WO2011122231A1 - Process for production of polypentamethyleneadipamide resin - Google Patents

Process for production of polypentamethyleneadipamide resin Download PDF

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Publication number
WO2011122231A1
WO2011122231A1 PCT/JP2011/054915 JP2011054915W WO2011122231A1 WO 2011122231 A1 WO2011122231 A1 WO 2011122231A1 JP 2011054915 W JP2011054915 W JP 2011054915W WO 2011122231 A1 WO2011122231 A1 WO 2011122231A1
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Prior art keywords
pressure
polymerization
mpa
max
polypentamethylene adipamide
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PCT/JP2011/054915
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French (fr)
Japanese (ja)
Inventor
松見大介
栗林隆宏
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東レ株式会社
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Priority to JP2011514914A priority Critical patent/JP4877433B2/en
Priority to CN201180012680.3A priority patent/CN102782010B/en
Publication of WO2011122231A1 publication Critical patent/WO2011122231A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes

Definitions

  • the present invention relates to a method for producing a polypentamethylene adipamide resin.
  • Patent Document 1 discloses an example in which a polypentamethylene adipamide resin using 1,5-diaminopentane obtained from a plant-derived raw material as a monomer component is highly polymerized on a test tube scale.
  • Patent Document 2 discloses an example in which a polypentamethylene adipamide resin is produced on a test tube scale at a relatively low heating temperature during polymerization.
  • Patent Document 3 Patent Document 4, Patent Document 5 and Patent Document 6 disclose a method for producing a polypentamethylene adipamide resin by a polymerization apparatus equipped with a stirrer as a scaled up production example.
  • JP 2004-75932 A JP 2009-195202 JP 2004-269549 A JP 2008-189661 JP 2009-179899 JP JP 2009-235352 A
  • Patent Documents 1 and 2 are all examples of production on a test tube scale, and the disclosure of a technology for industrially increasing the degree of polymerization of polypentamethylene adipamide resin or polymerizing at low temperature. There is no.
  • an object of the present invention is to make it possible to produce a polypentamethylene adipamide resin having an excellent color tone even if batch polymerization is repeated in a state where a part of the polymer of the previous batch remains.
  • the present inventors limit the amount of polymer remaining from the previous batch and its coloration by limiting the polymerization apparatus and pressure conditions during polymerization, and improve the color tone of the resulting polypentamethylene adipamide resin.
  • the present invention has been found.
  • an object of the present invention is a method for producing by repeating batch polymerization in which a polypentamethylene adipamide resin is pressurized from 1,5-diaminopentane and adipic acid and then released, and the polymerization is provided with a stirrer.
  • Polypentamethylene satisfying the following conditions (A) to (C) when the internal pressure is P [MPa (absolute pressure)] and the maximum value of P is P max [MPa (absolute pressure)]. Achieved by a manufacturing method of adipamide resin.
  • the method for producing the polypentamethylene adipamide resin of the present invention is such that the resulting polypentamethylene adipamide resin has a melting point of Tm [° C.], the polypentamethylene adipamide resin temperature during polymerization is Tp [° C.], Tp When the maximum temperature of Tp max [° C.] and the heating temperature during the polymerization are H [° C.], it is preferable to produce in the range satisfying the following relational expression.
  • the time when Tp ⁇ Tm is 0.5 hours or more and 2 hours or less.
  • the method for producing the polypentamethylene adipamide resin of the present invention preferably uses 1,5-diaminopentane obtained from a plant-derived raw material.
  • a polypentamethylene adipamide resin having an excellent color tone can be obtained even when batch polymerization is repeated in a state where a part of the polymer of the previous batch remains.
  • the present invention relates to a process for producing a polypentamethylene adipamide resin from 1,5-diaminopentane and adipic acid by pressurizing and releasing the batch polymerization.
  • Pressurization refers to an operation for increasing the pressure above atmospheric pressure
  • pressure release refers to an operation for decreasing the pressure from a pressurized state to atmospheric pressure.
  • Manufacturing by repeating this means that the inside of the apparatus is washed between cycles when one cycle is from the charging of the monomer into the batch polymerization apparatus to the completion of the polymerization through pressurization and release, and the discharge of the polymer. It means that the next cycle is carried out without repeating, and indicates that the polymerization is repeated with the remaining polymer in the previous batch in the polymerization apparatus.
  • the polypentamethylene adipamide resin used in the present invention is not particularly limited as long as it is a polyamide resin mainly composed of polypentamethylene adipamide units.
  • the pentamethylene adipamide unit is a structural unit composed of 1,5-diaminopentane and adipic acid.
  • it may contain other copolymerization component of less than 10 mol%, but preferably contains more pentamethylene adipamide units, more preferably 94 mol% or more, More preferably, it is 97 mol% or more.
  • it is particularly effective when 1,5-diaminopentane obtained from a biomass-derived compound is used.
  • Such a substance may contain impurities different from organic synthetic products that have been used in the past, and the resin may be easily colored. Can be improved.
  • 1,5-Diaminopentane obtained from a biomass-derived compound is synthesized from a biomass-derived compound such as glucose or lysine by enzymatic reaction, yeast reaction, fermentation reaction, etc. in the monomer synthesis step.
  • a biomass-derived compound such as glucose or lysine
  • polypentamethylene having a high melt storage stability can be prepared because the content of compounds such as 2,3,4,5-tetrahydropyridine and piperidine is small and high-purity 1,5-diaminopentane can be prepared. Since it becomes an adipamide resin, it is preferable.
  • a polypentamethylene adipamide resin is preferable, and it is preferable to polymerize using 1,5-diaminopentane adipate because it is easy to obtain a raw material with higher purity.
  • what is necessary is just to use what was manufactured by the conventionally well-known method about adipic acid, another diamine component, and a dicarboxylic acid component.
  • the polypentamethylene adipamide resin of the present invention may be copolymerized with 1,5-diaminopentane or other compounds in addition to adipine within a range not impairing the object of the present invention.
  • Structural units derived from the following components may be included.
  • aliphatic dicarboxylic acids oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid, octadecaneic acid Diacids
  • alicyclic dicarboxylic acids cyclohexanedicarboxylic acid, etc.
  • aromatic dicarboxylic acids terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxy Ethanedicarboxylic acid, diphenylethanedicarboxylic acid, 1,4-cycl
  • ethylenediamine 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminohepta Aliphatic diamines such as decane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane,
  • It may also contain structural units derived from amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and lactams such as ⁇ -caprolactam and ⁇ -laurolactam.
  • amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and lactams such as ⁇ -caprolactam and ⁇ -laurolactam.
  • the stirrer When the stirrer is not provided, heat transfer to the monomer or polymer in the polymerization apparatus becomes non-uniform, causing bumping of the polymer and increasing the residual polymer adhering to the inner wall of the apparatus, which may cause coloring.
  • the shape of the stirring blades disk turbine type, inclined paddle type, propeller type, anchor type, helical ribbon type, etc. are generally adopted, but since the liquid viscosity is high, it is inclined Paddle type, anchor type and helical ribbon type are preferably used.
  • the rotation speed of the stirrer is generally about 10 to 200 rpm, preferably about 20 to 150 rpm, and most preferably about 30 to 100 rpm. The rotation speed level can be changed depending on the polymerization stage.
  • the maximum value P max [MPa (absolute pressure)] of the internal pressure P [MPa (absolute pressure)] of the polymerization apparatus must be 1.0 MPa or more, preferably 1.3 MPa or more, more preferably 1.7 MPa or more.
  • the maximum value P max of the internal pressure P [MPa (absolute pressure)] is less than 1.0 MPa, the amount of evaporation of 1,5-diaminopentane, which is a monomer component, increases, resulting in the polypentamethylene azimuth obtained by breaking the molar balance. The degree of polymerization and the amount of amino groups of the pamide resin may be lowered.
  • the upper limit of the maximum value P max of the internal pressure P [MPa (absolute pressure)] is not particularly limited, but preferably 3.0 MPa or less, more preferably 2.0 MPa or less in consideration of the pressure resistance of the polymerization apparatus.
  • the pressure is controlled so that the natural logarithm of the pressure release time and the internal pressure P is linear, and the internal pressure P is 0. It is extremely important to set the pressure release time from 4 MPa to 0.1 MPa (atmospheric pressure) to 20 minutes or more. Specifically, it is expressed by the following equation.
  • P ( ⁇ ) indicates a pressure at an elapsed time ⁇ from the start of pressure release.
  • -[Ln (0.4) -ln (0.1)] / ⁇ 0.4-0.1 when the internal pressure P is 0.4 and 0.1 that is, when ln (P) is ln (0.4) and ln (0.1)
  • ⁇ [ln (0.4) ⁇ ln (0.1)] / 20 ⁇ 0.0693.
  • the above linear relationship is strictly a linear relationship, in actual operation, a slight pressure adjustment fee is generated. Specifically, the same effect can be obtained even if the internal pressure P exceeds 0.4 MPa in the region where the internal pressure P exceeds 0.4 MPa, and the internal pressure P in the region where the internal pressure P is 0.4 MPa or less is shifted by about ⁇ 0.02 MPa. It is assumed that there is a linear relationship. If the pressure is suddenly adjusted out of this range, not only the effect of the present invention can be obtained, but also the latent heat of evaporation taken away with the vaporization of the condensed water becomes too large, so that the internal liquid is solidified and cannot be polymerized. May be.
  • the foaming of the polymer can be sufficiently suppressed, and the color tone deterioration can be suppressed without increasing the heat history, and further, commercial continuous batch production Reproducibility to withstand.
  • the pressure release time until the internal pressure P becomes 0.4 MPa to 0.1 MPa is indispensable to be 20 minutes or more, preferably 25 minutes or more. If the pressure is returned to atmospheric pressure in a time shorter than 20 minutes, the polymer foams and causes the color tone of the next batch to deteriorate. Although there is no particular upper limit, when the retention time above the melting point is longer than 2 hours, the resulting polypentamethylene adipamide resin tends to be deteriorated, and therefore usually within 1.5 hours is selected.
  • the internal pressure P [MPa (absolute pressure)] of the polymerization apparatus is maintained at 0.1 MPa or higher, that is, atmospheric pressure or higher over the entire period of polymerization. Even when the internal pressure P is less than 0.1 MPa and the pressure is reduced, the polymer may foam and cause the color tone of the next batch to deteriorate. Therefore, in the present invention, in order to adjust the degree of polymerization, it is preferable to perform an operation (normal pressure polymerization) of passing the inert gas after the end of the pressure release to remove the condensed water.
  • the inert gas include helium gas, argon gas, and nitrogen gas, and nitrogen gas is preferably used from the viewpoint of manufacturing cost.
  • the normal pressure polymerization time it is usually carried out for 5 minutes or longer, preferably 10 minutes or longer in order to appropriately increase the degree of polymerization.
  • the upper limit is normally selected within 1 hour so that the time when Tp ⁇ Tm is within 2 hours in order to prevent the deterioration of the color tone.
  • the monomers used in the present invention, 1,5-diaminopentane and adipic acid are preferably added as an aqueous solution of these salts.
  • the water content of the monomer aqueous solution may be adjusted in consideration of handling and measurement, but is preferably 10% to 60%, more preferably 10% to 50%. It can also be used after being concentrated to an arbitrary moisture content in an apparatus different from the polymerization apparatus. In this case, the moisture content after concentration is preferably 10% to 30%, more preferably 10% to 20%. .
  • 1,5-diaminopentane or adipic acid is added before the polymerization in order to compensate for 1,5-diaminopentane distilled during the polymerization or to adjust the resulting polypentamethylene adipamide resin to a desired end group. It is also possible to add.
  • the internal liquid temperature of the polymerization apparatus continues to rise by heating the polymerization system from the time of pressurization to the release of pressure to complete the polymerization.
  • the heating temperature at the initial stage of polymerization is set higher than the target temperature of the internal liquid, and when the internal liquid temperature exceeds the melting point of the obtained polymer, It is preferable to lower it to the same level as the target temperature.
  • the melting point of the obtained polypentamethylene adipamide resin is Tm
  • the polypentamethylene adipamide resin temperature during polymerization is Tp [° C.]
  • the maximum temperature of Tp is Tp max [° C.]
  • the heating temperature during polymerization It is preferable to manufacture in the range which satisfies the following relational expression, when H is H [° C.].
  • the melting point Tm [° C.] of the obtained polypentamethylene adipamide resin means the target melting point of the polypentamethylene adipamide resin to be finally obtained.
  • the melting point of the finally obtained polypentamethylene adipamide resin is measured by differential scanning calorimetry (DSC). Polypentamethylene adipamide resin shows two melting points, and the higher peak temperature is taken as the melting point.
  • the polypentamethylene adipamide resin temperature Tp [° C.] during polymerization is usually measured by a thermometer inserted in the polymerization apparatus. If there is a temperature distribution in the apparatus, the average temperature is Tp [° C.].
  • Tp max [° C.] is the maximum temperature of T p [° C.] and is usually the temperature at the final stage of the polymerization.
  • the heating temperature H [° C.] during polymerization is the temperature of the heat transfer surface with the polymerization apparatus, and usually refers to the temperature of the heat medium.
  • a polymerization apparatus equipped with a heat medium jacket it refers to the temperature inside the jacket, and when a heat transfer coil is inserted into the polymerization apparatus, it refers to the temperature inside the coil.
  • the higher temperature is pointed out. If the temperature of the heat transfer surface with the polymerization apparatus has a temperature distribution in the apparatus, the highest temperature is set to H.
  • the heating temperature H during the polymerization there is a method in which an independent heating medium boiler separate from the polymerization apparatus is provided and the temperature-controlled heating medium is supplied to the jacket and / or coil of the polymerization apparatus.
  • the heat medium is supplied as vapor or liquid.
  • Tm + 10 ⁇ Tp max ⁇ Tm + 20 This indicates that the polymer temperature during the polymerization is controlled in the range of Tm + 10 ° C. or more and Tm + 20 ° C. or less.
  • the fluidity in the polymerization apparatus is kept good without excessively increasing the melt viscosity of the polymer, while the color tone of the resulting polyamide resin is also good.
  • heat transfer from the heat medium to the polymer may be efficiently performed.
  • it in addition to providing the polymerization apparatus with a stirring device, for example, it can be achieved by providing a sufficient heat transfer area or by strictly controlling the temperature of the heat medium supplied to the heat transfer surface. .
  • the time for maintaining the temperature within the melting point of the polypentamethylene adipamide resin obtained in the polymerization system affects the molecular weight of the resulting polypentamethylene adipamide resin.
  • the time during which the temperature is maintained above the melting point of the polypentamethylene adipamide resin is preferably controlled to 0.5 hours or more and 2 hours or less, more preferably 1 hour or more and 2 hours or less.
  • the time for maintaining the melting point or higher is controlled within this range, the molecular weight can be increased sufficiently, but the volatilization and cyclization of 1,5-diaminopentane are not promoted, and the resulting polypentamethylene azimuth is obtained. Pamide resin does not deteriorate.
  • a method for discharging the polymer after completion of the polymerization a method of pressurizing the polymerization apparatus with an inert gas, cooling the polymer extruded into a strand shape with water, and cutting to obtain pellets is preferably used.
  • extruding the polymer in as short a time as possible is effective in suppressing deterioration of the color tone, and is preferably extruded within 1 hour, more preferably within 40 minutes, and even more preferably within 30 minutes.
  • the relative viscosity of sulfuric acid of the polypentamethylene adipamide resin obtained by the present invention is preferably 2.1 or higher, more preferably 2.4 or higher, and further preferably 2.5 or higher.
  • the sulfuric acid relative viscosity is within this range, the strand diameter is stable when cutting the polymer extruded into a strand shape, and the yield of pellets having a normal shape can be increased.
  • it is preferably 4.0 or less from the viewpoint of preventing a decrease in yield due to an increase in the amount of polymer remaining in the polymerization apparatus.
  • the amino group amount [milli equivalent / kg] is preferably 30 to 70 [milli equivalent / kg], more preferably 35 to 65 [milli equivalent / kg], and further preferably 40 to 60 [milli equivalent / kg].
  • the amino group content is within the above preferred range, it is easy to dye when used as a fiber, while the stability during melting in post-processing can be maintained.
  • diamine component to be added at this time in addition to 1,5-diaminopentane which is a monomer component, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diamino Heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-di
  • the molecular weight of the polypentamethylene adipamide resin obtained by the present invention can be increased by further increasing the degree of polymerization by solid phase polymerization or a melt extruder.
  • Solid phase polymerization proceeds by heating in a vacuum or in an inert gas within a temperature range of 100 ° C. to the melting point.
  • end-capping agents monocarboxylic acid, monoamine, etc.
  • antioxidants heat stabilizers (hindered phenols, hydroquinones, Phosphites and their substitutes, copper halides, iodine compounds, etc.)
  • weathering agents resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines, etc.
  • mold release agents and lubricants aliphatic alcohols, fats
  • pigments titanium dioxide, cadmium sulfide, phthalocyanine, carbon black, etc.
  • dyes nigrosine, aniline black, etc.
  • crystal nucleating agents talc, silica, kaolin, clay) Etc.
  • plasticizer octyl p-oxybenzoate, N-butyl
  • the polypentamethylene adipamide resin of the present invention is useful for fibers, films, sheets, filaments, resins, adhesives, paints and the like.
  • Specific application examples include textiles for clothing, textiles for industrial materials, switches, ultra-small slide switches, DIP switches, switch housings, lamp sockets, cable ties, connectors, connector housings, connector shells, IC sockets Class, coil bobbin, bobbin cover, relay, relay box, condenser case, motor internal parts, small motor case, gear cam, dancing pulley, spacer, insulator, fastener, buckle, wire clip, bicycle wheel, caster, helmet, terminal Base, power tool housing, starter insulation, spoiler, canister, radiator tank, chamber tank, reservoir tank, fuse box, air cleaner case, air conditioner fan, Minal housing, wheel cover, intake / exhaust pipe, bearing retainer, cylinder head cover, intake manifold, water pipe impeller, clutch release, speaker diaphragm, heat-resistant container, microwave oven part, rice cooker part, printer ribbon guide,
  • LB medium 50 mL was placed in a 500 mL Erlenmeyer flask and steam sterilized in advance at 115 ° C. for 10 minutes.
  • the strain was precultured in this medium, and cultured for 24 hours under the condition of 30 cm in amplitude and 180 rpm while adjusting the pH to 6.0 with 1N aqueous hydrochloric acid.
  • the bacterial cells thus obtained were collected and a cell-free extract was prepared by ultrasonic disruption and centrifugation.
  • These lysine decarboxylase activities were measured according to a conventional method (Japan Biochemical Society, edited by Biochemical Experiment Course 11 “Amino Acid Metabolism and Biogenic Amine” P.179-191 (1976)).
  • lysine When lysine is used as a substrate, conversion by lysine monooxygenase, lysine oxidase and lysine mutase, which are considered to be the main main pathways, can occur. Therefore, for the purpose of blocking this reaction system, the E. coli JM109 strain is used at 75 ° C. for 5 minutes. The cell-free extract was heated. Furthermore, this cell-free extract was fractionated with 40% saturated and 55% saturated ammonium sulfate. The crude purified lysine decarboxylase solution thus obtained was used to produce 1,5-diaminopentane from lysine.
  • Reference Example 2 (Production of 1,5-diaminopentane) It was prepared so that lysine hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) was 50 mM, pyridoxal phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) was 0.1 mM, and crude lysine decarboxylase (prepared in Reference Example 1) was 40 mg / L. 1000 mL of the aqueous solution was reacted at 45 ° C. for 48 hours while maintaining the pH at 5.5 to 6.5 with 0.1N hydrochloric acid aqueous solution to obtain 1,5-diaminopentane hydrochloride.
  • 1,5-diaminopentane hydrochloride is converted to 1,5-diaminopentane, extracted with chloroform, and distilled under reduced pressure (8 mmHg, 70 ° C.) to obtain 1, 5-Diaminopentane was obtained.
  • Reference Example 3 (Production of polypentamethylene adipamide) An aqueous solution obtained by dissolving 12.3 kg of 1,5-diaminopentane obtained in Reference Example 2 in 30.0 kg of ion-exchanged water is immersed in an ice bath and stirred, and 17.7 kg of adipic acid (kirk) In the vicinity of the neutralization point in a water bath at 40 ° C to bring the internal temperature to 33 ° C, and equimolar of 1,5-diaminopentane and adipic acid having a pH of 8.32. 60.0 kg of a 50% by weight aqueous solution of salt was prepared.
  • This aqueous solution was put into a batch type polymerization can having an internal volume of 80 L equipped with a stirrer having a double helical ribbon blade and a heating medium jacket. After sufficiently substituting the inside of the polymerization can with nitrogen, heating was started at 260 ° C. with stirring at 30 rpm.
  • the heating is a system in which the heat medium vapor is supplied from a heat medium boiler independent from the polymerization apparatus, and the heat medium heating in the boiler is adjusted so that the indicated temperature of the thermometer inserted inside the jacket becomes a specified temperature. Concentration was started when the can internal pressure reached 0.3 MPa (absolute pressure), and the opening of the pressure relief valve was adjusted so as to keep the polymerization can internal pressure constant.
  • polypentamethylene adipamide had a sulfuric acid relative viscosity of 2.79, an amino terminal group amount of 4.55 ⁇ 10 ⁇ 5 mol / g, and a Tm of 254 ° C. (Examples 1 to 3) After carrying out Reference Example 3, heating was stopped, and the mixture was allowed to cool overnight until the internal temperature became 40 ° C.
  • Example 1 is the second batch
  • Example 2 is the third batch
  • Example 3 is the fourth batch
  • Example 6 The same operation as in Reference Example 3 and Example 1 was performed except that P max was set to 1.0 MPa.
  • Example 7 After releasing to atmospheric pressure, instead of performing normal pressure polymerization, the same operation as in Reference Example 3 and Example 1 was performed except that the pressure was reduced to 0.98 MPa (absolute pressure) and held for 15 minutes.
  • Example 8 The same operations as in Reference Example 3 and Example 1 were performed except that the heating temperature was changed to 275 ° C. when the internal pressure of the can reached 1.8 MPa (absolute pressure: P max ).
  • Example 9 The same operations as in Reference Example 3 and Example 1 were performed except that the heating temperature was changed to 280 ° C. when the internal pressure of the can reached 1.8 MPa (absolute pressure: P max ).
  • Example 10 The same operation as in Reference Example 3 and Example 1 was performed except that the stirring speed at the time of polymerization was 20 rpm and the heating temperature was changed to 277 ° C. when the internal pressure of the can reached 1.8 MPa (absolute pressure: P max ). went.
  • Example 11 The same operation as in Reference Example 3 and Example 1 was performed except that the stirring speed during polymerization was 15 rpm and the heating temperature was changed to 282 ° C. when the internal pressure of the can reached 1.8 MPa (absolute pressure: P max ). went.
  • Example 1 and Example 7 were compared with each other, although the extreme deterioration of the color tone was suppressed, the color tone of Example 7 subjected to reduced pressure polymerization was lowered.
  • Example 9 in which Tp max exceeded Tm + 20 ° C. had a lower color tone.
  • Example 11 in which H-Tp max exceeds 5 ° C. due to a decrease in stirring speed has a worse color tone. It was.
  • Example 1 and Example 12 were compared with each other, although the extreme deterioration in color tone was suppressed, the color tone was worse in Example 12 in which the time when Tp ⁇ Tm exceeded 2 hours.
  • a polypentamethylene adipamide resin having an excellent color tone can be provided industrially and stably even if batch polymerization is repeated with a part of the polymer of the previous batch remaining.

Abstract

A process for the production of polypentamethyleneadipamide resin from 1,5-diaminopentane and adipic acid by repeating batch polymerization that includes pressurization and depressurization successively, which comprises using a polymerizer provided with an agitator and which satisfies, when the internal pressure is referred to as P [MPa (absolute pressure)] and the maximum value of P is referred to as Pmax [MPa (absolute pressure), the following requirements (A) to (C): (A) 1.0 < Pmax, (B) in the depressurization operation, pressure control is so conducted that the relationship between depressurization time and In(P) becomes linear, and (C) in the depressurization, the time taken to decrease the internal pressure from 0.4MPa (absolute pressure) to atmospheric pressure is adjusted to 20 minutes or longer. The process can provide a polypentamethyleneadipamide resin with an excellent color tone, even when the batch polymerization is repeated in a state where the polymer produced in the preceding batch remains partially.

Description

ポリペンタメチレンアジパミド樹脂の製造方法Process for producing polypentamethylene adipamide resin
　本発明は、ポリペンタメチレンアジパミド樹脂の製造方法に関する。 The present invention relates to a method for producing a polypentamethylene adipamide resin.
　環境問題への意識の高まりから、植物由来原料を用いた環境配慮型ポリマーの開発が近年盛んに進められている。 The development of environmentally friendly polymers using plant-derived raw materials has been actively promoted in recent years due to the growing awareness of environmental issues.
　例えば、モノマー成分に植物由来原料から得られた１，５－ジアミノペンタンを用いたポリペンタメチレンアジパミド樹脂を試験管スケールで高重合度化した例が特許文献１に開示されている。 For example, Patent Document 1 discloses an example in which a polypentamethylene adipamide resin using 1,5-diaminopentane obtained from a plant-derived raw material as a monomer component is highly polymerized on a test tube scale.
　また、特許文献２には、重合時に比較的低い加熱温度でポリペンタメチレンアジパミド樹脂を試験管スケールで製造した例が開示されている。 Patent Document 2 discloses an example in which a polypentamethylene adipamide resin is produced on a test tube scale at a relatively low heating temperature during polymerization.
　特許文献３、特許文献４、特許文献５および特許文献６には、スケールアップした製造例として、撹拌機を具備した重合装置によってポリペンタメチレンアジパミド樹脂を製造する方法が開示されている。
特開2004-75932号公報 特開2009-195202号公報 特開2004-269549号公報 特開2008-189661号公報 特開2009-179899号公報 特開2009-235352号公報 Patent Document 3, Patent Document 4, Patent Document 5 and Patent Document 6 disclose a method for producing a polypentamethylene adipamide resin by a polymerization apparatus equipped with a stirrer as a scaled up production example.
JP 2004-75932 A JP 2009-195202 JP 2004-269549 A JP 2008-189661 JP 2009-179899 JP JP 2009-235352 A
　特許文献１、２に開示された技術はいずれもいずれも試験管スケールでの製造例であり、工業的にポリペンタメチレンアジパミド樹脂を高重合度化したり、低温で重合する技術についての開示はない。 The technologies disclosed in Patent Documents 1 and 2 are all examples of production on a test tube scale, and the disclosure of a technology for industrially increasing the degree of polymerization of polypentamethylene adipamide resin or polymerizing at low temperature. There is no.
　一方、商業レベルでバッチ重合によりポリアミド樹脂を得る場合、通常重合装置内に前バッチのポリマーが一部残存した状態で、次バッチの重合を実施する。ポリペンタメチレンアジパミド樹脂を前記特許文献３～６に記載の方法を含む公知の方法で繰り返し製造した場合、前バッチから残存したポリマーの着色が顕著に認められ、これが当該バッチのポリマーに混入することで、得られるペンタメチレンアジパミド樹脂の色調が悪化する問題があった。 On the other hand, when a polyamide resin is obtained by batch polymerization at a commercial level, the polymerization of the next batch is usually carried out with a part of the polymer of the previous batch remaining in the polymerization apparatus. When polypentamethylene adipamide resin is repeatedly produced by known methods including those described in Patent Documents 3 to 6, coloring of the polymer remaining from the previous batch is noticeable, and this is mixed into the polymer of the batch. As a result, there was a problem that the color tone of the resulting pentamethylene adipamide resin deteriorated.
　従って本発明では、前バッチのポリマーが一部残存した状態でバッチ重合を繰り返しても、色調に優れたポリペンタメチレンアジパミド樹脂の製造を可能とすることを課題とする。 Therefore, an object of the present invention is to make it possible to produce a polypentamethylene adipamide resin having an excellent color tone even if batch polymerization is repeated in a state where a part of the polymer of the previous batch remains.
　本発明者らは、重合装置と重合時の圧力条件などを限定することで、前バッチから残存するポリマーの量とその着色を抑え、得られるポリペンタメチレンアジパミド樹脂の色調を改善することが可能であることを見出し、本発明に到達した。 The present inventors limit the amount of polymer remaining from the previous batch and its coloration by limiting the polymerization apparatus and pressure conditions during polymerization, and improve the color tone of the resulting polypentamethylene adipamide resin. The present invention has been found.
　すなわち、本発明の目的は、１，５－ジアミノペンタンとアジピン酸からポリペンタメチレンアジパミド樹脂を加圧してから放圧するバッチ重合を繰り返すことにより製造する方法であって、攪拌機を具備した重合装置を用い、内圧をＰ［MPa（絶対圧）］、Ｐの最高値をＰmax［MPa（絶対圧）］としたときに、下記（Ａ）～（Ｃ）の条件を満足するポリペンタメチレンアジパミド樹脂の製造方法、により達成される。 That is, an object of the present invention is a method for producing by repeating batch polymerization in which a polypentamethylene adipamide resin is pressurized from 1,5-diaminopentane and adipic acid and then released, and the polymerization is provided with a stirrer. Polypentamethylene satisfying the following conditions (A) to (C) when the internal pressure is P [MPa (absolute pressure)] and the maximum value of P is P max [MPa (absolute pressure)]. Achieved by a manufacturing method of adipamide resin.
　（Ａ）１．０≦Ｐmax
　（Ｂ）放圧操作の際、放圧時間とln（Ｐ）が直線関係になるように圧力調整すること
　（Ｃ）放圧時間のうち、０．４[MPa（絶対圧）]から大気圧へ戻すまでの時間を２０分以上とすること
　本発明のポリペンタメチレンアジパミド樹脂の製造方法は、０．１≦Ｐとすることが好ましい。 (A) 1.0 ≦ P max
(B) During pressure relief operation, adjust the pressure so that the pressure relief time and ln (P) have a linear relationship. (C) From 0.4 [MPa (absolute pressure)] of the pressure relief time to atmospheric pressure Time to return to 20 minutes or more It is preferable that the manufacturing method of the polypentamethylene adipamide resin of the present invention satisfies 0.1 ≦ P.
　本発明のポリペンタメチレンアジパミド樹脂の製造方法は、得られるポリペンタメチレンアジパミド樹脂の融点をＴm［℃］、重合中のポリペンタメチレンアジパミド樹脂温度をＴp［℃］、Ｔpの最高温度をＴpmax［℃］、重合中の加熱温度をＨ［℃」としたときに、下記関係式を満足する範囲で製造することが好ましい。 The method for producing the polypentamethylene adipamide resin of the present invention is such that the resulting polypentamethylene adipamide resin has a melting point of Tm [° C.], the polypentamethylene adipamide resin temperature during polymerization is Tp [° C.], Tp When the maximum temperature of Tp max [° C.] and the heating temperature during the polymerization are H [° C.], it is preferable to produce in the range satisfying the following relational expression.
　　　Ｔm＋１０　≦　Ｔpmax　≦　Ｔm＋２０
　　　Ｈ－Ｔpmax　≦　５　（ただし、Ｔp≧Ｔm）
　本発明のポリペンタメチレンアジパミド樹脂の製造方法は、Ｔp≧Ｔmとなる時間が０．５時間以上２時間以下であることが好ましい。 Tm + 10 ≦ Tp max ≦ Tm + 20
H-Tp max ≤ 5 (where Tp ≥ Tm)
In the method for producing the polypentamethylene adipamide resin of the present invention, it is preferable that the time when Tp ≧ Tm is 0.5 hours or more and 2 hours or less.
　本発明のポリペンタメチレンアジパミド樹脂の製造方法は、植物由来原料から得られた１，５－ジアミノペンタンを用いることが好ましい。 The method for producing the polypentamethylene adipamide resin of the present invention preferably uses 1,5-diaminopentane obtained from a plant-derived raw material.
　本発明により、前バッチのポリマーが一部残存した状態でバッチ重合を繰り返しても、色調の優れたポリペンタメチレンアジパミド樹脂を得ることができる。 According to the present invention, a polypentamethylene adipamide resin having an excellent color tone can be obtained even when batch polymerization is repeated in a state where a part of the polymer of the previous batch remains.
　以下本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
　本発明は、１，５－ジアミノペンタンとアジピン酸からポリペンタメチレンアジパミド樹脂を加圧してから放圧するバッチ重合を繰り返すことにより製造する方法に関する。加圧とは大気圧以上に圧力を高める操作を指し、放圧とは加圧状態から大気圧まで圧力を減じる操作を指す。これを繰り返すことにより製造するとは、モノマーをバッチ式重合装置に仕込んでから加圧、放圧を経て重合を終了しポリマーを排出するまでを１サイクルとしたとき、サイクル間で装置内を洗浄することなく次のサイクルを行うことであり、重合装置内に前バッチの残存ポリマーを有した状態で繰り返し重合することを指す。 The present invention relates to a process for producing a polypentamethylene adipamide resin from 1,5-diaminopentane and adipic acid by pressurizing and releasing the batch polymerization. Pressurization refers to an operation for increasing the pressure above atmospheric pressure, and pressure release refers to an operation for decreasing the pressure from a pressurized state to atmospheric pressure. Manufacturing by repeating this means that the inside of the apparatus is washed between cycles when one cycle is from the charging of the monomer into the batch polymerization apparatus to the completion of the polymerization through pressurization and release, and the discharge of the polymer. It means that the next cycle is carried out without repeating, and indicates that the polymerization is repeated with the remaining polymer in the previous batch in the polymerization apparatus.
　本発明で用いるポリペンタメチレンアジパミド樹脂は、主としてポリペンタメチレンアジパミド単位からなるポリアミド樹脂であれば特に制限はない。ここでいう主としてとは、繰り返し単位の９０モル％以上がペンタメチレンアジパミド単位で構成されることを指す。ペンタメチレンアジパミド単位とは、１，５－ジアミノペンタンとアジピン酸とから構成される構造単位である。本発明の効果を損なわない範囲において１０モル％未満の他の共重合成分を含んでもよいが、よりペンタメチレンアジパミド単位を多く含むことが好ましく、９４モル％以上であることがより好ましく、９７モル％以上であることがさらに好ましい。また、バイオマス由来の化合物から得られた１，５－ジアミノペンタンを使用する場合に特に効果を発揮する。このような物質は、従来から用いられている有機合成品とは異なる不純物を含んで樹脂が着色しやすいことがあるが、本発明の方法によれば、このような場合でも着色を抑えて色調を改善させることができる。 The polypentamethylene adipamide resin used in the present invention is not particularly limited as long as it is a polyamide resin mainly composed of polypentamethylene adipamide units. Here, mainly means that 90 mol% or more of the repeating units are composed of pentamethylene adipamide units. The pentamethylene adipamide unit is a structural unit composed of 1,5-diaminopentane and adipic acid. In the range not impairing the effect of the present invention, it may contain other copolymerization component of less than 10 mol%, but preferably contains more pentamethylene adipamide units, more preferably 94 mol% or more, More preferably, it is 97 mol% or more. In addition, it is particularly effective when 1,5-diaminopentane obtained from a biomass-derived compound is used. Such a substance may contain impurities different from organic synthetic products that have been used in the past, and the resin may be easily colored. Can be improved.
　バイオマス由来の化合物から得られた１，５－ジアミノペンタンとは、モノマー合成工程において、グルコースやリジンなどのバイオマス由来の化合物から、酵素反応や、酵母反応、発酵反応などによって合成されるものである。これらの方法によれば、２，３，４，５－テトラヒドロピリジンやピペリジンといった化合物の含有量が少なく、高純度の１，５－ジアミノペンタンを調整できるため、溶融貯留安定性の高いポリペンタメチレンアジパミド樹脂となるため好ましい。具体的には、特開2002-223771号公報、特開2004-000114号公報、特開2004-208646号公報、特開2004-290091号公報や、特開2004-298034号公報、特開2002-223770号公報、特開2004-222569号公報等に開示された１，５－ジアミノペンタン、あるいは１，５－ジアミノペンタン・塩酸塩、１，５－ジアミノペンタン・アジピン酸塩を用いて重合されたポリペンタメチレンアジパミド樹脂であることが好ましく、より純度の高い原料を得やすいことから、１，５－ジアミノペンタン・アジピン酸塩を用いて重合されることが好ましい。またアジピン酸や、他のジアミン成分、ジカルボン酸成分については従来公知の方法で製造されたものを用いればよい。 1,5-Diaminopentane obtained from a biomass-derived compound is synthesized from a biomass-derived compound such as glucose or lysine by enzymatic reaction, yeast reaction, fermentation reaction, etc. in the monomer synthesis step. . According to these methods, polypentamethylene having a high melt storage stability can be prepared because the content of compounds such as 2,3,4,5-tetrahydropyridine and piperidine is small and high-purity 1,5-diaminopentane can be prepared. Since it becomes an adipamide resin, it is preferable. Specifically, JP-A-2002-223771, JP-A-2004-000114, JP-A-2004-208646, JP-A-2004-290091, JP-A-2004-298034, JP-A-2002- Polymerized using 1,5-diaminopentane, or 1,5-diaminopentane / hydrochloride, 1,5-diaminopentane / adipate disclosed in JP-A-223770, JP-A-2004-222569, etc. A polypentamethylene adipamide resin is preferable, and it is preferable to polymerize using 1,5-diaminopentane adipate because it is easy to obtain a raw material with higher purity. Moreover, what is necessary is just to use what was manufactured by the conventionally well-known method about adipic acid, another diamine component, and a dicarboxylic acid component.
　また本発明のポリペンタメチレンアジパミド樹脂は、１，５－ジアミノペンタンや、アジピン以外に、本発明の目的を損なわない範囲で他の化合物を共重合されたものであってもよく、例えば下記の成分から誘導される構造単位を含んでいてもよい。 The polypentamethylene adipamide resin of the present invention may be copolymerized with 1,5-diaminopentane or other compounds in addition to adipine within a range not impairing the object of the present invention. Structural units derived from the following components may be included.
　例えば脂肪族ジカルボン酸（シュウ酸、マロン酸、コハク酸、グルタル酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、ブラシリン酸、テトラデカン二酸、ペンタデカン二酸、オクタデカン二酸など）、脂環式ジカルボン酸（シクロヘキサンジカルボン酸など）、芳香族ジカルボン酸（テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、ジフェニルジカルボン酸、アントラセンジカルボン酸、フェナントレンジカルボン酸、ジフェニルエーテルジカルボン酸、ジフェノキシエタンジカルボン酸、ジフェニルエタンジカルボン酸、１，４－シクロヘキサンジカルボン酸、５－ナトリウムスルホイソフタル酸、５－テトラブチルホスホニウムイソフタル酸、など）から誘導される構造単位を含むことができる。 For example, aliphatic dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid, octadecaneic acid Diacids), alicyclic dicarboxylic acids (cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxy Ethanedicarboxylic acid, diphenylethanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, etc.) It is possible.
　またエチレンジアミン、１，３－ジアミノプロパン、１，４－ジアミノブタン、１，６－ジアミノヘキサン、１，７－ジアミノヘプタン、１，８－ジアミノオクタン、１，９－ジアミノノナン、１，１０－ジアミノデカン、１，１１－ジアミノウンデカン、１，１２－ジアミノドデカン、１，１３－ジアミノトリデカン、１，１４－ジアミノテトラデカン、１，１５－ジアミノペンタデカン、１，１６－ジアミノヘキサデカン、１，１７－ジアミノヘプタデカン、１，１８－ジアミノオクタデカン、１，１９－ジアミノノナデカン、１，２０－ジアミノエイコサン、２－メチル－１，５－ジアミノペンタンなどの脂肪族ジアミン、シクロヘキサンジアミン、ビス－（４－アミノヘキシル）メタンのような脂環式ジアミン、キシリレンジアミンのような芳香族ジアミンなどにから誘導される構造単位を含むことができる。 Also ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminohepta Aliphatic diamines such as decane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane, cyclohexanediamine, bis- (4-amino (Hexyl) alicyclic diamines such as methane, xylylenediamine Structural units derived from such aromatic diamines such as may include.
　また６－アミノカプロン酸、１１－アミノウンデカン酸、１２－アミノドデカン酸、パラアミノメチル安息香酸などのアミノ酸、ε－カプロラクタム、ω－ラウロラクタムなどのラクタムから誘導される構造単位を含むことができる。 It may also contain structural units derived from amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and lactams such as ε-caprolactam and ω-laurolactam.
　本発明では、攪拌機を具備した重合装置を用いることが必須である。攪拌機を有しない場合は、重合装置内のモノマーないしポリマーへの伝熱が不均一になり、それらの突沸を引き起こして、装置内壁に付着した残存ポリマーが増加し着色原因となることなどがある。攪拌翼の形状に特に制限はないが、ディスクタービン型、傾斜パドル型、プロペラ型、アンカー型、ヘリカルリボン型などが一般的に採用されるが、液粘性が高くなる系であることから、傾斜パドル型、アンカー型、ヘリカルリボン型が好ましく使用される。攪拌機回転数は通常１０～２００rpm程度、好ましくは２０～１５０rpm程度、最も好ましくは３０～１００rpm程度が採用され、重合の段階に応じて回転数レベルを変更することもできる。 In the present invention, it is essential to use a polymerization apparatus equipped with a stirrer. When the stirrer is not provided, heat transfer to the monomer or polymer in the polymerization apparatus becomes non-uniform, causing bumping of the polymer and increasing the residual polymer adhering to the inner wall of the apparatus, which may cause coloring. There are no particular restrictions on the shape of the stirring blades, but disk turbine type, inclined paddle type, propeller type, anchor type, helical ribbon type, etc. are generally adopted, but since the liquid viscosity is high, it is inclined Paddle type, anchor type and helical ribbon type are preferably used. The rotation speed of the stirrer is generally about 10 to 200 rpm, preferably about 20 to 150 rpm, and most preferably about 30 to 100 rpm. The rotation speed level can be changed depending on the polymerization stage.
　重合中、重合装置の内圧Ｐ［MPa（絶対圧）］の最大値Ｐmax［MPa（絶対圧）］は１．０MPa以上であることが必須であり、好ましくは１．３MPa以上、さらに好ましくは１．７MPa以上である。内圧Ｐ［MPa（絶対圧）］の最大値Ｐmaxが１．０MPa未満の場合、モノマー成分である１，５－ジアミノペンタンの蒸発量が多くなり、モルバランスが崩れて得られるポリペンタメチレンアジパミド樹脂の重合度やアミノ基量が低くなることがある。内圧Ｐ［MPa（絶対圧）］の最大値Ｐmaxの上限は特にないが、重合装置の耐圧などを考慮して好ましくは３．０MPa以下、さらに好ましくは２．０MPa以下が採用される。 During the polymerization, the maximum value P max [MPa (absolute pressure)] of the internal pressure P [MPa (absolute pressure)] of the polymerization apparatus must be 1.0 MPa or more, preferably 1.3 MPa or more, more preferably 1.7 MPa or more. When the maximum value P max of the internal pressure P [MPa (absolute pressure)] is less than 1.0 MPa, the amount of evaporation of 1,5-diaminopentane, which is a monomer component, increases, resulting in the polypentamethylene azimuth obtained by breaking the molar balance. The degree of polymerization and the amount of amino groups of the pamide resin may be lowered. The upper limit of the maximum value P max of the internal pressure P [MPa (absolute pressure)] is not particularly limited, but preferably 3.0 MPa or less, more preferably 2.0 MPa or less in consideration of the pressure resistance of the polymerization apparatus.
　本発明では、重合装置の内圧を大気圧に戻す操作（放圧）の際に、放圧時間と内圧Ｐの自然対数が直線関係になるように、圧力を制御することと、内圧Ｐが０．４MPaから０．１MPa（大気圧）になるまでの放圧時間を２０分以上にすることが極めて重要であり、具体的には次式で示される。 In the present invention, during the operation of returning the internal pressure of the polymerization apparatus to atmospheric pressure (release pressure), the pressure is controlled so that the natural logarithm of the pressure release time and the internal pressure P is linear, and the internal pressure P is 0. It is extremely important to set the pressure release time from 4 MPa to 0.1 MPa (atmospheric pressure) to 20 minutes or more. Specifically, it is expressed by the following equation.
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
　ここで、Ｐ（θ）は、放圧開始からの経過時間θにおける圧力を示す。－［ln(0.4)－ln(0.1)］／θ0.4-0.1は、内圧Ｐが０．４および０．１のとき（つまりln（Ｐ）がln(0.4)およびln(0.1)のとき）の二点を結ぶ直線の傾きを意味し、内圧Ｐが０．４MPaから０．１MPa（大気圧）になるまでの放圧時間であるθ0.4-0.1（分）に対する圧力の対数値の差で表したものである。たとえば内圧Ｐが０．４MPaから０．１MPaになるまでの放圧時間を２０分とすると、－［ln(0.4)－ln(0.1)］／２０＝－０．０６９３となる。 Here, P (θ) indicates a pressure at an elapsed time θ from the start of pressure release. -[Ln (0.4) -ln (0.1)] / θ 0.4-0.1 when the internal pressure P is 0.4 and 0.1 (that is, when ln (P) is ln (0.4) and ln (0.1)) The slope of the straight line connecting the two points, and the difference in the logarithmic value of the pressure relative to θ 0.4-0.1 (min), which is the pressure release time until the internal pressure P changes from 0.4 MPa to 0.1 MPa (atmospheric pressure) It is a representation. For example, assuming that the pressure release time until the internal pressure P becomes 0.4 MPa to 0.1 MPa is 20 minutes, − [ln (0.4) −ln (0.1)] / 20 = −0.0693.
　上記直線関係は厳密に直線関係であることが好ましいが、実際の操作においては若干の圧力調整代が生じるため、必ずしも厳密である必要はなく概ね直線関係であればよい。具体的には内圧Ｐが０．４MPaを超える領域では±０．０５MPa程度、内圧Ｐが０．４MPa以下の領域では±０．０２MPa程度ずれても同様の効果が得られるので、この程度であれば直線関係にあるとする。この範囲を逸脱して急激に圧力を調整すると、本発明の効果が得られないばかりか、縮合水の蒸気化に伴って奪われる蒸発潜熱が大きくなりすぎ、内液が固化して重合不能になることがある。 Although it is preferable that the above linear relationship is strictly a linear relationship, in actual operation, a slight pressure adjustment fee is generated. Specifically, the same effect can be obtained even if the internal pressure P exceeds 0.4 MPa in the region where the internal pressure P exceeds 0.4 MPa, and the internal pressure P in the region where the internal pressure P is 0.4 MPa or less is shifted by about ± 0.02 MPa. It is assumed that there is a linear relationship. If the pressure is suddenly adjusted out of this range, not only the effect of the present invention can be obtained, but also the latent heat of evaporation taken away with the vaporization of the condensed water becomes too large, so that the internal liquid is solidified and cannot be polymerized. May be.
　公知の方法、例えば「ポリアミド樹脂ハンドブック」（福本修編）日刊工業新聞社1988年1月30日発行の記載によれば、放圧時間と内圧Ｐが直線関係になるよう制御している。しかし、このような方法では内圧Ｐが０．４MPa以下の領域で、縮合水が蒸気する際にポリマーが発泡した状態となって非常に嵩高くなり、装置の内壁上部に付着するポリマーが極端に増加し、次バッチの色調悪化原因となる。発泡を避けるために圧力低下速度を下げると、放圧時間が長くなりすぎて色調悪化の原因となる。本発明の方法によれば、内圧Ｐが０．４MPa以下の領域においても、ポリマーの発泡を十分に抑えられ、かつ熱履歴を増大させることなく色調悪化を抑制でき、さらに商業的な連続バッチ生産に耐えうる程の再現性を有する。 According to a known method, for example, “Polyamide resin handbook” (Osamu Fukumoto) published by Nikkan Kogyo Shimbun, January 30, 1988, the pressure release time and the internal pressure P are controlled to be in a linear relationship. However, in such a method, in the region where the internal pressure P is 0.4 MPa or less, when the condensed water is vaporized, the polymer is in a foamed state and becomes very bulky, and the polymer adhering to the upper part of the inner wall of the apparatus is extremely large. It increases and causes color deterioration of the next batch. If the pressure reduction rate is lowered to avoid foaming, the pressure release time becomes too long, causing color deterioration. According to the method of the present invention, even in the region where the internal pressure P is 0.4 MPa or less, the foaming of the polymer can be sufficiently suppressed, and the color tone deterioration can be suppressed without increasing the heat history, and further, commercial continuous batch production Reproducibility to withstand.
　本発明において、内圧Ｐが０．４MPaから０．１MPa（大気圧）になるまでの放圧時間は、２０分以上であることが必須であり、２５分以上かけることが好ましい。２０分より短い時間で大気圧に戻すと、ポリマーが発泡して次バッチの色調悪化原因となる。上限は特にないが、融点以上に保持する時間が２時間より長い場合には、得られるポリペンタメチレンアジパミド樹脂が劣化する傾向があるため、通常１．５時間以内が選択される。 In the present invention, the pressure release time until the internal pressure P becomes 0.4 MPa to 0.1 MPa (atmospheric pressure) is indispensable to be 20 minutes or more, preferably 25 minutes or more. If the pressure is returned to atmospheric pressure in a time shorter than 20 minutes, the polymer foams and causes the color tone of the next batch to deteriorate. Although there is no particular upper limit, when the retention time above the melting point is longer than 2 hours, the resulting polypentamethylene adipamide resin tends to be deteriorated, and therefore usually within 1.5 hours is selected.
　本発明では、重合装置内圧Ｐ［MPa（絶対圧）］が重合中の全期間にわたり０．１MPa以上、すなわち大気圧以上に保たれることが好ましい。内圧Ｐが０．１MPaを下回って減圧になる場合も、ポリマーが発泡して次バッチの色調悪化原因となることがある。従って本発明では、重合度を調整するために、放圧終了後に不活性ガスを流通させて縮合水を除去する操作（常圧重合）を行うことが好ましい。不活性ガスとしては、ヘリウムガス、アルゴンガス、窒素ガスなどが挙げられ、中でも窒素ガスが製造コストの面から好ましく用いられる。この常圧重合時間に下限は特にないが、重合度を適当に高めるため、通常５分以上、好ましくは１０分以上実施される。上限は、色調悪化を防ぐためにＴp≧Ｔmとなる時間が２時間以内になるよう、通常１時間以内が選択される。常圧重合中は、空気を重合装置内に漏れ混ませないよう、流通させる不活性ガスの出口を水シールすることが好ましい。 In the present invention, it is preferable that the internal pressure P [MPa (absolute pressure)] of the polymerization apparatus is maintained at 0.1 MPa or higher, that is, atmospheric pressure or higher over the entire period of polymerization. Even when the internal pressure P is less than 0.1 MPa and the pressure is reduced, the polymer may foam and cause the color tone of the next batch to deteriorate. Therefore, in the present invention, in order to adjust the degree of polymerization, it is preferable to perform an operation (normal pressure polymerization) of passing the inert gas after the end of the pressure release to remove the condensed water. Examples of the inert gas include helium gas, argon gas, and nitrogen gas, and nitrogen gas is preferably used from the viewpoint of manufacturing cost. Although there is no particular lower limit to the normal pressure polymerization time, it is usually carried out for 5 minutes or longer, preferably 10 minutes or longer in order to appropriately increase the degree of polymerization. The upper limit is normally selected within 1 hour so that the time when Tp ≧ Tm is within 2 hours in order to prevent the deterioration of the color tone. During normal pressure polymerization, it is preferable to seal the outlet of the inert gas to be circulated with water so that air does not leak into the polymerization apparatus.
　本発明で用いるモノマーである、１，５－ジアミノペンタンとアジピン酸は、これらの塩の水溶液で添加することが好ましい。モノマー水溶液の水分率はハンドリングや計量の都合を考慮して調整すればよいが、１０％以上６０％以下が好ましく、１０％以上５０％以下がさらに好ましく採用される。一旦重合装置とは別の装置で任意の水分率に濃縮してから使用することもでき、この場合の濃縮後水分率は１０％以上３０％以下が好ましく、１０％以上２０％以下がさらに好ましい。さらに、重合中に留出する１，５－ジアミノペンタンを補ったり、得られるポリペンタメチレンアジパミド樹脂を所望の末端基にあわせるため、重合前に１，５－ジアミノペンタンまたはアジピン酸を追添加することも可能である。 The monomers used in the present invention, 1,5-diaminopentane and adipic acid are preferably added as an aqueous solution of these salts. The water content of the monomer aqueous solution may be adjusted in consideration of handling and measurement, but is preferably 10% to 60%, more preferably 10% to 50%. It can also be used after being concentrated to an arbitrary moisture content in an apparatus different from the polymerization apparatus. In this case, the moisture content after concentration is preferably 10% to 30%, more preferably 10% to 20%. . Furthermore, 1,5-diaminopentane or adipic acid is added before the polymerization in order to compensate for 1,5-diaminopentane distilled during the polymerization or to adjust the resulting polypentamethylene adipamide resin to a desired end group. It is also possible to add.
　また、本発明では、加圧してから放圧し重合を完結するまでに、重合系を加熱することにより重合装置の内液温度は上昇し続ける。内液温度を目標温度まで効率的に高めるために、重合初期の加熱温度は内液の目標温度より高くし、内液温度が、得られるポリマーの融点を超えたところで、加熱温度を内液の目標温度と同等程度まで下げることが好ましい。このとき、得られるポリペンタメチレンアジパミド樹脂の融点をＴm、重合中のポリペンタメチレンアジパミド樹脂温度をＴp［℃］、Ｔpの最高温度をＴpmax［℃］、重合中の加熱温度をＨ［℃］としたときに、下記関係式を満足する範囲で製造することが好ましい。 Further, in the present invention, the internal liquid temperature of the polymerization apparatus continues to rise by heating the polymerization system from the time of pressurization to the release of pressure to complete the polymerization. In order to efficiently increase the internal liquid temperature to the target temperature, the heating temperature at the initial stage of polymerization is set higher than the target temperature of the internal liquid, and when the internal liquid temperature exceeds the melting point of the obtained polymer, It is preferable to lower it to the same level as the target temperature. At this time, the melting point of the obtained polypentamethylene adipamide resin is Tm, the polypentamethylene adipamide resin temperature during polymerization is Tp [° C.], the maximum temperature of Tp is Tp max [° C.], and the heating temperature during polymerization It is preferable to manufacture in the range which satisfies the following relational expression, when H is H [° C.].
　　　Ｔm＋１０　≦　Ｔpmax　≦　Ｔm＋２０
　　　Ｈ－Ｔpmax　≦　５　（ただし、Ｔp≧Ｔm）
　ここで、得られるポリペンタメチレンアジパミド樹脂の融点Ｔm［℃］とは、最終的に得ようとするポリペンタメチレンアジパミド樹脂の目標融点を意味する。 Tm + 10 ≦ Tp max ≦ Tm + 20
H-Tp max ≤ 5 (where Tp ≥ Tm)
Here, the melting point Tm [° C.] of the obtained polypentamethylene adipamide resin means the target melting point of the polypentamethylene adipamide resin to be finally obtained.
　なお、最終的に得られたポリペンタメチレンアジパミド樹脂の融点は、示差走査熱分析（ＤＳＣ）により測定する。ポリペンタメチレンアジパミド樹脂は二つの融点ピークを示すが、高い方のピーク温度を融点とする。 The melting point of the finally obtained polypentamethylene adipamide resin is measured by differential scanning calorimetry (DSC). Polypentamethylene adipamide resin shows two melting points, and the higher peak temperature is taken as the melting point.
　重合中のポリペンタメチレンアジパミド樹脂温度Ｔp［℃］は、重合装置内に挿入された温度計により通常測定される。装置内で温度分布がある場合は、平均温度をＴp［℃］とする。 The polypentamethylene adipamide resin temperature Tp [° C.] during polymerization is usually measured by a thermometer inserted in the polymerization apparatus. If there is a temperature distribution in the apparatus, the average temperature is Tp [° C.].
　Ｔpｍａｘ［℃］はＴp［℃］の最高温度であり、通常は重合の最終段階の温度である。 Tp max [° C.] is the maximum temperature of T p [° C.] and is usually the temperature at the final stage of the polymerization.
　重合中の加熱温度Ｈ［℃］は、重合装置との伝熱面の温度であり、通常は熱媒体の温度を指す。熱媒ジャケットを装備した重合装置の場合、ジャケット内部の温度を指し、重合装置内部に伝熱用のコイルを挿入する場合、コイル内部の温度を指す。また、ジャケットとコイルの双方を装備した重合装置の場合は、いずれか高い方の温度を指す。重合装置との伝熱面の温度に装置内で温度分布がある場合は、最も高い温度をＨとする。重合中の加熱温度Ｈを厳密に制御するために、重合装置とは別の独立した熱媒ボイラーをもち、そこから温度制御された熱媒体を重合装置のジャケットおよび／またはコイルに供給する方法が好ましい。この場合、熱媒体は蒸気や液体で供給される。 The heating temperature H [° C.] during polymerization is the temperature of the heat transfer surface with the polymerization apparatus, and usually refers to the temperature of the heat medium. In the case of a polymerization apparatus equipped with a heat medium jacket, it refers to the temperature inside the jacket, and when a heat transfer coil is inserted into the polymerization apparatus, it refers to the temperature inside the coil. Moreover, in the case of the superposition | polymerization apparatus equipped with both the jacket and the coil, the higher temperature is pointed out. If the temperature of the heat transfer surface with the polymerization apparatus has a temperature distribution in the apparatus, the highest temperature is set to H. In order to strictly control the heating temperature H during the polymerization, there is a method in which an independent heating medium boiler separate from the polymerization apparatus is provided and the temperature-controlled heating medium is supplied to the jacket and / or coil of the polymerization apparatus. preferable. In this case, the heat medium is supplied as vapor or liquid.
　本発明では、上記したとおり、次の関係式を満たすことが好ましい。 In the present invention, as described above, it is preferable to satisfy the following relational expression.
　　　Ｔm＋１０　≦　Ｔpmax　≦　Ｔm＋２０
　これは、重合中のポリマー温度を、Ｔm＋１０℃以上かつＴm＋２０℃以下の範囲に制御することを示す。重合中のポリマー温度をかかる範囲内に制御すると、ポリマーの溶融粘度が上がりすぎることなく重合装置内での流動性が良好に保たれる一方、得られるポリアミド樹脂の色調も良好である。 Tm + 10 ≦ Tp max ≦ Tm + 20
This indicates that the polymer temperature during the polymerization is controlled in the range of Tm + 10 ° C. or more and Tm + 20 ° C. or less. When the polymer temperature during the polymerization is controlled within such a range, the fluidity in the polymerization apparatus is kept good without excessively increasing the melt viscosity of the polymer, while the color tone of the resulting polyamide resin is also good.
　本発明ではまた、上記したとおり、同時に次の関係式を満たすことが好ましい。 In the present invention, it is also preferable to satisfy the following relational expression at the same time as described above.
　　　Ｈ－Ｔpmax　≦　５　（ただし、Ｔp≧Ｔm）
　これは、ポリマーの融点以上の領域では、重合中の加熱温度ＨとＴpの最高温度Ｔpmaxの差を５℃以下に抑えること、すなわち異常加熱部の発生が抑制されていることを示す。ＨとＴpmaxの差をこの範囲に制御すると、得られるポリアミド樹脂の色調を良好に保つことができる。 H-Tp max ≤ 5 (where Tp ≥ Tm)
This indicates that in the region above the melting point of the polymer, the difference between the heating temperature H during polymerization and the maximum temperature Tp max between Tp is suppressed to 5 ° C. or less, that is, the occurrence of abnormally heated portions is suppressed. By controlling the difference between H and Tp max within this range, the color tone of the resulting polyamide resin can be kept good.
　なお、ＨとＴpmaxの差を小さくするには、熱媒体からポリマーへの伝熱を効率的に行えば良い。このためには、重合装置に撹拌装置を具備することのほか、例えば、伝熱面積を十分にもたせることや、伝熱面へ供給する熱媒体の温度を厳密に制御することなどにより達成される。 In order to reduce the difference between H and Tp max , heat transfer from the heat medium to the polymer may be efficiently performed. For this purpose, in addition to providing the polymerization apparatus with a stirring device, for example, it can be achieved by providing a sufficient heat transfer area or by strictly controlling the temperature of the heat medium supplied to the heat transfer surface. .
　さらに、本発明においては、重合系内を得られるポリペンタメチレンアジパミド樹脂の融点以上に保持する時間が、得られるポリペンタメチレンアジパミド樹脂の分子量に影響を及ぼすため、重合系内の温度をポリペンタメチレンアジパミド樹脂の融点以上に保持する時間が０．５時間以上２時間以下に制御することが好ましく、１時間以上２時間以下に制御することがより好ましい。融点以上に保持する時間をこの範囲に制御する場合には、分子量の上昇を十分にできる一方、１，５－ジアミノペンタンの揮発や環化が促進されることもなく、得られるポリペンタメチレンアジパミド樹脂が劣化することもない。 Furthermore, in the present invention, the time for maintaining the temperature within the melting point of the polypentamethylene adipamide resin obtained in the polymerization system affects the molecular weight of the resulting polypentamethylene adipamide resin. The time during which the temperature is maintained above the melting point of the polypentamethylene adipamide resin is preferably controlled to 0.5 hours or more and 2 hours or less, more preferably 1 hour or more and 2 hours or less. When the time for maintaining the melting point or higher is controlled within this range, the molecular weight can be increased sufficiently, but the volatilization and cyclization of 1,5-diaminopentane are not promoted, and the resulting polypentamethylene azimuth is obtained. Pamide resin does not deteriorate.
　本発明において、重合終了後にポリマーを排出する方法としては、不活性ガスにより重合装置を加圧し、ストランド状に押し出したポリマーを水冷後、カッティングしてペレットを得る方法が好ましく用いられる。このとき、ポリマーをできるだけ短時間で押し出すことが色調悪化抑制に効果的であり、好ましくは１時間以内、より好ましくは４０分以内、さらに好ましくは３０分以内に押し出される。 In the present invention, as a method for discharging the polymer after completion of the polymerization, a method of pressurizing the polymerization apparatus with an inert gas, cooling the polymer extruded into a strand shape with water, and cutting to obtain pellets is preferably used. At this time, extruding the polymer in as short a time as possible is effective in suppressing deterioration of the color tone, and is preferably extruded within 1 hour, more preferably within 40 minutes, and even more preferably within 30 minutes.
　本発明によって得られるポリペンタメチレンアジパミド樹脂の硫酸相対粘度は、２．１以上が好ましく、２．４以上がより好ましく、２．５以上がさらに好ましい。硫酸相対粘度がこの範囲であると、ストランド状に押し出したポリマーをカッティングする際に、ストランド径が安定し、正常形状のペレットの収率を高くできる。上限は特にないが、重合装置内に残存するポリマーが増えて収率が低下することを防ぐ観点から４．０以下とするのが好ましい。 The relative viscosity of sulfuric acid of the polypentamethylene adipamide resin obtained by the present invention is preferably 2.1 or higher, more preferably 2.4 or higher, and further preferably 2.5 or higher. When the sulfuric acid relative viscosity is within this range, the strand diameter is stable when cutting the polymer extruded into a strand shape, and the yield of pellets having a normal shape can be increased. Although there is no particular upper limit, it is preferably 4.0 or less from the viewpoint of preventing a decrease in yield due to an increase in the amount of polymer remaining in the polymerization apparatus.
　また、アミノ基量［ミリ当量/kg］は３０～７０［ミリ当量/kg］が好ましく、３５～６５［ミリ当量/kg］がより好ましく、４０～６０［ミリ当量/kg］がさらに好ましい。アミノ基量が上記好ましい範囲であると、繊維として用いた場合に染色しやすく、一方後加工における溶融時の安定性を保つことができる。 The amino group amount [milli equivalent / kg] is preferably 30 to 70 [milli equivalent / kg], more preferably 35 to 65 [milli equivalent / kg], and further preferably 40 to 60 [milli equivalent / kg]. When the amino group content is within the above preferred range, it is easy to dye when used as a fiber, while the stability during melting in post-processing can be maintained.
　硫酸相対粘度およびアミノ基量を制御するには、重合中に揮発するジアミン成分を考慮し、重合原料を仕込む際にジアミン成分をアジピン酸との等モルより過剰量添加することが好ましい。このとき添加するジアミン成分としては、モノマー成分である１，５－ジアミノペンタンのほか、エチレンジアミン、１，３－ジアミノプロパン、１，４－ジアミノブタン、１，６－ジアミノヘキサン、１，７－ジアミノヘプタン、１，８－ジアミノオクタン、１，９－ジアミノノナン、１，１０－ジアミノデカン、１，１１－ジアミノウンデカン、１，１２－ジアミノドデカン、１，１３－ジアミノトリデカン、１，１４－ジアミノテトラデカン、１，１５－ジアミノペンタデカン、１，１６－ジアミノヘキサデカン、１，１７－ジアミノヘプタデカン、１，１８－ジアミノオクタデカン、１，１９－ジアミノノナデカン、１，２０－ジアミノエイコサン、２－メチル－１，５－ジアミノペンタンなどの脂肪族ジアミン、シクロヘキサンジアミン、ビス－（４－アミノヘキシル）メタンのような脂環式ジアミン、キシリレンジアミンのような芳香族ジアミンなどを用いることができる。 In order to control the relative viscosity of sulfuric acid and the amount of amino groups, it is preferable to add an excess of the diamine component in an equimolar amount with adipic acid when charging the polymerization raw material in consideration of the diamine component that volatilizes during the polymerization. As the diamine component to be added at this time, in addition to 1,5-diaminopentane which is a monomer component, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diamino Heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl- Aliphatic diamines such as 1,5-diaminopentane, cyclohexanedi Min, bis - (4-aminohexyl) cycloaliphatic diamines, such as methane, and aromatic diamines such as xylylenediamine may be used.
　本発明によって得られるポリペンタメチレンアジパミド樹脂は、さらに固相重合あるいは溶融押出機で高重合度化することによって、分子量を上昇させることも可能である。固相重合は、１００℃～融点の温度範囲で、真空中、あるいは不活性ガス中で加熱することにより進行する。 The molecular weight of the polypentamethylene adipamide resin obtained by the present invention can be increased by further increasing the degree of polymerization by solid phase polymerization or a melt extruder. Solid phase polymerization proceeds by heating in a vacuum or in an inert gas within a temperature range of 100 ° C. to the melting point.
　本発明のポリペンタメチレンアジパミド樹脂を製造する際には、他の成分、例えば末端封鎖剤（モノカルボン酸、モノアミン等）、酸化防止剤、耐熱安定剤（ヒンダードフェノール系、ヒドロキノン系、ホスファイト系およびこれらの置換体、ハロゲン化銅、ヨウ素化合物等）、耐候剤（レゾルシノール系、サリシレート系、ベンゾトリアゾール系、ベンゾフェノン系、ヒンダードアミン系等）、離型剤及び滑剤（脂肪族アルコール、脂肪族アミド、脂肪族ビスアミド、ビス尿素及びポリエチレンワックス等）、顔料（二酸化チタン、硫化カドミウム、フタロシアニン、カーボンブラック等）、染料（ニグロシン、アニリンブラック等）、結晶核剤（タルク、シリカ、カオリン、クレー等）、可塑剤（ｐ－オキシ安息香酸オクチル、Ｎ－ブチルベンゼンスルホンアミド等）、帯電防止剤（アルキルサルフェート型アニオン系帯電防止剤、４級アンモニウム塩型カチオン系帯電防止剤、ポリオキシエチレンソルビタンモノステアレートのような非イオン系帯電防止剤、ベタイン系両性帯電防止剤等）、難燃剤（メラミンシアヌレート、水酸化マグネシウム、水酸化アルミニウム等の水酸化物、ポリリン酸アンモニウム、臭素化ポリスチレン、臭素化ポリフェニレンオキシド、臭素化ポリカーボネート、臭素化エポキシ樹脂あるいはこれらの臭素系難燃剤と三酸化アンチモンとの組み合わせ等）、充填剤（グラファイト、硫酸バリウム、硫酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化アンチモン、酸化チタン、酸化アルミニウム、酸化亜鉛、酸化鉄、硫化亜鉛、亜鉛、鉛、ニッケル、アルミニウム、銅、鉄、ステンレス、ガラス繊維、炭素繊維、アラミド繊維、ベントナイト、モンモリロナイト、合成雲母等の粒子状、繊維状、針状、板状充填材）、他の重合体（他のポリアミド、ポリエチレン、ポリプロピレン、ポリエステル、ポリカーボネート、ポリフェニレンエーテル、ポリフェニレンスルフィド、液晶ポリマー、ポリスルホン、ポリエーテルスルホン、ＡＢＳ樹脂、ＳＡＮ樹脂、ポリスチレン等）を任意の時点で添加することができる。 When producing the polypentamethylene adipamide resin of the present invention, other components such as end-capping agents (monocarboxylic acid, monoamine, etc.), antioxidants, heat stabilizers (hindered phenols, hydroquinones, Phosphites and their substitutes, copper halides, iodine compounds, etc.), weathering agents (resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines, etc.), mold release agents and lubricants (aliphatic alcohols, fats) Amides, aliphatic bisamides, bisureas, polyethylene waxes, etc.), pigments (titanium dioxide, cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, aniline black, etc.), crystal nucleating agents (talc, silica, kaolin, clay) Etc.), plasticizer (octyl p-oxybenzoate, N-butyl) Rubenzenesulfonamide, etc.), antistatic agent (alkyl sulfate type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine type Amphoteric antistatic agents, etc.), flame retardants (melamine cyanurate, magnesium hydroxide, aluminum hydroxide and other hydroxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resins or these Combinations of brominated flame retardants and 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, Nickel, aluminum, copper, iron, stainless steel, glass fiber, carbon fiber, aramid fiber, bentonite, montmorillonite, synthetic mica and other particulate, fibrous, needle-like, plate-like fillers), other polymers (other Polyamide, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, SAN resin, polystyrene, etc.) can be added at any time.
　本発明のポリペンタメチレンアジパミド樹脂は、繊維、フィルム、シート、フィラメント、樹脂、接着剤、塗料などに有用である。具体的な用途例としては、衣料用繊維、産業資材用繊維、スイッチ類、超小型スライドスイッチ、ＤＩＰスイッチ、スイッチのハウジング、ランプソケット、結束バンド、コネクタ、コネクタのハウジング、コネクタのシェル、ＩＣソケット類、コイルボビン、ボビンカバー、リレー、リレーボックス、コンデンサーケース、モーターの内部部品、小型モーターケース、ギヤ・カム、ダンシングプーリー、スペーサー、インシュレーター、ファスナー、バックル、ワイヤークリップ、自転車ホイール、キャスター、ヘルメット、端子台、電動工具のハウジング、スターターの絶縁部分、スポイラー、キャニスター、ラジエタータンク、チャンバータンク、リザーバータンク、ヒューズボックス、エアークリーナーケース、エアコンファン、ターミナルのハウジング、ホイールカバー、吸排気パイプ、ベアリングリテーナー、シリンダーヘッドカバー、インテークマニホールド、ウォーターパイプインペラ、クラッチレリーズ、スピーカー振動板、耐熱容器、電子レンジ部品、炊飯器部品、プリンタリボンガイドなどに代表される電気・電子関連部品、自動車・車両関連部品、家電・事務電気製品部品、コンピューター関連部品、ファクシミリ・複写機関連部品、機械関連部品、その他各種用途に有用である。 The polypentamethylene adipamide resin of the present invention is useful for fibers, films, sheets, filaments, resins, adhesives, paints and the like. Specific application examples include textiles for clothing, textiles for industrial materials, switches, ultra-small slide switches, DIP switches, switch housings, lamp sockets, cable ties, connectors, connector housings, connector shells, IC sockets Class, coil bobbin, bobbin cover, relay, relay box, condenser case, motor internal parts, small motor case, gear cam, dancing pulley, spacer, insulator, fastener, buckle, wire clip, bicycle wheel, caster, helmet, terminal Base, power tool housing, starter insulation, spoiler, canister, radiator tank, chamber tank, reservoir tank, fuse box, air cleaner case, air conditioner fan, Minal housing, wheel cover, intake / exhaust pipe, bearing retainer, cylinder head cover, intake manifold, water pipe impeller, clutch release, speaker diaphragm, heat-resistant container, microwave oven part, rice cooker part, printer ribbon guide, etc. It is useful for electrical / electronic related parts, automobile / vehicle related parts, home appliance / office electrical product parts, computer related parts, facsimile / copier related parts, machine related parts, and other various applications.
　以下に実施例を示し、本発明を更に具体的に説明するが、本発明はこれら実施例の記載に限定されるものではない。
［硫酸相対粘度（ηr）］
　試料０.２５ｇを濃度９８wt％の硫酸１００mLに対して１ｇになるように溶解し、オストワルド型粘度計を用いて２５℃での流下時間（Ｔ１）を測定した。引き続き、濃度９８wt％の硫酸のみの流下時間（Ｔ２）を測定した。Ｔ２に対するＴ１の比、すなわちＴ１／Ｔ２を硫酸相対粘度とした。
［アミノ基量］
　試料１ｇを５０mLのフェノール／エタノール混合溶液（フェノール／エタノール＝８０／２０）に、３０℃で振とう溶解させて溶液とし、この溶液を０．０２Ｎの塩酸で中和滴定し要した０．０２Ｎ塩酸量を求めた。また、上記フェノール／エタノール混合溶媒（上記と同量）のみを０．０２Ｎ塩酸で中和滴定し要した０．０２Ｎ塩酸の量を求める。そしてその差から試料１ｋｇあたりのアミノ基量［ミリ当量/kg］を求めた。
［融点（Ｔm）］
　パーキンエルマー社製示差走査型熱量計ＤＳＣ－７型を用い、試料１０ｍｇを昇温速度１５℃／分にて測定して得た示差熱量曲線において吸熱側に極値を示すピークを融解ピークと判断し、極値を与える温度を融点Ｔm（℃）とした。なお複数の極値が存在する場合は高温側の極値を融点とした。
［黄化度（ＹＩ）］
　スガ試験機（株）製のカラーコンピューターを用いてペレットのＹＩ値を測定した。
参考例１（リジン脱炭酸酵素の調整）
　E.coli JM109株の培養は以下のように行った。まず、この菌株をＬＢ培地５mLに１白金耳植菌し、３０℃ で２４時間振とうして前培養を行った。 Examples Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples.
[Sulfuric acid relative viscosity (ηr)]
0.25 g of a sample was dissolved to 1 g with respect to 100 mL of sulfuric acid having a concentration of 98 wt%, and the flow time (T1) at 25 ° C. was measured using an Ostwald viscometer. Subsequently, the flow time (T2) of only sulfuric acid having a concentration of 98 wt% was measured. The ratio of T1 to T2, that is, T1 / T2, was defined as sulfuric acid relative viscosity.
[Amino group content]
1 g of a sample was dissolved in 50 mL of a phenol / ethanol mixed solution (phenol / ethanol = 80/20) with shaking at 30 ° C. to obtain a solution, and this solution was neutralized and titrated with 0.02N hydrochloric acid to obtain 0.02N. The amount of hydrochloric acid was determined. Further, only the phenol / ethanol mixed solvent (the same amount as above) was neutralized and titrated with 0.02N hydrochloric acid to determine the amount of 0.02N hydrochloric acid required. From the difference, the amino group amount [milli equivalent / kg] per 1 kg of the sample was determined.
[Melting point (Tm)]
Using a differential scanning calorimeter DSC-7 manufactured by PerkinElmer, Inc., a peak showing an extreme value on the endothermic side in a differential calorific curve obtained by measuring 10 mg of a sample at a heating rate of 15 ° C./min is judged as a melting peak. The temperature giving the extreme value was defined as the melting point Tm (° C.). When a plurality of extreme values exist, the extreme value on the high temperature side was taken as the melting point.
[Yellowness (YI)]
The YI value of the pellet was measured using a color computer manufactured by Suga Test Instruments Co., Ltd.
Reference example 1 (adjustment of lysine decarboxylase)
The E. coli JM109 strain was cultured as follows. First, this platinum strain was inoculated into 5 mL of LB medium, and precultured by shaking at 30 ° C. for 24 hours.
　次に、ＬＢ培地５０mLを５００mLの三角フラスコに入れ、予め１１５℃、１０分間蒸気滅菌した。この培地に前培養した上記菌株を植え継ぎ、振幅３０cmで、１８０rpmの条件下で、１Ｎ塩酸水溶液でｐＨを６．０に調整しながら、２４時間培養した。こうして得られた菌体を集め、超音波破砕および遠心分離により無細胞抽出液を調製した。これらのリジン脱炭酸酵素活性の測定を定法に従って行った（日本生化学会編　生化学実験講座11「アミノ酸代謝と生体アミン　上」P.179-191(1976)）。 Next, 50 mL of LB medium was placed in a 500 mL Erlenmeyer flask and steam sterilized in advance at 115 ° C. for 10 minutes. The strain was precultured in this medium, and cultured for 24 hours under the condition of 30 cm in amplitude and 180 rpm while adjusting the pH to 6.0 with 1N aqueous hydrochloric acid. The bacterial cells thus obtained were collected and a cell-free extract was prepared by ultrasonic disruption and centrifugation. These lysine decarboxylase activities were measured according to a conventional method (Japan Biochemical Society, edited by Biochemical Experiment Course 11 “Amino Acid Metabolism and Biogenic Amine” P.179-191 (1976)).
　リジンを基質とした場合、本来の主経路と考えられるリジンモノオキシゲナーゼ、リジンオキシダーゼおよびリジンムターゼによる転換が起こり得るので、この反応系を遮断する目的で、７５℃で５分間、E.coli JM109株の無細胞抽出液を加熱した。さらにこの無細胞抽出液を４０％飽和および５５％飽和硫酸アンモニウムにより分画した。こうして得られた粗精製リジン脱炭酸酵素溶液を用いて、リジンから１，５－ジアミノペンタンの生成を行った。
参考例２（１，５－ジアミノペンタンの製造）
　リジン塩酸塩（和光純薬工業製）が５０mM、ピリドキサルリン酸（和光純薬工業製）が０．１mM、粗精製リジン脱炭酸酵素（参考例１で調製）が４０ｍｇ/Lとなるように調製した水溶液１０００mLを、０．１Ｎ塩酸水溶液でｐＨを５．５～６．５に維持しながら、４５℃で４８時間反応させ、１，５－ジアミノペンタン塩酸塩を得た。この水溶液に水酸化ナトリウムを添加することによって１，５－ジアミノペンタン塩酸塩を１，５－ジアミノペンタンに変換し、クロロホルムで抽出して、減圧蒸留（８mmHg、７０℃）することにより、１，５－ジアミノペンタンを得た。
参考例３（ポリペンタメチレンアジパミドの製造）
　参考例２で得られた１，５－ジアミノペンタン１２．３ｋｇをイオン交換水３０．０ｋｇ中に溶解した水溶液を、氷浴に浸して撹拌しているところに、１７．７ｋｇのアジピン酸（カーク製）を少量ずつ添加していき、中和点近傍では４０℃のウオーターバスで加温して内温を３３℃とし、ｐＨが８．３２の１，５－ジアミノペンタンとアジピン酸の等モル塩の５０重量％水溶液６０．０ｋｇを調製した。この水溶液を、ダブルヘリカルリボン翼をもった撹拌機と熱媒ジャケットを装備した内容積８０Lのバッチ式重合缶に入れた。重合缶内を充分に窒素置換した後、３０rpmで撹拌しながら２６０℃で加熱を開始した。なお、加熱は重合装置から独立した熱媒ボイラーから熱媒蒸気を供給する方式であり、ジャケット内部に挿入した温度計の指示温度が規定温度になるよう、ボイラーでの熱媒加熱を調整した。缶内圧力が０．３MPa（絶対圧）に到達した時点から濃縮を開始し、重合缶内圧を一定に保つように放圧弁の開度を調整した。留出水量が２４．７ｋｇになったら放圧弁を閉止し、加熱温度を２８５℃に変更した。缶内圧力が１．８MPa（絶対圧：Ｐmax）に到達した時点で加熱温度を２７０℃に変更し、缶内圧力を維持した。内温が２５４℃に到達した時点から下式でＰmax＝１．８、θ0.4-0.1＝２０分とした放圧カーブに従い４２分かけて徐々に０．１MPa（絶対圧）すなわち大気圧まで放圧した。 When lysine is used as a substrate, conversion by lysine monooxygenase, lysine oxidase and lysine mutase, which are considered to be the main main pathways, can occur. Therefore, for the purpose of blocking this reaction system, the E. coli JM109 strain is used at 75 ° C. for 5 minutes. The cell-free extract was heated. Furthermore, this cell-free extract was fractionated with 40% saturated and 55% saturated ammonium sulfate. The crude purified lysine decarboxylase solution thus obtained was used to produce 1,5-diaminopentane from lysine.
Reference Example 2 (Production of 1,5-diaminopentane)
It was prepared so that lysine hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) was 50 mM, pyridoxal phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) was 0.1 mM, and crude lysine decarboxylase (prepared in Reference Example 1) was 40 mg / L. 1000 mL of the aqueous solution was reacted at 45 ° C. for 48 hours while maintaining the pH at 5.5 to 6.5 with 0.1N hydrochloric acid aqueous solution to obtain 1,5-diaminopentane hydrochloride. By adding sodium hydroxide to this aqueous solution, 1,5-diaminopentane hydrochloride is converted to 1,5-diaminopentane, extracted with chloroform, and distilled under reduced pressure (8 mmHg, 70 ° C.) to obtain 1, 5-Diaminopentane was obtained.
Reference Example 3 (Production of polypentamethylene adipamide)
An aqueous solution obtained by dissolving 12.3 kg of 1,5-diaminopentane obtained in Reference Example 2 in 30.0 kg of ion-exchanged water is immersed in an ice bath and stirred, and 17.7 kg of adipic acid (kirk) In the vicinity of the neutralization point in a water bath at 40 ° C to bring the internal temperature to 33 ° C, and equimolar of 1,5-diaminopentane and adipic acid having a pH of 8.32. 60.0 kg of a 50% by weight aqueous solution of salt was prepared. This aqueous solution was put into a batch type polymerization can having an internal volume of 80 L equipped with a stirrer having a double helical ribbon blade and a heating medium jacket. After sufficiently substituting the inside of the polymerization can with nitrogen, heating was started at 260 ° C. with stirring at 30 rpm. The heating is a system in which the heat medium vapor is supplied from a heat medium boiler independent from the polymerization apparatus, and the heat medium heating in the boiler is adjusted so that the indicated temperature of the thermometer inserted inside the jacket becomes a specified temperature. Concentration was started when the can internal pressure reached 0.3 MPa (absolute pressure), and the opening of the pressure relief valve was adjusted so as to keep the polymerization can internal pressure constant. When the amount of distilled water reached 24.7 kg, the pressure release valve was closed and the heating temperature was changed to 285 ° C. When the internal pressure of the can reached 1.8 MPa (absolute pressure: P max ), the heating temperature was changed to 270 ° C. to maintain the internal pressure of the can. From the time when the internal temperature reaches 254 ° C., it gradually decreases to 0.1 MPa (absolute pressure), that is, atmospheric pressure over 42 minutes according to the pressure release curve with P max = 1.8 and θ 0.4-0.1 = 20 minutes in the following formula. The pressure was released.
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-M000002
　大気圧に到達したら窒素ガスを５L／分流通させて１５分間缶内をブローした。その後缶内に０．５MPa（絶対圧）の窒素圧をかけ、水浴中に吐出したポリマーをストランドカッターでペレタイズした。得られたポリペンタメチレンアジパミドの硫酸相対粘度は２．７９、アミノ末端基量は４．５５×１０－５mol/ｇ、Ｔmは２５４℃であった。
（実施例１～３）
　参考例３を実施した後加熱を停止し、内温が４０℃以下になるまで１晩放冷してから、参考例３と同じ操作を繰り返した（参考例１を１バッチ目とすると、実施例１は２バッチ目、実施例２は３バッチ目、実施例３は４バッチ目である）。
（実施例４）
　θ0.4-0.1＝２５分とした放圧カーブを用いたこと以外は、参考例３および実施例１と同じ操作を行った。
（実施例５）
　θ0.4-0.1＝３０分とした放圧カーブを用いたこと以外は、参考例３および実施例１と同じ操作を行った。
（実施例６）
　Ｐｍａｘを１．０MPaにした以外は、参考例３および実施例１と同じ操作を行った。
（実施例７）
　大気圧まで放圧した後、常圧重合を行う代わりに、０．９８MPa（絶対圧）に減圧し、１５分間保持した以外は、参考例３および実施例１と同じ操作を行った。
（実施例８）
　缶内圧力が１．８MPa（絶対圧：Ｐmax）に到達した時点で加熱温度を２７５℃に変更した以外は、参考例３および実施例１と同じ操作を行った。
（実施例９）
　缶内圧力が１．８MPa（絶対圧：Ｐmax）に到達した時点で加熱温度を２８０℃に変更した以外は、参考例３および実施例１と同じ操作を行った。
（実施例１０）
　重合時の撹拌速度を２０rpmとし、缶内圧力が１．８MPa（絶対圧：Ｐmax）に到達した時点で加熱温度を２７７℃に変更した以外は、参考例３および実施例１と同じ操作を行った。
（実施例１１）
　重合時の撹拌速度を１５rpmとし、缶内圧力が１．８MPa（絶対圧：Ｐmax）に到達した時点で加熱温度を２８２℃に変更した以外は、参考例３および実施例１と同じ操作を行った。
（実施例１２）
　θ0.4-0.1＝６０分とした放圧カーブを用いたこと以外は、参考例３および実施例１と同じ操作を行った。
（比較例１）
　θ0.4-0.1＝１５分とした放圧カーブを用いたこと以外は、参考例３および実施例１と同じ操作を行った。
（比較例２）
　内温が２５４℃に到達した時点から下式でＰmax＝１．８、θ0.4-0.1＝２０分とした放圧直線に従い１１３分かけて徐々に０．１MPa（絶対圧）すなわち大気圧まで放圧した以外は、参考例３および実施例１と同じ操作を行った。 When the atmospheric pressure was reached, nitrogen gas was circulated at 5 L / min and the inside of the can was blown for 15 minutes. Thereafter, nitrogen pressure of 0.5 MPa (absolute pressure) was applied to the can, and the polymer discharged into the water bath was pelletized with a strand cutter. The obtained polypentamethylene adipamide had a sulfuric acid relative viscosity of 2.79, an amino terminal group amount of 4.55 × 10 −5 mol / g, and a Tm of 254 ° C.
(Examples 1 to 3)
After carrying out Reference Example 3, heating was stopped, and the mixture was allowed to cool overnight until the internal temperature became 40 ° C. or lower, and then the same operation as in Reference Example 3 was repeated (when Reference Example 1 was taken as the first batch, the operation was performed). Example 1 is the second batch, Example 2 is the third batch, and Example 3 is the fourth batch).
Example 4
The same operation as in Reference Example 3 and Example 1 was performed, except that a pressure release curve with θ 0.4-0.1 = 25 minutes was used.
(Example 5)
The same operation as in Reference Example 3 and Example 1 was performed, except that a pressure release curve with θ 0.4-0.1 = 30 minutes was used.
(Example 6)
The same operation as in Reference Example 3 and Example 1 was performed except that P max was set to 1.0 MPa.
(Example 7)
After releasing to atmospheric pressure, instead of performing normal pressure polymerization, the same operation as in Reference Example 3 and Example 1 was performed except that the pressure was reduced to 0.98 MPa (absolute pressure) and held for 15 minutes.
(Example 8)
The same operations as in Reference Example 3 and Example 1 were performed except that the heating temperature was changed to 275 ° C. when the internal pressure of the can reached 1.8 MPa (absolute pressure: P max ).
Example 9
The same operations as in Reference Example 3 and Example 1 were performed except that the heating temperature was changed to 280 ° C. when the internal pressure of the can reached 1.8 MPa (absolute pressure: P max ).
(Example 10)
The same operation as in Reference Example 3 and Example 1 was performed except that the stirring speed at the time of polymerization was 20 rpm and the heating temperature was changed to 277 ° C. when the internal pressure of the can reached 1.8 MPa (absolute pressure: P max ). went.
(Example 11)
The same operation as in Reference Example 3 and Example 1 was performed except that the stirring speed during polymerization was 15 rpm and the heating temperature was changed to 282 ° C. when the internal pressure of the can reached 1.8 MPa (absolute pressure: P max ). went.
(Example 12)
The same operation as in Reference Example 3 and Example 1 was performed, except that a pressure release curve with θ 0.4-0.1 = 60 minutes was used.
(Comparative Example 1)
The same operation as in Reference Example 3 and Example 1 was performed except that a pressure release curve with θ 0.4-0.1 = 15 minutes was used.
(Comparative Example 2)
From the time when the internal temperature reaches 254 ° C., gradually decrease to 0.1 MPa (absolute pressure), that is, atmospheric pressure over 113 minutes according to the pressure release line with P max = 1.8 and θ 0.4-0.1 = 20 minutes in the following formula. The same operation as in Reference Example 3 and Example 1 was performed except that the pressure was released.
Figure JPOXMLDOC01-appb-M000003
Figure JPOXMLDOC01-appb-M000003
（比較例３）
　Ｐmaxを０．８MPaにした以外は、参考例３および実施例１と同じ操作を行った。得られたペレットのほとんどに形状異常が認められた。 (Comparative Example 3)
The same operation as in Reference Example 3 and Example 1 was performed except that P max was set to 0.8 MPa. Abnormal shape was observed in most of the obtained pellets.
　実施例および比較例で得られたポリペンタメチレンアジパミド樹脂の特性値は表１に示したとおりであった。 The characteristic values of the polypentamethylene adipamide resins obtained in Examples and Comparative Examples are as shown in Table 1.
　参考例３および実施例１～３は、バッチを繰り返して重合を行っているが、色調の悪化は全く認められない。 In Reference Example 3 and Examples 1 to 3, polymerization was carried out by repeating batches, but no deterioration in color tone was observed.
　実施例１、４、５、１２は放圧時間のうち、０．４MPa以下を本発明で規定した２０分以上としたため色調悪化は抑えられているが、１５分とした比較例１では色調が大幅に悪化した。放圧終盤のポリマー発泡に伴い残存ポリマーが増大したことが影響したと推定される。 In Examples 1, 4, 5, and 12, the color tone deterioration was suppressed because 0.4 MPa or less of the pressure release time was set to 20 minutes or more as defined in the present invention, but in Comparative Example 1 that was 15 minutes, the color tone was reduced. Deteriorated significantly. It is presumed that the increase in the residual polymer due to the polymer foaming at the end of the pressure release was affected.
　比較例２は、公知の方法にならい放圧時の圧力と時間が直線関係になるようにした結果、色調が大幅に悪化した。放圧終盤のポリマー発泡に伴い残存ポリマーが増大したことが影響したと推定される。 In Comparative Example 2, the color tone was greatly deteriorated as a result of having a linear relationship between the pressure and the time at the time of releasing according to a known method. It is presumed that the increase in the residual polymer due to the polymer foaming at the end of the pressure release was affected.
　実施例１、６および比較例３を比較すると、Ｐmaxが１．８MPa（実施例１）および１．０MPa（実施例６）では色調悪化が抑えられ、かつ硫酸相対粘度が十分であるが、Ｐmaxが０．８MPa（比較例３）では色調悪化は認められないものの、ジアミン成分の留出に伴うモルバランスのずれによって、硫酸相対粘度が低下し、ペレット形状が異常となった。 Comparing Examples 1 and 6 and Comparative Example 3, when P max is 1.8 MPa (Example 1) and 1.0 MPa (Example 6), color tone deterioration is suppressed, and sulfuric acid relative viscosity is sufficient. When P max was 0.8 MPa (Comparative Example 3), although the color tone was not deteriorated, the relative viscosity of sulfuric acid decreased due to the shift of the molar balance accompanying the distillation of the diamine component, and the pellet shape became abnormal.
　実施例１と実施例７を比較すると、いずれも極端な色調悪化は抑えられているものの、減圧重合を行った実施例７の方が色調が低下していた。 When Example 1 and Example 7 were compared with each other, although the extreme deterioration of the color tone was suppressed, the color tone of Example 7 subjected to reduced pressure polymerization was lowered.
　実施例１、８および９を比較すると、いずれも極端な色調悪化は抑えられているものの、ＴpmaxがＴm＋２０℃を超える実施例９の方が色調が低下していた。 When Examples 1, 8 and 9 were compared, although any extreme deterioration in color tone was suppressed, Example 9 in which Tp max exceeded Tm + 20 ° C. had a lower color tone.
　実施例１、１０および１１を比較すると、いずれも極端な色調悪化は抑えられているものの、撹拌速度が下がってＨ－Ｔpmaxが５℃を超える実施例１１の方が、色調が悪化していた。 Comparing Examples 1, 10 and 11, although any extreme deterioration in color tone is suppressed, Example 11 in which H-Tp max exceeds 5 ° C. due to a decrease in stirring speed has a worse color tone. It was.
　実施例１と実施例１２を比較すると、いずれも極端な色調悪化は抑えられているものの、Ｔp≧Ｔmとなる時間が２時間を超える実施例１２の方が、色調が悪化していた。 When Example 1 and Example 12 were compared with each other, although the extreme deterioration in color tone was suppressed, the color tone was worse in Example 12 in which the time when Tp ≧ Tm exceeded 2 hours.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明により、前バッチのポリマーが一部残存した状態でバッチ重合を繰り返しても、色調の優れたポリペンタメチレンアジパミド樹脂を工業的に安定して提供することができる。 According to the present invention, a polypentamethylene adipamide resin having an excellent color tone can be provided industrially and stably even if batch polymerization is repeated with a part of the polymer of the previous batch remaining.

Claims (5)

  1. １，５－ジアミノペンタンとアジピン酸からポリペンタメチレンアジパミド樹脂を加圧してから放圧するバッチ重合を繰り返すことにより製造する方法であって、攪拌機を具備した重合装置を用い、内圧をＰ［MPa（絶対圧）］、Ｐの最高値をＰmax［MPa（絶対圧）］としたときに、下記（Ａ）～（Ｃ）の条件を満足するポリペンタメチレンアジパミド樹脂の製造方法。
    　（Ａ）１．０≦Ｐmax
    　（Ｂ）放圧操作の際、放圧時間とln（Ｐ）が直線関係になるように圧力調整すること
    　（Ｃ）放圧時間のうち、０．４[MPa（絶対圧）]から大気圧へ戻すまでの時間を２０分以上とすること     A process for producing a polypentamethylene adipamide from 1,5-diaminopentane and adipic acid by repeating batch polymerization in which the resin is pressurized and then released. The polymerization apparatus is equipped with a stirrer and the internal pressure is P [ A process for producing a polypentamethylene adipamide resin that satisfies the following conditions (A) to (C) when the maximum value of P (MPa (absolute pressure)) and P max [MPa (absolute pressure)] is satisfied.
    (A) 1.0 ≦ P max
    (B) During pressure relief operation, adjust the pressure so that the pressure relief time and ln (P) have a linear relationship. (C) From 0.4 [MPa (absolute pressure)] of the pressure relief time to atmospheric pressure The time to return to 20 minutes or more
  2. ０．１≦Ｐとする請求項１記載のポリペンタメチレンアジパミド樹脂の製造方法。 The method for producing a polypentamethylene adipamide resin according to claim 1, wherein 0.1 ≦ P.
  3. 得られるポリペンタメチレンアジパミド樹脂の融点をＴm［℃］、重合中のポリペンタメチレンアジパミド樹脂温度をＴp［℃］、Ｔpの最高温度をＴpmax［℃］、重合中の加熱温度をＨ［℃」としたときに、下記関係式を満足する範囲で製造する請求項１または２に記載のポリペンタメチレンアジパミド樹脂の製造方法。
    　　　Ｔm＋１０　≦　Ｔpmax　≦　Ｔm＋２０
    　　　Ｈ－Ｔpmax　≦　５　（ただし、Ｔp≧Ｔm）     The melting point of the resulting polypentamethylene adipamide resin is Tm [° C.], the temperature of the polypentamethylene adipamide resin during polymerization is Tp [° C.], the maximum temperature of Tp is Tp max [° C.], and the heating temperature during polymerization 3. The method for producing a polypentamethylene adipamide resin according to claim 1, wherein the polypentamethylene adipamide resin is produced within a range satisfying the following relational expression when H is set to H [° C.]
    Tm + 10 ≦ Tp max ≦ Tm + 20
    H-Tp max ≤ 5 (where Tp ≥ Tm)
  4. Ｔp≧Ｔmとなる時間が０．５時間以上２時間以下である請求項１～３のいずれかに記載のポリペンタメチレンアジパミド樹脂の製造方法。 The process for producing a polypentamethylene adipamide resin according to any one of claims 1 to 3, wherein the time when Tp≥Tm is 0.5 hours or more and 2 hours or less.
  5. 植物由来原料から得られた１，５－ジアミノペンタンを用いる請求項１～４のいずれかに記載のポリペンタメチレンアジパミド樹脂の製造方法。 The method for producing a polypentamethylene adipamide resin according to any one of claims 1 to 4, wherein 1,5-diaminopentane obtained from a plant-derived raw material is used.
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