JPS59113033A - Azomethine (co)polymer and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

Synthetic polyamide dope (or solution) 1 (e.g. Quarreck CKwo1gk) (D U.S. Pat. No. 3.671.54)
Optical anisotropy is known for doped rocks. 7] Liquid crystalline behavior has been reported in the art for E'lyolefin bath melts. Literature K Ir, J-;jt riazomethine [or poly(ntuf base)] has been widely described. [For example, [Encyclopedia of Polymer Science and Technology]
lymer Science and iechnoL
og11') J No. 10 pages 659-670 (1960
), G.F.D'Alelio (G, I', D'AI
Written by e l io) Rice 1. fil = , :L-York, Inter→Noyens Publishers (In
tersigncg Prt, blishers) publication]. It is also described in bamboo patents such as Amada U.S. Patent Nos. 3,526,611 and 3,418°281. Four-part, still pressure molded polyazomethine is disclosed in U.S. Patent No. 3.418.281 and British Patent No. 1.080.
It is described in No. 526. These monomers are said to have good thermal stability and toughness. Is it possible to cast from a dilute solution? A polyazomethine film pressed at high pressure at a sick temperature was developed by Baker et al.
As stated in Official Gazette No. 1918005 dated January 1, 1974 (Defense Publications). However, none of these conventional methods describes that a certain amount of aromatic polyazomethine produces an anisotropic melt that can be melted into filaments. According to the present invention, novel aromatic and alicyclic melt-spun polyazomethanes having a polymer melting temperature lower than 375°C, a directed viscosity of at least 0.02 and optical anisotropy in the temporary melt state; An azomethine conjugate is provided. Furthermore, the present invention provides novel and useful oriented fibers spun from these polymers without subsequent drawing. When many spun fibers are heated in a substantially relaxed state or in a taut state above 100°C, but below their melting point, their orientation, strength, and overall increase occur. J
Mosoylus increases in summer. Other shaped bodies such as films and rods can be made from this polymer. According to the present invention, the polymer is a manure unit (1) +N A? 1 ``ヰ1 Z2 and (III) *C-111'3-IJ→basket 3 However, if the laurels ■ and II exist, they exist in substantial nitomolar form, and z1+ 22 and z3 are the same - or The hydrogen atoms and R3 can be different, and the hydrogen atoms and R3 are (1) a single or fused carbon ring 26j+ ring system, where the aromatic ring is present, if present: 8J5 ring carbon of the aromatic ring; one of them can also be replaced by a nitrogen, and the chain extension bonds of the ring system are fixed if the bonds are mono-bonded (i. (2) polycyclic groups of a carbocyclic hexanegative field system, located in parallel and oppositely oriented positions if attached to the root; The monkey is chemically bonded (L'
i length is more than 14 atoms, preferably not more than 4, connected by bridging units, and the chain extension bonds of each term are 1.
-R1 at position 4 is a group selected from the group consisting of polycyclic groups which can also be a chemical bond. It is possible to provide polyazomethine and azomethine coelectric @ bodies characterized by consisting essentially of repeating structural units selected from the following. An example of (1) is. An example of (2) is C1i, CM. It is. Included in the above-mentioned ring systems are those with Id and one or more substituents, such as lower alkyl (1 to 4 carbon atoms) and chloro groups. In addition, in the present invention, a maximum of 40 molar ratio, preferably a maximum of 25 molar ratio with respect to the total of the units of ■, ■, and ■ does not match the units of I, ■, and It can be substituted with polyazomethine-forming units that do not interfere with the bath melt-forming ability. These units include, but are not limited to, the following: The above-mentioned polyazomethine (co)polymer contains substantially equimolar units I and ■, or consists of units ■, or consists of a combination of units 1-It and III,
Of course, more than one eye position (1=fl and ■) can be present in the polymer. The preferred polyazomethine (co)polymer of the present invention is actually
Basically, it consists of units I and ■. In such series polymers, -R1 is chloro-, bromo-, metquin-,
Furzulow, methyl--hydroxy- and nitro-1,
4-phenylene i 4 , 4'-biphenylene; 3
, 3'-dumethyl-4,4'-biphenylene-1,4
-phenylene ill, 11'-methylene diphenylene;
4,4'-dumethylene diphenylene; 4,4'-
Trimethyleneduphenylene i4, 4'-tetramethyleneduphenylene;2,6-naphthylene;1,5-naphthylene;2,6-dichloro-1,4-phenylene; trans-1,4-cyclohexylene: trans-2-methyl-1,4-cyclohexylene; trans-4,4'-
methylene dicyclohexylene, 3. a +-dumethyl-4,4'-tetramethylenedioxyduphenylene;
4,4'-azoxodiphenylene i3,3'-
selected from dimethyl-4,4'-azosopherene and a single bond: R2 is 1,4-phenylene; chloro-1,4-phenylene; methyl-1,4-phenylene i 4 ,4'-biphenylene i41'i'-oxydiphenylene;4.4'-ethylenediphenylene; 4
, 4'-methyleneduphenylene i 4 , 4'-ethyleneduoxyduphenylene;2,5-biricinedyl;
1,5-naphthylene;2,6-naphthylene;1,4-naphthylene;2,5-fuchloro-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 ii4:
You can choose from. More preferably, at least 25% of the total number of such enclosing I and II ring systems consists of chloro and methyl groups for better processability and/or concomitantly better stability! The group chosen from 11 is used as a replacement. When only the unit ■ is present - or t'i-+ (: When it is present together with position I and ■, 173-digit 1,4-phenylene, methyl-1,4-phenylene-4,4' -oxydiphenylene + 2,6-naphthylene, 1,5-naphthylene and chloro-1,4-phenylene. I-I
consisting of a combination of I- and ■ units, at least 25% of the total number of ring systems of such units are substituted with groups selected from the group consisting of chloro and methyl groups; That's so clever. Preferred polymers include (1) methyl-1 for good processability;
, 4-phenylenenoamine and terephthalaldehyde.
- phenyleneduamine and terephthalaldehyde, and (3) bis(4-aminophenyl)ethane and hychloroterephthalaldehyde to produce highly crystalline J fibers with good hydrolysis resistance. It is made from. The azomethine (co)polymer of the present invention produces an optically anisotropic melting resistant material, which can be heated up to -375°C or less, preferably at 350°C.
It must be able to melt in a bath at temperatures below C and provide processability into fibers and other molded products. Depending on its structure, rapid decomposition of polyazomethine (co)polymers occurs at ambient temperatures. This octogen constitutes a region of parallel polymer chains. It is believed that this occurs during the spinning process and produces oriented edge fibers in the spun state. The polyazomethine (co)polymers of the present invention are melt-spun. "Melt-spinning ability" means that it is capable of bath-melt spinning;
This means that it can remain molten for the time required to spin the filament. Other polyazomethine (co)polymers do not dissolve 1 times. Furthermore, the pond material instantly softens or flows when wetted with water, and then hardens to become a non-bath-melting substance. This is believed to be due to the faster chassis. The bath melt spinning body of the present invention is kept in a bath melt state for at least 5 minutes.
-16-NH. cyamine as a dualdehyde or duketone of the formula, and/or 2HN-R,
-C=0 s aminoaldehydes or aminoketones, or by reacting such raw materials with functionally equivalent compounds. where +R, +R, and R5 are (1) a mono- or fused carbon ring system, and if an aromatic ring exists, one of the aromatic ring carbons is nitrogen. It can also be replaced by single and fused carbon terms in parallel and oppositely oriented positions if present; and 121
: 4-ring system, preferably carbon amorphous, monocyclic. Tensile bonds are located at positions 1 and 4, and 1 consists of a group of polygonal threads that can also be chemical bonds! ! 1. is a group selected from Zl, L,
and Z3 shall be selected from a hydrogen atom or methyl or ethyl group. The cyamine, which is useful for making the ifi body of this invention, is represented by the formula 112N-R, -NH3. Once I do, as mentioned above, 1- It spoils the taste. There is 1 in siamin
, 4-phenylenecyamine, chloro-1,4-phenylenenoamine, 10molar 1,4-phenylenediamine, fluoro-1,4-phenylenediamine, methyl-1,4
- Phenylenesoamine, methoxye. 4-phenylenediamine, nitro-1,4-phenylenediamine, 2,6-dichloro-1,4-7 2-2-diamine-4,4'-duaminobiphenyl, 3,3'-dumethyl-4,4'-du Aminobiphenyl. Bis(4-aminophenyl)ethane-1,3'-his(
4-7,? nophenyl)furo'7-1,4-bis(4
-aminophenyl)b:97. 2, 6-su7thalenduamine-trans-1,4-cyclohexane-di"amine-2-methyl-trans-1,4-cyclohexanduamine, bis(trans-4-aminocyclohexyl)methane-hydrazone, etc. The diamine can also be used in the form of a salt (e.g. dihydrochloride) by using a neutralizing agent (e.g. carbon=1') tium during the reaction. .In the drum, R2,2H and Z2 are consistent with the above definitions.Among these are 1,4-soacetylbenzene = 4.4'
-Diacetylbiphenyl, terephthalaldehyde, chloroterephthalaldehyde, methyl terephthalaldehyde -2,5-sifolumyl biridine, 4,4'-laformyl biphenyl. 2,6-diformylnaphthalene
1,5-siformylnaphthalene, 1,4-cyformylnaphthalene, bis(4-formylphenyl)methane, bis(4-formylphenyl)ethane-bis(4-
formylphenyl) ether + 1゜2-bis(4-
formylphenoxy)ethane, 2,5-sochloroterephthalaldehyde-2,5-dibromo terephthalaldehyde, 2,5-somethoxyterephthalaldehyde, 2-
Examples include bromo terephthalaldehyde, 2-methylterephthalaldehyde, 2-hydroxyterephthalaldehyde, and the like. The aminoaldehydes and aminoketones useful in making the polymers of this invention correspond to the formula %. In the eclipse, Z3 and I73 are convex 1 [having the meaning described above]. Among these are 4-amino-3-chlorobenzaldehyde, 4-amino-3-fluorobenzaldehyde-4-amino-3-methylbenzaldehyde-4-amino-3-chloroacetophenone, 4-amino-3-fluoroacetophenone, and 4-amino-3-methylacetophenone. Not all combinations of these raw materials result in anisotropic M melts. Combinations of raw materials that produce heavy bodies with melting points of 375° C. or higher must be avoided. This is because 'all the raw acid site products (eg, spinning into useful fibers) are difficult to obtain. Polymers made from a certain combination of raw materials momentarily soften and then combine to form a non-fusible monomer.
'I think it would be a shame if the A side was turned into one curse side. Such combination into one is outside the scope of the present invention. Applications are limited because bath melt spinning is not possible. However, if an end-capping agent or a continuous casting stopper is used in the process of forming such a polymer, the resulting product will have a bath l-lll! It is a 1F body whose ends exhibit optical anisotropy. The present invention 1/(l ld-, 1iJj) Adding an end-capping agent during the synthesis to ensure that the wood ends of the polymer are leaded or not. !!Producing a proboscis, azomethine (co)jF4.倚 (includes only this book). Some of the (co)polymers may be solid and unbathable in the solvent used to determine the viscosity (f).These (co)polymers, and the methods described below. If the intrinsic viscosity is at least 0.2, preferably at least 10.
Good fibers and films can be obtained from these. The degree of formation of the polymer depends on its intrinsic viscosity. That is, a polymer with a lower intrinsic viscosity melts at a slightly higher temperature than one with a higher intrinsic viscosity. Consolidation Conditions Polyazomethines and their copolymerizates can be made from a single compatible monomer by heating under anhydrous conditions, preferably in an inert group atmosphere. For example, the raw materials, duamine and soaldehyde (or its special ingredient, eg diacetal), are combined in a reaction vessel. The contents of the container are stirred with a stirring force of 11 (11 mm), and the contents are kept under nitrogen during this period.As the reaction materials are mixed, by-products (f/Il
water or alcohol). Once the chassis has progressed to the desired point. Take out the entire city and refine it. If the bath 1 is strange, at any time, pour the whole Yamana flavor directly into a suitable container, such as a spinning machine, and make a 4-piece pre-prepared product. The reaction materials are bathed in a solvent (eg, benzene) that helps create a co-Nβ mixture with the by-products and remove the by-products. (2) After the completion of the 11th batch, filter the precipitated raw F rinsing, divide the separated product into ρIif', L, and evaporate the remaining solvent. The (co)small polymer of the present invention uses a highly polar solvent. b! : 11. It can also be produced by the l-11r addition method. In one convenient method, diamines such as N,N
-dimethylacetamide (DA4A c )-A'-Methyl biloride y-2 (NMP"I, hexamethylphosphoramide C1iMPA) or mixtures thereof. Add soaldehyde and stir the reaction mixture. Allow the reaction to proceed for 7Q hours to several days. The reaction mixture is then combined with a non-boiling medium (e.g. water), collected and thoroughly (e.g. with water, ether, methanol)
, process after drying. In order to facilitate subsequent processing, it is advantageous to use these end capping agents or chain terminators during nailing. Aniline, 4-carboxybenzaldehyde, 4-aminoacetanilide-4-amino-3-methylbenzoic acid, benzaldehyde, and benzoyl chloride are included in these terminators. Although coarsening the benzoyl chloride gives satisfactory results, reagents that generally produce mineral acids degrade the polymer and should generally be avoided. These terminators serve to suppress or minimize the increase in molecular weight of the polymer during 44 melt spinning. For example, if further polymerization occurs during spinning and the molecular weight becomes too large, the spinning operation will result in poor quality fibers or be interrupted. When heat treatment is carried out in the form of fibers, it is desirable that the fibers grow to some extent. Chain suspensions that completely prohibit larger chassis must be avoided. If necessary, the end sealing can be carried out without adding any other reagents. For example, one building of anti-1,6-hara H is 11-
□・If used excessively (more than chemically expedited) and with other mechanisms to prevent the rapid loss of excess reaction materials - this acts as a fd end cut-off. do. This method has been described for other polymers by Elseviar IB Edition, Amsterdam, Netherlands, 1953.
Published by Earl Hill (lbi, l1ill) [attached width combination Y, 4y, ved (f”ibgrs J'rom 5yn
theticPolyrn,ers)J 106-1
As in Section 111i of Section 07, it is "Koga". When a thermally cheap acclimatization inhibitor is added to the reaction '(Li='), it plays a useful role in the processing of ribs. Due to the γC1-shaped anisotropy in the coalescent melt-like fibers, fibers made from these melts have orientation, strength, and initial modulus of i￥
The strength of some of these fibers is increased by heat treatment in a substantially relaxed or stretched state. The optical anisotropy of polyazomethine (co)polymer melts is determined by a known method with slight modifications. Translucent optically anisotropic materials transmit light in an optical system with crossed polarizers71. ) However, it is known that for an isotropic material VC, the light transmission is theoretically O. [For example, Nis Ni Duyaparin C8, A Jabarin
) and H7-Le Nis Sting CR, S, Stg.
In) Tsuyanaru Og Physii - JJ Lu') - Misdoly (J, Phys, Chsrn,) 7 Yu. 399 (1973)]. The anisotropic@melt of the present invention exhibits the former ψ motion. The thermo-optical test (TOT'
), use this percentage to add up the bath melt. equipment tl
I. Lgnbaum, R.B. Isaxo: y (ll. JJ, l5aa, cson) + and Lid C0F'gist, Limer Letters CPo111 wo, er I nog
f, tgrs'l Answer, M 2 + 8 9
7 to 9 0 1 (1964) ``I'' is the same as device 61 listed in 1. Combined T
d molded product. Molded products in one row, film, rod, or pond are:
1me II! ',,f'C-'s Atsushi 1-High 1) (Insert all the way through/thread-proof, casting. One can be made by taking out the father 4/e. In the industry, Tomo Naga is a molded product. 1! Direction IG) An! 'I must be small 1χ (for [
At the same time, it is possible to easily complete the processing at an appropriate processing temperature. The oriented side Al4 fibers are made from the above-mentioned polyazomethine chassis. To make a polymer, VC can be directly attached by melting the (co)polymer-forming components, or by melting the molten 19-coalescence mass obtained by dissolving 61 blocks of the (co)polymer, for example. Processing is carried out by following the spinning target, extruding the spinning material from the spinneret into a rapidly cooling atmosphere (for example, air kept at room temperature), and winding it up. '' refers to fibrils that do not undergo stretching, elongation, or sintering after extrusion and 11 ' is not possible in a normal, soft body, i.e., 100 or more than 4 l/l. It is convenient to make l&fiber from a single or multi-hole spinneret. The temperature to be maintained in the bath-melting zone and the spinneret depends of course on the polymer to be spun.Heat is preferably applied to the spinneret and a short bath-melting zone directly above it.This allows ri', L+ If the viscosity is less than 4JK, it can be easily spun.7J'
J filter screens and disks can be used in the spinneret pack. For quenching of L;
S) - It can be rolled up at a speed of, for example, less than 90 m/min to more than 1200 m/min. The spinning elongation rate varies depending on the size of the hole in the spinneret, the extrusion speed 1w, and the take-up speed, and is generally 5 or more. If necessary, you can apply a finishing agent to the delicate details of the +'tJ7 thread. Films can be made by conventional bath-melt pressing methods, and molded or extruded products 1, such as frames, can be made by conventional methods. The as-spun fibers of the present invention are highly oriented, as indicated by, for example, an X-line orientation angle of about 45° or less. Furthermore, the tensile strength and other properties are also desirable. For example, many freshly spun fibers have a strength of at least about 4 (initial t4JJ modulus at 7d is greater than 400 gpd (often greater than 500 gpd). In some such applications, the fibers are exposed to basic media or high temperatures; for example, reinforced resins are often cured using basic catalysts, rubber compounding components generally include organic amines, Curing is often carried out at high temperatures for a considerable period of time.The fibers of the present invention are generally resistant to the conditions mentioned above. Retention of strength) indicates raw material. The as-spun fibers of the present invention can be subjected to a heat treatment operation to produce heat treated fibers of the present invention having extremely high tensile properties useful, for example, in tire reinforcement. Ill? # (
Preferably, in a state of atrophic flaccidity, in the second 11th skein - or in the skein [fiber flux @ Ch'1bcr-Frctx], ] in the z-bin, Or under tension - for example, on a hard bobbin at temperatures above about 100°C - 1'MW4! (preferably within 20°C below the C point) When processed, the same area 1, which is a standard for a molecular analyzer, is obtained.
An increase of 15- occurs. Due to the lying process, the number of times the product is stored increases by 1 zu. 1y, wei is '1jfi to increase brother II
It was done. ! The temperature and time of the ridges are adjusted such that the viscosity increases by 1r-i1. It is preferable to keep the heating temperature below the C crystallinity at which fusion between filaments actually occurs. For commercial purposes, heating is carried out for as short a time as possible, sufficient to increase the strength by one point. Polymer υ thus R21l-e 5 seconds or generally at least I
A to 24 hours or Q': A longer heating time is used. Even if it is heated for more than 8 hours, an improvement of 5 or more in strength cannot be obtained. The heat treatment must be carried out in an inert atmosphere that does not adversely affect the fibers. Base 3≦ is perfectly suitable for this purpose. strength is at least 1
0 gpd fibers are preferred, and many of the spun fibers of the present invention can be heat treated to achieve this level of strength. fd X, I? with heat-treated fibers? An increase in orientation as measured by the il orientation angle is observed. Preferred heat-treated fibers of the present invention have a modulus of at least 150 gpL, an elongation of 2% or more, an orientation angle of 45° or less, and a melting point of f'J
: 1.75°C or higher, 2500°C or higher. Measurement method and test! Coating method X-ray orientation angle: X-ray orientation angle (Q, A
) is US Pat. No. 3.
671.542 method 2 method. Intrinsic viscosity: Intrinsic viscosity (η1nh) is defined by the formula %). ηral is the relative viscosity t), C
is a concentration of 0.5.9% of polymer per 100% of solvent. The relative viscosity ηrgl is obtained by multiplying γ+iU in a capillary viscometer by measuring the flow time of γ+iU by 1ξ with a suitable flow time. Unless otherwise specified, the dilute solution used to apply ηrel is a solution with a concentration expressed by ((,') above.
Determined at °C. The solvent is concentrated cough (98 H, 5O4
). Other solvents (eg methanesulfone 11i!
? ) can also be used for oysters that deteriorate during preparation. 113 Combined sample (or fiber) - 98 Closing soap and a closed bottle with 3 mm Teflon 0 cubic grains Combine in a bowl and place on a shaker for 10-25 minutes, usually to produce a bath.Cannon-Fenske (Cα
The viscometer is filled by the inversion method and placed in a constant temperature bath consisting of Showa water solution of dichromate potassium. Immediately measure the flow time three times in a row. Shake cultivation is carried out in the dark and all transfer steps are carried out rapidly in dim light. In item 4, the flow time of the bath liquid decreases with the next measurement. The maximum time is used for the total of ηinh. Morgan U.S. Patent No. 3.827.9
It is measured by the method described in No. 98. Average the valuation intensities of at least three times. Single filament properties and multifilament properties of the same sample
The results are different depending on the nature of the strand (thread). Unless otherwise specified, all properties are filament properties A
Ru. Optical anisotropy: Optical anisotropy is measured by the 1.7" Q i' method. The polarization needs to be very uniform - this is enough to prevent the optical system from becoming dirty and the pack ground transmission described below (90°) (which has 4 D photons and is still 1°). I have a light absorption□1yiC. Please report it here.
iLights CLpitz) 4-IH Dialux Ball (Dial u, x-Pol), 'I'H small bell was used. Add to this the Bolaroid 1, +1 photon binocular eyepiece, and 11 Kato units. 1 ml of Izuko Kokyo (photometer sensor) and Niugi Vkai
Add 1154 to the U section. L to visualization is 32 times lPi N
It has a long proboscis lens with a '+' activation stopper and a red l (pan-grade red) plate. (Sasa is used only when doing ?i:Q ?+111 with the crossed eyes, and is at an angle of 45 degrees with each polarizer). A photon of white light from an incident light source is traced through the sample on the heating stage, then through the analyzer and directed to the photodetector or eyepiece.A slider directs the image through the eyepiece to the photodetector. 4'J = 'J to the container. Heating table used 1ri500
Can be heated to ℃. “Unitron (Uhada tro)
n) J MHS mold tool fully heated table [Newton-Highlands, Mazachus, USA (A7s 7-butt OnHighla)
nds), Unitron Instrument Co., Ltd., 66 (02161') Street, N.D.S.) was used. The signal from the photodetector is processed by the amplifier of the photometer to the YI+ of the X-Y recorder.
Supply to 111. The response of the system to the intensity of light is linear, and the distance measurement accuracy in the first soil V is ±1.
It was within tnw. Two P and couple pairs are attached to the heating table. One of them is connected to the hX-Y recorder 〇X iFA+ to measure the temperature of the heating table, and one of the 1m is connected to the programmed temperature controller. Focus the microscope with your eyes on the composite specimen prepared and mounted as described below (for crossed polarizer f4). Remove the sample from the optical path, but leave the cover slip in place. Take out the Polaroid analyzer of the microscope 2131 from the optical path - move the slider to move the column 1 to 4" IJ to the light beam and adjust the thread. 'L (18α on the recording paper) corresponds to the photometer signal (, 36). This is (1) f on the Y axis of the recorder.
The intensity of the light beam is adjusted in advance by 1 Alq so that the intensity corresponds to 51, and (2) the amplification portion of the photometer is multiplied by 10 (this is done by adding 1). The entire IVA of the 18cTn of the final recorder corresponds to No. 48 (18150) XI 00 of the Buba Photometer, that is, the 36th section. Packground yield values are recorded with crossed (90°) polarizers, cover slips, and entire sample in the optical path. The background transmittance of the system used is independent of temperature and must be less than about 05α of the recording paper. Two samples each for the TOT test and flow temperature measurement are prepared as follows. 1. Place a few coats of pure polymer between the coverslips. 1] Visually observe the heat of polymerization between crossed (90°) polarizers while heating at a programmed rate of approximately 0° C./min. The sample temperature (7') at which the particle diameter becomes round is a measure of flow, and ζfL is recorded. Duplicate samples consisting of □□□ coalesced particles, each placed in a cover slip, are placed in a 2-β1 microscopy slide. this assembly. It is placed on a preheated heating plate such that the temperature measured by a thermocouple inserted into a steel plate above a part of the heating plate is (r+10° C.). As the assembly is heated to higher temperatures, a wooden push rod applies pressure to each sample until one particle fuses and flows, forming two thin liquid films. Immediately remove the assembly, cool, and separate the 1r11 pieces of film (held between cover slips) from the assembly. Since the polymer sample easily polymerizes further during this process,
It is important to minimize the 1 hour and 1 degree heating time of the sample during this process. The thickness of the polymer sample film is preferably 4-6 μm. J Films that are too fast or too thin may not show anisotropy in this test. However, if the sample exhibits anisotropy, there is no need to repeat the test for 4-6 μm separations. The Ji-:" wall of the sample can be measured by an interferometer.
3. Inject oil with a known refractive index between the cover slips surrounding the sample, and measure the thickness of the oil layer in the area 2 close to the sample part to be observed using the i"01' method, in the direction of the boundary with the h! gas. Once the thickness has been measured, the oil can be easily immersed in fluorocarbon of Freon TF and shaken with ultrasonic waves. One of the films inserted in the cover slip can be used for the TUT method, and the other can be used to determine the flow rate. This is the temperature at which the contour purity of the film image changes when the film is heated at a programmed rate of about 50°C/min in the O7' pupil. It should be noted that the dynamic temperature of It can be heated at a low temperature.The reported flow ``IJ'?=FR'' was measured by this method.A sample of the TOT method was placed on a heating table and a photodetector was used. Position the sample so that substantially all of the light passing through it passes through the sample.The sample is placed between the intersecting (90°) lM photons;
Light intensity and temperature are recorded on an X-Y IJ coder while the sample is ramped from 25°C to 465°C at a programmed rate of approximately 500/min under nitrogen. j
1 (temperature of the sample 1 from the temperature recorded using the hydrophilicity curve)
get tsu. The (co)weighting method for forming l゛dd melt is -+;'A: When a temperature above its flow temperature is applied between charge-crossing (90°) polarizers, if 4 forces are applied, then Anisotropic solution 1.I!l!If the light passing through the object is at least twice the quotient of the background transmitted light curve and less than 4b record 11. If a curve with a +- value is given, it is considered that an anisotropic melt is generated in the TOT method. When such a melt is generated, the transmission curve of light is (1) 11 (high) (a) is at least twice as large as the background transparency, 1!, and is at least 0.5 G+++ dog, or (2) is increased by at least this amount. .Song 1>j in the attached drawing
HB is usually 'I!' in systems that produce orthotropic melts. M
FIG. 1 is an example 1 of an intensity curve. The intensity of light passing through the analyzer when a polarizing heart fusion occurs (the sample must be fully saturated with light) at l-+l of crossed (90″) polarizers is substantially that of pack-ground transmission. It is the same as the curve (cross the sample without a knife and slip at 90 degrees (1tllll outside of the main field using the Oke Photon)
(obtained by K i + t). - When a translucent T6 melt occurs, the transmitted intensity of the light is either (1) substantially equal to the background transmitted intensity, or (2) reduced from a high value to such a value. The curve i in the drawing A is the intensity curve IJ of the small coalescence that produces the isotropic melting proboscis. They often exhibit optical anisotropy over a range from temperature to decomposition degree or maximum test temperature. However, in some polyazomethine undercarriages, when the bath melt thermally decomposes, a portion of it becomes isotropic. Some other kinds of shredded l',! As the temperature rises, the properties of the J-meter change from anisotropic to isotropic. LOL The small coalescence bath 11 reported in the Mli example is published by Interscience Publishers (In
tgrscigncePublishers'I 1
Preparative Methods of Polymer Chemistry
Po1i/mer Chern, 1-str1/)
J 2nd edition 57-59 Qii Is it possible to attack by method A described in my own paper?
Akira is determined to be cold. Hu) Many azomethine homogeneous and co-1r in the present invention
An example of sweet body is shown in the lower example of IJ1it. These are 7T mapped by the name /l'< of the 4d digit structure. For example, an azomethine homopolymer made from 2-methyl-1,4-phenylene diamino and terephthalaldehyde is
It is named +f IJ (nitrilo-2-methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine). Example 1 In this example, trilo-2-mef-1,4-phenylenenitriloethylidene-1,
4-phenylenemethylidine) is shown. 2-methyl-1,4-phenylenediamino (2,44,9-0,02 mol) and 1°4
Combine with -duacetylbenzene (3,24y-0,02 mol). Reaction mixture sound base (loose nitrogen gas)
Heated to 156°C for 1 hour in L, then 205°C for 2 hours.
Heat to. The product was extracted, crushed, washed separately with methanol and water in a blending area, and air-dried at 80°C for 7 hours.
7 inch = 0.5 chassis body 4.32, V was served. The PMT of this product was 370°C. '1-! : Example 2 The present H1 screen 11 uses 4-acetamidobenzene as a terminator and nitrilo-2-methyl-14-phenylenenitrilomethylidine-1,4-phenylenemethylidine/ Nitrilo-1,4-phenyleneoxy-1,4-phenylenenitrilomethylidine-1,4
-Hill ratio to phenylene methylidine: 90/10) Synthesis: A method of production is shown. 11MPA C25ml ”r NjVIP C25m
2-methyl-1,4-phenylenediamino (4,4,9
, 0,036 mol) and bis(4-aminophenyl]ether ((1,8Of 0.004 mol)) were stirred and mixed to form -4-acetamidobenzaldehyde (0,4
g). After a few minutes, terephthalaldehyde (5,
369-0.04 mol) was added. After 16 hours the reaction mixture becomes unstirrable. The reaction mixture was mixed with water, and the precipitated polymer was collected, washed, and dried as in Example 1 =
9.2 g of a vehicle body with B 1nh=1.1 was obtained. The PAiT of this copolymer is 306° C., resulting in an optically anisotropic melt. Table 1 below shows other (co-)car bodies of the present invention manufactured by the general method of Example 2 above. The dualdehydes used in the synthesis of these 11-etc. are terephthalaldehyde-methylterentaldehyde-1.2-bis(4-formylphenoxy)ethane and bis(4-formylphenyl)ether. The diamino used was 2-fluoro-12-chloro- and 2-methyl-1,4-phenylenediamine. 3.3'-dimethylbendedune, 4゜4'-azoxyduaniline-3.3'-dimethyl-4
゜4'-Diaminoazobenzene and 1,2-bis(4-
There is aminophenoxy)ethane. In Practical Example 7, the one-cycle bathing medium was I) A/A, c, and after heating this i-coupled body sample to 300°C for 5 minutes, it was heated to -325°C12
It was pressed for 20 seconds at 11 kg/14 lbs. and exposed to the film. 'x 1mCreate the copolymer of Example 9. Hexamethylene diamine and 2-methyl-1,4-phenylenesoamine dihydrochloric acid were used in equimolar amounts (0,005 mol each), and charcoal lithium (0,005 mol each) was used to neutralize the generated acid.
01 mol) was used. In Example 9-1, 0.002 mol of sodium chloride was used as the reaction raw material, and 5% Li was used as the reaction heating medium.
DMAClNMP < 1/1) containing C1. In Example 9-2, 0.0005 molar amount of the reaction raw material was used, and the motive medium was I) MAc (1,5
mA') and 7b0 end sweet chain anchor V neck 110.00
4. ! ? used for In Example 9-3 (d t'6 medium L
IJM Ac (1011/, ) containing 3% iCl
and Tanio, the raw material (<0.005 molar amount was used. All shown will form an anisotropic bath. Polyazomethyl (co)i Example R+ A'□CM , CH. CB. 1 ・Body: =N-R, -N=HC-R, -CH 2 Synthetic skin ↓ 3 hours None 0.2 days
none
1.8: 325Table 1 continued CB3 CB, CH - AA 4-aminoacetanilide *
Example 10 In this example, nitrilo-2-methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine/nitrilo-1,4 -phenylenenitrilomethylidine-1,4-phenylenemethylidine) (9515)
A method for producing a copolymer is shown. This copolymer was molded into rods. HMPAC20m1. ), NA4P (20m1) and L
♂C: 2-methyl-
1゜4-phenyleneduamine (4,64,9-0,03
8 mol) and 1,4-phenylenesoamine (0,22,L
Terephthalaldehyde (5.36 g, 0.04 mol) was added under nitrogen into a solution containing 0.002 mol). After stirring the reaction/1f″ compound at room temperature for 16 hours,
4j'I at 110°C was recovered simultaneously with Example 2.
middle) 771nh=4. 'l-PMT=260℃ co+
8.6 g of ij combined was obtained. This co-merged melt is optically anisotropic. A sample of this product is placed in a frame mold and held at 300°C for 15 minutes. The bending strength of this bar is 6.3 x 10" bonds/in2. , bending modulus is 4.3 x 105 lb/in 2, yield strength 4.3 x 10” lb/in 2 (
4.43,302-3.02kl respectively? /cnt)
It is. Example 11 This example shows a method for producing poly(trilo-2-methyl-1°4-phenylenenitrilomethylidine-1,4-phenylenemethylidine). This product produces an optically anisotropic melt that can be spun into strong ruts with enhanced tensile strength by a relaxing heat treatment. A solution of 2-methyl-1,4-phenylenenoamine (77,9,9,0,64 mol) in 200M ethanol is made at room temperature. A second solution of terephthalaldehyde (81,3,10,
61 mol) was produced. Simultaneous VC21) of these cold liquids
Pour into a beaker. Polymer precipitation begins within 1-3 minutes. The reaction mixture was allowed to stand in a room at a temperature of 5°C. Ethanol all ρζ emitted 1 meeting--+ij
The combined residual proboscis was washed with water for 14 minutes and incubated at 110°C for 1 hour.
5. Vacuum dry for 5 days. v>, the dried residue is finely polymerized in a heated screw extrusion mode/ζ. 111 Molding a part of the product to create a plug (ηi nh=6
．． 0 ) + 541st hole spinneret [
Diagonal hole diameter 0.018 cm - spinneret temperature 260°C
, spun at a melting point temperature (MZT') of 255~b and wound at a speed of +600 yd/min (548 m
/min bobbin A). Is the other bobbin (bobbin B) 900? /
d/min (822 m/min, MZT=260°C). The properties of the yarn of bobbin B, which was spun at ηin-79° with 4 fibers, are as follows. Gobiy T E Mi D
en. A 7.3 1.1 916 20. OB
6.4 0.92 900 15.1 The yarn sample of bobbin A was treated with fiber flux (/”♂bq
r-F'ra process] and heated in a furnace (continuously flowing nitrogen) under the following conditions. Room temperature 160°G/2 hours, 180°C 72 hours, 200°G/
4 hours, 712 hours at 250°C, the treated filament shows the following filament strength for 6 minutes. (Average of 15 samples). i
'/E'' 7M i/J)en, = 28
/3.2/939/4.3゜For one filament, i'/E/M i /Den, = 44/4
．． 2/1118/4.2゜In another process, a sample of yarn from bobbin A is separated into a single filament (j), which is perpendicularly drawn from the steel wire (1
) The sample was heated in a furnace under continuous nitrogen flow under the following conditions. Room temperature, 165°C 740 minutes, 165-230°C
71 hours, 232°G/1.3 o'clock music, 234°G/6.
3 hours. After this treatment, the fiber Vr,'l'/E/M i
/Den, =38 / 4.4 / 1012/3
．． All properties of 7 were shown. Example 12 This example describes a bath with optical 0"J anisotropy. 2-methylterephthalaldehyde ((+,
20 fj, 0.00135 mol')-1,4-phenylenediamine (0,146, !i', 0.00135
mole) and 0: L i Cl 5 % f-containing trliMPA
Anhydrous mixture of /NMP (50150 volume ratio) 3-
were mixed together and stirred to make a complete reaction mixture. 15 minute inoculation - acetamidobenzaldehyde (0,004,!i
') Add k. The reaction mixture was stirred overnight at room temperature under anhydrous conditions, water was added to precipitate the polymer, which was collected and mixed with water and ethanol (
Wash separately with water (anhydrous) and vacuum dry at 80°C. y7
1nh-0,7, PM'T=2'lO°C +1

[About 0.2I of coalescence was obtained. The properties of the fiber spun from this shot melt at 270°C are T/E/Mi/Den, = 3.5
It is 10.55/684/6.1. 2-methylterephthalaldehyde is 2-methyl-α, α
'-1,4-xylene diol Cm,p. 78-819C1 This is Nyström (Nyst
rom) and Brown [Journal of the American Chemical Society (J, A, m, Chgtn,
So, c, ) 69. 1197 (1947)] 2 -Methylu Telev Taril Chloride FL IA LH, Debu, Make Power, Debu]
, Ce (No3)a] using the general method of Trabavsky et al. [Journal of Organic Chemistry (J,
Org. Ch, ern, ) 32, 38 '65 (19
67") : ]. After heating and stirring for 30 minutes. The reaction mixture water bath solution was mixed with ether (2x) and keratinated methylene (
Extract at 1x). -Combined organic 414 kN a
After washing with ll CO, and water, dry over MQSO4. The dried material is separated in a furnace and the filtrate is evaporated to produce a soft product]-
Make a J-color solid and sublimate it at f65°C to obtain a melting point of 70~
A white powder at 71° C. is obtained. This powder is crystallized from water,
2-methylterephthaldehyde with a melting point of 71-72°C was obtained. EXAMPLE 13 This example demonstrates the preparation of polytrilo-2-chloro-1°4-phenylenenitrilomethylidine-1,4-phenylenemethylidine) and the strong fibers made therefrom. The melt of this polymer exhibits polymorphism. HMPAC (30 ml), NMP (30 ml and LiC
2-chloro-1,4- in a mixture containing 1 (3,0 g)
A solution containing phenylenediamine (8.58 g, 0806 mol) was stirred in a cylindrical flask under running water using a paddle stirrer, and 0.4 g'1 of 4-acetamidopenzaldehyde was added thereto. Within a few minutes, terephthalaldehyde (8,0410,06 moles) was produced. When the reaction mixture is stirred at room temperature for 4 hours, stirring becomes impossible after about 16 hours. Reaction t+V sounds were collected by the method of Example 2, 11nh=0.7, PMT=310°
138 g of polymer G was obtained. This polymer frame was put into a spinneret with one hole [10 diameter of hole = 0.0
09 in (0,023 boxes) Spinneret temperature = 320°C,
melting zone temperature = 310 °C, bag contains screen] in air through bath 1 type;
Wind up at 501/d/min (xa7.2 m/min). Properties of the filament of the spun \ fiber (η1nh = 4.5) 1d T / E / M i / Dan,
=7.4/1.3/683/10.9, O, A
, = 22°. A sample of this fiber is heated in a furnace on a bobbin wound with fiber flux. Temperature ~ 150°C/30 minutes, 150°C/30 minutes, 1
50-260°C/30 minutes, 260°C/35 hours. Remove from oven and cool to room temperature. The filament properties of this fiber are T/E/M i/l) g n. =15.3/1.9/844/11.1.0. A,=
10'. In lower Mf2 coat 11-A and n-B, azomethine (
The figure shows a fiber spun from a co)polymer and its optically anisotropic melt. Example 1 Polymers 14 to 19 were prepared by the general method shown in middle 1-1tI column 2, and practical example 11
-13 general methods. Dialdehydes that have been used include 4'-duformyl biphenyl, 2-chloroterephthalaldehyde, terephthalaldehyde, and isophthalaldehyde. The diamines used were 1,4-phenylenediamine + 2-methyl-1,
Includes 4-phenylenediamine and 4,4-ethylenedianiline. Examples 16.19, 19-2 (two diamines), 18 and 19-3 (two-stroke aldehyde) show copolymers. The spun fibers were heat treated as shown in Table ``-H'' to improve their strength and elongation.For the polymer of Example 19-1, 1,4
-Bis(3-methyl-4-aminophenoxy)-n-butane and terephthalaldehyde were refluxed in phenyl-α-naphthylamine as antioxidant in 1yz,yzh,yzhen. After collecting the benzene-water azeotrope compound - After separating the polymer precipitated from the remaining benzene -
Washed and dried. For the polymer of Example 1M91119-2, terephthalaldehyde, methyl-1,4-phenylenediamine and 1,12-bis(3-methyl-4-aminophenoxy)
The general method of Example 19-1 was repeated using -n-dodecane as anti-15 and J41 as the tar material. For the polymer of Example 19-3, one raw material was terephthalaldehyde, 4,4'-formylbiphenyl, methyl-1,4-phenylenediamine, and 4-aminoacetanilide (terminal one agent)
was carried out according to the general method of Example H9-x using methylene chloride as the solvent. Used in implementation/column 19-1], 4-bis(3-methyl-
4-aminophenoxy)-71-butane is 3-methyl-
It is produced by reacting equimolar amounts of 4-ditrophenol and 1,4-duglombutane in the presence of a mixture of anhydrous potassium charcoal and acetone. After allowing the females to grow for 48 hours, the solvent was completely removed and the solid product was collected.
-B Recrystallized from alcohol rn,, p, = 126
．． 1°4-bis(3-methyl-4-
Brightly colored needle crystals of (nitrophenoxy)-n-butane were obtained. The nitro compound is heated to 1000 to 15000 methanol at 70°C or higher. reduced to the desired diamine congener series using a Raney nickel catalyst at iW nd/in2. Separate the catalyst from the bath liquid, evaporate the solvent and recrystallize the desired diamine from ethanol (activated carbon). Melting point 108-110°c
o 1,12-bis(3-methyl-4-aminophenoquine)-n-dodeca used in Example 19-2 in the same manner:
, y (rrL, p, = 93~94°G) is 1,12
-Made from sopromododecane. Table ■ Azomethine (co) 4f sweet body: = N-R. central MC, example R, R22 1( 1( 1・li3, -N=IiC-R2-CM- and its yl&, n11
Time AMB O,5260>:260 262-
6.190 3 hours AA O, 3336334) 3343 hours, 4A Z9 260 249) 24
9 26j475 hours AA O,70260
256) 256 310 91.46 hours AA
1.5 260 246 ) 242 262
30.56 hours AA 1.4 2102
23 ) 220 230 786 Table n-A Continued (80/20) AkiB = 4-amino-3-methylbenzoic acid AA =
4-Aminoacetanilide* Properties during spinning T/E/Mi/Dgn, =5,4/
l, 2/4** CH, 80, H *** (11, 1 coefficient concentration) 6 hours None 0.46 220 23o >23
0 aoo 15281/1 (14 Example 20 This Example 711j is 2-chloroterephthalaldehyde. ,4-cyclohexanesoamine to force,
A method for synthesizing an azomethyl (co) 1-ji@ compound from a pair of soamines is shown. The potential of the copolymer of Oh L et al.
1v/11. -i has optical adhesion λ-tropism. HI'IPAC10ml)-NMP (10 penalties) and L
IC? A mixture of l(0,5,9)'q, of course, 4,4'-
Ethyleneduaniline (2,129-0,01 mol) and 2-chloroterephthalaldehyde (3.36 g, 0.02 mol N1JD) was added to a solution containing 4-phenylenediamine (1,08, L O, 01 mol) in a nitrogen gas stream. 7. (lii + ll Same as 1) ■♂ and pJ is 7.
dry at 0-75°C), y2 inh, 20.5-P
MT= 150℃ trilo-1,4-phenyleneethylene-1,4-phenylenenitrilomethylidene-2-chloro-1,4-phenylenemethylidine/nitrilo-1
,4-phenylenenitritumetyridine-2-chloro-
1°4, phenylene methylidine) (50150) copolymer was obtained. In Table 1 below, other copolymer compositions having the following repeating units were prepared using the pair of duamines described above and using the method described above. These monomers exhibit optical anisotropy in their melts. Vine copolymer unit = N - A 30/70 * T / E during spinning 7 M i / D e n
/ O,, /'l, = 2.97 lHH l O, 4290 0, 6272 1, 1/114/16/17゜Example 21 In this example, poly(d) IJ colo--methyl-1゜4
-phenylenenitrilomethylidine-1,4-phenylenemethylidine) fibers exhibit excellent retention of tensile properties after being stringed out in vaporized morpholine. 11MPAc 60ij')-NMP (60ral
) and L Z Cl (5, OI ) in a mixture of 2-
Methyl-1°phenylenediamine (12,2,9'-0
,01 mol) of 500 ml of bamboo under nitrogen.
In a fat pot, stir 1 [
，? -0.17 l) All added. Add the 30 minute ridge-aminoacetanilide (0,30,1) and continue stirring for a total of 16 hours. Real no j11! The reaction mixture was recovered as in Example 1, −η1nh=30, PA4T−256°C Polymer 2
1. '6 g was obtained. Polymer bath melting has optical anisotropy. -I] Melt-spun the coalesced rod. Spinneret temperature = 25
0°C1 melting zone temperature -240°C, burning rate approximately 500
? /d1min (457m/min). The tensile properties of the filament with weave shrinkage (ηinh, -3,3) during spinning are 'l' /E7M i /I)en, -9
/ 1.6'/789/6.4. Setsufi tenugui 1 (0,5,1 and Q, Q3+ff of morpholine was heated in a sealed vortex for 2 hours at 133° C. (steam bath). The fibers were removed and left in a gust of air for 1 hour. This treatment T/E /ivl i
/ Dan, = 8.2 / 1.1 / 73
It is 6/7.4. The fiber sample at the time of spinning was heat-treated under the following conditions. Room temperature 5-160°C/1 hour, 200°C/3 hours. %taT/lj of the treated filament, SEM,
/Mi/Den, = t 6/ 2.2/ 867 /
It was 7.2. Example 22 In this example, the fibers of the present invention (1) when heat aged in a high amine-containing rubber stock, and (2) t;
It is shown that it retains its strength well even when hydrolyzed at 1'. Part 1: Samples of threads produced by other methods for the copolymer of Example 10 were heat treated under the following conditions. 150℃/40min, tSO°
C/1 hour, 200°G/4 hours (initial furnace temperature 150°C
). This gives the property T/E/A-f i/D
p n, = 9.9 / 1.4 / 788 /
I got a score of 7.3. A full skein sample of this heat-treated yarn was heated in air at 154°C for 24 hours and T/E/M i 70g n, = 6.9.
/0.9/779/120 fibers were obtained. The heat-treated fibers were spliced into a 1,000 denier cord, and the cord was embedded in a rubber raw material containing O5 amine to form a composite. This complex was heated at 154°C for 2
Heat and age for 4 hours. Next, this rubber was swollen in toluene and fibers (cords) were taken out. For this code, T / E / M i = 'l 2 / 0.
80/472 (10 inch break). This is due to the fact that the strength was maintained at 32% under severe test conditions. Part 2 Example A yarn sample (4-filament) produced by another method of 100 ton coalescence was heat treated at 7200°C (initial furnace temperature 190°C) for 2 hours/190°C and 141 hours, and the properties of the filament were T.
/ E / M i / Dan, = 12.5/
A fiber with Z s/s 60/30.1 was obtained. This fiber sample was hydrolyzed as follows. Test B-1 Sewing a line of cloth with a length of 8 inches in length,
Heat in water at 795°C for 2 hours. Test B-2 This test is similar to B-1 except that an IN aqueous solution of sodium hydroxide was used instead of water. After testing, the fibers and cloth are soaked in water until the alkaline earth metal is removed. Remove the water from the waste, clean the fiber, dry it, and pull the filament! 1 I have decided on the identity. 11JQ B 1's N"inn il'
T/E/Ai S/Den, 2 8.
1/1.81512/34.7 6ノ(, F-B-2's ia [; i'/ )"; /
A4 t / J) en, = I Z 5/2
．． 0/717/23.3 Hero Example 23 Honmeiriki Ll; In the example, the azomethine (co) offing body V of the present invention
Fj indicates that the fiber retains its strength well when heated and aged in rubber. Copolymer sample of Example 116 (ηin, h, = 1.2
). Spinneret temperature for spinning copolymer Azusa
250-252°C), 288-1.271 m7/14+li, some (a, hy amine) iL is taken in the box. 1,271 m/min.
6.4/1.1. / 717 / 4.3. These 30 filaments were spun together (3 times/
inch) and heat-treated at 230°C for 7 hours to make it into thread. The treated yarn has T/E/A4i/Den, =11.4
/ 1.3/906/ 120.5 properties. Treat this thread (3 times/inch) in rubber and try again.
I tried it. The results are shown below. Thread sample [approximately 20 inches long] into two pieces each approximately 4 inches long.
Insert it lengthwise between two rubber plates. The rubber plates with the thread inserted between them are tightly clamped together and the protruding ends of the thread are taped to retain the twist. Sample piece? ? T' which was heated at 165℃ for 24 hours in hot air! After cooling to -'fl temperature, the end of the thread was clamped in an Instron testing machine to determine the breaking strength of the embedded thread. Separate rubber raw materials with high amine content and low amine content were used. I got the following results. Rubber raw material Maximum breaking load in pounds fjld High amine grade fJI Z 83 10. Fi 1
]; Amine content: 161 g, B These I11'4 retain strength by 94% and 86%, respectively, and have fC values. Example 24 A Fruit 7z1i is nitrilo-2-methyl-1,4-
An irregular ill containing phenylene nitrilo-methylidine-1,4 to phenylene methylidene and nitrilo-1,4-7 nylene methylidene units in a ratio of 4:4:l
-)-e ' Shows how to use M1 combination. 1 stirring chamber - 2 50 with a blowing pipe and a distillation head
m+? Three 07 Lasco Vc2-me-f-) L, -1,
4-phenylenediamine (7,32,LO, 06 mol). 4-aminobenzaldehyde “oligomer q[1,58
g, 0.015%#, η1nh=0.08, I
(La, borator
igs), US 7=nee E-1' state 7'lzunuyu-
(manufactured by Plainview)], and N+”-(1p
4-phenylenemethylidine)duaniline (17,88
, L O, 06 mol) was added. - Stir the combined ingredients and heat to 2500G for 30 minutes under room temperature. Next, the 5 mm and 11 g was heated under 250'C for 10 minutes, and then the reaction (it@[27 (optically anisotropic molten proboscis)] was cooled to room temperature. Distill and collect water and the natural by-products of aniline. The resulting solid mixture is crushed in a mixture and washed with acetone therein. At 80°C. Really dry. η1nh = 3.2,
PMT = 210°C (13.3 g' of rJ copolymer was obtained. This yields a M melt with optical anisotropy. The copolymer rod was placed in a one-hole spinneret [hole diameter 0.009
in (0,023cm), spinneret? temperature ÷ 230℃
, b melting zone temperature 225°C] in nitrogen gas.
Spun the resulting fiber at 5GO1/d/min (457,2
Roll up at ml/min. The properties of the filaments of the fiber during spinning are T / E / A4 i / J) g n, =
3.7/Q, 7/556/7.2. A portion of this fiber was wrapped around a fiber flux hobbin and heat-treated in a furnace at 240° C. for 6 hours in a nitrogen gas stream. The properties of the processed filament are 7”/E/nf
i/Dpn. =10.3/1.7/659/'7.2. Part 2 = tIJ o -2-Methyl-1,4-phenylenenitrilo-methylidine-2-chloro-1,4-phenylenemethylidine and nitrilo-1,4-phenylenemethylidine units (2+2i1) fzr Co-I] i Create a union. This copolymer has an optical anisotropy of 3.
1: Causes n-su. Repeat the method in Part 1 above and the trap will be 4
．． 88.9 (0.04 mol) of duamine, 2.12F (
0.02 mol] of “oligomer” and I Z 74 g
(o, 04 mol) (1) Using N r N'-(2-chloro-1,4-phenylenemethylidine) dianiline and heating at 250° C. and atmospheric pressure for 20 minutes,
The mixture was heated to 250°G for 20 minutes at a pressure of 10 Hfj. η1nh=1.5% PMT=230℃ co-offshore body ii,
7y was obtained. This produces a melt with optical anisotropy. Example 25 Honji, the thread 1; 1 is polytrilo-2-methyl-1゜4
-phenylenenitrilomethylidine-2,6-naphthylenemethylidine); In a reaction vessel equipped with a stirring mode and a 5-distillation head, 2
-Methyl-1,4-phenyleneduamine (1,229-
0.01 mol) and #,N'-(2,6-naphthylenedumethylidine)-dianiline (3.3 g, 0.01 mol) are added. The reaction raw materials of Koj et al. were heated at 250°C for 20
The mixture was bath melted and stirred for a minute. The aniline sub-fIZ product is collected (iL. Reaction product sound?)), and the product is collected 4. Wash with acetone and dry to obtain PAb T-2450C1η1
Polymer 3,229 with nh=06 was obtained. This produces a Vi optical 1, ν-oriented bath melt. j, N'-(2,6-naphthylenedumethylidine) dianiline is first converted into ethylene glycoldumethylethyl ether (1
2,6-naphthylenesocarponyl chloride (50.6 g, 0.02 mol) in 50,112). It was prepared from π by anchoring with 'tf'G solution containing lithium tri-t-butoxyaluminum hydride (103,9) in enalene glycol methyl ether (700d). No. 1 Rescue chloride exists at -70°C under the starry sky. A total of 4 hours (1:ql) was added and the combined ingredients were stirred overnight and allowed to warm at room temperature. Pour the reaction mixture onto ice. White product precipitated. Collect and extract while still wet with hot (boiling) 2B alcohol. Separate the hot alcohol and all remaining solids, and distill the alcohol (output) to obtain a crude yellow condensate of 02,6-naphthylenedualdehyde, f≠
°1! A point of 162 to 190°C (with some unmelted material remaining) remained. Next, Japanese soaldehyde (40!j) was dissolved in ethanol (200 ml) with stirring. Add aniline (6 Biao) to this solution. The reaction mixtures were refluxed together for B (+), cooled and the above yellow precipitate of dianiline (r) collected, washed and dried.
d point = 180-182°C. In the following Table 2 (Examples 26 to 38), other optically anisotropic samples of the present invention made by the liquid coating method of the present invention (i.e., HMPA, NMP, l1cC1, AA stop cutting) are shown. Figure 2 shows azomethine (co)polymers, fibers and films producing melts. The duamine reaction raw materials used include 2-methyl-1,4-phinylene diamine, 1,4-duacetylbenzene bishydracine, and 2,6-fuchloro 1.4
-phenyleneduamine, 1,2-bis(4-aminophenyl)ethane-bis(4-aminophenyl)methane-bisc4--fminophenyl)thioether, 1,5-diaminonaphthalene, 2-chloro-1, Included are 4-phenylenediamine, hexamethylene diamine and 4-aminobenzoyl hydrazide. The four-phase l'ζ dialdehyde reaction raw materials include 2-chloroterephthalaldehyde-1,2-bis(4-formylphenyl)ethane, 2,5-dichloroterephthalaldehyde, terephthalaldehyde, l,2-bis(4-formylphenyl)ethane, -Formylph, enoxy)ethane. 2.5-dichloroterephthalaldehyde, terephthalaldehyde, 1,2-bis(4-7 ormylphenogizo)
Ethane includes 4.4'-sobenzaldehyde and isophthalaldehyde. W47nj+N26 odor-C contained bishydrazone. This product, 4-y acetylbenzene, was refluxed (48 hours) in 2B alcohol with excess hydrazone hydrate.
The reaction mixture was allowed to cool, producing a product with a melting point of 184°C! The proboscis is made by (i). The dialdehyde used in Embodiment 135 was obtained by first q-dimenting dimethyl ester of 1,2-bis(4-carboxyphenoxy)ethane with L i A l li4 in tetrahydrofuran.
-bis(4-hydroquinemethylphenoxy)ethane-m
It is created by creating a point t74-176°C. This was published in the Journal of Organic Chemistry (J, Org, Chgtn,, ”) 32,
3865-8 (1967) with ammonium cerium nitrate in glacial acetic acid/water to give the desired dialdehyde. Melting point 1125-114°C. The dialdehyde used in Example 36 was prepared as the trimethyl ester of 4,4'-bibenzoic acid, fLiAIB, in tetrahydrofuran at about 5°C. It is made by converting it into 4,4'-bipendul alcohol.This alcohol journal organic chemistry magazine 32+386
5-8 (ice jYf- by the -F method of the 196'l war
1-'e+/T-t-y reaction with nitric acid and ammonium cerium in water to give the desired dialdehyde. For this novel artist, the midpoint is 141-143°O. All stated deniers are filament values. 1-hole spinneret [hole diameter 0.009Jn. (0023Crn)] The fibers were bath-melt spun. Table ■ Continued (70/30) 1 (90/10) ★* Heat treatment mT/E/Mi/Den, = 15/3.7
/455/4°Fiber when spun 0.5 228 2.5 0.96 321 30
19°1.1 245 4.4 0.97 489
39.3 22゜1.7 270 3.4 1.2
353 4.7 -0.4 4.0 1.
4 424 6.5 -. 235°C/3hr). Example 39 This practical example shows that the tensile properties of the present invention are significantly enhanced by the use of heat treatment. A case where the brewing time in this step is short or the spraying τWl is low will be exemplified. Azomethine copolymer filaments (T / E / M i / Dan, =
3.4 /1, 2/353/4.7) was doubled into a thread (5 filaments), passed through a bed of talc, then fired, -67, me, -c, e, t y + t.
eylFIJ. This sample was placed in a furnace flushed with nitrogen, and then! 7iAITk 40 minutes-cyt On/Hara 15
Keep in it for 4-2o minutes on 0'C. The sample is cooled in the oven to about 50'C for 1", removed from the oven and cooled to room temperature. The treated fibers are heated to 7"/g/M i /
i) e n=9. 2/2, 0/43915.
Shows the properties of 7. A portion of this treated fiber is wound onto a bobbin and heated again in a furnace under nitrogen), 40
Heat from room temperature to 260°C for 3 hours and keep at 260°C for 3 hours and 20 minutes. It is then cooled and removed under the conditions described above. The filaments of this treated fiber are T /E/
A4 i /Den, = 20. O/3.8/47
015.5 is shown. In the following Parts 2 and 3, an azomethine (-co)polymer polymer consisting of one block + san structural unit=NR, -N=HC-R-CIi= was used. In Part 3, the polymer corresponds to that made in Example 7ifb Example 17, but the -! It was created according to the Law on Promoting Popular Markets. In the third part, the one-vehicle assembly was made in the same way as in the second part, but by the 1-volume polymerization method. The synergistic combination and fiber f4 used were implemented f! l
There were 37 items. Spinning was carried out in the same manner as described above. Part 2: In this process, the spun polyazo fibers are subjected to 111°C for 20 seconds at the indicated temperature.
Lower it. This one-time treatment significantly strengthens the tensile force (l=,a). Part 3 In this process, the azomethine (co) offing fiber during spinning is wound onto a metal bobbin coated with flux and heated in a furnace (nitrogen atmosphere) at the temperature shown below for 2 hours. . As shown in Table 1, the tensile properties of the fibers were significantly improved at one treatment temperature. Example 40 Optically anisotropic melt-forming azomethine (co) whose repeating structural unit corresponds to the formula % shown in the table below
Indicates a polymer. The (co)polymer was prepared by melt polymerization IC of reaction raw materials selected from newly synthesized 4-aminobenzaldehyde, 2-methyl-4-aminobenzaldehyde, and 3-methyl-4-aminobenzaldehyde. In a typical method for items 1-4, a suitable monomer (approximately 0.
0.02 mol) is added together with aniline (lffl/!'l) in a reaction vessel fitted with a stirrer, distillation head and nitrogen blowing tube. Heat for .5 hours. Then stop the nitrogen flow and heat (stir) the reaction materials at 250 °C for 0.5 hour at a pressure below 1. Omaxi 9. Cool the reaction mixture and remove the product. Collect, wash with acetone, and dry.For the copolymer of item 5, 0.096 mole of each aminobenzaldehyde and 0.0 mole of methyl-1,4-phenyleneduamine (used as a viscosity stabilizer). 0057 mol and xylene (350 ml) and trifluoroacetic acid m (0,25
+IIA) together with -. The reaction mixture is allowed to stand for 3 hours (to remove the benzene-water azeotrope), and the copolymer is filtered off, washed with acetone, and dried in vacuo. A copolymer rod was spun as in Example 13 [spinneret temperature = 240°C, melting zone temperature = 232° (, L fiber was wound at 155yrL/min. ζ after spinning: The fiber samples were treated with Merck and then heated at 222°G for 1
Heat in an oven for 63 hours (N, ). Trial i-4
was 6 inches (15.2 m) long and supported on a screen. Heat treated fibers are T/E 7M i
= 10.871.9 / 709 ”'C'lr. \ Table ■ Azomethine (co)polymer, =C ) C1i, C113 R3-N- 1,0210 0.4 200 0.4 178 0.3 310 λ3 214

[Brief explanation of the drawing]

The attached drawings are solid polyazomethine with two different glazes and m-
Figure 2 shows the light intensity and background transmission curves obtained for each state. Curved thing! (IJ) is based on one piece of the present invention, and the other curve (A) is based on a polymer that provides isotropic bath melting. 171 Song People Yi I Du, I? hmm·
de nimoas and co.

Claims (1)

[Scope of Claims] 1. An electrolyte having a bath melting temperature of 375°C, which exhibits optical anisotropy in the molten mII state and can be spun on the bath surface into oriented filaments without drawing. Lower azomethine (co) undercarriage. 2 The polymer has the following units (1') -4=#-R1-N Takashi Z, Z2 and (III) KiC-Rr-N4 Z. However, if the units I and (2) are present, they exist in substantially equimolar size in 1'S), +Z, +22 and Z3 can be different in the same molar size, and can be a hydrogen atom, or a methyl or ethyl group. selected from R, -R2 and R31d (1) a mono- or fused six-membered carbocyclic ring system in which one of the ring carbons of the aromatic ring, if present, is replaced with nitrogen; The chain-extending bonds of the ring system can be linked to one another if they are attached to a single ring.
single and fused carbocyclic six-membered ring system radicals located in the 4-position and in parallel and oppositely oriented positions if attached to different rings; and (2) A polycyclic system in which the individual rings are connected by chemical bonds or bridging units whose length does not exceed 14 atoms, and the chain extension bonds of each term are in the 1 and 4 positions, and + R, is a chemical bond. Azomethine according to claim 1, characterized in that it is a group selected from the group consisting of polycyclic groups, which can consist essentially of repeating structural units selected from (Both)
Polymer. 2. 40 moles of sales dogs for all units of I, ■ and m. Units other than the I, ■, and ■ units in the patent claim are directly replaced by polyazomethine-forming units that do not interfere with the optically anisotropic bath melt-forming ability of the azomethine (co)polymer. Azomethine (co)heptatomer according to Range 1. Special IF of a polymer consisting essentially of I and ■ at position 31! f
The azomethine (co)polymer described in item 2 of the d·1 box for fj. 4, R is 1,4-phenylene, chloro-, bromo-, methoxy, fluoro-methyl, hydroxy- and nitro-1,4-phenylene, 4,4'-biphenylene-3,3'-tumethyl-4, 4'-biphenylene, 4.
4'-methylenediphenylene, 4゜4'-dimethyleneduphenylene, 4.4'-t! J methyleneduphenylene,
4.4'-tetramethylene diphenylene, 2,6-naphthylene, 1,5-naphthylene, 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'-tetramethylenedioxyduphenylene, 4
, 4'-azoxydiphenylene. 3. selected from the group consisting of 3'-methyl-4,4'-azo diphenylene and the chemical bond: R7 is 1,4-phenylene, chloro-1,4-phenylene, methyl-1,4
-Phenylene, 4,4'-biphenylene, 4,4'-oxydiphenylene-4,4'-ethylenediphenylene, 4,4'-methyleneduphenylene, 4,4'-ethyleneduoxyduphenylene- 2゜5-pyridinedinyl, 1
,5-naphthylene-2゜6-naphthylene, 1,4-naphthylene, 2,5-fuchloro1,4-phenylene-2,
5-dibromo-1,4-phenylene, 2,5-somethoxy-1,4-phenylene, 2-10mo-1,4-phenylene, 2-methoxy-1,4-phenylene, and 2-hydroxy-1,4-phenylene Selected from the group '
H2 %rf request d; Section 3 4. Azomethine (co)polymer of Azomethine (co)heterogen as described in the desired species section vJ4 item Wr2. 6. Characteristic f where R1 is methyl-1,4-phenylene;
The azomethine (co)polymer according to item 4 of the F5W desired range. 7, 11. The azomethine (co)polymer according to claim 4, wherein is 1,4-phenylene. 8. The azomethine (co)polymer according to claim 4, in which two or more types of units (2) are present.・'9. The azomethine (co)polymer according to claim 4, wherein R2 is //rolow-1,4-phenylene. 4”F M+ where 10, # is 1,4-phenylene
Azomethine (co)polymer according to item 4, range of WR powder. 11. A material consisting essentially of nests (1), in which at least the 25th ring of the unit (2) is substituted with a group selected from the group consisting of chloro and methyl groups (1t-F) Claim 4 azomethine (co)polymer. 12. The azomethine (co-)small aggregate according to claim 2, wherein the wood ends are tasselled. 13. The azomethine (co)polymer according to claim 4, wherein the wood ends are blocked. 14, 1 formula 11, N-R with optional presence of terminal capping agent
, -NH2 2,2°, and optionally an aminoaldehyde or aminoketone of the formula 1 formula % or a functionally equivalent derivative of such a raw material. However, in the above, "+ -R2)'h and R3 are m mono- or 1l-i fused carbocyclic six-membered ring system, and if an aromatic ring exists, the trench carbon of the aromatic ring One of the 11h' atoms can also be exchanged with the element 11h', and the chain extension bonds of the ring system are in positions 1,4 from each other if the bonds are attached to ilt-111':L. - groups of a fused carbocyclic six-membered ring system which are located in parallel and opposite positions if attached to different rings and (2) a polycyclic ring system in which two The individual rings are connected by chemical bonds or bridging units whose length does not exceed 14 atoms, and the connecting link of each term is in the 1,4 position, and -R, can also be a chemical bond. A group selected from the group consisting of ring-based groups -2, +22 and Z
, can be cyclic or different and are distant from a hydrogen atom or a methyl or ethyl group. A method for producing an azomethine (co)polymer which exhibits optical anisotropy in a bath-melt state and has a polymer melting temperature lower than 375° C. and can be melt-spun into oriented filaments without drawing.