JPS5823826A - Manufacture of polyamide - 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 The present invention provides spinnable boriacells by conversion and polycondensation of dinitriles with aliphatic α,ω-zoamines and excess water in the presence of inorganic or organic catalysts. Regarding how to.

Conventionally, azopic acid, which can only be obtained from aromatic compounds, has been used in the abori. The method of producing diazobic acid by saponification of azinitrile does not give a favorable quantitative reaction and is impractical.

Currently, azo 4-nitrile can be economically produced electrochemically from glopyrene or acrylonitrile, and
It can be prepared catalytically on a large scale and in high purity by the conversion of fazoenes and cyanides.

Currently, adipic acid is in solid form, and hexamethylene cyanide is in liquid form with a small amount of water, each in separate containers or in a mixture of adipic acid and hexamethylene cyanide each at a concentration of about 6011. It is transported in heated tank cars as a solution. In this case, in addition to the difficulty of transporting it over long distances, it also has the disadvantage of increasing costs since approximately 40 kg of water must be transported together.

Even when transporting as a solid salt consisting of equimolar amounts of azopic acid and hexamethylenecyanate, ie, an AH-salt, the above-mentioned difficulties cannot be overcome. This is because the AH-salt evaporates or precipitates from water or methanol, resulting in increased costs. Also, 60%AH-
Since water is increased in the salt solution due to the reaction, it must be evaporated during the condensation polymerization in subsequent processing.

Azinitrile, hexamethylene cyanide and excess O
It was previously thought that the reaction between water and water was not similar to that of a car. For example, U.S. Patent No. 2,245.129 describes an example requiring a reaction time of 20 hours or more, and U.S. Patent No. 3.847.876 describes an economical continuous process, but It is said to contain at least 100% of free ammonia, and the total reaction time is 8 hours or more.

Experience shows that due to the thermal instability of I-lyhexamethylene azo/4mide, short residence times and good residence times are required. In proportion to the rise in , it becomes 1).

The present invention has been made in view of the above circumstances, and is
From nitrile, hexamethylene cyanide, water chloride and additives to spinnable / lJ quinamethylene chloride V! This is a method in which a catalyst is continuously used in a cascade reactor and a final reactor to accelerate the reaction, and 2') the reaction is carried out at a temperature above SC to generate free ammonia. It is an object of the present invention to provide a method in which 040 is less than or equal to 1.Furthermore, the present invention is a method for fabricating spinnable polyhexamethene azo A electrode OiI, in which It is an object of the present invention to provide a method for using azo-nitriles which can be obtained from inexpensive materials such as glylene and ltazoene.

Furthermore, this invention is an equimodal mixture of azyl and hexamethylene cyanide (by adding a small amount of water).
It is an object of the present invention to provide a method that can advantageously carry out long-distance transportation by using a liquid at room temperature by using only a /4 last with an extremely small amount of labor.

Additionally, the present invention provides a process for making spinnable lyhexamethylene polymers that is more intensive in terms of energy and reactants compared to prior methods. For example, (龜) Conventionally, 1.1601Q of AH-salt was used to produce irihexamethitone? In contrast, in the present invention, an equimolar mixture of axamethyl and ninoacin was added to 992 to 91i.
! It's just a matter of doing.

(b) According to the invention? For each ton of sameethylene azinamide, 9:150 ammonia is formed as a by-product, suitable for sale in gaseous form or as an aqueous solution, which helps reduce production costs.

(e) According to the conventional law? Liheki-methylene water (starting from 60* A-H-salt solution) must be generated, but according to the invention about 130 #
It is only necessary to evaporate 150 kl of water and 150 kl of ammonia.

Furthermore, the present invention uses ammonia-containing water and oxygen-containing phosphorus compounds as esters, acids or salts; preferably ammonium salts! This is part of a method for producing spinnable/9-hexamethylene adiamide which shortens the overall reaction time and stabilizes the reaction. Examples of such oxygen-containing phosphorus compounds are hyposinous acid, cynic acid, phosphorous acid, and phosphonic acid, which can be added as ammonium salts to esters, alcohols, or aqueous solutions. can.

Furthermore, sulfuric acid, sulfonic acid, boric acid, haphydrogen acid,
strength! A catalyst selected from the aSS form of organic acids is used, and the amount of catalyst is azo, tolyl, and oos ~ 0.5.
The range of - weight is the allowance. Although it is possible to add more than this upper limit amount, no special effect can be obtained by doing so.

Furthermore, the present invention is characterized in that 9 mD2 to 30 mol of monoamine heptanoic acid is added as a chain length regulator to an equimolar mixture 1 of azyl/'-)lyl and hexamethylene diamine at the start of the reaction. The purpose of this method is to stabilize the remer melt, thereby making it possible to maintain a constant viscosity of the melt in subsequent processing steps.

Furthermore, this invention provides spinnable I with good light and thermal stability.
Particularly when used as textiles, tire cords, characterized in that they provide lyhexamethylene azo 4-a-densylamines, known thermal stabilizers such as realylamines, N-substituted 97
．． Phenylene-cyanine, mercagutopenediole azole, copper salt, io-compound in a single form! IS is used in combination.

The addition point may be before the reaction, during the reaction, or at the end of the reaction.

The multi-step envying reaction of the present invention between azilla trichloride and an excess of water can be carried out as shown in the following formula.

Addition and conversion of the nitrile group with water; the necessary intermediate products of low molecular weight, namely different acid amides, such as cyanopallelic acid amide and adipic acid cyanide, are obtained. According to the reaction conditions according to the invention, pure adiponitrile is completely converted and completely consumed in a short reaction time without significant evolution of ammonia.

The formed acid and nitride groups react with the atom group of hexamethylenediamine in the form of transamidation to form ammonia, which in turn reacts further to form an electrolytic noalkylated acid atom. Then, the first four rear-hard products are formed. It is possible that part of the nitrile groups or the resulting saponification of the acid oxides becomes the corresponding acid or ammonia-containing water.

As the most thermally unstable compound in this method, azo-nitrile readily reacts intermolecularly to form 2-cyanocyclopentanone imine, which further reacts leading to gelation and decolorization.

In contrast to the disclosure of the home patent N@, 3,847,876, the present Hibiki 9 conditions, i.e., self-heating pressure, 22-24
Due to the physical conditions of the present invention, it is always possible to keep the ammonia below 1% by choosing a high temperature of 225°C or higher. The amount of ammonia that ranks is 0.3
The higher the amount of ammonia in the above patent, the higher the pressure, e.g.

A lower temperature is required at the beginning of the reaction.

The advantages of the present invention are that the pressure can be up to 25/4 liters, the equipment is economical, the reaction time is short, good quality is obtained, and water consumption is low. ,
.

Hereinafter, the present invention will be described with reference to illustrated examples.

As shown in FIG. 1, hexamethylene cyanide 2 and a5711! Nitrile 3 is continuously supplied in molar quantities to the heatable conditioner 6. At the same time, catalyst melt 111
2 (approximately l-aqueous solution) and deionized water (or an-S
Ni-containing water 4) is added under stirring. This homogeneous mixture is heated continuously by a control piston 1 and heated by a heat exchanger JK to about 220 CK and introduced into the first stage 9 of the reaction cascade at a temperature of 245°C and a pressure of 24°C. Under the reaction conditions of /fl, the partial pressure causes the gas and water to scatter from the relief pulp 12 via the dephlegmator 11. Most of the water is condensed by the dephlegmator stt and returned to the reactor. Dephlegmator 11 is operated at approximately 45°C.

If desired, a pigment, for example titanium dioxide, is added to azo-nitrile or a mixture thereof with water, from 10 to 40 Is1.
Once added to the suspension I, it is introduced into the first stage t of the reaction cascade via line 10 with the Kome Pigment Co. dispersant. As this dispersant, polymethasilicate, polyphosphate, vinyl alcohol, etc. are used. The concentration of pigment is 0.1 to 3 wt.
is preferred.

Due to the height difference K of the reaction cascade, the partially converted reaction products are introduced continuously at equal pressure into the second stage 13 of the reaction force scale. This second step 1
3. Heat to 270-280°C.

The liberated ammonia and water are trapped to flow from this second stage 13 to the common relief pump 12 and through the deflation meter 14.

Most of the water is condensed by the dephlegmator 14, and then flows back to the reactor 1s. This dephlegmator 14
The stone is operated at a temperature of approximately 55°C.

A small amount of released ammonia and water is transferred to condensation receiver rg (
219) from K to another ammonia collector 25 at about 351.

The second stage of the reaction cascade 13? The initial condensate is sent to a stirred precondensation reactor 15 using a controlled relief pallet. The reactant J#d is operated at a pressure of 1.5 to 3.0 par, to which unsaturated steam or inert gas 20 is added. Ammonia is discharged from the reactor 14 and is sent together with excess water to the cooler 11 via the relief pulp 11, and further sent to the condensation receiving tank l#.
It does not dissolve at normal pressure; the ammonia is scattered together with the reaction cascade and the ammonia via the upward cooler 21- to the ammonia recovery gIHz.

In the finisher, the reaction product converted in the condensation polymerization reactor 15 at 285'C is appropriately processed in consideration of the final desired state, ie, the degree of polymerization, etc. Therefore, the 4 reactors in the condensation polymerization reactor IJ are continuously discharged to the ear pump F21, and the heat exchanger JJK is heated to a temperature of 1290℃.
~SOO'' CKII clause and introduced into the finishing system. The finishing system has an expansion vessel 24 for the final release of the remaining volatile compounds, which is connected to a -type reactor 24. This expansion container 2
A heated inert gas 21 can be supplied in the form of pure nitrogen or unsaturated steam to accelerate the remainder of the polycondensation reaction, and additional additives can be supplied in line 26. Hmm, I can do it.

In the present invention, a double screw reactor 28 having a degassing zone 2# is used. Depending on the purpose, 4-lyamide products can be prepared with relative solution viscosities of nA, l.

This relative solution viscosity Fi25°C, 96-sulfuric acid, 1.9/1001L4! It is measured by concentration. The spinnable amide melt produced in this finisher may be directed to conventional granule production or directly to a spinning process.

Next, depending on the purpose? The relative solution viscosity of lyhexamethylene azonohydride is shown.

Relative solution viscosity (a) Ill fiber filament 2.
4-2.6(d) Cart fabric...
2,7~2.8, (C) Quantity fit trimmer...2.8~3.2 and #1 for use as tire cord fiber, or these 4 reands can be requested with a four tie fit trimmer. It can be used for many other applications. For example, molded products, films and molding containers.

The sheacene suitable for use in the method of the invention has a carbon atom number i~
It is 20° cyan. These cyano groups may be linear or branched aliphatic, aromatic, or heteroatom-containing; is a group whose substituents are inert under the reaction conditions.・Among these, preferable cyanogens are aliphatic or aromatic cyanogens having 4 to 12 longitudinal atoms, such as hequinamethylenedione, 1,4
-Cia (butane, 1,5-cyaminopentane, 1.8
-cya ζ-octane, 1.10-cyaminodecane,
1,12-cyanododecane, 2,5-dimethylhexane-2,5cyaquine, 4,4'-cyamodicyclohexyl sulfur, V-cyamodicyclohexylmethane, 4
, 4'-diannodicyclohexyl ether, octamethylenecyamine, tetramethylenecyamine, and other cyanide of the following general formula.

R') IN -W -Nun' In the above formula, R'' is an alkylene or arylene group having 4 to 12 carbon atoms, and 8' is a hydrogen atom or a -valent organic radical.The most preferred cyanide is α , ω is an aliphatic cyanide.

The dinitrile used in the present invention is a dinitrile having 2 to 20 carbon atoms. These dinitriles may be aliphatic, linear or branched, or aromatic or heteroatom-containing; substituted dinitriles may be used if the substituents are inert under the reaction conditions. More preferred examples include aliphatic or aromatic dinitriles having 4 to 12 carbon atoms, such as azo/di)lyl, succinonitrile, glutanitrile, spanitrile, sepaconitrile, 1.10 -5''candinitrile, isophtatenitrile, tetraphthalonitrile, and other dinitriles of the following general formula.

NC-R-CN This is an alkylene or arylene group having 2 to 1 G of carbon atoms.

The above-mentioned thin catalysts include alkyl- or aryl phosphinic acids, alkyl-aryl phosphonic acids or esters thereof, ammonium salts, and ammonium alkyl salts. In addition, the catalyst is selected from (1) oxygen-containing boron metals, (2) acidic oxygen-containing sulfur compounds, (3) hydrogen hatinide, or ammonium salts and ammonium alkyl salts thereof.

Although the present invention is preferably carried out continuously in a reaction cascade under the above reaction conditions, it may also be carried out under a wide range of conditions and with extremely simple equipment.

This reaction takes place in a pressurized container with the exclusion of air. This O reaction is usually carried out initially at a pressure above atmospheric pressure, and then the pressure is lowered to atmospheric pressure and carried out. Excess water and ammonia are then preferably removed from the reaction system by reducing the pressure below atmospheric pressure or by adding an inert gas. In this polymerization step, it is preferred to liberate the ammonia while initially maintaining at least some or all of the water in the reaction system, this being done, for example, by the use of a reflux cooler.

Examples 1-18 Equimolar amounts of adi-nitrile and hexamethylene cyanide, various amounts of water, and suitable amounts of inorganic or organic catalysts were prepared as shown in the table, with 100 p'pm of silicon antifoam agent.
1. The mixture was introduced into a stainless steel autoclave (equipped with a stirrer) and mixed. This autoclave was equipped with a dephlegmator, and was also equipped with a lowering cooler via a pressure reel pallet. Take this! Heat exchange: Oil was heated steplessly and continuously. Rinse the filled autoclave several times with nitrogen before starting each test.
Then, make it into a no-pressure state.

The reaction mixture in the autoclave was heated with continuous stirring, increasing the temperature to 225° C. in 45 minutes. Next, the self-heating pressure was set to 22 to 24 and pearl. During pressurization for 50 minutes, the ammonia generated by heating was continuously released via a dephlegmator. At the same time,
Steam (water) was returned to the autoclave as ≠7 legmates.

Furthermore, after 135 minutes, when the product temperature reached 275-285°C, the pressure was released and 22,724 pearls were
Descend to the bar in 60 minutes. Next, the average time is 45 minutes! After the curing time, the contents of the autoclave are evacuated by applying excessive nitrogen pressure.9.

Dry the obtained pre-and as much as possible into a rod shape,
The analyzed zero degree of polymerization was calculated by determining the relative viscosity of the solution. Note that the 4-lyamide concentration was measured for polyamide II at 9625° C. for 1001. The results are shown in the table.

Example 19 Azionitrile 3 from a production vessel surrounded by purified nitrogen
8.0-, hexamethylene cyanide 40, 8-1 water 21
．． 1 part skin, 1 part 9 homogeneous mixture consisting of 0.1 part cincinous acid
was continuously fed into the reaction cascade at a rate of 4 times per hour. The reaction cascade consisted of two 2-1 mixing reactors, each with a filling level of 75%. Both mixing reactors were equipped with partial condensers and -) W in-gas systems. They can be operated at different temperatures, but with the same filling level.

During continuous operation, the following dalameters were maintained:

Reactor l: Pressure = 24 pallets Temperature:
242℃ Dephlegmator temperature = 55℃ Reactor l: Pressure crab 24 pallet temperature:
265-270℃ Dephlegmator temperature: After cooling to 30℃, reactor! The ammonium gas flow from and ■ reached about 17317 hours.

The reaction product from reactor 1 was fed continuously to a mixing vessel heated to 280 DEG C. and the pressure was released to 5-6 bar, while the steam produced was condensed using a descending cooler.

The transparent and colorless initial condensation product is periodically removed from this mixing container, and then 1*1. It was solidified into a white body with a relative viscosity of 1.8.

As is well known, this initial polycondensation product can be further polymerized continuously or discontinuously to form a spinnable polymer 4-lyhexamethylene azide/4-mide. Furthermore, solid state condensation polymerization may be performed.

[Brief explanation of the drawing]

1 is a flow diagram illustrating a method for producing spinnable lyamide according to the method of the present invention. In the figure, 1...catalyst solution, 2...hexamethylenezoanne, 3...azinitrile, 4...ammonia. Contained water, 5... Ionized water, 6...? Irah, 1...
・Ing, 8... Heat exchanger, 9... First stage, 11
... Dephlegmator, 12 ... Relief pulp, 1
3... Second stage, 14... Dephlegmator, 16...
... Condensation receiver tank, 19 ... Cooler, 22 ... Relief pulp, 25 ... Recovery device, 27 ... Inert gas, 2
8...Screw type reactor, 29...Degassing zone. Applicant's representative Patent attorney Takehiko Suzue Continued from page 1 Priority claim ■May 18, 1981■United States (US)■
264982 @ April 20, 1982 B @ United States (US) ■3
70271 Procedural amendment (method) % formula % 1. Indication of the case Patent application Sho (7-?27Pl No. 2, title of the invention, power of 'SoysP' 7.83. Make amendments) Relationship with the Patent Case Patent Applicant Da... Lord 1. Relationship to the case No. 57-82981 Patent application name: Davey Matsky Der-6, subject of amendment 7, signature of amendment 1) The scope of the patent claims is amended as shown in the attached sheet. (In the 21st specification, bottom line, "Dephlegmator temperature:" is corrected to "Dephlegmator temperature: 90°C.") 11 2. Claims (11 Dinitri lt/, aliphatic diamine and A process for the preparation of lyamide, which involves contacting excess water with excess water in the presence of a catalytic amount of an oxygen-containing phosphorus compound catalyst. The second method involves reacting under superatmospheric pressure, in which equal amounts of (-)adiponitrile and hequinamezolediamine are continuously fed into a reheating production container, and the container is maintained at a temperature of 30° or higher. (b) Adding excess water to the vessel under a catalytic amount of an acid-containing phosphorus compound to form an initial mixture; (c) Reacting the azo I nitrile, hexamethylene diamine and water in at least two steps. converting the reaction cascade continuously in a cascade and converting this reaction cascade into l 5
(d) producing at least 65% of the initial polycondensation product and ammonia gas; (@) Continuously scatter the generated ammonia gas under superatmospheric pressure from reflux cooler 12, (f) Release the pressure of the initial condensation product in two stages, (,g) Release the pressure of the initial condensation product. While returning the pressure to atmospheric pressure, the above-mentioned initial polycondensation product is heated. (h) Continuing the polycondensation step to remove excess water and ammonia; - to produce polyhexamethylene azotukumide having spinnability. A manufacturing method according to claim 1, comprising: How to send. Claim 104 further adding α2 pigment
13. The manufacturing method according to claim 12, wherein the pigment 1 dispersant, azodanitrile, is added in the form of a suspension. (c) The dispersant is polymethane silica, polyphosphate,
or a manufacturing method selected from 4-rivinyl alcohol. ae Water damage method where the reaction mixture is 15-45% by weight based on the total amount of zonitrile, zoamile and water. The manufacturing method according to claim 7. Second Claim I! The reaction is carried out at a temperature of 220'O to 300'O! The manufacturing method according to item 1. a* Retaining at least a portion of the water in the production-reaction system as claimed in claim 1, wherein the pressure is maintained above 20 Norms until at least 65 mole % of the nidosil is converted to polyamide. 21. The manufacturing method according to claim 20, wherein means is provided for releasing the ammonia produced during the production of the QD. 142. The manufacturing method according to claim 141, wherein the catalyst is the sum of diamine, nitrile, and water. ell) -, 'Nitrile, aliphatic diamine and excess water, (1) oxygen-containing boron compounds, (2) acidic oxygen-containing sulfur compounds, (3) hydrogen halides, or ammonium salts or ammonium alkyl salts thereof. A method for producing a polyamide comprising contacting the polyamide in the presence of a catalyst selected from the following. (To) The catalyst is boric acid, hydrogen iodide, ammonium iodide,
ammonium sulfupume), 4-) luenesulfone &
, 2-naphthalenesulfonic acid, the dinitrile is adiponitrile,
32. The manufacturing method according to claim 31, wherein the diamine is hexamethylene diamine. 04 Dinitrile is scvnonitrile, geltalonitrile, suberonitrile, sepaconitrile. (To) The diamine is 1.4-diaminobutane, 1.57
t-nopentane, 1,8-diaminooctane. Minododecane, 2,5-dimethylhexane-2,5-diamine, p-diaminodicyclohexylmethane, 4w4
'-Diaminozocyclohequinyl ether, 4.4'-
The manufacturing method according to claim 1, wherein diaminodicyclohexylernalpha and octamethylene are used. Applicant's agent Patent attorney Suzu Ebuhiko Commissioner of the Patent Office
Arrival Kazuo Sugi Tono 1, special request for display of the incident! $7-82981 No. 2, Title of the invention 4 Method of manufacturing a rear door 3, Relationship with the case of the person making the amendment Patent applicant name: Chevy Matsuki Cheegoo 6, Specification subject to amendment? , [Contents of

Claims (2)

[Claims] (1) Contacting dinitrile, aliphatic cyanide and excess water in the presence of an oxygen-containing phosphorus compound - rear
Method of manufacturing de. (2) A method in which the compound is a spinnable hexamethylene azide/transfer, and azo 4 nitrile and hexamethylene cyanide are reacted in excess water under heating and superatmospheric pressure, This is accomplished by continuously feeding equal amounts of azinitrile and hexamethylene cyano into a reheating production container, maintaining this container at 30°C or higher, and (b) removing excess amounts of Adding a certain amount of an acid-containing sulfur compound in a catalytic amount,
forming an initial mixture; (.) converting the azinitrile, hexamethylene cyanide and water continuously in at least two reaction cascades;
(d) producing an initial polycondensation product of 6516 or more and ammonia gas; (・) continuously discharging the produced ammonia gas under super atmospheric pressure through a reflux cooler; (f) releasing the pressure of the initial condensation polymer in two stages; (g) returning the pressure of the initial condensation polymer to atmospheric pressure and heating the initial condensation polymer; (h) condensation polymerization step. The manufacturing method according to claim 1, comprising: removing excess water and ammonia by removing the excess water and ammonia, thereby producing /lyhexamethylene azonomide having spinnability. .