150 gpD, an elongation of at least 2%, an orientation angle of 45 ° or less, and do not melt at 175 ° C. or less (preferably 250 ° C. or less).

[Measurement and test]

X-ray orientation angle

The above mentioned X-ray orientation angles (O.A) values are obtained using the two methods described in kwolek US Pat. No. 3,171,542.

[Unique viscosity]

경화의 등량을 밀폐된 병에 혼합하고 극히 짧은시간, 통상적으로 10 내지 25분 동안 기구에 방치하여 용액을 형성한다. 요동(shaking) 케논-펜스크(Cannon-Fenske) 점도계는 전환 기술로 충전하고 포타슘 디크로메트의 포화수용액으로 이루워진 일정한 온도욕에 방치한다. 3연속 유동시간은 즉시 측정하고 요동조작은 어두운데에서 행하고 모든 이송단계는 빛이 없는 곳에서 즉시 행한다. 용액유동시간이 연속 측정으로 감소한다면, 가장 긴시간은 η inh를 산출하는데 사용된다.Intrinsic viscosity (η inh) is defined by the following equation: η inh = In (η rel) / C, where (η rel) is the relative viscosity and C is the concentration of 0.5 g of polymer in 100 ml of solvent. Relative viscosity (η rel) is determined by dividing the flow time in the capillary viscometer of the dilute solution of the polymer by the flow time for the pure solvent. The dilution solution used above to determine (3 rel) is the concentration represented by (C) above, the flow time is determined at 30 ° C., the solvent is concentrated sulfuric acid (98% H ₂ SO ₄ ), and other solvents (ie Methanesulfonic acid) is used when the decomposition takes place in sulfuric acid. Polymer Sample (or Fiber) 98% Sulfuric Acid, and 3mm Telfon

Equivalent amounts of curing are mixed in a closed bottle and left in the apparatus for a very short time, typically 10-25 minutes, to form a solution. Shaking The Cannon-Fenske viscometer is filled with the conversion technique and left in a constant temperature bath consisting of saturated aqueous solution of potassium dichromet. 3 Continuous flow time is measured immediately, rocking operation is done in the dark, and all transfer steps are done immediately in the absence of light. If the solution run time is reduced by continuous measurements, the longest time is used to calculate η inh.

[Fiber Tension]

The properties of the filaments and yarns are measured by the method shown in Morgan, US Pat. No. 3,827,998, with at least three cuts averaged. It should be noted that different values are obtained from the single filament (filament properties) and the multifilament strands (satellites) of the same sample. Unless specifically different, all properties given herein are filamentary properties.

[Optical anisotropy]

Optical anisotropy is measured by the TOT method described below.

[TOT measuring device and flow temperature measuring device]

The optical test (TOT) requires a polarization microscope, which has a sufficiently high extinction coefficient having an optical system free of contamination and a crossover (90 °) polarizer capable of measuring the background transmittance described below. Leitz Dialux-Pol microscope was used for the measurement method reported here. A polaroid polarizer, a binocular welding eyepiece, and a heating table are attached to this.

The photodetector is attached to the top through a microscope. The microscope has a 32-fold magnification, a long objective lens with a working distance, and an optical (first absorption color) plate (the latter can only be used when the eye can be visualized using a cross polarizer). Has an angle of 45 °). The white light source from the incident light source is directed through the polarizer through the sample to the heating object and then through the analyzer to the photodetector or the eyepiece. The abnormality is moved from the eyepiece to the photodetector by the slide. It can heat to 500 degreeC used heated. The Unifrom MHS vacuum heater (Newton Highland, Massachusetts, USA) and Unitron Instruments of Needham Street 66 (02161) were used. The signal from the photodetector is amplified by the amplifier of the photodetector and supplied to the Y axis of the X-Y recorder. The response of the system to the light intensity was linear, and the accuracy of the measurement at the recording site was within ± 1 mm. The heating table is equipped with two attached thermocouples. 2 is connected to the X-axis of one X-Y recorder to record the temperature of the heating zone and the other is connected to the programmed thermostat. The microscope focuses visually on the attached polymer sample as follows (using a cross polarizer). The sample is taken out from the light, but the cover slip is left as it is. The polaroid analyzer of the microscope is taken out of the light, the slide is transported, the image is moved to the photodetector, and the yarn is adjusted so that the full width fluctuation (18 cm on the recording sheet) corresponds to 36% of the signal of the photodetector on the Y axis of the XY recorder. Let's do it. This is done by (1) adjusting the intensity of the light source to a preselected value corresponding to 5 cm of the view of the Y-axis of the recording paper and (2) increasing the amplification factor of the photodetector by 10 times. As a result, the full width of 8 cm of the recorder corresponds to (18/50) x 100, or 36% of the signal of the photodetector. The transmission in the background is recorded by placing the cross (90 °) polarizer and the cover slip in a light path without the sample. The background transmittance of the service system should be about 0.5 cm or less of the recording paper without depending on the temperature. For the TOT test and the measurement of the flow temperature, two samples are each made as follows. A small number of pure polymer particles were placed between the cover slips and visually observed while heating at a programmed rate of about 50 ° C./min on a heating table between cross (90 °) polarizers. The sample temperature (T) at which the rust of the particles becomes equal is visible to the eye of the flow, and this is recorded. Replica samples from polymer particles, each sandwiched on the cover slip, are inserted into two microscope slides. This finished product is placed on a heating tube preheated to a temperature (T + 10 ° C.) measured by a thermocouple inserted in the configuration on top of a portion of the heating plate. The finished product is heated to a higher temperature, so the pressure is applied to each sample with a wooden push rod, until the particles fuse and flow to form two thin liquid films. The finished product is immediately taken out, cooled and the solid film (as retained between cover slips) is separated from the finished product. Since the polymer sample is easily polymerized by this process, it is important to minimize heating time and completeness during preparation of the sample by this process.

TF의 붙화탄소중에 짧은 시간동안 침적하여 이것을 초음파로 진탕하는 것에 의하여 용이하게 제거할 수가 있다. 그리고 커버슬리프에 삽입한 필름의 다른 하나는 TOT법으로 사용하고 다른 하나는 유동온도의 결정에 사용한다. 유동온도는 시료를 TOT장치중에 약 50℃/분의 프로그램된 속도로 가열했을때에 필름의 상의 등고선이 변화하는 온도이다. 이들의 (공)중합체 또는 섬유의 유동온도는 그 변력에 의하여 변화하는 것을 주의해야 한다. 예를들면 계단상의 가열을 하면 통상 유동온도는 상승한다. 이것에 의하여 최초의 유동온도이상이지마는 새로이 도달한 유동온도보다 낮은 온도로 가열할 수 있다. 보고된 유동온도는 이 방법에 의하여 측정된 것이다.It is preferable that the thickness of a polymer sample film is 4-6 micrometers. A film that is too thick or too thin may not display anisotropy on this sample. However, if the sample shows anisotropy, the test does not need to be repeated for samples of 4 to 6 μm. The thickness of the sample is measured by an interferometer. To do this, an indirect method of measuring the thickness of the oil layer in terms of economy with the air in the region close to the sample to be observed by the TOT method by injecting a known oil between the cover slips surrounding the sample is convenient. If you measure the thickness of the oil is

It can be easily removed by immersing in TF carbon for a short time and shaking it with ultrasonic waves. The other film inserted in the cover slip is used by the TOT method and the other is used to determine the flow temperature. The flow temperature is the temperature at which the contour of the phase of the film changes when the sample is heated at a programmed rate of about 50 ° C./min in the TOT apparatus. It should be noted that the flow temperature of these (co) polymers or fibers changes with their variation. For example, when heated on a step, the flow temperature usually rises. This allows heating to less than the original flow temperature but below the newly reached flow temperature. The reported flow temperature is measured by this method.

The sample of law is placed on a heating table so that substantially all of the light that crosses the photodetector passes through the sample. The intensity and temperature of the light is recorded on the X-Y recorder while the sample is placed between crossed (90 °) polarized light and the sample corresponds from 25 ° to 465 ° C. at a programmed rate of about 50 ° / min under nitrogen. Obtain the temperature of the sample from the recorded temperature using the appropriate calibration curve. When the (co) polymer that produces the melt is heated to a temperature above its flow temperature between the cross (90 °) polarizers, if the light passing through the obtained anisotropic melt is on the recording sheet, the height of the curve of transmitted light in the background A curve with at least 2 times and a height of at least 0.5 cm higher than that was found to be an anisotropic melt produced by the TOT method. When such a melt forms, the transmission curve of light (1) 2 is at least doubled to the background transmission curve and is at least about 0.5 cm larger than 2, or (2) at least to this value. Curve B in the accompanying drawings is an example of the strength curves commonly observed for systems producing anisotropic melts. When an isotropic melt (sample must be completely melted) between the cross (90 °) polarizers, the intensity of light passing through the analyzer is substantially the same as the background transmission curve (samples without a cover slip) Obtained by placing it outside the field of view using a 90 ° cross polarizer). When an isotropic melt is formed, the transmission intensity of light is (1) substantially equal to the background transmission intensity or (2) from a high value to this value. Curve A in the accompanying figures is an example of the strength curve of a polymer resulting in an isotropic melt.

The polyazomethine and azomethine (co) polymers of the invention sometimes exhibit optical anisotropy over the entire temperature range of the molten state, ie from the flow temperature of the polymer to the decomposition temperature or the highest test temperature. However, in some types of polyazomethine (co) polymers, some of the melt is isotropically thermally decomposed. In another class, the melt decomposes completely from anisotropic to isotropic as the temperature rises.

[Polymer Melt Temperature (PMT)]

EXAMPLES Polymer Melting Temperatures (Unless Otherwise Specified) Hot Bars, Prepartive Method of Polymer Chemistry Sorenson and Campbell 2nd Ed. Interscience Pub. (1968) (Pages 57-59). The polymer is in this form in the form of particles, a parent, a film or a fiber. The examples described below are large azomethine homo- and copolymers within the background of the present invention. These are represented by structurally defined naming, that is, homopolyazomethine prepared from 2-methyl-1,4-phenylenediamine and terephthalaldehyde is poly (nitrilo-2-methyl-1,4-phenylenenitrilomethyl) Din-1,4-phenylenemethylidine).

Example 1

This example describes the salt preparation of poly (nitrilo-2-methyl-1,4-phenylenenitriloethylidine-1,4-phenyleneethylidine) to form an optically anisotropic melt. 2-methyl-1,4-phenylenediamine (2.44 g, 0.02 mol) and 1,4-diacetylbenzene (3.24 g, 0.02 mol) are mixed in a 12-inch (30.5 cm) polymer tube. The reaction is heated for 1 hour at 156 ° C. and 2 hours at 205 ° C. under gentle nitrogen inflow. The product was collected and washed separately with water and methanol in a mixer and then dried at 80 ° C. under a weaver to yield 4.32 g of a polymerization product.

ηinh = 0.5

Polymer Melting Temperature: 370 ℃

Example 2

This example uses copoly- (nitrilo-2-methyl-1,4-phenylene nitrilomethylidine-1,4-phenylenemethylidine / nitrile using 4-acetamidobenzaldehyde as the reaction terminator. The preparation of methylidine-1,4-phenylenemethylidine) (90/10, molar base) with -1,4-phenyleneoxy-1,4-phenylene-nitrile will be described. 2-methyl-1,4-phenylenediamine (4.g, 0.036 mol) and bis (4-aminopropyl) ether (0.08 g) in a mixture of HMPA (25 ml), NMP (25 ml) and lithium chloride (2.0 g) 4-acetamidobenzaldehyde (0.4 g) was added to the solution. After a few minutes, terephthalaldehyde (5.36 g, 0.04 mol) is added. After 16 hours the reaction mixture is left to stand. The reaction mixture is mixed with water, the precipitated polymer is collected, washed and dried as in Example 1. Yield: 9.2 g.

ηinh = 1.1

The melting temperature of the copolymer is 306 ° C. and forms an anisotropic melt.

The following table (I) shows another (co) polymer of the present invention prepared according to the general preparation of Example 2. The dialdehydes used for this synthesis are terephthal aldehyde, methyl terephthalaldehyde, 1,2-bis (4-formylphenoxy) ethane and bis (4-formylphenyl) -ether. Diamines used are 2-fluoro, 2-chloro and 2-methyl-1,4-phenylene-diamine, 3,3'-dimethylbenzidine, 4,4'-axicydianiline, 3,3'-dimethyl- 4,4'-diaminoazobenzene and 1,2-bis (4-aminophenoxy) ethane. In Example 7, the reaction solvent is DMAc: A sample of this polymer is heated at 300 ° C. for 5 minutes and then pressed at a pressure of 211 kg / cm ² for 20 seconds at 325 ° C. to produce a flexible film. In preparing the copolymer of Example 9, hexamethylenediamine and 2-methyl-1,4-phenylenediamine dihydrochloride are used in equivalent amounts (each 0.005 mol), and lithium carbonate (0.01 mol) is generated. Used to neutralize acids. In Example 9-1, the reactant was DMAc / NMP (1/1) containing 0.002 molar amount of the reaction solvent containing 5% lithium chloride. In Example 9-2 the reactant was used in 0.0005 molar amount and the solvent was DMAC (1.5 ml) containing 5% lithium chloride and 0.004 g of the end cap was used. In Example 9-3 the solvent was DMAC (10 ml) containing 5% lithium chloride and 0.005 molar amount of each reactant was used. All samples were shown to form an anisotropic melt.

TABLE 1

(Co) polyazomethine synthesis: = NR ₁ -N = HC-R ₂ -CH =

* In methanesulfonic acid

AA-4-aminoacetanilide

Example 10

This example shows copoly (nitrilo-2-methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine / nitrilo-1,4-phenylenenitrilomethylidine-1, The manufacturing method of 4-phenylene methylidine) (95/5) is demonstrated. The copolymer is molded into a mold bar.

2-methyl-1,4-phenylenediamine (4.64 g, 0.038 mol) and 1.4-phenylenediamine (0.22 g, 0.002 mol) were added to a mixture of HMPA (20 ml), NMP (20 ml) and lithium chloride (2 g). To the solution is added terephthalaldehyde (5.36 g, 0.04 mol) under nitrogen. The reaction mixture was stirred for 16 hours at room temperature and treated as in Example 2 to obtain 8.6 g of copolymer. (Oven temperature 110 ℃)

ηinh = 4.7, PMT = 260 ° C

The copolymer melt is optically anisotropic. A sample of this product is placed in a bar mold and run at 300 ° C. for 15 minutes. The bars represent a flexural strength of 6.3 × 10 ³ lb / in ² , a flexural strength of 4.3 × 10 ⁵ lb / in ² , and a yield strength of 4.3 × 10 ³ lb / in ² , respectively. (4.43, 302 and 3.02kg / mm ² )

Example 11

This example describes a method for producing poly (nitillolo-2-methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine). This product is in the form of an anisotropic melt, spun into strong fibers and the tensile property is enhanced by relaxed heat treatment. A 2-methyl-1.4-phenylenediamine solution in 200 ml of ethanol is prepared at room temperature. A secondary solution of terephthalaldehyde (81.3 g, 0.61 mole) is prepared in 200 ml of reflux ethanol and these solutions are poured simultaneously into a 2-liter beer beaker. Polymerization starts in 1 to 3 minutes. The reaction mixture is left overnight at room temperature (under nitrogen). After the ethanol evaporated, the polymer residue was washed with 1 liter of water and dried in vacuo at 110 ° C for 1.5 hours. The dried residue is further polymerized in a heated spiral extruder.

A part of the extrudate is cast into a plug (ηinh = 6.0) and spun into air through a 5-hole A hole, 0.007 (0.018 cm) in diameter for each hole, spinneret temperature = 260 ° melt zone temperature (MZT) = It is wound at a speed of 600 yards / minute (548 meters / minute, bobbin A) from 225 to 262 ° C. Another bobbin, bobbin B, is wound at 900 yards / minute (822 meters / minute, MZT = 260 ° C.). Ηinh = 7.9 of bobbin “B” fibers. These properties are investigated in terms of spinning.

(Strength) (height) (initial elasticity) (density)

Bobbin Hoburn T E M Den.

A 7.3 1.1 916 20.0

B 6.4 0.92 900 15.1

A sample of the yarn from bobbin “A” is wound on a fiber-frax coated bobbin and heated in an oven under the following conditions.

(Continuously removing nitrogen): Normal temperature 160 ° C./2 hours, 180 ° C./2 hours, 200 ° C./4 hours, 250 ° C./12 hours After the operation, the fibers exhibit the filament properties as follows.

(Average of 15 specimens): T / E / Mi / Een: 28 / 3.2 / 939 / 4.3 The filament represents T / E / Mi / Den: 44 / 4.2 / 1118 / 4.2.

In another treatment, the specimen of the bobbin “A” thread is separated into short filaments (5) suspended vertically from the copper wire and heated under the following conditions while continuously removing nitrogen from the oven: 165 ° C / 40 minutes at room temperature, 165 To 230 ° C./1 hour, 232 ° C./1.3 hour, 234 ° C./6.3 hour.

After this treatment the fibers exhibit the filament properties as follows: T / E / Mi / Den. : 38 / 4.4 / 1012 / 3.7

Example 12

This example illustrates the preparation of poly (nitrilo-1,4-phenylenenitrilomethylidine-2-methyl-1,4-phenylenemethylidine) to produce an anisotropic melt.

The reaction mixture was subjected to HMPA / NMP (50/50 vol) containing 2-methyl terephthalaldehyde (0.20 g, 0.00135 mol), 1,4-phenylenediamine (0.146 g, 0.00135 mol) and 5% lithium chloride at room temperature. Obtained by stirring 3 ml of anhydrous mixture with stirring: After 15 minutes 4-acetamidobenzaldehyde (0.004 g) is added. The reaction mixture was stirred overnight at room temperature under anhydrous state, mixed with water to precipitate the polymer, which was collected, washed with water and anhydrous ethanol, respectively, and dried under vacuum at 80 ° C. About 0.2 g of polymer is obtained.

ηinh = 0.7, PMT = 270 ° C

Fibers from the melt at 270 ° C. exhibit filament tensile properties as follows:

T / E / Mi / Den. : 3.5 / 0.55 / 684 / 6.1

2-methyl terephthalaldehyde is 2-methyl-α /, α′-1,4-xylenediol [melting point 78 to 81 ° C .: 2-methyl terephthal oil by lithium aluminum hydride, Nystrom and Brown, J. Am. .Chem. Prepared by reduction by the general method described in Soc, 69, 1197 (1947), using a 1N ceric ammonium nitrate (NH ₄ ) ₂ Ce (NO ₃ ) ₆ . J. Org. It is prepared by oxidation by the general method of Chem 32, 3865 (1967). After stirring and heating for 30 minutes, the aqueous reaction mixture is extracted with ether (twice) and methylene chloride (twice). The combined organic layers are washed with aqueous sodium bicarbonate and water and dried over magnesium sulfate. The latter is filtered and the filtrate is evaporated to give a soft white solid which is sublimed at 65 ° C. to obtain a white powder. Melting point 70 to 71 ° C. The powder is recrystallized from water to produce 2-methyl-terephthalaldehyde. Melting Point: 71-72 ° C

Example 13

This example illustrates the production of poly (nitrilo-2-chloro-1,4-phenylenenitrilomethylidene-1,4-phenylenemethylidine) and its strong fibers. The melt of this polymer is optically anisotropic.

Stir the solution of 2-chloro-1,4-phenylenediamine (8.58 g, 0.06 mol) in a mixture of HMPA (30 ml), NMP (30 ml) and lithium chloride (3.0 g) in a tubular flask, remove nitrogen and remove 4 Add acetamidobenz aldehyde (0.4 g). Within a few minutes terephthal aldehyde (8.04 g, 0.06 mol) is added. The reaction mixture is stirred at room temperature, but after 16 hours it is not stirred. The reaction mixture proceeds as in Example 2 to give 13.8 g of polymer.

ηinh = 0.7, PMT = 310 ℃

The polymer is melt spun into the air through a 1-hole spinneret [hole diameter = 0.009 inch (0.023 cm) spinning lifting temperature = 320 ° C., melting part temperature = 310 ° C., pack with screen]

The resulting fiber is wound at 150 yards / minute (137.2 meters / minute). Spinning fibers (ηinh = 4.5) exhibit the following filament properties:

T / E / Mi / Den. : 7.4 / 1.3 / 683 / 10.9; O.A = 22 °

The fiber samples on the bobbin coated with Fiber-Frak are heat-treated in the oven as follows:

Heat treatment at room temperature 150 ° C., 30 minutes, 150 ° C. for 30 minutes, 150 ° to 260 ° C., 30 minutes and then at 260 ° C. for 3.5 hours. Then, taken out of the oven and cooled to room temperature, the fibers exhibit filament tensile properties as follows.

T / E / Mi / Den. 15.3 / 1.9 / 844 / 11.1; O.A = 10 °

Tables II-A and II-B below show the spun fibers from (co) polyazomethine and anisotropic melts. The polymer of Examples 14-19 is prepared by the general method of Example 2 and the spinning follows the general method of Examples 11-13. Dialdehydes used include 4,4′-diformyl-biphenyl, 2-chloroterephthalaldehyde, terephthalaldehyde and isophthalaldehyde. Diamines used include 1,4-phenylenediamine, 2-methyl-1,4-phenylenediamine and 4,4'-ethylenedianiline. Copolymers are shown in Examples 16, 19, and 19-2 (2-diamine) and 18 and 19-3 (2 aldehydes).

In order to give the fiber high strength and extensibility, heat is applied as indicated in Table II-B.

To prepare the polymer of Example 19-1, 1,4-bis (3-methyl-4-amino-phenoxy) -η-butane and terephthal aldehyde were combined with the antioxidant phenyl-α-naphthalamine in benzene. Reflux. The benzene-water azeotrope is collected and the precipitated polymer is filtered from the remaining benzene, washed with water and dried.

The polymer of Example 19-2 was selected from terephthalaldehyde, methyl-1,4-phenylenediamine and 1,12-bis (3-methyl-4-aminophenoxy) -η-dode by the general method of Example 19-1. Prepare cells with reactants.

The polymer of Example 19-3 was reacted with terephthalaldehyde, 4,4′-formylbiphenyl, methyl-1,4-phenylenediamine, 4-aminoacetanilide (terminal cap) and methylene glolide as a solvent. To prepare according to Example 19-1.

Table II-A

(Co) polyazomethine and fiber: NR ₁ -N = HC-R ₂ -CH =

TABLE II-B

Heat treatment of (co) polyazomethine fiber

1,4-bis (3-methyl-4-aminophenoxy) -η-butane, used in Example 19-1, was prepared in the same amount of 3-methyl-4-nitrophenol and 1, in the presence of anhydrous calcium carbonate dissolved in acetone. Prepared by reacting 4-dibromobutane. After refluxing for 48 hours, the solvent is removed and the solid product is recrystallized from 2-B alcohol to give brown needles 1,4-bis (3-methyl-4-nitrophenoxy) -η-butane. Melting Point: 126.5 ~ 127.5 ℃

The nitro compound is reduced to the desired diamino compound using hydrogen in the presence of a Ranickel catalyst and methanol (solvent) at a temperature of 1,000 to 15,000 lb / in ² , 70 ° C. or higher. The catalyst is separated from the solution, the solvent is evaporated and the desired diamine is recrystallized from ethanol (charcoal). Fusion: 108 to 110 ℃

In a similar manner, the 1,12-bis (3-methyl-4-aminophenoxy) -η-dodecane used in Example 19-2 is prepared from 1,12-dibromododecane.

Example 20

This example comprises group 4 ,, '-ethylenedianiline; A method for preparing copolyazomethine from a pair of diamines obtained from 1,4-phenylenediamine, bis (4-aminophenyl) ether and 1,4-cyclohexane diamine and 2-chloroterraphthalaldehyde. will be. The melt of such copolymers is optically anisotropic.

4,4′-ethylenedianiline (2.2 g, 0.01 mole) and 1,4-phenylenediamine (1.08 g, 0.01 mole) were added to HMPA (10 ml), NMP (10 ml) and lithium chloride (0.5 g) under nitrogen atmosphere. To the mixture was dissolved 2-chloroterephthalaldehyde (3.36 g: 0.02 mol) in a solution under nitrogen atmosphere. After 15 minutes 4-amino-acetanilide (0.12 g) is added. The reaction mixture was stirred overnight at room temperature and reacted as in Example 1 (drying at 70-75 ° C.) to methyl polydine 2-chloro with copoly (nitrilo-1,4-phenyleneethylene-1,4-phenylnitrile). 5.3 g of -1,4-phenylenemethylidine / nitrilo-1,4-phenylenenitrilomethylidine-2-chloro-1,4phenylene methylidine (50/50) are obtained.

Intrinsic viscosity: 0.5, polymer melting temperature: 150 ℃

Table III below relates to other copolymer compositions prepared according to the method using the pair of diamines described above to obtain copolymers having the indicated repeat units.

TABLE III

* Radiation T / E / Mi / Den / O.A = 2.9 / 4.1 / 114/16/17 °

Heat Treatment T / E / Mi / Den = 9.3 / 7.1 / 163/16

Example 21

This Example is excellent in tensile properties even after exposing fibers of poly (nitrilo-2-methyl, 1,4-phenylene nitrile to methylidine-1,4-phenylene-methylidine) to vaporized morpholine. Explain what is kept. A solution of 2-1,4-phenylenediamine (12.2 g, 0.01 mol) in a mixture of HMPA (60 ml), NMP (60 ml) and lithium chloride (5.0 g) was stirred in a 500 ml barrel of resin and terephthal aldehyde ( 0.30 g) is added. After 30 minutes 4-aminoacetanilide (0.30 g) is added and stirring is continued for a total of 16 hours. When the reaction mixture was reacted as in Example 1, 21.6 g of a polymer was obtained. Intrinsic viscosity = 3.0, polymer melting temperature = 256 占 폚, and the polymer melt is optically anisotropic.

The plug of the polymer is melt-spun. Spinneret temperature = 250 ° C, melted part temperature = 240 ° C, take-up speed = about 500 yards / minute (475 meters / minute) The spinning fiber (high viscosity = 3.3) shows the next filament tensile property.

T / E / Mi / Den / 9 / 1.6 / 789 / 6.4, a small sample of fiber and 0.03 ml of morpholine, were heated at 133 ° C. for 2 hours in a closed tube (steam bath). The fibers are taken out and left to stand in air for 1 hour. The fibers thus treated were T / E / Mi / Den = 8.2 / 1.1 / 736 / 7.4. Spinned fiber samples are heat treated under the following conditions.

The heat-treated fiber exhibits filament properties as follows at room temperature -160 ° C for 1 hour and at 200 ° C for 3 hours.

T / E / Mi / Den = 16 / 2.2 / 867 / 7.2

Example 22

This example demonstrates that even when the fibers of the present invention are thermally matured in a rubber stock containing (1) equivalents of amine, and (2) basic hydrolysis, the strength is excellent.

[part]

Another provided sample of the copolymer of Example 10 was heat treated under the following conditions to obtain the filament properties as follows at 150 ° C./40 minutes, 180 ° C./1 hour and 200 ° C./4 hour (early oven temperature 150 ° C.). To produce fibers.

T / E / Mi / Den = 9.9 / 1.4 / 788 / 7.3

The specimen heat-treated as above was wound on a skein and heat-treated at 154 ° / 24 hours at air pressure to obtain fibers having the following properties.

T / E / Mi / Den = 6.9 / 0.9 / 779/120

Thus, the heat-treated fiber is twisted with a 1000 denier cord, and the cord is buried in a rubber stock containing a large amount of amine to prepare a composite. The composite is thermally matured at 154 ° C. for 24 hours. The rubber is swollen with toluene and the fibers (cord) are taken out. The code's T / E / Mi = 2.2 / 0.80 / 472 (10 inch cut). This represents 32% strength retention under severe test conditions.

[Part B]

Example 10 Another Preparation of Polymer A sample yarn (4 filaments) was heat treated at 190 ° C. for 2 hours at 200 ° C. for 4 hours (initial oven temperature 190 ° C.) to have fibers having the filament properties as follows.

T / E / Mi / Den = 12.5 / 2.5 / 560 / 30.1

This fiber sample is hydrolyzed as follows.

Exam B-1

The 8 inch long fibers are lined in cheese cloth and heated in water for 2 hours / 95 ° C.

[Exam B-2]

This test is the same as B-1, except that 1N aqueous sodium hydroxide is used instead of water. After the test, the fibers and cloths are immersed in water to eliminate alkalinity. The hydrolysis treatment is followed by washing to determine the filament tensile properties of the dry fibers.

Test B-1 Fiber: T / E / Mi / Den: 8.1 / 1.8 / 512 / 34.7

Test B-2 Fiber: T / E / Mi / Den: 12.5 / 2.0 / 717 / 23.3

Example 23

This example demonstrates that the steel fabric retains excellent retention when the copolyazomethine fibers of the present invention are thermally matured in rubber. Copolymer of Example 16 Another sample is prepared. Intrinsic Viscosity = 1.2

The plug is spun (spindle temperature -250 to 252 ° C.) and several bobbins of fiber are wound in the range of 288-1,271 meters / minute speed. Bobbin filament T / E / Mi / Den = 6.4 / 1.1 / 717 / 4.3 at 1271 meters / min. Thirty of these filaments were heat treated at 230 ° C. for 7 hours to form tiny yarns together (3 turns / inch). The fibers thus treated exhibit the following properties.

T / E / Mi / Den = 11.41 / 1.3 / 906 / 120.5

Treat this thread (twist / inch twist) in rubber and retest as follows:

Sample yarns (approximately 20 inches long) are placed vertically between no pads, each 4 inches long. Tighten the rubber pad with the sampler and tie off the end of the thread to keep it twisted. The test specimen is heated for 24 hours at 165 ° C in air, cooled to room temperature, the end of the thread is fixed in an Instron tester, and the breaking strength of the embedded thread is determined. High concentrations and low concentrations of separated rubber stock are used.

The following results are obtained.

Cutting force of rubber stock

lb g / d

High concentration amines 2.83 10.7

Low Concentration Amine 2.61 9.8

These values represent 94% and 86% retention of strength, respectively.

Example 24

In this embodiment, the nitrilo-2-methyl-1,4-phenylene-nitrile, methylridine-1,4-phenylenemethylidine and nitrilo-1,4-phenylenemethylidine units are 4: 4: 1. It describes the melting production of rare copolymers in the ratio of. A 3-neck 250 ml round bottom flask was equipped with a stirrer, a nitrogen tube and a distillation head in which 2-methyl-1,4-phenylene diamine (7.32 g, 0.06 mol) 4-amino benzenealdehyde “oligomer” (1.58 g, 0.015 mol, intrinsic viscosity = 0.08, manufactured by Kard K Laboratories Plainview, NY) and N, N '-(1,4-phenylenemethylidine) dianiline (17.88 g, 0.06 mol) are combined. The blended ingredients are stirred and heated at 250 ° C. for 30 minutes under nitrogen. The reaction mixture (anisotropic melt) is then cooled to room temperature after heating at 250 ° C. for 10 minutes under reduced pressure of 5 mmHg. Upon heating, water and aniline, which are byproducts of polymerization, are distilled off. The remaining solid copolymer is collected, cut in the blender, washed with acetone and dried under vacuum at 80 ° C. 13.3 g of copolymer is obtained. Intrinsic viscosity = 3.2 Polymer Melting Temperature = 210 ° C. The copolymer forms an anisotropic melt.

The fiber produced was melt-spun into the air with a 1-hole spinneret (hole diameter = 0.009 inches (0.023 cm), spinneret temperature = 230 ° C melt range temperature = 225 ° C) and produced 500 yards / min (457.2). Wind at a rate of meters / minute).

Spinning fibers exhibit the following filament properties.

T / E / Mi / Den: 3.7 / 0.7 / 556 / 7.2

A portion of this fiber is wound up to a fiber-fax failure and heated in nitrogen in an oven at 240 ° C. for 6 hours. Treated filaments exhibit the following properties.

T / E / Mi / Den: 10.3 / 1.7 / 659 / 7.2

[Part B]

Nitrilo-2-methyl-1,4-phenylene nitrilo, methylridine-2-chloro-1,4-phenylene-methylidine and nitrilo-1,4-phenylenemethylidine unit (2: 2: 1 ratio) to prepare a copolymer.

This copolymer forms an anisotropic melt. Repeat the procedure from Part A above, but 4.88 g (0.04 mole) diamine, 2.12 g (0.02 mole) “oligomer” and 12.74 g (0.04 mole) N, N- (2-chloro-1,4-phenylene Methylidine) dianiline was used for 20 minutes at 250 ° C. at atmospheric pressure and then at 250 ° C. for 20 minutes at 10 mmHg pressure.

11.7 g of copolymer are obtained. Intrinsic viscosity = 1.5, polymer cloth melting temperature = 230 ℃

The copolymer forms an anisotropic melt.

Example 25

This example illustrates the preparation of poly (nitrilo-2-methyl-1,4-phenylene nitrile methylridine-2,6-naphthalin-methylidine).

2-methyl-1,4-phenylenediamine (1.22 g, 0.01 mol) and N, N '-(2,6-naphthalene dimethylidine)-dianiline (3.3 g, 0.01 in a reaction vessel with a distillation head Mole).

These reactants are melted and stirred at 250 ° C. for 20 minutes. Aniline sub-products are distilled and collected.

The reaction product was cooled, collected, washed with acetone and dried to yield 3.22 g of polymer.

Polymer melting temperature = 245 ° C., intrinsic viscosity = 0.6

The polymer forms an anisotropic melt.

N, N '-(2,6-naphthalin dimethylidine) dianiline is a mixture of 2,6-naphthalene dicarbonyl chloride (50.6 g, 0.02 mol) in ethylene glycol dimethyl ether (150 ml) and ethylene glycol dimethyl ether (700 ml) It is prepared by reduction with lithium tri-tert-butoxyaluminum hydride (103 g) in water. The stirred acid chloride was placed under -70 ° C nitrogen and a reducing agent was added dropwise over 4 hours, and then the combined components were stirred overnight and then allowed to warm to room temperature.

The reaction mixture is poured onto ice and when white product precipitates, it is taken out and extracted with hot (boiling) 2B alcohol (with moisture). Separation of hot alcohol and residual solids and distillation of the alcohol extracts leave crude yellow crystals 2,6-naphthalin dialdehyde. Melting point 162 to 190 ° C. (slightly unmelted material remains)

Crude dialdehyde (4.0 g) is dissolved in ethiol (200 ml) with stirring. Aniline (6 ml) is added to this solution.

The reaction is refluxed for 8 hours and then cooled to precipitate the yellow precipitate of the mentioned aniline, which is collected, washed with water and dried. Melting Point 180 ~ 182 ℃

The following Table IV (Examples 26-38) describes another anisotropic application-forming (co) polyazomethine of the present invention and is prepared by the solution polymerization process described herein (ie HMPA, NMP, Iridium). Chloride, using the "AA" terminator).

There are several types of fibers and films. Diamine reactants used include 2-methyl-1,4-phenylenediamine; 1,4-diacetylbenzene bishydrazone; 2,6-dichloro-1,4-phenyldiamine; 1,2-bis (4-aminophenyl) ethane; Bis (4-aminophenyl) methane; Bis (4-aminophenyl) thioether; 1,5-diamino naphthalin; 2-chloro-1,4-phenylenediamine; Hexamethylenediamine and 4-aminobenzoyl hydrazide are used, and the dialdehyde reactant is 2-chloro terephthalaldehyde; 1,2-bis (4-formylphenyl) ethane; 2,5-dichloroterephthalaldehyde; terephthalaldehyde; 1,2-bis (4-formylphenoxy) ethane; 2,5-dichloroterephthalaldehyde; Teretalaldehyde; 1,2-bis (4-formylphenoxy) ethane; 4,4′-dibenzaldehyde and isophthalaldehyde.

Bishydrazone is used in Example 26. Excess hydrazine hydrate and 1,4-diacetyl benzene in 2B alcohol are refluxed and the reaction mixture is cooled to yield the product. Melting Point: 184 ℃ (Decomposition)

The dialdehyde used in Example 35 was first reduced with dimethyl ester of 1,2-bis (4-carboxyphenoxy) to lithium aluminum in tetrahydrofuran to produce 1,2-bis (4-hydroxy methylphenoxy) ethane. To form. Melting Point: 174 to 176 ° C

The latter is oxidized with ceric ammonium nitrate in glacial acetic acid / water, followed by the general method described in J. Organic Chemistry, 32, 3865-8 (1967) to obtain the desired aldehyde.

The dialdehyde used in Example 36 is prepared by reducing the dimethyl ester of 4,4′-bibenzoic acid with lithium aluminum hydride in tetrahydrofuran at 4 ° C. to 4,4′-bibenzyl alcohol. Melting Point: 190 ~ 192 ℃

The alcohol is oxidized with ceric ammonium nitrate in glycial acetic acid / water followed by the general method described in J. Organics, Chemistry, 32, 3865-8 (1967) to obtain the desired aldehyde. Aldehyde melting point 141 to 143 ° C

All deniers represent filament values. The fibers are melt spun through the one-hole spinneret. [Hole diameter = 0.009 inch (0.023 cm)]

Table IV

* Heat-treated fiber (oven N ₂ -atmospheric, fiber proxy wrapped with bobbin 235 ° C./3 hours), filament T / E / Mi / Den = 6.6 / 1.4 / 517/37.

** Heat Treatment T / E / Mi / Den = 15/37/455/4.

Example 39

It is described in detail in this example that the tensile properties of the fibers of the present invention are further strengthened by heat treatment. It is shown that this process can be produced by short exposure time or low exposure temperature.

[Part A]

에 권취된다. 견본은 질소를 제거한 솔에 넣고 온도는 40분 동안 실온에서 150℃까지 올려주고 20분 동안 그 온도를 유지시킨다. 견본은 솔에서 약 50℃까지 냉각시키고 그후 견본을 꺼내어 실온까지 냉각시킨다. 처리된 섬유는 다음과 같은 필라멘트 성질을 나타낸다 :The spun copolyazomethine filament of Example 37 (T / E / Mi / Den = 3.4 / 1.2 / 353 / 4.7) was passed through a talc layer and made into yarn (5 filaments) packed with fiber bobbins with metal bobbins.

Is wound up. The specimen is placed in a denitrated brush and the temperature is raised from room temperature to 150 ° C. for 40 minutes and held at that temperature for 20 minutes. The specimen is cooled to about 50 ° C. in the brush and then the specimen is removed and cooled to room temperature. Treated fibers exhibit the following filament properties:

T / E / Mi / Den: 9.2 / 2.0 / 439 / 5.7 The treated fiber sections are wound in bobbins and heated again at room temperature to 260 ° C. over 40 minutes in a kiln (under nitrogen).

The sample is kept at 260 ° C. for 3 hours 20 minutes before cooling off and the conditions are removed.

The treated fibers exhibit the following filament properties:

T / E / Mi / Den = 20.0 / 3.8 / 470 / 5.5. Part B and C fibers of the following repeating structural unit polyazomethine composition are taken.

= NR ₁ -N = AC-R ₂ -CH =

The polymer in part B corresponds to that prepared in Example 17, but in part C prepared by the general melt polymerization reaction of Example 24, the polymer is prepared by solution polymerization as in part B. The co-polymer and the fibers used were the same as in Example 37. Spinning is done as described herein.

[Part B]

In this treatment, the spun polyazomethine fiber is left for 20 seconds at the indicated pressure and the indicated temperature. This short treatment time enhances the tensile properties. Polymer (high viscosity = 0.8,

[Part C]

에 권취되고 2시간(아래의 온도) 동안 솔(질소기압) 안에서 가열시킨다. 섬유인장성질의 개선은 표 5와 같은 처리온도를 사용하므로서 성취시킬 수 있다.In these treatments, the spun (co) polyazomethine fibers are fiber-prox wrapped with metal bobbins.

It is wound in and heated in a brush (nitrogen air pressure) for 2 hours (temperature below). Improvements in fiber tensile properties can be achieved by using the treatment temperatures shown in Table 5.

TABLE V

Heat-treated fiber

Treatment temperature T / E / Mi / Den

Example 40

Anisotropic melt-forming (co) polyazomethine having a repeating structure corresponding to formula (VI) is represented as follows.

The (co) polymer is prepared by melt polymerization of a reactant selected from the group of 4-aminobenzaldehyde, 2-methyl-4-aminobenzaldehyde and 3-methyl-4-aminobenz aldehyde. In a typical way to synthesize items 1-4, the monomers (about 0.02 mole) are mixed with aniline (1 ml) in a reaction vessel equipped with a stirrer, a distillation probe and a nitrogen supply. The stirred reactant is heated to 250 ° C. for 0.5 h in an oil bath under nitrogen. The nitrogen supply is then stopped and the reactant is added and stirred at 250 ° C. for 0.5 hour (at a pressure of 1.0 mmHg or less). The reaction mixture is cooled and the collected product is washed with acetone and dried. For the polymer of item 5, 0.096 moles of aminobenzaldehyde and 0.0057 moles of methyl 1,4-phenylenediamine (used as a viscosity stabilizer) are mixed with xylene (β50 ml) and trifluoroacetic acid (0.25 ml). The reaction mixture is refluxed for 3 hours (benzene-water azeotrope is removed) and cooled, the copolymer is filtered off, washed with acetone and dried in vacuo. The copolymer plug was spun as in Example 13 (spindle temperature = 240 ° C., melt zone temperature = 232 ° C.) and the fiber was wound at a rate of 155 meters / minute. Spinning fiber is T / E / M = 3.6 / 0.8 / 638.

The fiber samples were treated with talc and heated in the oven at 222 ° C. for 163 hours (N ₂ ):

The specimen was placed on the screen 6-inch (15.2 cm) in length and the heat treated fiber was T / E / Mi = 10.8 / 1.9 / 709.

Table VI

Claims (1)

Melting with a diamine of formula (I) and a dialdehyde or diketone of formula (II) and / or an amino aldehyde or aminoketone of formula (III) or a functionally equivalent derivative such as Process for the preparation of spinnable (co) polyazomethine.

In the above formula, R ₁ , R ₂ and R ₃ are (1) single and bonded 6-membered carbocycle ring (if necessary, one cyclic carbon of aliphatic ring can be substituted with nitrogen atom, wherein the chain extension bond of ring is monocyclic When attached to, in the 1,4-position to each other, when attached to several other rings, in parallel and opposite directions) or (2) polycyclic, preferably carbocycle rings (each ring being connected by a chemical bond, Or a linkage unit having a valence of 14 or less, preferably 4 or less, wherein each ring's chain extension is at 1,4- and R ₁ is a chemical bond) and Z ₁ , Z ₂ , Z ₃ are Hydrogen atom or methyl or ethyl group.