WO2011065346A1 - ポリアミドの製造方法 - Google Patents
ポリアミドの製造方法 Download PDFInfo
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- WO2011065346A1 WO2011065346A1 PCT/JP2010/070857 JP2010070857W WO2011065346A1 WO 2011065346 A1 WO2011065346 A1 WO 2011065346A1 JP 2010070857 W JP2010070857 W JP 2010070857W WO 2011065346 A1 WO2011065346 A1 WO 2011065346A1
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- pressure
- dicarboxylic acid
- polyamide
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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
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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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
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
Definitions
- the present invention relates to a method for producing a polyamide obtained by polycondensing a dicarboxylic acid component and a diamine component in the absence of a solvent. More specifically, a method for producing an efficient and homogeneous polyamide when polycondensation is carried out using a diamine component containing paraxylylenediamine and a dicarboxylic acid component using a batch reactor equipped with a condenser. About.
- a general polyamide production method uses nylon salt or an aqueous solution thereof as a feedstock, and in a batch system, the aqueous nylon salt solution is heated under pressure in a single reaction tank, and polymerization is performed in a uniform phase while suppressing distillation of the diamine component. Then, after fixing the diamine component, the water vapor in the system is gradually released, and finally the pressure is reduced to normal pressure or reduced pressure to complete the polymerization. At this time, it is common to use an aqueous solution of about 50 wt% nylon salt as a feedstock, but a large amount of water and condensed water as a solvent must be removed.
- Patent Document 3 discloses a polymerization method in which nylon salt and an aqueous solution of nylon salt are not used as a feedstock, and a reaction is performed by dropping a diamine component containing a small amount of water into a dicarboxylic acid component at a temperature of 220 ° C. or lower under normal pressure.
- Patent Documents 4 and 5 disclose a method in which a diamine component is dropped into a dicarboxylic acid component under normal pressure and reacted. Although these methods are technically and economically advantageous, there are problems associated with adding the diamine component to the dicarboxylic acid component under normal pressure.
- the dicarboxylic acid component in the molten state has sublimability, and the sublimate of the dicarboxylic acid component adheres to the ceiling of the polymerization apparatus.
- the inner walls of various pipes connected to the upper part of the polymerization apparatus for example, the inlet for additives, the addition port for diamine components, and pipes for leading steam mainly composed of condensed water generated by the polymerization reaction from the reaction tank to the condenser.
- a sublimate of a dicarboxylic acid component also adheres to the inner wall and the inside of the condenser. Most of the attached sublimation product of the dicarboxylic acid component is dissolved and washed by the vapor of condensed water generated during the polymerization reaction.
- the sublimate of the dicarboxylic acid component is generated not only when the molten dicarboxylic acid component is present alone in the polymerization apparatus, but also during the addition step of the diamine component in which the dicarboxylic acid component is not sufficiently fixed.
- the sublimate of the dicarboxylic acid component adhering to the inside of the polymerization apparatus reacts with the diamine component entrained by the condensed water vapor generated by the polycondensation reaction to produce a nylon salt or oligomer.
- the salt composed of metaxylylenediamine and dicarboxylic acid has low solubility in water, so as the content of paraxylylenediamine in the diamine component increases, What is not dissolved increases.
- the amidation reaction proceeds to become an oligomer, and the solubility in water decreases.
- the pipe and the condenser that lead the vapor mainly composed of condensed water generated by the polymerization reaction from the reaction tank to the condenser are the most deposited nylon salt or oligomer in the part of the polymerization equipment. These pipes and partial condensers are blocked, and continuous batch production cannot be performed.
- Patent Document 6 discloses a method in which a total amount of a diamine component is added to a dicarboxylic acid component in a very short time and reacted under pressure. This method involves various disadvantages because the total amount of the diamine component is added in a very short time. In this method, it is necessary to take measures for avoiding foaming, liquid level fluctuation, solidification of the polymer due to latent heat of evaporation of the water, distillation of the monomer, etc. due to the condensed water generated in a large amount in a short time.
- a high pressure is required for the pressure, and in the process of decreasing the pressure in order to proceed with the polymerization, it takes a long time to reduce the pressure while suppressing foaming, and during that time, the polyamide is exposed to a high temperature and the polyamide molecules are oxidized. Deterioration is accelerated and yellowing is likely.
- a large amount of condensed water generated in a short time is removed, and the temperature of the entire reaction system is maintained so that a fluid state can be maintained. There are many technical and economic issues such as the installation of heating means.
- Patent Document 6 discloses a method for producing a polyamide obtained by polycondensation of a dicarboxylic acid component and a diamine component under pressure, with respect to the step of decreasing the pressure to proceed polymerization, after the polycondensation under pressure is completed.
- a method for lowering is disclosed. In this method, the polyamide is exposed to a high temperature while the pressure is lowered, and the oxidative degradation of the polyamide molecules is promoted and easily yellowed. After adding the entire amount of the diamine component to the dicarboxylic acid component, the desired degree of polymerization is reached in a short time. It is desirable to make it reach.
- Patent Document 6 does not disclose a method for reducing the pressure while avoiding monomer distillation during the polycondensation, that is, during the step of adding the diamine component to the dicarboxylic acid component.
- Patent Document 7 discloses a method of lowering the paraxylylenediamine concentration in the diamine in the latter half of the reaction when the reaction is carried out by adding a diamine component containing metaxylylenediamine and paraxylylenediamine to adipic acid. ing.
- this method it is necessary to prepare diamines having different compositions, so that not only the number of equipment increases, but also switching operation of diamine to be added during the reaction becomes complicated and the operation becomes complicated, so it is difficult to say that it is an efficient method. . Therefore, when polycondensation is performed using a diamine component containing paraxylylenediamine and a dicarboxylic acid component, a method for producing an efficient and homogeneous polyamide has been desired.
- An object of the present invention is to provide a polyamide batch-wise production method in which a diamine component containing paraxylylenediamine and a dicarboxylic acid component are polycondensed using a batch reactor equipped with a condenser. It is an object to provide a method for producing a particularly advantageous polyamide.
- the inventors of the present invention have used a batch reactor equipped with a condenser, and a dicarboxylic acid component containing a diamine component containing 20 mol% or more of xylylenediamine containing 70 mol% or more of xylylenediamine. Addition of diamine component under pressure while maintaining the whole reaction system in a flow-type production process for polyamide to be added and polycondensed, and to reduce the pressure during a specific molar ratio while continuing the addition Thus, a method for producing an economically and quality advantageous polyamide was found and the present invention was completed.
- the present invention uses a batch reactor equipped with a condenser, and a diamine component containing 70 mol% or more of xylylenediamine containing 20 mol% or more of paraxylylenediamine and a dicarboxylic acid component are not present in the absence of a solvent.
- the present invention relates to a method for producing a polyamide obtained by polycondensation below, which comprises the following steps (1) to (3).
- the diamine component is continuously added to the dicarboxylic acid component until the molar ratio (B / A) of the diamine component (B) to the charged dicarboxylic acid component (A) is 0.60 while the entire system is maintained in a fluid state.
- the step (3) of intermittent addition maintains the fluid state of the entire reaction system, and the diamine component (A) with respect to the charged dicarboxylic acid component (A) is added continuously or intermittently to the dicarboxylic acid component.
- the method for producing a polyamide of the present invention brings about the following effects.
- (Ii) Nylon salts and oligomers can be prevented from adhering to the reaction system, and distilling out of the diamine component can be suppressed. Therefore, it is extremely easy to control the molar balance, that is, control the degree of polymerization. Polyamide is obtained.
- dicarboxylic acid component used in the production method of the present invention examples include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid;
- aromatic dicarboxylic acids such as acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and among them, adipic acid is preferable in view of practical properties of the obtained polyamide.
- the dicarboxylic acid component is preferably a dicarboxylic acid containing 70 mol% or more of adipic acid, more preferably a dicarboxylic acid containing 90 mol% or more.
- the diamine component used in the production method of the present invention is a diamine containing xylylenediamine in an amount of 70 mol% or more, preferably 90 mol% or more in view of the practical physical properties of the resulting polyamide.
- xylylenediamine contains 20 mol% or more, preferably 30 mol% or more of paraxylylenediamine in view of the crystallinity of the resulting polyamide.
- the xylylenediamine is preferably composed of two components, metaxylylenediamine and paraxylylenediamine.
- the amount of paraxylylenediamine in the xylylenediamine is preferably 20 to 65 mol%, more preferably 30.
- diamine components include aliphatic groups such as tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane.
- Aromatic diamines such as diamine, metaphenylene diamine, and paraphenylene diamine, and alicyclic diamines such as 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, etc. are included in the total diamine. It can be used in the range of mol% or less.
- the polyamide-forming component other than the diamine component and the dicarboxylic acid component is not particularly limited, but a lactam such as caprolactam, valerolactam, laurolactam, and undecalactam; an aminocarboxylic acid such as 11-aminoundecanoic acid and 12-aminododecanoic acid These may include one or two or more of these.
- Phosphorus compounds can be added to the polyamide due to the coloring properties during melt polymerization.
- hypophosphorous acid compounds such as hypophosphorous acid and hypophosphite
- phosphorous acid compounds such as phosphorous acid, phosphite and phosphorous acid ester
- phosphoric acid compounds such as phosphoric acid, phosphate and phosphoric acid ester, etc.
- hypophosphites include potassium hypophosphite, sodium hypophosphite, calcium hypophosphite, magnesium hypophosphite, manganese hypophosphite, nickel hypophosphite, cobalt hypophosphite and the like.
- phosphites include potassium phosphite, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite, nickel phosphite, cobalt phosphite and the like.
- Phosphite esters include methyl phosphite, phosphite Examples include phosphoric acid ethyl ester, phosphorous acid isopropyl ester, phosphorous acid butyl ester, phosphorous acid hexyl ester, phosphorous acid isodecyl ester, phosphorous acid decyl ester, phosphorous acid stearyl ester, phosphorous acid phenyl ester, and the like.
- Examples of the phosphate include potassium phosphate, sodium phosphate, calcium phosphate, magnesium phosphate, manganese phosphate, nickel phosphate, and cobalt phosphate.
- Examples of the phosphate ester include phosphoric acid methyl ester, phosphoric acid ethyl ester, phosphoric acid isopropyl ester, and phosphoric acid butyl ester. And hexyl phosphate, isodecyl phosphate, decyl phosphate, stearyl phosphate, and phenyl phosphate. These phosphorus compounds may be used alone or in combination.
- Examples of the method of adding these phosphorus compounds include a method of adding to a diamine component or dicarboxylic acid component which is a raw material of polyamide, a method of adding during the reaction, and the like, but the present invention is not limited thereto.
- ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Polyamide is produced in the absence of a solvent because of its economical advantage.
- “in the absence of a solvent” means not to exclude the presence of a small amount of solvent that does not affect the effect of the present invention as well as the absence of a solvent.
- the batch-type reaction tank in the present invention is equipped with a pressure reducer and, if necessary, a stirrer, and has a pressure-resistant design. Moreover, in order to suppress the distillation of a diamine component and a dicarboxylic acid component, it is desirable to include a voltage divider that can control the temperature of the heat transfer surface.
- the molar balance of charging is arbitrarily selected.
- the method for adjusting the molar balance of charging is, for example, measuring a dicarboxylic acid component in a molten state with a melting tank and supplying it to a reaction tank, and then measuring the diamine component entering the storage tank with a mass measuring instrument.
- the method of supplying a component to a reaction system can be illustrated.
- a mass meter such as a load cell or a balance can be suitably used.
- the method for producing a polyamide of the present invention includes the following steps (1) to (3).
- Step (1) the dicarboxylic acid component is charged into the reaction vessel, and then the pressure in the reaction vessel is increased to a pressure of 0.2 MPaG or more.
- step (1) the dicarboxylic acid component is charged into the reaction vessel, and then the pressure in the reaction vessel is increased to a pressure of 0.2 MPaG or more.
- the dicarboxylic acid component Prior to charging the dicarboxylic acid component into the reaction vessel for the purpose of avoiding oxidative coloring of the polyamide, it is desirable to sufficiently replace the inside of the reaction vessel with an inert gas such as nitrogen in advance. Further, when the dicarboxylic acid component is melted, it is preferably carried out in an inert gas atmosphere. Even if the dicarboxylic acid component is heated above its melting point in the reaction tank to be in a molten state, it is heated in a dedicated melting tank different from the reaction tank to be in a molten state and then charged into the reaction tank in a molten state. Either method is acceptable. From the viewpoint of increasing the utilization efficiency of the reaction tank, it is preferable to use a dedicated melting tank.
- the step of pressurizing the pressure in the reaction tank to a pressure of 0.2 MPaG or more may be completed before the addition of the diamine component to the dicarboxylic acid component in the reaction tank is started.
- Pressurization in the reaction tank can be performed with an inert gas such as nitrogen or water vapor.
- the pressure in the reaction vessel varies depending on the diamine component and dicarboxylic acid component to be used, it is preferable to select from the range of 0.2 to 0.4 MPaG from the above viewpoint.
- Step (2) the pressure in the reaction vessel is maintained at 0.2 MPaG or more, preferably in the range of 0.2 to 0.4 MPaG, and the whole reaction system is maintained in a fluid state while the charged dicarboxylic acid is charged.
- the diamine component is continuously or intermittently added to the dicarboxylic acid component until the molar ratio (B / A) of the diamine component (B) to the acid component (A) reaches 0.60.
- the pressure of 0.2 MPaG or more is maintained. From the viewpoint of suppressing a large amount of the diamine component from being extracted to the outside of the system, the pressure within the above pressure range is used.
- the predetermined pressure reached in step (1) may be kept constant at a pressure within the above pressure range. .
- the pressure may be controlled to be constant.
- Constant pressure does not need to be completely constant as long as the effect of the present invention is exhibited, and includes a thing with some variation.
- the mole fraction of the diamine component and dicarboxylic acid component in the gas phase decreases, and the evaporation amount of the diamine component and dicarboxylic acid component decreases accordingly. Or the adhesion deposit amount of an oligomer is suppressed. Further, the gas temperature in the gas phase and the temperature of the internal reflux liquid mainly composed of the diamine component are increased, and the oligomer is melted. Therefore, the internal reflux liquid is effectively cleaned, and the amount of deposited oligomer is suppressed. In addition, when the saturated water vapor pressure increases, the dew point temperature of water increases, and the solubility of nylon salt in water increases accordingly.
- nylon salts and oligomers adhering to the reaction system during the reaction are suppressed, and washing is effectively performed with condensed water generated by the polycondensation reaction between the diamine component and the dicarboxylic acid component, thereby suppressing adhesion.
- washing is effectively performed with condensed water generated by the polycondensation reaction between the diamine component and the dicarboxylic acid component, thereby suppressing adhesion.
- the dicarboxylic acid is preferably heated to a temperature of 150 ° C. or higher, which is the temperature at which the amidation reaction proceeds, and the oligomer and / or low molecular weight polyamide produced as an intermediate It is preferable that is in a molten state and the entire reaction system is maintained in a fluid state.
- the addition is more preferably performed at a temperature usually selected from 180 to 340 ° C.
- the rate of temperature rise depends on the heat of the amidation reaction, the latent heat of vaporization of the condensed water, the heat of supply, etc., so the addition rate of the diamine component is adjusted in a timely manner. Less than (+ 35 ° C.), more preferably less than (melting point + 15 ° C.), more desirably (melting point + 5 ° C.) or more and less than (melting point + 10 ° C.).
- the melting point in the present invention refers to an endothermic peak temperature due to the heat of crystal fusion observed by a differential scanning calorimeter (DSC) measurement or the like, and the melting point of the reaction system can be confirmed by appropriately measuring by DSC or the like.
- the specific operation of adding the diamine component in the present invention is to stir the dicarboxylic acid component in a molten state in the reaction vessel, continuously or intermittently add the diamine component, and preferably sequentially increase the temperature of the reaction mixture.
- the temperature is raised to the above temperature, and the whole reaction system is maintained in a fluid state.
- the addition rate of the diamine component in the present invention is appropriately selected so that the foaming accompanying the condensed water generated in the polycondensation reaction can be suppressed, and the time required for the addition of the diamine component. It is preferably 30 minutes or longer and within 4 hours, more preferably 60 minutes or longer and within 2 hours. When added in a very short time, it is economically advantageous, but the liquid level rises due to foaming accompanying condensed water generated in a short amount of time, and the polymer adheres to the side surface of the reaction tank or the stirring blade. These are not melted in subsequent batches, and the amount of adhesion increases with each batch and the heat history is received.
- the addition time is generally preferably within 4 hours.
- the total addition time may be the same as the addition time in the said continuous addition.
- the condensed water produced as the reaction proceeds is distilled out of the reaction system through a partial condenser and further a cooler.
- the steam side outlet temperature of the partial condenser is controlled to 155 ° C. or lower from the viewpoint of suppressing the amidation reaction inside the partial condenser.
- the steam side outlet temperature of the partial condenser is preferably controlled to 155 ° C. or lower in the reaction step after step (3) or step (3) described later, and is preferably 155 ° C. or lower and the dew point temperature of water. It is more preferable that the temperature is controlled in the range of + 5 ° C. or less.
- a diamine component distilled out of the reaction system as a vapor together with the condensed water, a dicarboxylic acid component distilled off by evaporation, and the like are separated from water vapor by a partial condenser and returned to the reaction tank again.
- the amidation reaction of nylon salt or oligomer that is not dissolved in the reflux liquid (condensed water or diamine component) proceeds in the partial condenser. Since it is polymerized, it becomes more difficult to dissolve in the reflux liquid.
- the number of batches is increased, the amount of polymer inside the reducer increases, causing blockage inside the reducer and making continuous batch production difficult.
- the steam side outlet of the condenser is used in step (2), step (3), and further in the reaction step after step (3). It is desirable to set the temperature to 155 ° C. or lower and control the temperature within the range of the dew point temperature of water to the temperature + 5 ° C. or lower.
- the steam side outlet temperature of the partial condenser is much higher than the dew point temperature of water, the reflux liquid amount of the partial condenser is reduced, so that the cleaning effect of the nylon salt or oligomer adhering to the partial condenser cannot be expected. There is.
- the steam side outlet temperature of the partial condenser is adjusted to 143 ° C. to 148 ° C.
- step (3) the reaction system as a whole is maintained in a fluid state, and the diamine component (B) is added to the dicarboxylic acid component (A) while the diamine component is continuously or intermittently added to the dicarboxylic acid component. While the ratio (B / A) is 0.60 to 0.95, the pressure in the reaction vessel is decreased to less than 0.2 MPaG, preferably 0.1 MPaG or less. At this time, it is preferable to select a pressure drop rate that does not exceed the condensing capacity of the partial condenser.
- the separation efficiency of the condensing unit is reduced, and it is difficult to avoid distilling a large amount of the diamine component out of the reaction system. Can be difficult.
- the molar ratio (B / A) is 0.60 to 0.95.
- the molar fraction of the component and the dicarboxylic acid component is increased, and accordingly, the evaporation amount of the diamine component and the dicarboxylic acid component is increased, and the deposition amount of the nylon salt or oligomer in the reaction system is increased.
- the pressure drop starts when the molar ratio (B / A) is higher than 0.95, the molten polymer thickens, so the liquid level rises greatly with foaming. Polymer adheres. Since these are not melted in the next batch and remain in the reaction tank, the amount of adhesion increases each time the number of batches is increased, and a heat history is received. In addition to problems such as breakage of the stirring blade.
- the dew point temperature of water decreases as the pressure in the system decreases, it is more preferable to control the steam side outlet temperature of the condenser to a temperature in the range of the temperature + 5 ° C. or less from the dew point temperature of water.
- the whole reaction system is maintained in a fluid state, and is preferably maintained at a pressure at the end of the addition of the diamine component for 5 minutes or more and 3 hours or less, preferably 10 minutes or more and 1 hour or less. More preferably.
- the reaction rate of the diamine component that is, the immobilization rate is extremely fast.
- a considerable amount of carboxyl groups is consumed at the end of the addition, and the immobilization rate of the diamine component is extremely slow compared to the initial stage of addition.
- the increase in the degree of polymerization lowers the stirring efficiency of the reaction mixture, which is further disadvantageous for immobilizing the diamine component.
- the diamine component that has not been immobilized is present in the reaction mixture or in the gas phase in the reaction system, or the condensed diamine component is added to the reaction mixture again. After completing the addition of the diamine component, the diamine component is fixed by holding the pressure at the end of the addition of the diamine component for at least 5 minutes, and the molar balance of the preparation is accurately reproduced in the polyamide molar balance. Is done.
- maintains a pressure is dependent on the condition of fixation of a diamine component, it cannot be said unconditionally. However, holding more than necessary after immobilization of the diamine component is meaningless, and may cause inconveniences such as an increase in heat history and a decrease in productivity. Accordingly, the holding time is generally preferably within 3 hours.
- the pressure in the reaction vessel is reduced to atmospheric pressure or lower at a pressure reduction rate of 0.1 to 1.0 MPa / hour. At that time, it is preferable to lower the pressure to a reduced pressure, preferably 80 kPa or less, to distill off the water vapor present in the gas phase portion out of the reaction system, and to further increase the degree of polymerization using amidation equilibrium. During the pressure drop, the entire reaction system maintains a fluid state. In the process of lowering the pressure in the reaction vessel, a pressure reduction rate at which foaming of the produced polyamide is suppressed is selected.
- the pressure decreasing rate is preferably in the range of 0.3 to 0.6 MPa / hour, and more preferably in the range of 0.4 to 0.5 MPa / hour.
- the reaction vessel When the obtained polyamide is discharged from the reaction vessel after the pressure drop, the reaction vessel is usually pressurized. In this case, it is preferable to use an inert gas such as nitrogen. According to the present invention, since there is little adhesion of nylon salt or oligomer in the reaction tank after discharge, the reaction of the next batch can be continued, so that continuous batch production is possible.
- a polyamide having a higher molecular weight can be produced by performing solid phase polymerization using the polyamide obtained by the present invention as a raw material and further proceeding with the polymerization. Further, the polyamide obtained by the present invention can be supplied to a continuous polymerization machine in a molten state, and the polymerization can be further advanced to produce a higher molecular weight polyamide.
- the polyamide obtained by the present invention can be blended with other resins such as nylon 6, nylon 66, nylon 6,66, polyester, olefin, etc., as long as the purpose is not impaired.
- Agents Glass flakes, talc, kaolin, mica, montmorillonite, plate-like inorganic fillers such as organic clay, impact modifiers such as various elastomers, crystal nucleating agents; fatty acid amides, fatty acid metal salts, etc.
- Lubricants Copper compounds, organic or inorganic halogen compounds, hindered phenols, hindered amines, hydrazines, sulfur compounds, phosphorus compounds, and other antioxidants; heat stabilizers, anti-coloring agents, benzotriazoles, etc.
- Additives such as UV absorbers, mold release agents, plasticizers, colorants, flame retardants, and compounds that provide oxygen scavenging ability
- Anti-gelling compound and a polyamide resin containing a cobalt metal may be added an additive of an alkali compound such as for the purpose of that.
- Terminal carboxyl group concentration Polyamide resin 0.3 to 0.5 g was precisely weighed and dissolved in 30 cc of benzyl alcohol with stirring at 160 to 180 ° C. in a nitrogen stream.
- YI 100 (1.28X-1.06Z) / Y (5)
- Amount of distilled xylylenediamine distilled away Using gas chromatography (manufactured by Shimadzu Corporation, GC-2010), the mixed xylylenediamine concentration in the condensed water distilled out of the reaction system during production was measured. The mixed xylylenediamine distillate amount was calculated from the weight of the condensed water.
- Adipic acid (purity: purity: precisely) in a 50 liter stainless steel reaction vessel with a jacket equipped with a partial condenser, a full condenser, a stirrer, a nitrogen gas introduction pipe and a diamine dropping port through which temperature-controlled oil flows. (99.85 wt%) 15.000 kg was charged and sufficiently purged with nitrogen. A heating medium at 300 ° C. was passed through the jacket to start the temperature rise, and adipic acid was dissolved while stirring to make it flow. Meanwhile, supply of nitrogen was started in the reaction tank, and the pressure in the reaction tank was increased to 0.30 MPaG.
- the temperature is continuously increased and the heating is adjusted so that the liquid temperature at the end of the dripping of the mixed xylylenediamine is 265 ° C., and the steam distilled is cooled. It was condensed through a vessel and removed from the reaction system. After completion of the dropwise addition of the mixed xylylenediamine, the temperature rising rate was increased at 0.2 ° C./min with continued stirring, and the pressure in the reaction vessel was maintained at 0.06 MPaG for 15 minutes. Further, the pressure was reduced to 80 kPaA at a rate of 0.6 MPa / hour and held at 80 kPaA for 8 minutes.
- the heating was stopped, the pressure was increased with nitrogen, the strand was taken out from the nozzle at the bottom of the reaction vessel, cooled with water, and then cut into a pellet shape to obtain a polyamide having a YI of ⁇ 6 in an amorphous state.
- the end group concentration of the obtained polyamide was quantified.
- the molar ratio (B / A) of the polyamide was 0.994, and the number average molecular weight was 15,500.
- the amount of mixed xylylenediamine distilled out of the reaction system it was 10 g. When the conditions inside the reactor and the inside of the condenser were observed, no deposits such as nylon salts or oligomers were observed.
- the total process time from the start of the dropwise addition of the mixed xylylenediamine to the start of the discharge of the polymer was 2 hours and 21 minutes.
- Example 2 In the same manner as in Example 1, 10.998 kg of mixed xylylenediamine (purity: 99.95 wt%) was continuously added dropwise over 1 hour, and the molar ratio (B / A) reached 0.788. During this time, the pressure in the reaction vessel was controlled at 0.30 MPaG, and the steam temperature at the outlet side of the partial condenser was controlled at 144 to 147 ° C. Thereafter, 2.896 kg of mixed xylylenediamine was continuously added dropwise over 50 minutes, while the molar ratio (B / A) was 0.866 to 0.949 at a rate of 0.72 MPa / hour over 20 minutes.
- the pressure was reduced from 0.30 MPaG to 0.06 MPaG, and the pressure was maintained at 0.06 MPaG until the end of dropping.
- the vapor outlet temperature of the condenser was controlled at a temperature in the range from the dew point of water to the temperature + 5 ° C or lower. While the mixed xylylenediamine is continuously dripped, the temperature is continuously increased and the heating is adjusted so that the liquid temperature at the end of the dripping of the mixed xylylenediamine is 265 ° C., and the steam distilled is cooled. It was condensed through a vessel and removed from the reaction system.
- the temperature rising rate was increased at 0.2 ° C./min with continued stirring, and the pressure in the reaction vessel was maintained at 0.06 MPaG for 15 minutes. Further, the pressure was reduced to 80 kPaA at a rate of 0.6 MPa / hour and held at 80 kPaA for 8 minutes. Thereafter, the heating was stopped, the pressure was increased with nitrogen, the strand was taken out from the nozzle at the bottom of the reaction vessel, cooled with water, and then cut into a pellet shape to obtain a polyamide having a YI of ⁇ 6 in an amorphous state. The end group concentration of the obtained polyamide was quantified.
- the molar ratio (B / A) of the polyamide was 0.994, and the number average molecular weight was 15,500.
- the amount of mixed xylylenediamine distilled out of the reaction system it was 10 g.
- the total process time from the start of the dropwise addition of the mixed xylylenediamine to the start of the discharge of the polymer was 2 hours and 21 minutes.
- Adipic acid (purity: purity: precisely) in a 50 liter stainless steel reaction vessel with a jacket equipped with a partial condenser, a full condenser, a stirrer, a nitrogen gas introduction pipe and a diamine dropping port through which temperature-controlled oil flows. (99.85 wt%) 15.000 kg was charged and sufficiently purged with nitrogen. A heating medium at 300 ° C. was passed through the jacket to start the temperature rise, and adipic acid was dissolved while stirring to make it flow. Meanwhile, supply of nitrogen was started in the reaction tank, and the pressure in the reaction tank was increased to 0.30 MPaG.
- the temperature is continuously increased and the heating is adjusted so that the liquid temperature at the end of the dripping of the mixed xylylenediamine is 265 ° C., and the steam distilled is cooled. It was condensed through a vessel and removed from the reaction system. After completion of the dropwise addition of the mixed xylylenediamine, the temperature rising rate was increased at 0.2 ° C./min with continued stirring, and the pressure in the reaction vessel was maintained at 0.12 MPaG for 15 minutes. Further, the pressure was reduced to 80 kPaA at a rate of 0.6 MPa / hour and held at 80 kPaA for 8 minutes.
- the heating was stopped, the pressure was increased with nitrogen, the strand was taken out from the nozzle at the bottom of the reaction vessel, cooled with water, and then cut into a pellet shape to obtain a polyamide having a YI of ⁇ 6 in an amorphous state.
- the end group concentration of the obtained polyamide was quantified.
- the molar ratio (B / A) of the polyamide was 0.994, and the number average molecular weight was 15,600.
- the amount of mixed xylylenediamine distilled out of the reaction system it was 11 g. When the conditions inside the reactor and the inside of the condenser were observed, no deposits such as nylon salts or oligomers were observed.
- the total process time from the start of the dropwise addition of the mixed xylylenediamine to the start of the discharge of the polymer was 2 hours and 27 minutes.
- Example 4 In the same manner as in Example 3, 8.422 kg of mixed xylylenediamine (purity: 99.95 wt%) was continuously added dropwise over 47 minutes, and the molar ratio (B / A) reached 0.603. During this time, the pressure in the reaction vessel was controlled at 0.30 MPaG, and the outlet side steam temperature of the partial condenser was controlled at 144 to 147 ° C. Thereafter, 5.474 kg of mixed xylylenediamine was continuously added dropwise over 63 minutes, while the molar ratio (B / A) was from 0.603 to 0.945 at a rate of 0.22 MPa / hour over 55 minutes.
- the pressure was reduced from 0.30 MPaG to 0.10 MPaG, and the pressure was maintained at 0.10 MPaG until the end of dropping.
- the vapor outlet temperature of the condenser was controlled at a temperature in the range from the dew point of water to the temperature + 5 ° C or lower. While the mixed xylylenediamine is continuously dripped, the temperature is continuously increased and the heating is adjusted so that the liquid temperature at the end of the dripping of the mixed xylylenediamine is 265 ° C., and the steam distilled is cooled. It was condensed through a vessel and removed from the reaction system.
- the temperature rising rate was increased at 0.2 ° C./min with continued stirring, and the pressure in the reaction vessel was maintained at 0.10 MPaG for 15 minutes. Further, the pressure was reduced to 80 kPaA at a rate of 0.6 MPa / hour and held at 80 kPaA for 8 minutes. Thereafter, the heating was stopped, the pressure was increased with nitrogen, the strand was taken out from the nozzle at the bottom of the reaction vessel, cooled with water, and then cut into a pellet shape to obtain a polyamide having a YI of ⁇ 6 in an amorphous state. The end group concentration of the obtained polyamide was quantified.
- the molar ratio (B / A) of the polyamide was 0.994, and the number average molecular weight was 15,700.
- the amount of mixed xylylenediamine distilled out of the reaction system was measured and found to be 9 g. No deposits such as nylon salts or oligomers were observed.
- the total process time from the start of the dropwise addition of mixed xylylenediamine to the start of polymer discharge was 2 hours and 25 minutes.
- Adipic acid (purity: purity: precisely) in a 50 liter stainless steel reaction vessel with a jacket equipped with a partial condenser, a full condenser, a stirrer, a nitrogen gas introduction pipe and a diamine dropping port through which temperature-controlled oil flows. (99.85 wt%) 15.000 kg was charged and sufficiently purged with nitrogen. A heating medium at 300 ° C. was passed through the jacket to start the temperature rise, and adipic acid was dissolved while stirring to make it flow. Meanwhile, supply of nitrogen was started in the reaction tank, and the pressure in the reaction tank was increased to 0.30 MPaG.
- the temperature is continuously increased and the heating is adjusted so that the liquid temperature at the end of the dripping of the mixed xylylenediamine is 265 ° C., and the steam distilled is cooled. It was condensed through a vessel and removed from the reaction system. After completion of the dropwise addition of the mixed xylylenediamine, the temperature rising rate was increased at 0.2 ° C./min with continued stirring, and the pressure in the reaction vessel was maintained at atmospheric pressure for 15 minutes. Further, the pressure was reduced to 80 kPaA at a rate of 0.6 MPa / hour and held at 80 kPaA for 8 minutes.
- the heating was stopped, the pressure was increased with nitrogen, the strand was taken out from the nozzle at the bottom of the reaction vessel, cooled with water, and cut into pellets to obtain a polyamide having a YI of ⁇ 7 in an amorphous state.
- the end group concentration of the obtained polyamide was quantified.
- the molar ratio (B / A) of the polyamide was 0.993, and the number average molecular weight was 15,100.
- the amount of mixed xylylenediamine distilled out of the reaction system was measured and found to be 13 g. When the conditions inside the reactor and the inside of the condenser were observed, no deposits such as nylon salts or oligomers were observed.
- the total process time from the start of the dropwise addition of the mixed xylylenediamine to the start of the discharge of the polymer was 1 hour 45 minutes.
- Adipic acid (purity: purity: precisely) in a 50 liter stainless steel reaction vessel with a jacket equipped with a partial condenser, a full condenser, a stirrer, a nitrogen gas introduction pipe and a diamine dropping port through which temperature-controlled oil flows. (99.85 wt%) 15.000 kg was charged and sufficiently purged with nitrogen. A heating medium of 320 ° C. was flowed through the jacket to start the temperature rise, and adipic acid was dissolved and brought into a fluid state while stirring. Meanwhile, supply of nitrogen into the reaction vessel was started, and the pressure in the reaction vessel was increased to 0.40 MPaG.
- the temperature is continuously raised to adjust the heating so that the liquid temperature at the end of the dropwise addition of the mixed xylylenediamine is 285 ° C., and the distilled steam is cooled. It was condensed through a vessel and removed from the reaction system. After completion of the dropwise addition of the mixed xylylenediamine, the temperature rising rate was increased at 0.2 ° C./min with continued stirring, and the pressure in the reaction vessel was maintained at 0.07 MPaG for 15 minutes. Further, the pressure was reduced to 80 kPaA at a rate of 0.6 MPa / hour and held at 80 kPaA for 5 minutes.
- the heating was stopped, the pressure was increased with nitrogen, the strand was taken out from the nozzle at the bottom of the reaction vessel, cooled with water, and then cut into a pellet shape to obtain a polyamide in which the YI was -3.
- the end group concentration of the obtained polyamide was quantified.
- the molar ratio (B / A) of the polyamide was 0.994, and the number average molecular weight was 15,500.
- the amount of mixed xylylenediamine distilled out of the reaction system was measured and found to be 9 g. When the conditions inside the reactor and the inside of the condenser were observed, no deposits such as nylon salts or oligomers were observed.
- the total process time from the start of the dropwise addition of the mixed xylylenediamine to the start of the discharge of the polymer was 2 hours and 19 minutes.
- ⁇ Comparative Example 1> Adipic acid (purity: purity: precisely) in a 50 liter stainless steel reaction vessel with a jacket equipped with a partial condenser, a full condenser, a stirrer, a nitrogen gas introduction pipe and a diamine dropping port through which temperature-controlled oil flows. (99.85 wt%) 15.000 kg was charged and sufficiently purged with nitrogen. A heating medium at 300 ° C. was passed through the jacket to start the temperature rise, and adipic acid was dissolved while stirring to make it flow. Meanwhile, supply of nitrogen was started in the reaction tank, and the pressure in the reaction tank was increased to 0.30 MPaG.
- the temperature was continuously raised and the heating was adjusted so that the liquid temperature at the end of the dropwise addition of the mixed xylylenediamine was 265 ° C.
- the pressure in the reaction vessel was controlled at 0.30 MPaG
- the outlet side of the condenser The steam temperature was controlled to 144 to 147 ° C., and the distilled steam was condensed through a cooler and removed out of the reaction system.
- the temperature increase rate was increased at 0.2 ° C./min with continued stirring, and the pressure in the reaction vessel was maintained at 0.3 MPaG for 15 minutes.
- the pressure was reduced to 80 kPaA at a rate of 0.6 MPa / hour and held at 80 kPaA for 8 minutes. Thereafter, the heating was stopped, the pressure was increased with nitrogen, the strand was taken out from the nozzle at the bottom of the reaction vessel, cooled with water, and then cut into a pellet shape to obtain a polyamide having a YI of ⁇ 6 in an amorphous state.
- the end group concentration of the obtained polyamide was quantified.
- the molar ratio (B / A) of the polyamide was 0.994, and the number average molecular weight was 15,600.
- the amount of mixed xylylenediamine distilled out of the reaction system it was 10 g.
- the temperature is continuously increased and the heating is adjusted so that the liquid temperature at the end of the dripping of the mixed xylylenediamine is 265 ° C., and the steam distilled is cooled. It was condensed through a vessel and removed from the reaction system. After completion of the dropwise addition of the mixed xylylenediamine, the temperature rising rate was increased while continuing stirring at 0.2 ° C./min, and the pressure in the reaction vessel was maintained at 0.04 MPaG for 15 minutes. Further, the pressure was reduced to 80 kPaA at a rate of 0.6 MPa / hour and held at 80 kPaA for 8 minutes.
- the heating was stopped, the pressure was increased with nitrogen, the strand was taken out from the nozzle at the bottom of the reaction vessel, cooled with water, and then cut into a pellet shape to obtain a polyamide having a YI of ⁇ 6 in an amorphous state.
- the end group concentration of the obtained polyamide was quantified.
- the molar ratio (B / A) of the polyamide was 0.990, and the number average molecular weight was 14,100.
- the amount of mixed xylylenediamine distilled out of the reaction system it was 61 g, and the amount of the diamine component distilled out of the reaction system increased.
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Abstract
Description
従って、パラキシリレンジアミンを含むジアミン成分とジカルボン酸成分を使用して重縮合を行う際に、効率的、且つ均質なポリアミドを製造する方法が望まれていた。
(1)反応槽にジカルボン酸成分を仕込み、次いで反応槽内の圧力を0.2MPaG以上の圧力まで加圧する工程
(2)反応槽内の圧力を0.2MPaG以上の圧力を維持し、且つ反応系全体が流動状態を維持しつつ、仕込みのジカルボン酸成分(A)に対するジアミン成分(B)のモル比(B/A)が0.60になるまで、ジカルボン酸成分にジアミン成分を連続的にもしくは間欠的に添加する工程
(3)反応系全体が流動状態を維持し、ジカルボン酸成分にジアミン成分を連続的にもしくは間欠的に添加しつつ、仕込みのジカルボン酸成分(A)に対するジアミン成分(B)のモル比(B/A)が0.60~0.95の間に反応槽内の圧力を、0.2MPaG未満に低下させる工程
(i)溶媒、特に水を使用しないジアミン成分とジカルボン酸成分の重縮合反応で製造される為、容積当たりのポリアミド収量が増え、反応時間の短縮ができる。
(ii)反応系内へのナイロン塩やオリゴマーの付着防止、ならびにジアミン成分の留出を抑えることができる為、高度なモルバランスの制御、つまり重合度の制御が極めて容易となり、均質で良好なポリアミドが得られる。
(iii)分縮器の閉塞、ならびに反応槽内のポリマーの堆積を抑制することができる為、連続した回分式生産が可能になる。
(iv)ポリアミドが高温に曝される時間が短縮される為、ポリアミドの黄変が減少、反応時間の短縮ができる。
(v)高度な耐圧仕様の重合装置、複雑な分縮器設計、ならびに過大な加熱手段を設置する必要がない為、製造装置を安価に建設できる。
<工程(1)>
工程(1)では、反応槽にジカルボン酸成分を仕込み、次いで反応槽内の圧力を0.2MPaG以上の圧力まで加圧する。反応系内を加圧することで、ジカルボン酸成分の蒸発は抑制される為、重合装置内のジカルボン酸の付着堆積量が低減し、合成中のナイロン塩もしくはオリゴマーの生成を抑制する効果を得ることができる。ポリアミドの酸化着色を避ける目的から反応槽へジカルボン酸成分を仕込むに先立ち、反応槽内を予め窒素等の不活性ガスで十分に置換することが望ましい。さらにジカルボン酸成分を溶融する場合は不活性ガスの雰囲気下で行われることが望ましい。ジカルボン酸成分は反応槽内でその融点以上に加熱されて溶融状態にしても、反応槽とは異なる専用の溶融槽で加熱されて溶融状態にした後に溶融状態で反応槽に仕込まれても、いずれの方法でも構わない。反応槽の利用効率を高める観点から、専用の溶融槽の利用が好ましい。
工程(2)では、反応槽内の圧力を0.2MPaG以上、好ましくは0.2~0.4MPaGの範囲内の圧力を維持し、且つ反応系全体が流動状態を維持しつつ、仕込みのジカルボン酸成分(A)に対するジアミン成分(B)のモル比(B/A)が0.60になるまで、ジカルボン酸成分にジアミン成分を連続的にもしくは間欠的に添加する。工程(1)で加圧した後は前記0.2MPaG以上の圧力を維持するが、系外へのジアミン成分の多量の留出を抑制する点から、上記圧力範囲内の圧力で、工程(1)で到達した所定の圧力を運転・品質上不都合がない範囲で制御することが望ましく、上記圧力範囲内の圧力で、工程(1)で到達した所定の圧力を一定に維持しても構わない。本発明においては、工程(1)で反応槽内の圧力を0.2MPaG以上の圧力迄加圧した後、後述の工程(3)で圧力を低下させるまでの間、運転・品質上不都合がない範囲で制御することが好ましく、圧力を一定に制御しても構わない。ここで「圧力を一定に」とは、本発明の効果を奏する限りにおいて、完全に一定である必要はなく、ある程度の変動を伴うものも包含する趣旨である。
工程(3)では、反応系全体が流動状態を維持し、ジカルボン酸成分にジアミン成分を連続的にもしくは間欠的に添加しつつ、仕込みのジカルボン酸成分(A)に対するジアミン成分(B)のモル比(B/A)が0.60~0.95の間に反応槽内の圧力を0.2MPaG未満、好ましくは0.1MPaG以下に低下させる。その際、分縮器の凝縮能力を上回らない圧力低下速度を選択することが好ましい。分縮器の凝縮能力を上回る圧力低下速度で圧力を低下させた場合、分縮器の分離効率が低下し、ジアミン成分の反応系外への大量の留出が避けがたく、モルバランスの制御が難しくなることがある。反応槽の規模や圧力にもよるが、モル比(B/A)が0.60~0.95の間に反応槽内の圧力を低下させることが好ましい。モル比(B/A)が0.60より低いときに圧力低下を開始すると、反応系内では未反応のジアミン成分やジカルボン酸成分が多く存在し、圧力を低下することにより気相部のジアミン成分やジカルボン酸成分のモル分率が上がり、これに伴いジアミン成分やジカルボン酸成分の蒸発量は増加し、反応系内のナイロン塩もしくはオリゴマーの付着堆積量は増加する為、好ましくない。またモル比(B/A)が0.95より高いときに圧力低下を開始すると、溶融ポリマーは増粘している為に発泡に伴い液面が大きく上昇し、反応槽側面や撹拌翼等にポリマーが付着する。これらは次バッチ以降で融解されずに反応槽内に残存する為、バッチ数を重ねる毎に付着量は増加し熱履歴を受け、これらの付着堆積物が欠落した場合、ポリマーに混入すると品質不良を招くほか、撹拌翼を破損する等の問題点があり好ましくない。系内の圧力低下に伴い、水の露点温度が低下する為、分縮器の蒸気側出口温度を水の露点温度から該温度+5℃以下の範囲の温度に制御することがより好ましい。
本発明によって得られたポリアミドには、目的を損なわない範囲で、ナイロン6、ナイロン66、ナイロン6,66、ポリエステル、オレフィン等の他樹脂をブレンドでき、また、ガラス繊維、炭素繊維などの無機充填剤;ガラスフレーク、タルク、カオリン、マイカ、モンモリロナイト、有機化クレイなどの板状無機充填剤、各種エラストマー類などの耐衝撃性改質材、結晶核剤;脂肪酸アミド系、脂肪酸金属塩系化合物等の滑剤;銅化合物、有機もしくは無機ハロゲン系化合物、ヒンダードフェノール系、ヒンダードアミン系、ヒドラジン系、硫黄系化合物、リン系化合物等の酸化防止剤;熱安定剤、着色防止剤、ベンゾトリアゾール系等の紫外線吸収剤、離型剤、可塑剤、着色剤、難燃剤などの添加剤、酸素捕捉能を付与する化合物であるコバルト金属を含む化合物やポリアミド樹脂のゲル化防止を目的としたアルカリ化合物等の添加剤を添加することができる。
(1)末端アミノ基濃度
ポリアミド樹脂0.3~0.5gを精秤し、フェノール/エタノール=4/1容量溶液30ccに20~30℃で攪拌溶解した。完全に溶解した後、撹拌しつつN/100塩酸水溶液で中和滴定して求めた。
(2)末端カルボキシル基濃度
ポリアミド樹脂0.3~0.5gを精秤し、ベンジルアルコール30ccに窒素気流下160~180℃で攪拌溶解した。完全に溶解した後、窒素気流下80℃以下まで冷却し、撹拌しつつメタノールを10cc加え、N/100水酸化ナトリウム水溶液で中和滴定して求めた。
(3)数平均分子量
末端アミノ基および末端カルボキシル基の滴定定量値から次式により求めた。
数平均分子量=2 /(〔NH2〕+〔COOH〕)
(〔NH2〕は末端アミノ基濃度(μeq/g)、〔COOH〕は末端カルボキシル基濃度(μeq/g)を表す。)
(4)黄色度(YI)
色差計(日本電色工業(株)製、Σ80型)を用い、試料の反射によるXYZ表色系の三刺激値X、Y、ZをJIS-K7103に従い測定し、次式から求めた。
YI=100(1.28X-1.06Z)/Y
(5)混合キシリレンジアミン留去量
ガスクロマトグラフィー(島津製作所(株)製、GC-2010)を用い、製造中に反応系外に留去した縮合水中の混合キシリレンジアミン濃度を測定し、縮合水の重量より混合キシリレンジアミン留出量を算出した。
温度調整されたオイルが流通する分縮器、全縮器、撹拌機、窒素ガス導入管およびジアミンの滴下口を備えたジャケット付き50リットルのステンレス製の反応槽に精秤したアジピン酸(純度:99.85wt%)15.000kgを仕込み、十分窒素置換した。300℃の熱媒をジャケットに流して昇温を開始し、撹拌しつつアジピン酸を溶解させ流動状態にした。その間、反応槽内に窒素の供給を開始し、反応槽内の圧力を0.30MPaGまで加圧した。190℃まで加熱したところで、溶融したアジピン酸を撹拌しながら、メタキシリレンジアミン70モル%とパラキシリレンジアミン30モル%含有する混合キシリレンジアミン(純度:99.95wt%)10.998kgを1時間かけて連続的に滴下し、モル比(B/A)は0.788に到達した。この間、反応槽の圧力を0.30MPaGで制御し、分縮器の出口側蒸気温度を144~147℃に制御した。その後、混合キシリレンジアミン2.896kgを50分間かけて連続的に滴下しつつ、モル比(B/A)が0.829~0.911の間に20分間かけて0.72MPa/時の速度で圧力を0.30MPaGから0.06MPaGへ低下させ、滴下終了まで圧力を0.06MPaGで保持した。圧力低下に伴い分縮器の蒸気側出口温度を水の露点温度から該温度+5℃以下の範囲の温度で制御した。混合キシリレンジアミンを連続的に滴下している間、連続的に昇温して混合キシリレンジアミンの滴下終了時の液温が265℃になるように加熱を調節し、留出する蒸気は冷却器を通して凝縮させ、反応系外に除いた。混合キシリレンジアミンの滴下終了後、引き続き撹拌しながら0.2℃/分の昇温速度を昇温し、15分間反応槽の圧力を0.06MPaGで保持した。更に80kPaAまで0.6MPa/時の速度で圧力を低下させ、80kPaAで8分間保持した。その後、加熱を中止し、窒素で加圧して反応槽下部のノズルからストランドとして取り出し、水冷した後ペレット形状に切断し、YIが-6の非晶状態にあるポリアミドを得た。得られたポリアミドの末端基濃度の定量を行った。結果、ポリアミドのモル比(B/A)は0.994、数平均分子量は15,500であった。反応系外に留去した混合キシリレンジアミン量を測定した結果、10gであった。反応槽内および分縮器内部の状況を観察したところ、ナイロン塩もしくはオリゴマー等の付着物は認められなかった。混合キシリレンジアミンの滴下を開始してからポリマーの排出開始前までの全工程時間は2時間21分であった。
実施例1と同様に混合キシリレンジアミン(純度:99.95wt%)10.998kgを1時間かけて連続的に滴下し、モル比(B/A)は0.788に到達した。この間、反応槽の圧力を0.30MPaGで制御し、分縮器の出口側蒸気温度を144~147℃に制御した。その後、混合キシリレンジアミン2.896kgを50分間かけて連続的に滴下しつつ、モル比(B/A)が0.866~0.949の間に20分間かけて0.72MPa/時の速度で圧力を0.30MPaGから0.06MPaGへ低下させ、滴下終了まで圧力を0.06MPaGで保持した。圧力低下に伴い分縮器の蒸気側出口温度を水の露点温度から該温度+5℃以下の範囲の温度で制御した。混合キシリレンジアミンを連続的に滴下している間、連続的に昇温して混合キシリレンジアミンの滴下終了時の液温が265℃になるように加熱を調節し、留出する蒸気は冷却器を通して凝縮させ、反応系外に除いた。混合キシリレンジアミンの滴下終了後、引き続き撹拌しながら0.2℃/分の昇温速度を昇温し、15分間反応槽の圧力を0.06MPaGで保持した。更に80kPaAまで0.6MPa/時の速度で圧力を低下させ、80kPaAで8分間保持した。その後、加熱を中止し、窒素で加圧して反応槽下部のノズルからストランドとして取り出し、水冷した後ペレット形状に切断し、YIが-6の非晶状態にあるポリアミドを得た。得られたポリアミドの末端基濃度の定量を行った。結果、ポリアミドのモル比(B/A)は0.994、数平均分子量は15,500であった。反応系外に留去した混合キシリレンジアミン量を測定した結果、10gであった。反応槽内および分縮器内部の状況を観察したところ、ナイロン塩もしくはオリゴマー等の付着物は認められなかった。混合キシリレンジアミンの滴下を開始してからポリマーの排出開始前までの全工程時間は2時間21分であった。
温度調整されたオイルが流通する分縮器、全縮器、撹拌機、窒素ガス導入管およびジアミンの滴下口を備えたジャケット付き50リットルのステンレス製の反応槽に精秤したアジピン酸(純度:99.85wt%)15.000kgを仕込み、十分窒素置換した。300℃の熱媒をジャケットに流して昇温を開始し、撹拌しつつアジピン酸を溶解させ流動状態にした。その間、反応槽内に窒素の供給を開始し、反応槽内の圧力を0.30MPaGまで加圧した。190℃まで加熱したところで、溶融したアジピン酸を撹拌しながら、メタキシリレンジアミン70モル%とパラキシリレンジアミン30モル%含有する混合キシリレンジアミン(純度:99.95wt%)8.422kgを47分間かけて連続的に滴下し、モル比(B/A)は0.603に到達した。この間、反応槽の圧力を0.30MPaGで制御し、分縮器の出口側蒸気温度を144~147℃に制御した。その後、混合キシリレンジアミン5.474kgを63分間かけて連続的に滴下しつつ、モル比(B/A)が0.603~0.728の間に20分間かけて0.54MPa/時の速度で圧力を0.30MPaGから0.12MPaGへ低下させ、滴下終了まで圧力を0.12MPaGで保持した。圧力低下に伴い分縮器の蒸気側出口温度を水の露点温度から該温度+5℃以下の範囲の温度で制御した。混合キシリレンジアミンを連続的に滴下している間、連続的に昇温して混合キシリレンジアミンの滴下終了時の液温が265℃になるように加熱を調節し、留出する蒸気は冷却器を通して凝縮させ、反応系外に除いた。混合キシリレンジアミンの滴下終了後、引き続き撹拌しながら0.2℃/分の昇温速度を昇温し、15分間反応槽の圧力を0.12MPaGで保持した。更に80kPaAまで0.6MPa/時の速度で圧力を低下させ、80kPaAで8分間保持した。その後、加熱を中止し、窒素で加圧して反応槽下部のノズルからストランドとして取り出し、水冷した後ペレット形状に切断し、YIが-6の非晶状態にあるポリアミドを得た。得られたポリアミドの末端基濃度の定量を行った。結果、ポリアミドのモル比(B/A)は0.994、数平均分子量は15,600であった。反応系外に留去した混合キシリレンジアミン量を測定した結果、11gであった。反応槽内および分縮器内部の状況を観察したところ、ナイロン塩もしくはオリゴマー等の付着物は認められなかった。混合キシリレンジアミンの滴下を開始してからポリマーの排出開始前までの全工程時間は2時間27分であった。
実施例3と同様に混合キシリレンジアミン(純度:99.95wt%)8.422kgを47分間かけて連続的に滴下し、モル比(B/A)は0.603に到達した。この間、この間、反応槽の圧力を0.30MPaGで制御し、分縮器の出口側蒸気温度を144~147℃に制御した。その後、混合キシリレンジアミン5.474kgを63分間かけて連続的に滴下しつつ、モル比(B/A)が0.603~0.945の間に55分間かけて0.22MPa/時の速度で圧力を0.30MPaGから0.10MPaGへ低下させ、滴下終了まで圧力を0.10MPaGで保持した。圧力低下に伴い分縮器の蒸気側出口温度を水の露点温度から該温度+5℃以下の範囲の温度で制御した。混合キシリレンジアミンを連続的に滴下している間、連続的に昇温して混合キシリレンジアミンの滴下終了時の液温が265℃になるように加熱を調節し、留出する蒸気は冷却器を通して凝縮させ、反応系外に除いた。混合キシリレンジアミンの滴下終了後、引き続き撹拌しながら0.2℃/分の昇温速度を昇温し、15分間反応槽の圧力を0.10MPaGで保持した。更に80kPaAまで0.6MPa/時の速度で圧力を低下させ、80kPaAで8分間保持した。その後、加熱を中止し、窒素で加圧して反応槽下部のノズルからストランドとして取り出し、水冷した後ペレット形状に切断し、YIが-6の非晶状態にあるポリアミドを得た。得られたポリアミドの末端基濃度の定量を行った。結果、ポリアミドのモル比(B/A)は0.994、数平均分子量は15,700であった。反応系外に留去した混合キシリレンジアミン量を測定した結果、9gであった。ナイロン塩もしくはオリゴマー等の付着物は認められなかった。混合キシリレンジアミンの滴下を開始してからポリマーの排出開始前までの全工程時間は2時間25分であった。
温度調整されたオイルが流通する分縮器、全縮器、撹拌機、窒素ガス導入管およびジアミンの滴下口を備えたジャケット付き50リットルのステンレス製の反応槽に精秤したアジピン酸(純度:99.85wt%)15.000kgを仕込み、十分窒素置換した。300℃の熱媒をジャケットに流して昇温を開始し、撹拌しつつアジピン酸を溶解させ流動状態にした。その間、反応槽内に窒素の供給を開始し、反応槽内の圧力を0.30MPaGまで加圧した。190℃まで加熱したところで、溶融したアジピン酸を撹拌しながら、メタキシリレンジアミン70モル%とパラキシリレンジアミン30モル%含有する混合キシリレンジアミン(純度:99.95wt%)10.998kgを30分間かけて連続的に滴下し、モル比(B/A)は0.788に到達した。この間、反応槽の圧力を0.30MPaGで制御し、分縮器の出口側蒸気温度を144~147℃に制御した。その後、混合キシリレンジアミン2.896kgを50分間かけて連続的に滴下しつつ、モル比(B/A)が0.788~0.949の間に39分間かけて0.46MPa/時の速度で圧力を0.30MPaGから大気圧へ低下させ、滴下終了まで圧力を大気圧で保持した。圧力低下に伴い分縮器の蒸気側出口温度を水の露点温度から該温度+5℃以下の範囲の温度で制御した。混合キシリレンジアミンを連続的に滴下している間、連続的に昇温して混合キシリレンジアミンの滴下終了時の液温が265℃になるように加熱を調節し、留出する蒸気は冷却器を通して凝縮させ、反応系外に除いた。混合キシリレンジアミンの滴下終了後、引き続き撹拌しながら0.2℃/分の昇温速度を昇温し、15分間反応槽の圧力を大気圧で保持した。更に80kPaAまで0.6MPa/時の速度で圧力を低下させ、80kPaAで8分間保持した。その後、加熱を中止し、窒素で加圧して反応槽下部のノズルからストランドとして取り出し、水冷した後ペレット形状に切断し、YIが-7の非晶状態にあるポリアミドを得た。得られたポリアミドの末端基濃度の定量を行った。結果、ポリアミドのモル比(B/A)は0.993、数平均分子量は15,100であった。反応系外に留去した混合キシリレンジアミン量を測定した結果、13gであった。反応槽内および分縮器内部の状況を観察したところ、ナイロン塩もしくはオリゴマー等の付着物は認められなかった。混合キシリレンジアミンの滴下を開始してからポリマーの排出開始前までの全工程時間は1時間45分であった。
温度調整されたオイルが流通する分縮器、全縮器、撹拌機、窒素ガス導入管およびジアミンの滴下口を備えたジャケット付き50リットルのステンレス製の反応槽に精秤したアジピン酸(純度:99.85wt%)15.000kgを仕込み、十分窒素置換した。320℃の熱媒をジャケットに流して昇温を開始し、撹拌しつつアジピン酸を溶解させ流動状態にした。その間、反応槽内に窒素の供給を開始し、反応槽内の圧力を0.40MPaGまで加圧した。190℃まで加熱したところで、溶融したアジピン酸を撹拌しながら、メタキシリレンジアミン50モル%とパラキシリレンジアミン50モル%含有する混合キシリレンジアミン(純度:99.95wt%)10.998kgを1時間かけて連続的に滴下し、モル比(B/A)は0.788に到達した。この間、反応槽の圧力を0.40MPaGで制御し、分縮器の出口側蒸気温度を151~155℃に制御した。その後、混合キシリレンジアミン2.896kgを50分間かけて連続的に滴下しつつ、モル比(B/A)が0.788~0.949の間に39分間かけて0.51MPa/時の速度で圧力を0.40MPaGから0.07MPaGへ低下させ、滴下終了まで圧力を0.07MPaGで保持した。圧力低下に伴い分縮器の蒸気側出口温度を水の露点温度から該温度+5℃以下の範囲の温度で制御した。混合キシリレンジアミンを連続的に滴下している間、連続的に昇温して混合キシリレンジアミンの滴下終了時の液温が285℃になるように加熱を調節し、留出する蒸気は冷却器を通して凝縮させ、反応系外に除いた。混合キシリレンジアミンの滴下終了後、引き続き撹拌しながら0.2℃/分の昇温速度を昇温し、15分間反応槽の圧力を0.07MPaGで保持した。更に80kPaAまで0.6MPa/時の速度で圧力を低下させ、80kPaAで5分間保持した。その後、加熱を中止し、窒素で加圧して反応槽下部のノズルからストランドとして取り出し、水冷した後ペレット形状に切断し、YIが-3の非晶状態にあるポリアミドを得た。得られたポリアミドの末端基濃度の定量を行った。結果、ポリアミドのモル比(B/A)は0.994、数平均分子量は15,500であった。反応系外に留去した混合キシリレンジアミン量を測定した結果、9gであった。反応槽内および分縮器内部の状況を観察したところ、ナイロン塩もしくはオリゴマー等の付着物は認められなかった。混合キシリレンジアミンの滴下を開始してからポリマーの排出開始前までの全工程時間は2時間19分であった。
温度調整されたオイルが流通する分縮器、全縮器、撹拌機、窒素ガス導入管およびジアミンの滴下口を備えたジャケット付き50リットルのステンレス製の反応槽に精秤したアジピン酸(純度:99.85wt%)15.000kgを仕込み、十分窒素置換した。300℃の熱媒をジャケットに流して昇温を開始し、撹拌しつつアジピン酸を溶解させ流動状態にした。その間、反応槽内に窒素の供給を開始し、反応槽内の圧力を0.30MPaGまで加圧した。190℃まで加熱したところで、溶融したアジピン酸を撹拌しながら、メタキシリレンジアミン70モル%とパラキシリレンジアミン30モル%含有する混合キシリレンジアミン(純度:99.95wt%)13.896kgを110分間かけて滴下した。この間、連続的に昇温して混合キシリレンジアミンの滴下終了時の液温が265℃になるように加熱を調節し、反応槽の圧力を0.30MPaGで制御し、分縮器の出口側蒸気温度を144~147℃に制御し、留出する蒸気は冷却器を通して凝縮させ、反応系外に除いた。混合キシリレンジアミンの滴下終了後、引き続き撹拌しながら0.2℃/分の昇温速度を昇温し、15分間反応槽の圧力を0.3MPaGで保持した。更に80kPaAまで0.6MPa/時の速度で圧力を低下させ、80kPaAで8分間保持した。その後、加熱を中止し、窒素で加圧して反応槽下部のノズルからストランドとして取り出し、水冷した後ペレット形状に切断し、YIが-6の非晶状態にあるポリアミドを得た。得られたポリアミドの末端基濃度の定量を行った。結果、ポリアミドのモル比(B/A)は0.994、数平均分子量は15,600であった。反応系外に留去した混合キシリレンジアミン量を測定した結果、10gであった。反応槽内および分縮器内部の状況を観察したところ、ナイロン塩もしくはオリゴマー等の付着物は認められなかった。混合キシリレンジアミンの滴下を開始してからポリマーの排出開始前までの全工程時間は2時間45分であった。
実施例1と同様な条件で混合キシリレンジアミンを滴下しつつ、モル比(B/A)が0.328~0.949の間に74分間かけて0.21MPa/時の速度で圧力を0.30MPaGから0.04MPaGへ低下させ、滴下終了まで圧力を0.04MPaGで保持した。圧力低下に伴い分縮器の蒸気側出口温度を水の露点温度から該温度+5℃以下の範囲の温度で制御した。混合キシリレンジアミンを連続的に滴下している間、連続的に昇温して混合キシリレンジアミンの滴下終了時の液温が265℃になるように加熱を調節し、留出する蒸気は冷却器を通して凝縮させ、反応系外に除いた。混合キシリレンジアミンの滴下終了後、引き続き撹拌しながら0.2℃/分の昇温速度を昇温し、15分間反応槽の圧力を0.04MPaGで保持した。更に80kPaAまで0.6MPa/時の速度で圧力を低下させ、80kPaAで8分間保持した。その後、加熱を中止し、窒素で加圧して反応槽下部のノズルからストランドとして取り出し、水冷した後ペレット形状に切断し、YIが-6の非晶状態にあるポリアミドを得た。得られたポリアミドの末端基濃度の定量を行った。結果、ポリアミドのモル比(B/A)は0.990、数平均分子量は14,100であった。反応系外に留去した混合キシリレンジアミン量を測定した結果、61gであり、反応系外へのジアミン成分の留去量は多くなった。反応槽内および分縮器内部の状況を観察したところ、反応槽の気相部へのナイロン塩もしくはオリゴマーが多量付着し、分縮器内部で白色固形物が認められた。
Claims (7)
- 分縮器を備えた回分式反応槽を用い、パラキシリレンジアミンを20モル%以上含むキシリレンジアミンを70モル%以上含むジアミン成分とジカルボン酸成分とを、溶媒の非存在下に重縮合してなるポリアミドの製造方法であって、以下の工程(1)~(3)を含むことを特徴とするポリアミドの製造方法。
(1)反応槽にジカルボン酸成分を仕込み、次いで反応槽内の圧力を0.2MPaG以上の圧力まで加圧する工程
(2)反応槽内の圧力を0.2MPaG以上の圧力を維持し、且つ反応系全体が流動状態を維持しつつ、仕込みのジカルボン酸成分(A)に対するジアミン成分(B)のモル比(B/A)が0.60になるまで、ジカルボン酸成分にジアミン成分を連続的にもしくは間欠的に添加する工程
(3)反応系全体が流動状態を維持し、ジカルボン酸成分にジアミン成分を連続的にもしくは間欠的に添加しつつ、仕込みのジカルボン酸成分(A)に対するジアミン成分(B)のモル比(B/A)が0.60~0.95の間に反応槽内の圧力を、0.2MPaG未満に低下させる工程 - 工程(2)および工程(3)における分縮器の蒸気側出口温度を155℃以下、且つ水の露点温度から該温度+5℃以下の範囲の温度に制御する請求項1に記載のポリアミドの製造方法。
- 工程(2)における反応槽内の圧力を0.2~0.4MPaGの範囲に制御する請求項1に記載のポリアミドの製造方法。
- 工程(3)における反応槽内の圧力を0.1MPaG以下まで低下させる請求項1に記載のポリアミドの製造方法。
- 工程(1)における反応槽内の圧力を0.2MPaG以上の圧力迄加圧してから、工程(3)で圧力を低下させるまでの間、圧力を一定に制御する請求項1に記載のポリアミドの製造方法。
- ジカルボン酸成分が70モル%以上のアジピン酸を含有する請求項1に記載のポリアミドの製造方法。
- キシリレンジアミンがメタキシリレンジアミンとパラキシリレンジアミンの二成分からなる請求項1に記載のポリアミドの製造方法。
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EP10833192.7A EP2505598B1 (en) | 2009-11-27 | 2010-11-24 | Process for production of polyamide |
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US13/512,179 US9260563B2 (en) | 2009-11-27 | 2010-11-24 | Process for production of polyamide |
JP2011543252A JP5633519B2 (ja) | 2009-11-27 | 2010-11-24 | ポリアミドの製造方法 |
RU2012121840/04A RU2560164C2 (ru) | 2009-11-27 | 2010-11-24 | Способ получения полиамида |
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JP2017110101A (ja) * | 2015-12-16 | 2017-06-22 | 三菱瓦斯化学株式会社 | ポリアミド樹脂および成形品 |
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WO2014065594A1 (ko) * | 2012-10-23 | 2014-05-01 | 제일모직 주식회사 | 폴리아미드의 제조방법 |
JP7397511B2 (ja) * | 2019-05-17 | 2023-12-13 | 成都肆零壹科技有限公司 | 環境に優しいポリアミド樹脂の製造方法 |
KR102525718B1 (ko) | 2019-12-12 | 2023-04-25 | 한화솔루션 주식회사 | 폴리아마이드 제조 장치 및 방법 |
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