JP2000256460A - Production of nylon resin and production of nylon resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a high-quality resin at a high efficiency and a low energy cost by producing a nylon resin having a terminal group concentration in a specified range and removing monomers and oligomers from the nylon resin by using a vertically agitated thin-film evaporator. SOLUTION: Nylon-forming materials are polymerized to produce a nylon resin having a degree of polymerization of 1.0-3.5 (as measured in a 0.01 g/ml sulfuric acid solution at 25 deg.C), a terminal amino concentration and a terminal carboxyl concentration each in the range of 1×10-5 to 12×10-5 mol/g and satisfying the relationships: terminal amino concentration < (terminal carboxyl concentration-0.02×10-5 mol/g). This resin is fed into a vertical agitator-equipped thin-film evaporator and passed through it at a temperature of the melting point of the nylon resin to 400 deg.C and a pressure of 0.01-700 mmHg in an atmosphere having an oxygen concentration of 500 ppm or below to evaporate and remove the monomers and the oligomers from the nylon resin. The molten resin after the evaporation treatment is extruded, and the extrudate is pelletized to obtain nylon resin pellets.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved method for removing monomers and oligomers contained in a nylon resin by using a vertical stirring type thin film evaporator. More specifically, the present invention relates to a method for producing a high-efficiency and high-quality nylon resin by removing monomers and oligomers using 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.

[0003] A polyamide resin mainly composed of caprolactam is usually produced by heating caprolactam in the presence of a small amount of water. This manufacturing method is a relatively simple process, and is a manufacturing method widely used in the world. Pages 63-65 of "Polyamide Resin Handbook" (Osamu Fukumoto, published by Nikkan Kogyo Shimbun, 1988)
The following is a summary of the most common caprolactam polymerization methods described on page: Caprolactam is melted with a melter, and a polymerization degree regulator such as acetic acid is added. This raw material is supplied to a normal pressure polymerization tower heated to about 260 ° C., and after staying in this polymerization tower for about 10 hours, the mixture is discharged into a water tank in the form of a strand from the lower part of the tower and pelletized. The polyamide 6 resin pellets thus obtained contain caprolactam monomers and oligomers generated at the polymerization equilibrium and are supplied to the hot water extraction tower. After countercurrent extraction with hot water sent from the lower part of the tower, it is taken out from the lower part. Since the pellets after extraction contain a large amount of water, they are dried at about 100 ° C. in a vacuum or an inert gas atmosphere.

As described above, the polymerization process of caprolactam is extremely simple, but a hot water extraction for removing unreacted caprolactam and oligomers and a drying process after the hot water extraction are essential. The cost accounts for a large proportion of the manufacturing cost, and it is desired to develop a process in which these two steps are omitted. Therefore, a method of removing unreacted caprolactam and oligomers by treating the polyamide after polymerization in a molten state at a high temperature and under a high vacuum has been devised.

For example, JP-A-53-111394 discloses a method for removing monomers and oligomers from nylon 6 resin using a centrifugal thin film evaporator.
JP-A-60-101120 describes a method of simultaneously removing unreacted monomers from nylon 6 resin and performing post-polymerization. Further, JP-A-7-258408
Japanese Patent Application Laid-Open Publication No. H11-176,086 describes a method for removing unreacted lactams and oligomers from a nylon 6 resin having a terminal group blocked with a monocarboxylic acid.

[0006]

However, Japanese Patent Application Laid-Open Nos. Sho 53-111394 and 60-1011 describe the above.
According to the methods described in JP-A No. 20 and JP-A-7-258408, it has been difficult to remove both monomers and oligomers with high efficiency. Therefore, the present inventors have solved the above-mentioned problems of the prior art and can omit the step of extracting and removing unreacted monomers and oligomers with hot water, resulting in high production efficiency and low energy cost, A main object is to provide a production method capable of producing a nylon resin having a low content and a low oligomer content.

[0007]

As a result of intensive studies to solve the above-mentioned problems, a nylon resin having a terminal group concentration within a certain range is produced by polymerization, and this nylon resin is formed into a vertical stirring type thin film. The present inventors have found that when a monomer and an oligomer are removed using an evaporator, it is possible to produce a high-quality nylon resin with high efficiency, and arrived at the present invention.

That is, the present invention is as follows. 1. A method for removing monomers and oligomers contained in a nylon resin produced by polymerization using a vertical stirring type thin film evaporator, wherein the terminal group concentration of the nylon resin satisfies the formula (1). Nylon resin manufacturing method. Terminal amino group concentration <[terminal carboxyl group concentration−0.02 × 10 ⁻⁵ mol / g] (1) Nylon resin is nylon 6, nylon 66, nylon 11, nylon 12, nylon 6,10, nylon 6,12, nylon 6T unit and / or nylon 6I
2. The method for producing a nylon resin according to the above item 1, which is either a semi-aromatic nylon containing units or a copolymer of these nylons. 3. 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. 3. The method for producing a nylon resin according to the above item 1 or 2, which is an apparatus. 4. 4. A nylon resin is produced by the method according to any one of the above items 1 to 3, and then the obtained nylon resin is introduced into an extruder connected to a vertical stirring type thin film evaporator, and an additive and / or a filler is charged. A method for producing a nylon resin composition, comprising mixing and mixing materials. 5. 5. A nylon resin composition is produced by the method according to any one of the above items 1 to 3, and the nylon resin is melt-discharged and pelletized, or the nylon resin composition is produced by the method according to the above item 4. A method for producing nylon resin pellets in which pellets are produced by melting and discharging an object and pelletizing. 6. The method according to any one of the above items 1 to 3, 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 4 and then the nylon resin composition is molded. 6. A method for producing a molded article of a nylon resin, wherein the molded article is produced by producing a nylon resin pellet composition by the method described in the above item 5, or by molding the nylon resin composition.

[0009]

Embodiments of the present invention will be described below.

[0010] 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. 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 hermetic 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 a shaft, a thinning unit disposed below the dispersion unit, and a screw blade discharge device attached to a lower rotation shaft located in a lower extension cylindrical portion of the closed container body. Have, and
The thin film evaporator has an apparatus structure in which an upper rotating shaft and a lower rotating shaft are separately driven and rotated, and a bearing of the upper rotating shaft is arranged as a built-in bearing in the 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 nylon resin in a molten state 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. 13) Swirling stirring blade (14)
Thereby, the thin film is developed on the heating evaporation surface to promote the evaporation of the volatile components, the polymerization proceeds, and the thin film is lowered to be transferred 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-like lower rotating shaft (17) which is connected below the upper rotating shaft (9) but is separately driven to rotate.
Is provided on the central longitudinal axis (1), and the lower rotating shaft (17)
A discharge mechanism (18) composed of a screw blade is mounted on the upper part of the container body (3) from directly below the scooping auxiliary wing (16).

Although there is no particular limitation on the shape and 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 terms of the efficiency of removing volatile components and the efficiency of transferring liquid substances. 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.

The target nylon resin in the method of the present invention is:
Lactam, aminocarboxylic acid, mixture of dicarboxylic acid / diamine, mixture of dicarboxylic acid derivative / diamine, salt of dicarboxylic acid / diamine, and nylon resin obtained by polymerizing a mixture of two or more of these. Specific examples of lactams include 2-azetidinone, 2-pyrrolidinone, δ-valerolactam, ε-caprolactam,
Enanthractam, 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.

As a specific example of the aminocarboxylic acid, 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. Aliphatic dicarboxylic acids such as acids, brassic acid, tetradecandioic acid, pentadecandioic acid, octadecandioic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and 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 dicarboxylic acid / diamine salt used as the diamine include:
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 includes nylon 6, nylon 66, nylon 11, nylon 12, nylon 6.10, nylon 6.12, nylon 6T and / or semi-aromatic containing 6I units. Examples include nylon or a copolymer of these nylon resins.

Terminal amino group concentration and terminal of nylon resin
The carboxyl group concentration only needs to satisfy the formula (1).
Although the absolute value is not particularly limited, it is usually 1 × 10^-Five~ 12 ×
10 ^-Fivemol / g, preferably 2 × 10^-Five~ 11 × 10
^-Fivemol / g, more preferably 3 × 10^-Five-10 × 10
^-Fivemol / g. Terminal amino group concentration <[terminal carboxyl group concentration−0.02 × 10^-Fivemol / g] (1) Relationship between terminal amino group concentration and terminal carboxyl group concentration
Is preferably Formula (2). Terminal amino group concentration <[terminal carboxyl group concentration-0.05 x 10^-Fivemol / g] (2) More preferably, formula (3). Terminal amino group concentration <[terminal carboxyl group concentration-0.1 x 10^-Fivemol / g] (3)

In the method of the present invention, the method of adjusting the terminal group concentration of the nylon resin supplied to the vertical stirring type thin film evaporator includes, for example, a method of adding a predetermined amount of a terminal group blocking agent at the time of polymerization, and a method of adding a terminal group at the end of polymerization. There is a method in which a predetermined amount of a base blocking agent is added and melt-kneaded. The terminal blocking agent may be added as it is, or may be added after dissolving in a small amount of a solvent. As the terminal group blocking agent, a carboxylic acid compound or an amine compound is used.

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, palmitic acid, stearic acid, oleic acid, linoleic acid, Aliphatic monocarboxylic acids such as arachinic acid, cyclohexanecarboxylic acid, alicyclic monocarboxylic acids such as methylcyclohexanecarboxylic acid, benzoic acid, toluic acid, 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, dodecandioic acid, brassic acid, tetradecandioic acid, pentadecandioic acid, octadecandioic acid Aliphatic dicarboxylic acids, such as cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and aromatic dicarboxylic acids such as naphthalene dicarboxylic acid.
Further, anhydrides of these carboxylic acid compounds may be used.

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.

The amount of the terminal blocking agent may be selected according to the desired amount of the terminal group.
0.001 to 5 mol%, preferably 0.01 to 3 mol%, more preferably 0.1 to 2 mol, per 100 mol.
1%.

In the present invention, the degree of polymerization of the nylon resin supplied to the vertical stirring type thin film evaporator is not particularly limited, but usually the relative viscosity of the 0.01 g / mL sulfuric acid solution at 25 ° C. is 1.0 to 3 And preferably 1.5 to 3.0.
It is. If the relative viscosity exceeds 3.5, the melt viscosity is high,
The polymer is degraded due to shear heat in the vertical stirring type thin film evaporator, and the efficiency of removing monomers and oligomers is reduced.

In the method of the present invention, the temperature at which the monomers and oligomers are removed by passing through a vertical stirring type thin film evaporator is not particularly limited, and is determined according to the target amount of the remaining monomers and oligomers. Usually, the melting point of the supplied nylon resin to 400 ° C, preferably the melting point of the supplied nylon resin to 350 ° C, particularly preferably the melting point of the supplied nylon resin to 300 ° C. The pressure at that time is also not particularly limited, and is determined according to the target amount of the remaining monomers and oligomers. Usually 0.01-700mmH
g, preferably 0.05 to 600 mmHg, more preferably 0.1 to 500 mmHg. 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 resin supplied to a vertical stirring type thin film evaporator by polymerization, and a step of passing a monomer / oligomer through the vertical stirring type thin film evaporator. The removing step may be performed in a consistent continuous process or may be performed in a batch 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 to produce a nylon resin composition in a process continuous with polymerization. You can also.

Specific examples of various additives and fillers to be added 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 by a usual method, similarly to a conventional nylon resin (composition), or 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.

[0028]

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 a polyamide resin which was once melted and then quenched was accurately weighed, and a DSC- manufactured by Perkin-Elmer was used.
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).

Reference Example 1 (Polymerization of Nylon 6) 10 kg of ε-caprolactam, 43.2 g of benzoic acid, and 200 g of water were charged into a 30-liter stainless steel autoclave, sealed after nitrogen replacement, and heated and stirred at 250 ° C. for 7 hours. Thus, a nylon 6 resin was prepared. The obtained nylon 6 resin has 9.18% of a monomer and 2.18% of an oligomer.
It contained 51%. After extraction with boiling water for 15 hours, the polymer was dried at 80 ° C./vacuum overnight, and the relative viscosity ηr of sulfuric acid and the terminal group concentration of the polymer were as follows. ηr =
2.35, terminal amino group concentration = 3.90 × 10 ⁻⁵ mol
/ G, terminal carboxyl group concentration = 7.32 × 10 ⁻⁵ mo
1 / g.

Reference Example 2 (Nylon 6 polymerization) A 30 L stainless steel autoclave was charged with 10 kg of ε-caprolactam, 41.1 g of hexamitylenediamine, and 200 g of water, sealed with a nitrogen atmosphere, and heated at 250 ° C. for 7 hours. Nylon 6 resin was prepared by stirring. The obtained nylon 6 resin has 9.31% of monomer,
The oligomer contained 2.45%. In addition, 1 with boiling water
After extraction for 5 hours, the polymer was dried at 80 ° C./vacuum overnight and the sulfuric acid relative viscosity ηr and terminal group concentration of the polymer were as follows. ηr = 2.36, terminal amino group concentration 10.98
× 10 ^-5 mol / g, terminal carboxyl group concentration = 3.9
0 × 10 ⁻⁵ mol / g.

Reference Example 3 (Nylon 6 polymerization) A 30 L stainless steel autoclave was charged with 10 kg of ε-caprolactam, 2.16 g of benzoic acid, and 200 g of water, and sealed after nitrogen replacement, followed by heating at 250 ° C. for 12 hours.
Nylon 6 resin was prepared by stirring. The resulting nylon 6 resin contained 9.20% monomer and 2.52% oligomer. After extraction with boiling water for 15 hours, the polymer was dried at 80 ° C./vacuum overnight, and the relative viscosity ηr of sulfuric acid and the terminal group concentration of the polymer were as follows. η
r = 2.69, terminal amino group concentration 5.25 × 10 ⁻⁵ mo
1 / g, terminal carboxyl group concentration = 5.61 × 10 ⁻⁵ m
ol / g.

Reference Example 4 (Polymerized Nylon 66) An 80% aqueous solution of adipic acid / hexamethylenediamine equimolar salt and benzoic acid (adipic acid / hexamethylenediamine equimolar salt 1) were placed in a 30 L stainless steel autoclave.
1.86 g) for 0 kg, and the internal temperature is 250 ° C.
Polymerization was performed for 3 hours while maintaining the internal pressure at 15 to 20 kg / cm ² . Thereafter, the internal pressure was returned to normal pressure while gradually releasing the steam, the internal temperature was raised to 270 to 280 ° C., and the polymerization reaction was further performed for 1 hour.
Pelletized. The resulting nylon 66 resin contained 0.11% of monomer and 1.66% of oligomer. After extraction with boiling water for 15 hours, the polymer was dried at 80 ° C./vacuum overnight, and the relative viscosity ηr of sulfuric acid and the terminal group concentration of the polymer were as follows. ηr = 2.65, terminal amino group concentration 5.38 × 10 ⁻⁵ mol / g, terminal carboxyl group concentration = 5.63 × 10 ⁻⁵ mol / g.

Reference Example 5 (Nylon 66 polymerization) A 30 L stainless steel autoclave was charged with an 80% aqueous solution of adipic acid / hexamethylenediamine equimolar salt and hexamethylenediamine (adipic acid / hexamethylenediamine equimolar salt per 10 kg). .77g)
Keep the internal temperature at 250 ° C and the internal pressure at 15-20kg / cm2
Polymerized for hours. Thereafter, the internal pressure was returned to normal pressure while gradually releasing the steam, the internal temperature was raised to 270 to 280 ° C., and the polymerization reaction was further performed for 1 hour, and then the strand was pulled out from the lower part of the polymerization can with a strand and pelletized. The resulting nylon 66 resin contained 0.10% monomer and 1.64% oligomer. After extraction with boiling water for 15 hours, 80 ° C /
Sulfuric acid relative viscosity ηr of the polymer after drying in vacuum overnight,
The end group concentrations were as follows. ηr = 2.66, terminal amino group concentration 5.68 × 10 ⁻⁵ mol / g, terminal carboxyl group concentration = 5.36 × 10 ⁻⁵ mol / g.

Example 1 (Production of Nylon 6 Resin) The nylon 6 resin obtained in Reference Example 1 was 155 mm in inner diameter.
× a vertical stirring type thin film evaporator comprising a cylinder having 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 (resin temperature: 247 to 276 ° C, degree of pressure reduction: 0.5 to 5 mmHg, Stirrer blade rotation speed: 800 to 10
(00 rpm), and the mixture was treated in a molten state under reduced pressure to carry out polymerization. Table 1 shows the analysis values and various evaluation results of the obtained nylon resin.

Example 2 Preparation of Nylon 6 Resin / Glass Fiber Composition The vertical stirring type thin film evaporator of Example 1 was placed behind 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 1 (Production of Nylon 6 Resin) A nylon resin was produced in the same manner as in Example 1 except that the nylon 6 resin obtained in Reference Example 2 was used. Table 1 shows the analysis values and various evaluation results of the obtained nylon resin. Comparative Example 2 (Production of Nylon 6 Resin / Glass Fiber Composition) A nylon resin was produced in the same manner as in Example 2 except that the nylon 6 resin obtained in Reference Example 2 was used. Table 1 shows the analysis values and various evaluation results of the obtained nylon resin composition.

Example 3 (Production of Nylon 6 Resin) A nylon 6 resin was produced in the same manner as in Example 1 except that the nylon 6 resin obtained in Reference Example 3 was used. Table 1 shows the analysis values and various evaluation results of the obtained nylon 6 resin. Example 4 (Production of nylon 6 resin / glass fiber composition) A nylon resin composition was produced in the same manner as in Example 2 except that the nylon 6 resin obtained in Reference Example 3 was used. Table 1 shows the analysis values and various evaluation results of the obtained nylon resin composition.

From Example 1 and Comparative Example 1, a high-quality nylon 6 resin can be obtained if the terminal group concentration is within the range of the present invention, but it can be obtained if the terminal group concentration deviates from the range of the present invention. It can be seen that the quality of the nylon 6 resin deteriorates. Further, from Example 2 and Comparative Example 2, the same can be said for the case of using a glass fiber reinforced composition. Examples 1-4
It can be seen from the above that even if the degree of polymerization changes, a high-quality nylon 6 resin and composition can be obtained by the present invention.

[0040]

[Table 1]

Example 5 (Production of nylon 66 resin) The nylon 66 resin obtained in Reference Example 4 was 155 mm in inner diameter.
A vertical stirring type thin film evaporator composed of a cylinder of φ × 430 mm in height and inclined multi-stage stirring blades rotating while maintaining a clearance of 2 mm from the inner wall of the cylinder (resin temperature: 283 to 322 ° C., degree of pressure reduction: 0.5 to 3 mmHg) , Stirring blade rotation speed: 600-80
0 rpm), and the mixture was treated in a molten state 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.

Example 6 (Production of Nylon 66 Resin / Glass Fiber Composition) After the vertical stirring type thin film evaporator of Example 5, a 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 2 shows the evaluation results of the obtained compositions.

Comparative Example 3 (Production of Nylon 66 Resin) A nylon 66 resin was produced in the same manner as in Example 5 except that the nylon 66 resin obtained in Reference Example 5 was used. Table 2 shows the analysis values and various evaluation results of the obtained nylon 66 resin.
Shown in Comparative Example 4 (Production of Nylon 66 Resin / Glass Fiber Composition) A nylon resin composition was produced in the same manner as in Example 6, except that the nylon 6 resin obtained in Reference Example 5 was used. Table 2 shows the analysis values and various evaluation results of the obtained nylon resin composition.

From Example 5 and Comparative Example 5, a high-quality nylon 66 resin can be obtained if the terminal group concentration is within the range of the present invention, whereas it can be obtained if the terminal group concentration deviates from the range of the present invention. It can be seen that the quality of nylon 66 resin deteriorates. Further, from Example 6 and Comparative Example 6, the same can be said for the case of using a glass fiber reinforced composition.

[0045]

[Table 2]

[0046]

According to the production method of the present invention, monomers and oligomers can be efficiently removed, and a high-quality nylon resin or nylon resin composition can be produced with high efficiency.

[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

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[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]

3. A nylon resin was prepared by the method of mounting according to claim 1 or 2 SL, subsequently, introduced into the nylon resin obtained vertical stirring thin-film evaporator to linked extruder, additives and A method for producing a nylon resin composition, comprising mixing and / or mixing a filler.

By wherein the pelletizing of melted discharge the nylon resin to produce a nylon resin by the method of mounting according to claim 1 or 2 SL, or the manufacture of nylon resin composition by the method of claim 3, wherein A method for producing nylon resin pellets, in which a nylon resin composition is melt-discharged and pelletized to produce pellets.

5. By molding the nylon resin after producing the nylon resin by the method of mounting according to claim 1 or 2 SL, the nylon resin composition after the production of the nylon resin composition by the method of claim 3, wherein Or a nylon resin pellet by the method according to claim 4.
The <br/> Rukoto be molded from the nylon resins pellets after producing the Tsu preparative method for producing a nylon resin moldings for producing a molded article.

Continued on the front page F-term (reference) 4J001 DA01 DB01 DB02 DD07 EA06 EA07 EA08 EB08 EB36 EB37 EC08 EC09 FD03 GC03 GC04 GC05 GD01 HA02 JA01 JA10 JA12 4J002 CL011 CL031 FD010 FD020 FD060 FD070 FD090 CC03 FD100 FD130 CC03 CF01 CG04 CG07 CG13 CG17 CG25 CG39

Claims (6)

[Claims] 1. A method for removing monomers and oligomers contained in a nylon resin produced by polymerization using a vertical stirring type thin film evaporator, wherein the terminal group concentration of the nylon resin satisfies the formula (1). A method for producing a nylon resin. Terminal amino group concentration <[terminal carboxyl group concentration−0.02 × 10 ⁻⁵ mol / g] (1) 2. The nylon resin is nylon 6, nylon 66, nylon 11, nylon 12, nylon 6.1.
The method for producing a nylon resin according to claim 1, wherein the nylon resin is any one of 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. 3. 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 disposed 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. 3. The method for producing a nylon resin according to claim 1, which is a thin film evaporator having an apparatus structure. 4. A nylon resin is produced by the method according to any one of claims 1 to 3, and 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 by 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 nylon resin is produced by the method according to claim 4, wherein the nylon resin is produced by producing the nylon resin by the method according to claim 1. A method for producing a molded article of nylon resin, wherein the molded article is produced by molding the composition or by producing the nylon resin pellet composition by the method according to claim 5 and then molding the nylon resin composition.