JP2000256461A - Production of nylon resin and production of nylon resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a nylon resins high in production efficiency and quality as well. SOLUTION: In the process for producing a nylon resin by increasing the degree of polymerization of the nylon pre-polymerized product prepared by polymerization, the nylon pre-polymerized product is passed in the molten state through a vertical agitation type thin film evaporator to increase the degree of polymerization. It is preferred that the relative viscosity in sulfuric acid of the nylon pre-polymerized product is not greater then 2.6 and, simultaneously, is preferably lower than that of the nylon resin to be obtained.by increasing the degree of polymerization by not smaller than 0.1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a high-quality nylon resin in a short time by increasing the degree of polymerization by passing through a vertical stirring type thin film evaporator.

[0002]

2. Description of the Related Art Nylon resins are used for clothing fibers and industrial fibers by taking advantage of their excellent properties. In addition, they are used as injection molded products in the automotive, electric and electronic fields, and mainly for food packaging. Also widely used as extruded and stretched films. A very commonly used method for producing a nylon resin is to heat a polymerization raw material and carry out polymerization while removing volatile components such as water. For example, in the polymerization of lactams represented by caprolactam and laurolactam, a polymer is produced by adding a small amount of water to these lactam raw materials and heating.

"Polyamide Resin Handbook" (Osamu Fukumoto, published by Nikkan Kogyo Shimbun, 1988), pp. 63-65
The page describes the following as a method for producing nylon 6 resin. Caprolactam is melted with a melter, and a polymerization degree regulator such as acetic acid is added. About 26
The mixture is supplied to a normal pressure polymerization tower heated to 0 ° C., and is allowed to stay in the polymerization tower for about 10 hours to polymerize. Thereafter, the mixture is formed into a strand from the bottom of the tower and discharged into a water tank to be pelletized.

[0004] In addition, as an example of polymerization when an aminocarboxylic acid such as aminocaproic acid, a mixture of dicarboxylic acid and diamine such as adipic acid and hexamethylenediamine, or a salt of dicarboxylic acid and diamine is used as a polymerization raw material, A summary of a very common polymerization method of nylon 66 described in "Polyamide Resin Handbook", pp. 142-144, is given below.

(In the case of batch polymerization) A raw material in which an additive such as a polymerization degree modifier is mixed with an aqueous solution of an equimolar salt of hexamethylenediamine and adipic acid is charged into a concentration tower, and the precipitation of salt is prevented. The mixture is concentrated under heating at about 150 ° C. under a slight pressure until the concentration becomes about 80%. This concentrated liquid is supplied to the polymerization tower and the internal temperature is heated to about 250 ° C., and the internal pressure is controlled at 15 to 20 atm. The heating is continued, the internal pressure is returned to normal pressure while gradually releasing the water vapor in the tank, and the internal temperature is raised to 270 to 280 ° C. Further, when the polycondensation is completed by keeping the pressure for several minutes to several tens of minutes under normal pressure or reduced pressure, a nylon 66 resin having a number average polymerization degree of about 100 is obtained.
The total reaction time is 4-6 hours.

(In the case of continuous polymerization) In the first step, 50% of an equimolar salt of hexamethylenediamine and adipic acid is used.
The aqueous solution is continuously supplied to the heat exchanger and preheated to 196 ° C. and 10 atm. After preheating, the mixture is heated to 230 ° C. in order to further proceed the reaction, and the steam is released to concentrate and prepolymerize the salt to a concentration of 95%. The residence time here is about 50 minutes. In the second step, the prepolymer sent from the previous step is flushed into a reactor at 9 atmospheres and 272 ° C. to release steam. Residence time is about 3
It is as short as 0 minutes. The third step is a finishing reactor,
The polycondensation is completed at 270 ° C. and 30 mmHg for 40 minutes.
The total residence time is around 2 hours.

[0007] As a method of simplifying the above polymerization method and producing a small amount in a compact apparatus suitable for the production of other types of products, a nylon oligomer is introduced into an extruder, and the
A method for producing a nylon resin while heating at 350 ° C. and removing moisture from the opening is disclosed in Japanese Patent Application Laid-Open No. 61-1668.
No. 33 proposes this.

[0008] Further, as a method for stably producing a nylon 66 resin without producing any gel-like material for a long period of time, a primary condensate having a relative viscosity of 1.01 to 2.5 is produced. Then, a method of increasing the degree of polymerization of the primary condensate with a melter is proposed in Japanese Patent Application Laid-Open No. 5-230208.

Similarly, as a method for simplifying the process, stably producing a nylon resin containing 6T units (hexamethylenediamine-terephthalic acid unit) without generating a gel for a long time, Viscosity 1.01-2.
JP-A-5-230204 describes a method for producing a primary condensate of No. 5 and then increasing the degree of polymerization of the primary condensate with a melter.

[0010]

The polymerization method of nylon 6 described in the above-mentioned "Polyamide Resin Handbook", pp. 63-65, requires about 10 hours for the polymerization time.
The polymerization reaction efficiency is extremely low, and a polymerization method capable of increasing the degree of polymerization in a short time has been desired. In addition, the method for producing nylon 66 described in the “Polyamide Resin Handbook”, pp. 142-144, requires 4-6 hours in a batch system and 2-3 hours in a continuous system, so that the polymerization reaction efficiency is extremely low. A polymerization method that is low and can increase the degree of polymerization in a short time has been desired.

As a method for improving these polymerization methods, the methods for producing nylon resins described in JP-A-61-166833, JP-A-5-230208, and JP-A-5-230204 are all described as melting. It is a method of promoting polymerization using an extruder.It is excellent in that it can be processed in a short time, but the surface renewal effect is small and a high degree of vacuum cannot be achieved. There is a problem that it has to be set high and the quality of the obtained nylon resin deteriorates. In addition, when processing at a relatively low temperature, it is necessary to lengthen the residence time, and it is necessary to connect a plurality of melt extruders in series.

Therefore, the present inventor has proposed that the polymerization can be carried out in a short time, the residual amount of volatile components such as monomers, oligomers and water is small, and the content of the gel component due to thermal deterioration,
It is a main object to provide a method for producing a high-quality nylon resin with little coloring.

[0013]

As a result of diligent studies to solve the above problems, the vertical stirring type thin film evaporator has a high surface renewal effect. Using a thin film evaporator, it has been found that the degree of polymerization can be increased in a short time, and that a high-quality nylon resin can be produced.

That is, the present invention is as follows. 1. In a method for producing a nylon resin by increasing the degree of polymerization of a nylon prepolymer produced by polymerization, a nylon that increases the degree of polymerization by passing the nylon prepolymer in a molten state through a vertical stirring type thin film evaporator. Method of manufacturing resin. 2. 2. The method for producing a nylon resin according to the above 1, wherein the relative viscosity of sulfuric acid of the nylon prepolymer is 2.6 or less and the relative viscosity of sulfuric acid of the nylon resin obtained by increasing the degree of polymerization is 0.1 or more. 3. The nylon resin is a semi-aromatic nylon containing nylon 6, nylon 66, nylon 11, nylon 12, nylon 6.10, nylon 6.12, nylon 6T unit and / or nylon 6I unit, or a combination of these nylons. 3. The method for producing a nylon resin according to the above item 1 or 2, which is a polymer. 4. The vertical stirring type thin film evaporator is capable of decompression in a circular shape in which an upper rotating shaft and a lower rotating shaft provided on a central longitudinal axis, and an inner peripheral surface disposed on an outer peripheral side of the rotating shaft are a heating and evaporating surface. A closed container main body, a rotating dispersion unit attached to the upper rotation shaft, a thinning unit disposed below the dispersion unit, and a lower rotation shaft located in a lower extension cylindrical portion of the closed container body A thin film evaporator with a device structure that has a screw blade discharge device attached to the shaft and the upper and lower rotating shafts are separately driven and rotated, and the bearing of the upper rotating shaft is arranged as a built-in bearing in the lower rotating shaft. 4. The method for producing a nylon resin according to any one of the above items 1 to 3, which is an apparatus. 5. A nylon resin is produced by the method according to any one of the above items 1 to 4, and then the obtained nylon resin is introduced into an extruder connected to a vertical stirring type thin film evaporator, and additives and / or fillers are added. A method for producing a nylon resin composition, which comprises mixing and mixing. 6. 5. A nylon resin composition is produced by the method according to any one of the above items 1 to 4, and the nylon resin is melt-discharged and pelletized to produce a nylon resin composition. A method for producing nylon resin pellets in which pellets are produced by melting and discharging an object and pelletizing. 7. The method according to any one of the above items 1 to 4, wherein the nylon resin is produced and then the nylon resin is molded, and then the nylon resin composition is produced according to the method according to the item 5 and then the nylon resin composition is molded. 7. A method for producing a molded article of nylon resin, wherein the molded article is produced by producing the nylon resin pellet composition by the method described in the above item 6, or by molding the nylon resin composition.

[0015]

Embodiments of the present invention will be described below.

The vertical stirring type thin film evaporator used in the production method of the present invention is a vertically long container having a decompression function, and when the raw material is charged from the upper part thereof, the raw material is dropped or forcedly scraped to form a thin film of the raw material. Is formed and moves to the lower part of the container, and at the same time, the volatile component contained in the raw material is removed under reduced pressure. Although there is no particular limitation as long as the device satisfies such requirements, a device having the following structure is preferable.

An upper rotating shaft and a lower rotating shaft provided on a central longitudinal axis, a circular decompressible closed container body having an inner peripheral surface disposed on the outer peripheral side of the rotating shaft serving as a heating and evaporating surface; A rotating dispersion unit attached to the upper rotating shaft,
A thinning unit disposed below the dispersion unit, and a screw blade discharge device attached to a lower rotating shaft located in a lower extension cylinder of the hermetically sealed container body; and an upper rotating shaft and a lower rotating shaft. The rotating shaft is separately driven and rotated, and the thin film evaporator has a device structure in which a bearing of an upper rotating shaft is arranged as a built-in bearing in a lower rotating shaft.

FIG. 1 shows a typical example. FIG. 1 schematically shows a vertical cross-sectional view of a vertical stirring type thin film evaporator,
The hermetically sealed container body (2) has a shape in which the inner peripheral surface (4) has a cylindrical shape around the central longitudinal axis (1) and the lower portion has an inverted cone shape. By passing the heat medium through the heat medium nozzles (6) and (7) through the outer jacket (5), the heat evaporating surface and the heat retaining surface are formed over almost the entire height of the inner peripheral surface (4). The inside of the container body (2) can be depressurized by connecting the upper volatile component vapor outlet nozzle (8) to a vacuum pump (not shown) via an external condenser. The upper rotating shaft (9) is supported on the central longitudinal axis (1) by a sealed bearing (10) in the upper top wall penetration and a lower built-in bearing (not shown). (Not shown). A dispersing unit (11) is mounted on the upper rotating shaft (9) in the upper part of the vessel, a thinning unit (13) having a stirring blade (14) is mounted on the lower part, and a lower part of the container main body lower part is further mounted thereunder. At the height of, a scraping auxiliary wing (16) is attached.

The molten nylon prepolymer is supplied into the vessel from a material inlet nozzle (12), is dispersed around the entire inner peripheral surface of the vessel by a rotating dispersion unit (11), and descends. The swirling agitating blades (14) of the unit (13) are spread in a thin film on the heating and evaporating surface to promote the evaporation of volatile components and promote polymerization, and the thin film is lowered to be transported downward. . The generated vapor of the volatile component is extracted from the vapor outlet nozzle (8) to the outside of the apparatus, and the evaporated liquid is finally discharged to the outside of the apparatus from the processing liquid outlet (15). A sleeve-shaped lower rotating shaft (17), which is connected below the upper rotating shaft (9) but is separately driven and rotates, is provided on the central longitudinal axis (1), and the lower rotating shaft (17) is scratched. A discharge mechanism (18) composed of screw blades is attached from directly below the lower auxiliary wing (16) to the inside of the lower extension cylindrical portion (3) of the container body.

Although there is no particular limitation on the shape and the mounting position of the stirring blade (14), the inclination angle of the stirring blade with respect to the vertical direction should be 10 to 60 in view of the efficiency of removing volatile components and the transfer efficiency of the liquid substance. Degree, preferably 12 to 50 degrees, particularly preferably 15 to 45 degrees. The distance L between the lower end of the upper wing and the upper end of the lower wing is not particularly specified, but is 1/100 to 1/3, preferably 1/50 of the wing span (diameter of a circle drawn by the wing tip). To 1/4, particularly preferably 1/30 to 1/5. In an actual apparatus, the viscosity tends to increase in the lower direction, and in that case, it is preferable to decrease L in the lower direction.

In the method of the present invention, nylon resins to be polymerized at a high degree of polymerization include lactams, aminocarboxylic acids, mixtures of dicarboxylic acids / diamines, mixtures of dicarboxylic acid derivatives / diamines, salts of dicarboxylic acids / diamines, and mixtures thereof. It means a nylon resin obtained by polymerizing a mixture of two or more kinds. Specific examples of lactams include 2-azetidinone, 2-pyrrolidinone, δ-valerolactam, ε-caprolactam, enantholactam, caprylactam,
Undecalactam, laurolactam and the like can be mentioned, among which ε-caprolactam, undecalactam and laurolactam are preferred, and ε-caprolactam is particularly preferred. In addition, these lactams can also be used as a mixture of two or more.

Specific examples of aminocarboxylic acids include 6-
Aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. Acids, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and 6-aminocaproic acid is particularly preferred. In addition, these aminocarboxylic acids can be used in a mixture of two or more. A mixture of dicarboxylic acids / diamines, a mixture of dicarboxylic acid derivatives / diamines,
Specific examples of the dicarboxylic acid used in the dicarboxylic acid / diamine salt include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid and dodecanediacid. Acid, brassic acid, aliphatic dicarboxylic acid such as tetradecandioic acid, pentadecandioic acid, octadecandioic acid, alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid And aromatic dicarboxylic acids. Preferred are adipic acid, sebacic acid, dodecandioic acid, terephthalic acid and isophthalic acid, and particularly preferred are adipic acid, terephthalic acid and isophthalic acid. In addition, these dicarboxylic acids can be used in a mixture of two or more.

Specific examples of the dicarboxylic acid / diamine mixture, the dicarboxylic acid derivative / diamine mixture, and the diamine used in the dicarboxylic acid / diamine salt are:
4-diaminobutane, 1,5-diaminopentane, 1,
6-diaminohexane, 2-methyl-1,5-diaminopentane (MDP), 1,7-diaminoheptane, 1,
8-diaminooctane, 1,9-diaminononane, 1,
10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,1
5-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-
Aliphatic diamines such as diaminooctadecane, 1,19-diaminononadecane and 1,20-diaminoeicosane, cyclohexanediamine, alicyclic diamines such as bis- (4-aminohexyl) methane, m-xylylenediamine; Examples thereof include aromatic diamines such as p-xylylenediamine, and aliphatic diamines are particularly preferable.
Particularly, hexamethylenediamine is preferably used. In addition, these diamines can also be used in a mixture of two or more.

The nylon resin to which the method of the present invention is preferably applied is a semiaromatic containing nylon 6, nylon 66, nylon 11, nylon 12, nylon 6, 10, nylon 6, 12, nylon 6T and / or 6I units. Examples include nylon or a copolymer of these nylon resins.

In the method of the present invention, the nylon prepolymer supplied to the vertical stirring type thin film evaporator is required to have a high degree of polymerization in the vertical stirring type thin film evaporator in order to take advantage of the high polymerization degree. Is preferably not too high, for example, 0.01
g / mL sulfuric acid solution has a relative viscosity of sulfuric acid at 25 ° C. of 2.
It is preferably at most 6, more preferably at least 0.1, more preferably at least 0.3, lower than the sulfuric acid relative viscosity of the nylon resin obtained by increasing the degree of polymerization.

This nylon prepolymer is produced, for example, by a nylon polymerization method in which a nylon raw material is heated in the presence or absence of a catalyst. Stirring may or may not be performed during the polymerization, but it is preferable to stir to obtain a homogeneous product. The polymerization temperature can be arbitrarily set according to the desired degree of polymerization of the prepolymer, the reaction yield, and the reaction time, but a lower temperature is preferable in consideration of the quality of the finally obtained nylon resin. The reaction rate can also be set arbitrarily. Although it may contain unreacted monomers,
If the amount of the residual monomer is large, the monomer is removed when the degree of polymerization is increased, and the final polymer yield is reduced. Therefore, a higher reaction rate is preferable. The reaction rate is usually 50% or more, preferably 60% or more, and more preferably 7% or more.
0% or more. The pressure is not particularly limited, and the pressure in the system may be reduced in order to extract the condensed water generated during the reaction to the outside of the system. Conversely, a pressurized system may be used to suppress the volatilization of the monomer.

The degree of polymerization of the nylon resin obtained by increasing the degree of polymerization of this nylon prepolymerized product by a vertical stirring type thin film evaporator varies depending on its use, but is generally 0.01%.
g / mL sulfuric acid solution at 25 ° C. relative sulfuric acid viscosity 2.
0-8.0, preferably 2.2-7.5, more preferably 2.3-6.5, most preferably 2.3-5.0. If the sulfuric acid relative viscosity is too low, the desired mechanical properties are insufficiently developed, and if it exceeds 8.0, the melt viscosity is too high and molding becomes difficult.

The nylon resin treated in the method of the present invention may have its terminal blocked with a carboxylic acid compound or an amine compound, if necessary. When a monocarboxylic acid and / or a monoamine is added to end-block, the resulting nylon resin has a lower end group concentration than when no end-blocking agent is used. On the other hand, when the terminal is blocked with a dicarboxylic acid or a diamine, the total amount of terminal groups does not change, but the ratio of amino terminal groups to carboxyl terminal groups changes.

Specific examples of the carboxylic acid compound include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myristoleic acid, Aliphatic monocarboxylic acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, and arachinic acid, cyclohexanecarboxylic acids, alicyclic monocarboxylic acids such as methylcyclohexanecarboxylic acid, benzoic acid, toluic acid, and ethylbenzoic acid Aromatic monocarboxylic acids such as phenylacetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecanedioic acid, brassic acid, Like tetradecandioic acid, pentadecandioic acid, octadecandioic acid Aliphatic dicarboxylic acids, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and aromatic dicarboxylic acids such as naphthalene dicarboxylic acid.

Specific examples of the amine compound include butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, and pentaamine. Aliphatic monoamines such as decylamine, hexadecylamine, octadecylamine, nonadecylamine, and icosylamine; cycloaliphatic monoamines such as cyclohexylamine, methylcyclohexylamine; benzylamine; aromatic monoamines such as β-phenylethylamine; 4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Aminodecane, 1,11-di-aminoundecanoic, 1,12-amino-dodecane, 1,13
Diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane,
Aliphatic diamines such as 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, cyclohexanediamine, alicyclic diamines such as bis- (4-aminohexyl) methane, xylylenediene And aromatic diamines such as amines.

There is no particular limitation on the terminal group concentration of the nylon resin obtained by increasing the degree of polymerization according to the method of the present invention. However, when it is necessary to enhance the dyeing properties in the fiber application or in the resin application, a material suitable for alloying is designed. In such a case, it is preferable that the terminal amino group concentration is high. On the other hand, when it is desired to suppress coloring and gelation under long-term aging conditions, on the contrary, the terminal amino group concentration is preferably lower. Furthermore, in order to suppress lactam regeneration during remelting, thread breakage during melt spinning due to oligomer formation, mold deposit during continuous injection molding, and die mark generation in continuous extrusion of film, both terminal carboxyl group concentration and terminal amino group concentration are required. A lower one is preferred. The concentration of the terminal group may be adjusted depending on the application to be applied, and both the concentration of the terminal amino group and the concentration of the terminal carboxyl group are preferably from 1.0 × 10 ^{−5 to} 15.0 × 10 ⁻⁵ eq / g, more preferably. 2.0 × 10 ^{-5 to} 12.0 × 10 ^-5 eq /
g, particularly preferably 3.0 × 10 ^{−5 to} 11.0 × 10 ^−5.
eq / g.

The terminal blocking agent may be added at the same time as the raw materials such as caprolactam and the like at the beginning of the polymerization, added during the polymerization, or added to remove the unreacted caprolactam and oligomer in the molten state of the nylon resin. The method is adopted. The terminal blocking agent may be added as it is, or may be added after being dissolved in a small amount of a solvent.

The temperature of the nylon prepolymer when passing through the vertical stirring type thin film evaporator is not particularly limited as long as it can be passed in a molten state, and may be determined according to the desired degree of polymerization. Is required to be higher than the melting point of the nylon prepolymer, and at most 400 ° C or lower, preferably 3 ° C or lower.
The temperature is preferably 50 ° C. or lower, particularly preferably 300 ° C. Also, there is no particular limitation on the pressure at that time,
Usually 0.01 to 700 mmHg, preferably 0.05 to
600 mmHg, more preferably 0.1 to 500 mmH
g. Since the polyamide resin tends to be colored and deteriorated when heated in the presence of oxygen, the oxygen concentration in the atmosphere at that time is preferably 500 ppm or less, more preferably 100 ppm or less.

In producing a nylon resin according to the method of the present invention, a step of producing a nylon prepolymer to be supplied to a vertical stirring type thin film evaporator and a high degree of polymerization by passing through a vertical stirring type thin film evaporator. The step may be performed in a consistent and continuous process, or may be performed in a batch-type process. A batch method is effective for small-quantity production of other products, but a continuous method is preferred for producing the same product in large quantities over a long period of time.

Further, in the method of the present invention, a melt extruder is connected after a vertical stirring type thin film evaporator to continuously mix various additives and fillers. Products can also be manufactured.

Specific examples of the various additives and fillers to be incorporated at this time include antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites and their substitutes, copper halides, iodine Compounds), weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agents and lubricants (aliphatic alcohol, aliphatic amide, aliphatic bisamide, bisurea, polyethylene wax, etc.) , Pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, aniline black, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzene) Sulfonamides), antistatic agents (alkyl sulfate type ani Antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc.), flame retardants (melamine cyanurate, Hydroxides such as magnesium hydroxide and aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resin, or combinations of these brominated flame retardants with antimony trioxide) , Fillers (graphite, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, antimony oxide, titanium oxide, aluminum oxide, zinc oxide, iron oxide, zinc sulfide, zinc, lead, nickel, aluminum,
Particles such as copper, iron, stainless steel, glass fiber, carbon fiber, and aramid fiber, fibrous, needle-like, and plate-like fillers), other polymers (other polyamides, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene ether) , Polyphenylene sulfide, liquid crystal polymer,
Polysulfone, polyether sulfone, ABS resin, S
AN resin, polystyrene, etc.).

The nylon resin (composition) obtained by the production method of the present invention can be formed into pellets produced by a usual method, similarly to a conventional nylon resin (composition), or it can be produced by a usual molding method. It can be a molded article. The molded article referred to here includes not only a molded article in a narrow sense by injection molding or the like but also fibers, films, and the like.

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples. The analysis and measurement described in Examples and Comparative Examples were performed according to the following methods. (1) Sulfuric acid relative viscosity (ηr) A 98% sulfuric acid solution of 0.01 g / mL was prepared and measured at 25 ° C. using an Ostwald viscometer. (2) Terminal Carboxyl Group Concentration [COOH] 0.5 to 2.0 g of a polyamide resin was accurately weighed and dissolved in 20 mL of benzyl alcohol at 195 ° C. Add phenolphthalein as an indicator to this solution,
It was titrated with a 0.02 N potassium hydroxide ethanol solution. (3) Terminal amino group concentration [NH ₂ ] 0.5 to 2.0 g of the polyamide resin was accurately weighed and dissolved in 25 mL of a phenol / ethanol mixed solution (ratio: 84/16% by weight) at room temperature. Thymol blue was added to this solution as an indicator, and titrated with 0.02 N hydrochloric acid.

(4) Glass transition temperature and melting point Approximately 7 mg of polyamide resin, which was once melted and then quenched, was accurately weighed, and was measured by DSC-manufactured by Perkin-Elmer.
7, the glass transition temperature and the melting point were measured at a heating rate of 20 ° C./min. (5) Tensile properties Tensile strength and tensile elongation at break were measured in accordance with ASTM D638. (6) Izod impact value Measured according to ASTM D256. (7) Bending properties Measured according to ASTM D790. (8) Pellet color tone YI value (Yellow) of the pellet by a color machine
(Index).

Example 1 (Production of Nylon 6 Resin) A 30 L stainless steel autoclave was charged with 10 kg of ε-caprolactam and 200 g of water, replaced with nitrogen, sealed, and heated and stirred at 250 ° C. for 10 hours. A prepolymer was prepared. This prepolymer was placed in a vertical stirring type thin film evaporator (resin temperature: 24) consisting of a cylinder having an inner diameter of 155 mmφ × a height of 430 mm and inclined multi-stage stirring blades rotating while maintaining a clearance of 2 mm from the inner wall of the cylinder.
The polymerization was carried out by introducing the mixture under a reduced pressure of 7 to 276 ° C., a degree of reduced pressure of 0.5 to 5 mmHg, and a rotation speed of a stirring blade of 800 to 1000 rpm), and treating the mixture in a molten state under reduced pressure. Table 1 shows the analytical values and various evaluation results of the prepolymer and the finally obtained nylon resin.

Comparative Example 1 (Production of Nylon 6 Resin) A nylon 6 prepolymer produced in the same manner as in Example 1 was twin-screw extruder (resin temperature: 30 mmφ, L / D = 42)
253-288 ° C., degree of reduced pressure: 3-10 mmHg, screw rotation speed: 150-200 rpm), and the mixture was melted and treated under reduced pressure to carry out polymerization. Table 1 shows the analytical values and various evaluation results of the prepolymer and the finally obtained nylon resin.

Comparative Example 2 (Production of Nylon 6 Resin) ε-caprolactam was melted with a melter and the water content was 0.4
After adjusting to wt%, it is charged into a vertical atmospheric pressure polymerization tower preheated to about 260. After staying in the polymerization tower for about 10 hours, nylon 6 resin was discharged in a strand form from the lower part of the tower and pelletized. This pellet is put into a vertical countercurrent extraction tower, and after being countercurrently extracted with hot water sent from below,
It is taken out continuously from the lower part. The obtained pellet was dried by heating under reduced pressure. Table 1 shows the analysis values and various evaluation results of the obtained nylon resin.

Example 2 (Production of Nylon 6 Resin / Glass Fiber Composition) After the vertical stirring type thin film evaporator of Example 1, a 30 mmφ
A twin-screw extruder (temperature: 261 ° C.) with L / D = 42 was connected, and nylon 6 resin discharged from a vertical stirring type thin film evaporator was directly introduced into the twin-screw extruder, and a fiber diameter was supplied from a side feeder. 9 μm glass fiber having a strand length of 3 mm was supplied to prepare a composition of nylon 6 resin / glass fiber = 70/30 parts by weight. Table 1 shows the evaluation results of the obtained nylon resin compositions.

Comparative Example 3 (Production of Nylon 6 Resin / Glass Fiber Composition) Behind the twin screw extruder of Comparative Example 1, an additional 30 mmφ, L /
D = 42 twin screw extruder (temperature: 260 ° C.) is connected, followed by nylon 6 resin discharged from the twin screw extruder for polymerization.
Introduced into the screw extruder, fiber diameter 9μ from side feeder
m, a glass fiber having a strand length of 3 mm was supplied to produce a composition of nylon 6 resin / glass fiber = 70/30 parts by weight. Table 1 shows the evaluation results of the obtained nylon resin compositions.

Comparative Example 4 (Preparation of Nylon 6 Resin / Glass Fiber Composition)
D = 42 into a twin screw extruder (temperature: 260 ° C.), and a fiber diameter of 9 μm and a strand length of 3 m from a side feeder
m glass fiber was supplied to prepare a composition of nylon 6 resin / glass fiber = 70/30 parts by weight. Table 1 shows the evaluation results of the obtained nylon resin compositions.

From Examples 1 and 2 and Comparative Examples 1 to 4, it can be seen that high quality nylon 6 resin or nylon 6 resin composition can be obtained with high efficiency by using the production method of the present invention.

[0047]

[Table 1]

Example 3 (Production of nylon 66 resin) An 80% aqueous solution of a molar salt of adipic acid / hexamethylenediamine was charged into a 30 L stainless steel autoclave, the internal temperature was 240 ° C., the internal pressure was 18 kg / cm 2, and the residence time was 8
A nylon 66 prepolymer was prepared under the condition of 0 minutes. This prepolymer is 155 mm in inner diameter x 430 mm in height
Vertical stirring type thin-film evaporator composed of a cylinder and an inclined multistage stirring blade rotating while maintaining a clearance of 2 mm from the inner wall of the cylinder (resin temperature: 279 to 316 ° C., degree of pressure reduction: 0.5 to 5 m)
(mHg, rotation speed of stirring blade: 800 to 1000 rpm), and the mixture was melted and treated under reduced pressure to carry out polymerization. Table 2 shows the analytical values of the prepolymer and the finally obtained nylon resin and various evaluation results.

Comparative Example 5 (Production of Nylon 66 Resin) A nylon 66 prepolymer produced in the same manner as in Example 1 was twin-screw extruder having a diameter of 30 mm and L / D = 42 (resin temperature: 283 to 324 ° C., (11 mmHg, screw rotation speed: 100 to 200 rpm), and polymerization was carried out by treating in a molten state under reduced pressure. Table 2 shows the analysis values and various evaluation results of the prepolymer and the finally obtained nylon resin.

Comparative Example 6 (Production of Nylon 66 Resin) An 80% aqueous solution of a molar salt of adipic acid / hexamethylenediamine was charged into a 30 L stainless steel autoclave and heated to an internal temperature of 250 ° C. and an internal pressure of 15 to 20 kg / cm 2.
The polymerization was carried out for 3 hours while maintaining the temperature. Thereafter, the internal pressure is returned to normal pressure while gradually releasing the steam, and the internal temperature is raised to 270 to 280 ° C. After the polymerization reaction was further performed for 1 hour, it was pulled out from the lower part of the polymerization can with a strand and pelletized. Table 2 shows the analysis values and various evaluation results of the obtained nylon resin.

Example 4 (Production of Nylon 66 Resin / Glass Fiber Composition) After the vertical stirring type thin film evaporator of Example 3, a 30 mmφ
Nylon 66 discharged from a vertical stirring type thin film evaporator by connecting a twin screw extruder (temperature: 289 ° C.) with L / D = 42
The resin was directly introduced into the twin-screw extruder, and a glass fiber having a fiber diameter of 9 μm and a strand length of 3 mm was supplied from a side feeder to produce a composition of nylon 66 resin / glass fiber = 70/30 parts by weight. Table 2 shows the evaluation results of the obtained compositions.

Comparative Example 7 (Production of Nylon 66 Resin / Glass Fiber Composition) Behind the twin-screw extruder of Comparative Example 6, an additional 30 mmφ, L /
A twin-screw extruder (temperature: 290 ° C.) with D = 42 was connected, and nylon 66 resin discharged from the twin-screw extruder for polymerization was introduced into the subsequent twin-screw extruder, and the fiber diameter was 9 μm from the side feeder.
m, a glass fiber having a strand length of 3 mm was supplied to produce a composition of nylon 66 resin / glass fiber = 70/30 parts by weight. Table 2 shows the evaluation results of the obtained nylon resin compositions.

Comparative Example 8 (Preparation of Nylon 66 Resin / Glass Fiber Composition)
/ D = 42 into a twin screw extruder (temperature: 290 ° C.)
Fiber diameter 9 μm from side feeder, strand length 3
mm glass fiber was supplied to produce a composition of nylon 66 resin / glass fiber = 70/30 parts by weight. Table 2 shows the evaluation results of the obtained nylon resin compositions.

From Examples 3 and 4 and Comparative Examples 5 to 8, high-quality nylon 66 was obtained by using the production method of the present invention.
It can be seen that a resin or nylon 66 resin composition can be obtained with high efficiency.

[0055]

[Table 2]

Example 5 (Production of Nylon 66 Resin) An 80% aqueous solution of a molar salt of adipic acid / hexamethylenediamine was charged into a 30 L stainless steel autoclave, the internal temperature was 240 ° C., the internal pressure was 18 kg / cm 2, and the residence time was 3
A nylon 66 prepolymer was prepared under the condition of 0 minutes. This prepolymer is 155 mm in inner diameter x 430 mm in height
Vertical stirring type thin-film evaporator (resin temperature: 283 to 322 ° C., degree of pressure reduction: 0.5 to 3 m) composed of a cylindrical cylinder and an inclined multistage stirring blade rotating while maintaining a clearance of 2 mm from the inner wall of the cylinder.
mHg, stirring blade rotation speed: 600-800 rpm), and the mixture was treated in a molten state under reduced pressure to carry out polymerization. Table 3 shows analytical values of the prepolymer and the finally obtained nylon resin and various evaluation results.

Comparative Example 9 (Production of Nylon 66 Resin) A nylon 66 prepolymer produced in the same manner as in Example 5 was twin-screw extruder having a diameter of 30 mmφ and L / D = 42 (resin temperature: 2S 92-332 ° C., 4- (11 mmHg, screw rotation speed: 150-200 rpm), and the mixture was melted and treated under reduced pressure to carry out polymerization. Table 3 shows analysis values and various evaluation results of the prepolymer and the finally obtained nylon resin. Example 6 (Production of nylon 66 resin / glass fiber composition) Behind the vertical stirring type thin film evaporator of Example 5, 30 mmφ
Nylon 66 discharged from a vertical stirring type thin film evaporator by connecting a twin screw extruder (temperature: 290 ° C.) with L / D = 42
The resin was directly introduced into the twin-screw extruder, and a glass fiber having a fiber diameter of 9 μm and a strand length of 3 mm was supplied from a side feeder to produce a composition of nylon 66 resin / glass fiber = 70/30 parts by weight. Table 3 shows the evaluation results of the obtained compositions.

Comparative Example 10 (Production of Nylon 66 Resin / Glass Fiber Composition) Behind the twin screw extruder of Comparative Example 9, an additional 30 mmφ, L /
A twin-screw extruder (temperature: 290 ° C.) with D = 42 was connected, and nylon 66 resin discharged from the twin-screw extruder for polymerization was introduced into the subsequent twin-screw extruder, and the fiber diameter was 9 μm from the side feeder.
m, a glass fiber having a strand length of 3 mm was supplied to produce a composition of nylon 66 resin / glass fiber = 70/30 parts by weight. Table 3 shows the evaluation results of the obtained nylon resin compositions.

As compared with Examples 5 to 6 and Comparative Examples 9 to 10, even if a prepolymer having a low degree of polymerization was used, high-quality nylon 6 was used.
It can be seen that 6 resin or nylon 66 resin composition can be obtained with high efficiency.

[0060]

[Table 3]

Example 7 [(Nylon 6T / Nylon 6
6) Production of Copolymer Resin] Nylon 6T / Nylon 66 salt = 50% aqueous solution of a nylon salt mixture equivalent to 55/45% by weight was charged into a 30 L polymerization vessel, the internal temperature was 300 ° C., the internal pressure was 35 kg / cm 2, and the residence time was The prepolymer was polymerized under the conditions of 60 minutes. This prepolymer was placed in a vertical stirring type thin film evaporator (resin temperature: 305 to 330 ° C., pressure reduction degree) consisting of a cylinder having an inner diameter of 155 mmφ × a height of 430 mm and an inclined multistage stirring blade rotating while maintaining a clearance of 2 mm from the inner wall of the cylinder. : 0.6-4mmH
g, rotation speed of a stirring blade: 800 to 1000 rpm), and the mixture was treated in a molten state under reduced pressure to carry out polymerization. Table 4 shows the analysis values and various evaluation results of the prepolymer and the finally obtained nylon resin.

Comparative Example 11 (nylon 6T / nylon 66
Production of Copolymer Resin) Nylon 6T / Nylon 66 copolymer prepolymer produced in the same manner as in Example 7 was 30 mmφ, L / D = 42.
Twin screw extruder (resin temperature: 315 to 340 ° C., degree of vacuum:
1 to 10 mmHg, screw rotation speed: 150 to 200
rpm), and the mixture was treated in a molten state under reduced pressure to carry out polymerization. Table 4 shows the analysis values and various evaluation results of the prepolymer and the finally obtained nylon resin.

Example 8 [(Nylon 6T / Nylon 6
6) Production of Copolymer Resin / Glass Fiber Composition] 30 mmφ behind the vertical stirring type thin film evaporator of Example 7,
Nylon 6T connected to a twin screw extruder (temperature: 320 ° C) with L / D = 42 and discharged from a vertical stirring type thin film evaporator
/ Nylon 66 copolymer is introduced into a twin screw extruder, and glass fibers having a fiber diameter of 9 μm and a strand length of 3 mm are supplied from a side feeder (nylon 6T / nylon 66 copolymer resin) / glass fiber = 70/30. Parts by weight of the composition were prepared. Table 4 shows the evaluation results of the obtained compositions.

Comparative Example 12 After the twin-screw extruder of Comparative Example 11, an additional 30 mmφ, L
/ D = 42 (331 ° C.) and discharged from the twin-screw extruder for polymerization (nylon 6T / nylon 6
6 copolymer resin) was introduced into the subsequent twin screw extruder, and glass fibers having a fiber diameter of 9 μm and a strand length of 3 mm were supplied from a side feeder (nylon 6T / nylon 66 copolymer resin) / glass fiber = 70/30. Parts by weight of the composition were prepared. Table 4 shows the evaluation results of the obtained nylon resin compositions.

From Examples 7 to 8 and Comparative Examples 11 to 12, high-quality nylon 6T / nylon 66 copolymer resin or nylon 6T / nylon 66 copolymer resin composition was obtained by using the production method of the present invention. It can be seen that efficiency is obtained.

[0066]

[Table 4]

Example 9 (Production of Nylon 6 / Nylon 66 Copolymer Resin) A 30 L stainless steel autoclave was charged with nylon 6 / nylon 66
Nylon 66: An 80% aqueous solution of caprolactam and equimolar salt of adipic acid / hexamethylenediamine in a ratio corresponding to 10/90 wt% is charged, and the internal temperature is 241 ° C. and the internal pressure is 18
A nylon 6 / nylon 66 copolymer prepolymer was prepared under the conditions of kg / cm ² and a residence time of 75 minutes. This prepolymer was placed in a vertical stirring type thin film evaporator (resin temperature: 268 to 294 ° C., pressure reduction degree : 0.7-2mmH
g, rotation speed of a stirring blade: 800 to 1000 rpm), and the mixture was treated in a molten state under reduced pressure to carry out polymerization. Table 5 shows analytical values of the prepolymer and the finally obtained nylon resin and various evaluation results.

Comparative Example 13 (Production of Nylon 6 / Nylon 66 Copolymer Resin) Nylon 6 / Nylon 6 produced in the same manner as in Example 9
6-copolymer prepolymer is a twin-screw extruder with 30 mmφ and L / D = 42 (resin temperature 269 to 299 ° C., degree of reduced pressure: 4 to
11 mmHg, screw rotation speed: 150 to 200 rpm
m) and polymerization was carried out by treating in a molten state under reduced pressure. Table 5 shows the reaction conditions, analytical values of the finally obtained nylon resin, and various evaluation results.

From Example 9 and Comparative Example 13, it can be seen that high-quality nylon 6 / nylon 66 copolymer resin can be obtained with high efficiency by using the production method of the present invention.

[0070]

[Table 5]

[0071]

By producing a nylon resin or a nylon resin composition by the production method of the present invention, it is possible to produce a high-quality nylon resin or a nylon resin composition having a quality equal to or higher than that of the conventional production process with high efficiency. it can.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view schematically showing one example of a vertical stirring type thin film evaporator used in a production method of the present invention.

[Description of References] (1) Center longitudinal axis, (2) Hermetic container body,
(3) Lower extension cylinder, (4) Circumferential surface, (5) Jacket, (6), (7) Heat medium nozzle, (8) Steam outlet nozzle, (9) Upper rotating shaft, (10) Upper seal (11) Distributed unit, (1)
2) Raw material input nozzle, (13) Thinning unit,
(14) stirring blade, (15) processing liquid outlet,
(16) Scooping auxiliary wing, (17) Lower rotating shaft,
(18) Screw blade discharge mechanism

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 30, 1999 (1999.11.
30)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

4. A nylon resin is produced by the method according to any one of claims 1 to 3 , and then the obtained nylon resin is introduced into an extruder connected to a vertical stirring type thin film evaporator and added. A method for producing a nylon resin composition, comprising mixing and mixing agents and / or fillers.

5. A nylon resin composition is produced by the method according to any one of claims 1 to 3, and the nylon resin is melt-discharged and pelletized to produce a nylon resin composition according to the method according to claim 4. A method for producing nylon resin pellets, wherein the nylon resin composition is melt-discharged and pelletized to produce pellets.

6. A method for producing a nylon resin by the method according to claim 4 , wherein the method comprises the steps of: producing a nylon resin by the method according to any one of claims 1 to 3; and molding the nylon resin. by molding a composition, or, if the nylon resins pellets after producing the nylon resin pellet by the method of claim 5, wherein
By RaNaru shape, manufacturing method of the nylon resin moldings to produce a molded article.

Continued on the front page F-term (reference) 4J001 DA01 EA02 EA05 EA06 EA07 EA08 EA14 EA15 EA16 EA17 EB04 EB05 EB06 EB07 EB08 EB09 EB10 EB14 EB35 EB36 EB37 EC04 EC07 EC08 EC09 EC10 EC14 EC16 EC01 GC04 GC02 GB01 GB01 CL031 FD010 FD020 FD070 FD080 FD090 FD100 FD130 FD160 FD170 4J031 CA06 CA32 CC02 CC05 CC09 CE01 CE08 CE09 CF01 CG04 CG07 CG39

Claims (7)

[Claims] 1. A method for producing a nylon resin by increasing the degree of polymerization of a nylon prepolymer produced by polymerization, comprising: passing the nylon prepolymer in a molten state through a vertical stirring type thin film evaporator. A method for producing a nylon resin characterized by increasing the degree of polymerization. 2. The relative viscosity of sulfuric acid of a nylon prepolymer is as follows:
2. The method for producing a nylon resin according to claim 1, wherein the relative viscosity of sulfuric acid of the nylon resin obtained by increasing the degree of polymerization is 0.1 or less. 3. The nylon resin is nylon 6, nylon 66, nylon 11, nylon 12, nylon 6.1.
3. The method for producing a nylon resin according to claim 1, wherein the nylon resin is a semi-aromatic nylon containing 0, nylon 6.12, a nylon 6T unit and / or a nylon 6I unit, or a copolymer of these nylons. 4. A vertical stirring type thin film evaporator comprises an upper rotating shaft and a lower rotating shaft provided on a central longitudinal axis, and an inner peripheral surface arranged on an outer peripheral side of the rotating shaft serves as a heating evaporation surface. A circular decompressible hermetic container body, a rotating dispersion unit attached to the upper rotation shaft, a thinning unit disposed below the dispersion unit, and a lower extension cylindrical portion of the hermetic container body. A screw blade discharge device attached to the lower rotating shaft located, and the upper rotating shaft and the lower rotating shaft are separately driven and rotated, and the bearing of the upper rotating shaft is arranged as a built-in bearing in the lower rotating shaft. The method for producing a nylon resin according to any one of claims 1 to 3, which is a thin film evaporator having an apparatus structure. 5. A nylon resin is produced by the method according to claim 1, and then the obtained nylon resin is introduced into an extruder connected to a vertical stirring type thin film evaporator and added. A method for producing a nylon resin composition, comprising mixing and mixing agents and / or fillers. 6. A nylon resin composition is produced by the method according to any one of claims 1 to 4, and the nylon resin is melt-discharged and pelletized to produce a nylon resin composition according to the method according to claim 5. A method for producing nylon resin pellets, wherein the nylon resin composition is melt-discharged and pelletized to produce pellets. 7. A nylon resin is produced by a method according to claim 5, wherein the nylon resin is produced by the method according to claim 1 after producing the nylon resin by the method according to claim 1. A method for producing a nylon resin molded article, wherein the molded article is produced by molding the composition, or after producing the nylon resin pellet composition by the method according to claim 6, followed by molding the nylon resin composition.