WO2019189145A1 - 半芳香族ポリアミド樹脂、及びその製造方法 - Google Patents
半芳香族ポリアミド樹脂、及びその製造方法 Download PDFInfo
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- WO2019189145A1 WO2019189145A1 PCT/JP2019/012803 JP2019012803W WO2019189145A1 WO 2019189145 A1 WO2019189145 A1 WO 2019189145A1 JP 2019012803 W JP2019012803 W JP 2019012803W WO 2019189145 A1 WO2019189145 A1 WO 2019189145A1
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- polyamide resin
- aromatic 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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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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
- C08G69/04—Preparatory processes
- C08G69/06—Solid state polycondensation
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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
- C08G69/48—Polymers modified by chemical after-treatment
Definitions
- the present invention is excellent in heat resistance and heat discoloration, and further can suppress mold contamination due to outgas during melt molding, and has excellent melt fluidity and gelation properties, such as automobile parts, bicycle parts, electric / electronic parts, etc.
- the present invention relates to a semi-aromatic polyamide resin suitable for a resin composition for a molded article.
- thermoplastic resins polyamide resins have been used for clothing, industrial material fibers, engineering plastics, etc., taking advantage of their excellent properties and ease of melt molding.
- engineering plastics are used not only for automobile parts and industrial machine parts but also for various industrial parts, housing parts, electrical / electronic parts, and the like.
- 6T nylon composed of hexamethylenediamine (6) and terephthalic acid (T) is widely known as a polyamide that has been used for engineering plastics and the like.
- a copolyamide obtained from an equivalent molar salt of hexamethylenediamine and terephthalic acid and 11-aminoundecanoic acid has been proposed.
- This copolymerized polyamide has heat resistance, low water absorption, and excellent stability in the surface mounting process.
- the glass transition temperature of the resin is 90 ° C., and injection at a relatively low mold temperature. It is a resin that enables molding and satisfies moldability.
- the present invention has been made against the background of the problems of the prior art. That is, the object of the present invention is to provide a semi-aromatic polyamide resin that is excellent in heat resistance and heat discoloration, and can suppress mold contamination due to outgas during melt molding, and has excellent melt fluidity and gelling properties. There is to do.
- this invention consists of the following structures.
- the relative viscosity (RV) is in the range of formula (1), and an amino group A semi-aromatic polyamide resin in which the relationship between the terminal concentration (AEG), the carboxy group terminal concentration (CEG), and the terminal concentration (EC) in which the amino group terminal is blocked with a monocarboxylic acid satisfies the formulas (2) and (3).
- RV relative viscosity
- the structural unit obtained from hexamethylenediamine and terephthalic acid is 55 to 75 mol%, the structural unit obtained from 11-aminoundecanoic acid or undecane lactam is 45 to 25 mol%, and the melting point is 280 to 330 ° C.
- the sum (P3) of the phosphorus atom content derived from the phosphorus compound detected in the structure of the structural formulas (P1) and (P2) in the semi-aromatic polyamide resin is 30 ppm or more.
- R 1 and R 2 are hydrogen, alkyl group, aryl group, cycloalkyl group or arylalkyl group
- X 1 to X 3 are hydrogen, alkyl group, aryl group, cycloalkyl group, arylalkyl group, alkali metal Or an alkaline earth metal, and one of each of X 1 to X 3 and R 1 to R 2 in each formula may be linked to each other to form a ring structure
- [5] preparing a raw material aqueous solution constituting the semi-aromatic polyamide resin; A raw material introduction step of continuously introducing an aqueous raw material solution into the tubular reactor; An amidation step in which the introduced raw material is passed through a tubular reactor to amidate to obtain a reaction mixture containing an amidated product and condensed water; Introducing the reaction mixture into a continuous reactor capable of separating and removing water, and performing melt polymerization;
- the method for producing a semi-aromatic polyamide resin according to any one of [1] to [4], comprising a step of solid-phase polymerization under vacuum or under a nitrogen stream.
- the present invention it is possible to provide a semi-aromatic polyamide resin which is excellent in heat resistance and heat discoloration, further can suppress mold contamination due to outgas during melt molding, and has excellent melt fluidity and gelling properties. .
- the “semi-aromatic polyamide resin” includes a polymerization catalyst compound described later. Although it can be said to be a kind of “composition” in that it contains things other than a chemical substance called “semiaromatic polyamide”, the amount of the polymerization catalyst compound is very small. Resin ". Even when the chemical substance “semi-aromatic polyamide” is described, it may be referred to as “semi-aromatic polyamide resin”.
- the semi-aromatic polyamide resin is composed of a structural unit obtained from hexamethylenediamine and terephthalic acid (hereinafter also referred to as 6T unit), and a structural unit obtained from 11-aminoundecanoic acid or undecane lactam (hereinafter referred to as 6T unit). , Sometimes referred to as 11 units).
- 6T unit hexamethylenediamine and terephthalic acid
- 11 11-aminoundecanoic acid or undecane lactam
- the ratio of 6T units and 11 units in the semi-aromatic polyamide resin is not particularly limited, but it is desirable that 6T units are 45 to 85 mol% and 11 units are 55 to 15 mol%.
- the 6T unit of the semi-aromatic polyamide resin is preferably 55 to 75 mol%, 11 unit is preferably 45 to 25 mol%, 6T unit is 60 to 70 mol%, and 11 unit is more preferably 40 to 30 mol%. More preferably, the unit is 62 to 68 mol%, and the 11 unit is 38 to 32 mol%. If the 6T unit is less than 55 mol%, the crystallinity and mechanical properties tend to decrease. If the 6T unit exceeds 75 mol%, the melting point of the semi-aromatic polyamide resin exceeds 340 ° C., and the processing temperature required for molding the semi-aromatic polyamide composition by injection molding or the like becomes extremely high. The product may be decomposed during processing and the desired physical properties and appearance may not be obtained. Moreover, since an amide bond density
- the semi-aromatic polyamide resin may be copolymerized with a copolymerizable component other than 6T units and 11 units.
- copolymerizable diamine components include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, and 2-methyl-1,5-pentamethylenediamine.
- copolymerizable dicarboxylic acid components include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 2,2′-diphenyldicarboxylic acid.
- 4,4'-diphenyl ether dicarboxylic acid 5-sulfonic acid sodium isophthalic acid, 5-hydroxyisophthalic acid and other aromatic dicarboxylic acids, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 2-Cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarbo Acid, and an aliphatic or alicyclic dicarboxylic acids such as dimer acid.
- lactams such as ⁇ -caprolactam, 12-aminododecano
- the total number of terminals which is the sum of the amino group terminal concentration (AEG), carboxyl group terminal concentration (CEG), and terminal concentration (EC) blocked with monocarboxylic acid or / and monoamine, and relative viscosity ( RV) is correlated.
- the semi-aromatic polyamide resin of the present invention satisfies the above-described formula (1) and satisfies the ranges shown by the formulas (2) and (3), so that heat resistance and heat discoloration are satisfied.
- EC refers to the terminal concentration of the amino group terminal blocked with a monocarboxylic acid.
- the amino group end, carboxyl group end, and end blocked with monocarboxylic acid or / and monoamine may be referred to as AEG, CEG, and EC, respectively.
- (AEG + CEG) of the semi-aromatic polyamide resin of the present invention is 10 to 140 eq / t, preferably 20 to 130 eq / t, more preferably 30 to 100 eq / t.
- (AEG + CEG) is less than 10 eq / t, the reactive end group does not remain, and the viscosity cannot be increased to RV that can ensure the mechanical strength of the molded product.
- (AEG + CEG) exceeds 140 eq / t, the amount of terminal blocking is small and the remaining amount of AEG and CEG is large, so that the viscosity increases during melt molding and gelation occurs.
- (AEG + CEG) / (AEG + CEG + EC) of the semi-aromatic polyamide resin of the present invention is 0.50 or less, preferably 0.45 or less, more preferably 0.40 or less.
- (AEG + CEG) / (AEG + CEG + EC) exceeds 0.50, the content of the end-blocking agent is small, and the remaining amount of AEG and CEG is large, so that the viscosity increases during melt molding and gelation occurs.
- a polyamide resin undergoes thickening by reacting an amino group terminal and a carboxyl group terminal. However, thickening may proceed due to the reaction of CEG with EC.
- AEG, CEG, and EC need only satisfy the above-described relationship, but preferred ranges thereof are as follows.
- AEG is preferably 5 to 70 eq / t, more preferably 10 to 40 eq / t, and further preferably 15 to 40 eq / t.
- CEG is preferably 5 to 100 eq / t, more preferably 5 to 70 eq / t, and further preferably 15 to 50 eq / t.
- the EC is preferably 60 to 240 eq / t, more preferably 80 to 200 eq /, and still more preferably 80 to 170 eq / t.
- the semi-aromatic polyamide resin of the present invention has a relative viscosity (RV) of 1.95 to 3.50, preferably 1.95 to 3.00, more preferably 2.00 to 2.95, More preferably, it is 2.05 to 2.90.
- RV relative viscosity
- RV is less than 1.95, the mechanical strength of the molded product cannot be obtained.
- RV is larger than 3.50, the fluidity at the time of melt molding becomes low, which is not preferable in terms of melt processability.
- the amount of gas (outgas) generated when the semi-aromatic polyamide resin is thermally decomposed at 330 ° C. for 20 minutes is 500 ppm or less.
- the measurement of outgas is performed by the method described in the section of Examples described later.
- RV By setting the above-mentioned specific terminal, RV, a semi-aromatic polyamide resin with low outgas can be obtained.
- the outgas is preferably 450 ppm or less, more preferably 400 ppm or less, and even more preferably 350 ppm or less.
- the lower limit of outgas is preferably 0 ppm, but is about 250 ppm in the semi-aromatic polyamide resin of the present invention.
- the sum of phosphorus atom contents (P3) derived from phosphorus compounds detected by the structures of structural formulas (P1) and (P2) in the semiaromatic polyamide resin is 30 ppm or more. It is preferable that P3 is 10% or more based on the total amount of phosphorus atoms remaining in the semi-aromatic polyamide resin.
- the phosphorus atom is derived from a phosphorus compound used as a catalyst. P3 is more preferably 40 ppm or more, and further preferably 50 ppm or more.
- P3 In order for P3 to be 30 ppm or more and P3 to be 10% or more based on the total amount of phosphorus atoms remaining, a low-order condensate obtained by polymerizing the polycondensation step at a low temperature was obtained by setting the oxygen concentration of the storage layer to 10 ppm or less. Then, it can achieve by adjusting to a predetermined viscosity by solid phase polymerization with little heat history. Since P3 is 30 ppm or more with respect to the total amount of phosphorus atoms remaining, the total amount of phosphorus atoms remaining in the semi-aromatic polyamide resin is preferably 200 to 400 ppm.
- R 1 and R 2 are hydrogen, alkyl group, aryl group, cycloalkyl group, or arylalkyl group
- X 1 to X 3 are hydrogen, alkyl group, aryl group, cycloalkyl group, arylalkyl group, alkali metal Or an alkaline earth metal, and one of each of X 1 to X 3 and R 1 to R 2 in each formula may be linked to each other to form a ring structure
- R 1 and R 2 are hydrogen
- X 1 to X 3 are hydrogen or sodium, respectively.
- ⁇ Co-b before and after heat treatment in the atmosphere at 260 ° C. for 10 minutes can be 12 or less.
- the semi-aromatic polyamide which makes the gelation time when it heat-processes at 330 degreeC under nitrogen stream for 4 hours or more can be obtained.
- ⁇ Co-b and gelation time are determined by the methods described in the Examples section below.
- a step of preparing a raw material aqueous solution constituting the semi-aromatic polyamide resin a raw material introduction step of continuously introducing the raw material aqueous solution into the tubular reactor, and The raw material is passed through a tubular reactor and amidated to obtain a reaction mixture containing an amidated product and condensed water, and the reaction mixture is introduced into a continuous reactor capable of separating and removing water to perform melt polymerization.
- a step of performing solid phase polymerization under a vacuum or a nitrogen stream is
- Preparation process A predetermined amount of hexamethylenediamine, terephthalic acid, and 11-aminoundecanoic acid or undecane lactam are charged into a pressure resistant reactor. At the same time, water is added so that the raw material concentration becomes 30 to 90% by weight, and a phosphorus compound as a polymerization catalyst and a monocarboxylic acid as a terminal blocking agent are charged. In addition, a foaming inhibitor is added to those that foam in the subsequent process.
- dimethylphosphinic acid dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, ethyl hypophosphite, phosphorous acid compounds and hydrolysates thereof, As well as condensates.
- metal salt, ammonium salt, and ester are mentioned.
- Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony.
- ester ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester and the like can be added.
- sodium hypophosphite is preferred as the catalyst.
- sodium hydroxide it is preferable to add sodium hydroxide from the viewpoint of improving the melt residence stability.
- the timing for adding the end-capping agent is preferably at the time of raw material charging, but it may be at the start of polymerization, at the end of polymerization, or at the end of polymerization.
- the end-capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but acid anhydrides such as monocarboxylic acid or monoamine, phthalic anhydride, mono Isocyanates, monoacid halides, monoesters, monoalcohols, and the like can be used.
- terminal blocking agent examples include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid.
- aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid.
- Acid cycloaliphatic carboxylic acid and other alicyclic monocarboxylic acids, benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and other aromatic monocarboxylic acids, maleic anhydride , Acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, fats such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine Group monoamines, Examples thereof include alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphth
- the salt concentration of the raw material aqueous solution varies depending on the type of polyamide and is not particularly limited, but it is generally desirable that the salt concentration be 30 to 90% by mass. If the salt concentration exceeds 90% by mass, the salt may precipitate due to slight fluctuations in temperature and clog the piping. Also, because the salt solubility needs to be increased, the equipment must be high temperature and high pressure resistant. This is disadvantageous in terms of cost. On the other hand, when the salt concentration is less than 30% by mass, not only is the amount of water evaporated after the initial polymerization step increased, which is disadvantageous in terms of energy, but also causes an increase in cost due to a decrease in productivity. A desirable salt concentration is 35 to 85% by mass.
- the preparation of the salt aqueous solution is generally in the range of 60 to 180 ° C and the pressure of 0 to 1 MPa.
- the equipment has a high temperature and high pressure resistance specification, so that the equipment cost increases, which is disadvantageous.
- the temperature is less than 60 ° C. or the pressure is less than 0 MPa, it not only causes trouble such as clogging of piping due to salt precipitation, but also makes it difficult to increase the salt concentration. It will cause a decline.
- Desirable conditions are a temperature of 70 to 170 ° C. and a pressure of 0.05 to 0.8 MPa, more preferably 75 to 165 ° C. and 0.1 to 0.6 MPa.
- the salt solution storage tank basically has no problem unless salt is precipitated, and the conditions of the salt formation process can be applied as they are.
- the aqueous salt solution prepared in this way is continuously supplied to the amidation step by a supply pump in the raw material introduction step.
- the feed pump used here must be excellent in quantitativeness.
- the fluctuation in the supply amount is a process fluctuation in the amidation process, and as a result, an unstable quality polyamide having a large relative viscosity (RV) deviation is obtained. In this sense, it is recommended to use a plunger pump having excellent quantitativeness as the supply pump.
- Atmospheric oxygen concentration during raw material preparation greatly affects the color tone of the resulting polyamide.
- the atmospheric oxygen concentration at the time of raw material preparation is 10 ppm or less, but if the oxygen concentration exceeds 10 ppm, the yellowishness of the resulting polyamide tends to be strong and the product quality tends to deteriorate.
- the lower limit of the oxygen concentration is not particularly defined, but is, for example, 0.05 ppm or more.
- the oxygen concentration is less than 0.05 ppm, but in order to achieve less than 0.05 ppm, the oxygen removal process becomes more complicated than necessary, and color tone and There is almost no effect on other physical properties.
- a desirable oxygen concentration range is 0.05 ppm or more and 9 ppm or less, and more desirably 0.05 ppm or more and 8 ppm or less.
- the raw material is supplied to a mixing tank (melting tank or raw material salt forming tank) in which oxygen is previously removed and the oxygen concentration is 10 ppm or less, or the raw material is charged into the mixing tank (melting tank or raw material salt forming tank). Later, oxygen is removed and the atmosphere in the mixing tank is adjusted to an oxygen concentration of 10 ppm or less, or both may be used in combination. This may be selected in terms of equipment or operation. Moreover, it is also preferable that the atmosphere in a storage tank shall be 10 ppm or less of oxygen concentration.
- a vacuum replacement method As a method for removing oxygen, there are a vacuum replacement method, a pressure replacement method, or a combination thereof.
- the degree of vacuum or pressurization applied to the substitution and the number of substitutions may be selected under the most efficient conditions for achieving the desired oxygen concentration.
- amidation step the aqueous salt solution introduced continuously at the inlet of the tubular reactor is passed through the tubular reactor for amidation, and the amidation product and condensed water having a low polymerization degree are condensed.
- a reaction mixture comprising: In the tubular reactor, water is not separated and removed.
- the tubular reactor preferably has an L / D of 50 or more, where the inner diameter of the tube is D (mm) and the length of the tube is L (mm).
- the tubular reactor has advantages such as no need for liquid level control due to its structure, high plug flow properties, excellent pressure resistance, and low equipment costs.
- L / D is less than 50, when L is small, the residence time of the reaction mixture flow is shortened, and the degree of increase in relative viscosity (RV) is small.
- RV relative viscosity
- D is large, plug flow properties are small and the residence time is low. A time distribution is created and the desired function is not performed.
- the upper limit of L / D is not particularly defined, but is about 3000 in consideration of the increase in residence time and relative viscosity (RV).
- L / D is more preferably 60 or more for the lower limit, further preferably 80 or more, more preferably 2000 or less for the upper limit, and further preferably 1000 or less. Further, L is preferably 3 m or more for the lower limit, more preferably 5 m or more, and preferably 50 m or less, more preferably 30 m or less for the upper limit.
- the reaction conditions vary depending on the structure of the polyamide and the desired degree of polymerization.
- the internal temperature is 110 to 310 ° C.
- the internal pressure is 0 to 5 MPa
- the average residence time in the tube of the reaction mixture is 10 to 120 minutes. is there.
- the degree of polymerization of the amidation product can be controlled by the internal temperature, internal pressure and average residence time.
- the average residence time is shorter than 10 minutes, the degree of polymerization of the amidation product having a low degree of polymerization is lowered, and as a result, the diamine component is easily scattered during the polycondensation step, making it difficult to adjust the end groups.
- the average residence time is longer than 120 minutes, the amidation reaches equilibrium and the rise in RV reaches its peak, while thermal degradation proceeds, which is not preferable.
- a desirable average residence time is 12 to 110 minutes, more desirably 15 to 100 minutes.
- the average residence time can be controlled by adjusting the inner diameter D of the tube of the tubular reactor, the length L of the tube, or changing the raw material supply amount.
- the relative viscosity (RV) of the reaction mixture is preferably increased by 0.05 to 0.6 at the inlet and outlet of the tubular reactor by the polycondensation reaction in the amidation step.
- RV relative viscosity
- the increase in RV is less than 0.05, the diamine component is likely to be scattered during the polycondensation step, making it difficult to adjust the end groups.
- the increase in RV is greater than 0.6, thermal degradation tends to proceed due to the influence of coexisting condensed water (in the case of the salt forming method, water used for salt formation and condensed water).
- a reaction mixture having an excessively high viscosity causes piping blockage, which may adversely affect the operation.
- a desirable range of RV increase in the amidation step is 0.15 to 0.5, and more desirably 0.2 to 0.4.
- the reaction conditions in the initial polymerization step are an internal pressure of 0 to 5 MPa, an average residence time of 10 to 150 minutes, and the internal temperature is determined according to the Flory melting point lowering formula based on the residual moisture content in the can. Is done. Desirable reaction conditions are an internal temperature of 230 to 285 ° C., an internal pressure of 0.5 to 4.5 MPa, an average residence time of 15 to 140 minutes, and a more desirable reaction condition of an internal temperature of 235 to 280. ° C, the internal pressure is 1.0 to 4.0 MPa, and the average residence time is 20 to 130 minutes.
- reaction conditions deviate from the lower limit of the above range, the ultimate degree of polymerization is too low or the resin is solidified in the can. If the reaction conditions deviate from the upper limit of the above range, decomposition and side reactions of the P3 component occur simultaneously, and P3 is less than 30 ppm, which is disadvantageous for heat-resistant yellowing and gelation characteristics.
- Solid-phase polymerization step The solid-phase polymerization referred to in the present invention refers to a step of proceeding the polymerization reaction under a vacuum or a nitrogen stream at an arbitrary temperature within a range where the semi-aromatic polyamide resin does not melt.
- the equipment for performing the solid phase polymerization is not particularly limited, and examples thereof include a blender and a vacuum dryer. Desirable reaction conditions are an internal temperature of 200 to 260 ° C. and an internal pressure of 0.7 KPa or less, and further desirable reaction conditions are an internal temperature of 210 to 250 ° C. and an internal pressure of 0.4 KPa or less.
- the semi-aromatic polyamide resin of the present invention is particularly preferably used in molding applications and can be formed into a molded body.
- a normal molding method is used. Examples of the molding method include hot melt molding methods such as injection molding, extrusion molding, blow molding, and sintering molding.
- RV t / t 0 (However, t 0 : solvent dropping time t: sample solution dropping time)
- the 31 P resonance frequency is 202.5 MHz
- the detection pulse flip angle is 45 °
- the data acquisition time is 1.5 seconds
- the delay time is 1.0 second
- the integration number is 1000 to 20000 times
- the measurement temperature is room temperature
- Analysis was performed under the conditions of complete proton decoupling, and the molar ratio of the phosphorus compound represented by the structural formula (P1) and the phosphorus compound represented by the structural formula (P2) was determined by the integration ratio.
- Example 1 1,6-hexamethylenediamine 9.13 kg (78.6 mol), terephthalic acid 12.24 kg (73.7 mol), 11-aminoundecanoic acid 7.99 kg (39.7 mol), hypophosphorous acid as catalyst 30.4 g of sodium, 354 g (5.9 mol) of acetic acid as end-capping agent, and 16.20 kg of ion-exchanged water adjusted to a dissolved oxygen concentration of 0.5 ppm or less by bubbling with nitrogen were charged into a 50 liter autoclave. The pressure was increased to 05 MPa with N 2 , the pressure was released, and the pressure was returned to normal pressure.
- This operation was performed 10 times, N 2 substitution was performed, and then uniform dissolution was performed at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, heated to 260 ° C. with a heating pipe, and heat was applied for 0.5 hours. Thereafter, the reaction mixture was supplied to a pressure reaction can, heated to 270 ° C., and a part of water was distilled off so as to maintain the internal pressure of the can at 3 MPa to obtain a low-order condensate. Then, this low-order condensate was taken out in the atmosphere at room temperature and normal pressure, and then dried under an environment of 70 ° C. and a vacuum degree of 0.07 KPa or less using a vacuum dryer.
- the low-order condensate was reacted for 8 hours in an environment of 225 ° C. and a vacuum degree of 0.07 KPa using a blender (capacity 0.1 m 3 ) to obtain a semi-aromatic polyamide resin. Details of the properties of the obtained semi-aromatic polyamide resin are shown in Table 1.
- Example 2 The amount was changed to 9.07 kg (78.1 mol) of 1,6-hexamethylenediamine and 286 g (4.8 mol) of acetic acid as the end-capping agent, and vacuum drying was performed in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), reaction was carried out for 8 hours in an environment of 240 ° C. and a degree of vacuum of 0.07 KPa to obtain a semi-aromatic polyamide resin.
- Example 3 The amount was changed to 9.10 kg (78.3 mol) of 1,6-hexamethylenediamine and 301 g (5.0 mol) of acetic acid as an end-blocking agent, followed by vacuum drying in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), reaction was carried out for 8 hours in an environment of 240 ° C. and a degree of vacuum of 0.07 KPa to obtain a semi-aromatic polyamide resin.
- Example 4 The amount was changed to 8.93 kg (76.9 mol) of 1,6-hexamethylenediamine and 197 g (3.3 mol) of acetic acid as an end-blocking agent, followed by vacuum drying in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), the reaction was carried out for 15 hours in an environment of 245 ° C. and a vacuum degree of 0.07 KPa to obtain a semi-aromatic polyamide resin.
- Example 5 The amount was changed to 8.84 kg (76.1 mol) of 1,6-hexamethylenediamine and 286 g (4.8 mol) of acetic acid as an end-capping agent, followed by vacuum drying in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity: 0.1 m 3 ), reaction was performed in an environment of 230 ° C. and a vacuum degree of 0.07 KPa for 8 hours to obtain a semi-aromatic polyamide resin.
- Example 6 The amount was changed to 9.21 kg (79.3 mol) of 1,6-hexamethylenediamine and 315 g (5.2 mol) of acetic acid as an end-capping agent, and vacuum drying was performed in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), reaction was carried out for 8 hours in an environment of 240 ° C. and a degree of vacuum of 0.07 KPa to obtain a semi-aromatic polyamide resin.
- Example 7 The amount was changed to 9.11 kg (78.4 mol) of 1,6-hexamethylenediamine and 612 g (5.0 mol) of benzoic acid as a terminal blocking agent, and vacuum drying was performed in the same manner as in Example 1 to obtain a low-order condensate. .
- a blender capacity 0.1 m 3
- reaction was carried out for 8 hours in an environment of 240 ° C. and a degree of vacuum of 0.07 KPa to obtain a semi-aromatic polyamide resin.
- Example 8 1,6-hexamethylenediamine 8.00 kg (68.8 mol), terephthalic acid 10.82 kg (65.2 mol), 11-aminoundecanoic acid 10.31 kg (51.2 mol), 280 g of acetic acid as a terminal blocking agent (4.7 mol) was changed to vacuum drying in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), reaction was carried out for 8 hours in an environment of 240 ° C. and a degree of vacuum of 0.07 KPa to obtain a semi-aromatic polyamide resin.
- Example 9 9.67 kg (83.2 mol) of 1,6-hexamethylenediamine, 13.00 kg (78.3 mol) of terephthalic acid, 6.75 kg (33.6 mol) of 11-aminoundecanoic acid, 284 g of acetic acid as a terminal blocking agent (4.7 mol) was changed to vacuum drying in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), reaction was carried out for 8 hours in an environment of 240 ° C. and a degree of vacuum of 0.07 KPa to obtain a semi-aromatic polyamide resin.
- Example 10 1,6-hexamethylenediamine 6.69 kg (57.6 mol), terephthalic acid 8.98 kg (54.1 mol), 11-aminoundecanoic acid 13.3 kg (66.1 mol), 296 g of acetic acid as end-capping agent (4.9 mol) was changed to vacuum drying in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), the reaction was carried out in an environment of 230 ° C. and a vacuum degree of 0.07 KPa for 6 hours to obtain a semi-aromatic polyamide resin.
- Example 11 1,6-hexamethylenediamine 10.8 kg (92.6 mol), terephthalic acid 14.5 kg (87.3 mol), 11-aminoundecanoic acid 4.38 kg (21.8 mol), 310 g of acetic acid as end-capping agent (5.2 mol) was changed to vacuum drying in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), the reaction was carried out in an environment of 230 ° C. and a vacuum degree of 0.07 KPa for 6 hours to obtain a semi-aromatic polyamide resin.
- Example 12 The amount was changed to 8.96 kg (77.1 mol) of 1,6-hexamethylenediamine, 9 g of sodium hypophosphite, and 223 g (3.7 mol) of acetic acid. Obtained. Next, using a blender (capacity 0.1 m 3 ), the reaction was carried out in an environment of 230 ° C. and a vacuum degree of 0.07 KPa for 6 hours to obtain a semi-aromatic polyamide resin.
- Example 13 1,6-hexamethylenediamine 9.00 kg (77.4 mol), terephthalic acid 12.24 kg (73.7 mol), 11-aminoundecanoic acid 7.99 kg (39.7 mol), hypophosphorous acid as catalyst 30.4 g of sodium, 226 g (3.8 mol) of acetic acid as an end-blocking agent, and 16.20 kg of ion-exchanged water adjusted to a dissolved oxygen concentration of 0.5 ppm or less by bubbling with nitrogen were charged into a 50 liter autoclave, and the pressure was changed from normal pressure to 0. The pressure was increased to 05 MPa with N 2 , the pressure was released, and the pressure was returned to normal pressure.
- This operation was performed 10 times, N 2 substitution was performed, and then uniform dissolution was performed at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, heated to 260 ° C. with a heating pipe, and heat was applied for 0.5 hours. Thereafter, the reaction mixture was supplied to a pressure reaction can, heated to 290 ° C., and a part of water was distilled off so as to maintain the internal pressure of the can at 3 MPa to obtain a low-order condensate. Then, this low-order condensate was taken out in the atmosphere at room temperature and normal pressure, and then dried under an environment of 70 ° C. and a vacuum degree of 0.07 KPa or less using a vacuum dryer.
- the low-order condensate was reacted for 6 hours in an environment of 230 ° C. and a vacuum degree of 0.07 KPa using a blender (capacity 0.1 m 3 ) to obtain a semi-aromatic polyamide resin.
- Example 14 The amount was changed to 8.87 kg (76.3 mol) of 1,6-hexamethylenediamine and 114 g (1.9 mol) of acetic acid, and vacuum drying was performed in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), the reaction was carried out in an environment of 210 ° C. and a vacuum degree of 0.07 KPa for 10 hours to obtain a semi-aromatic polyamide resin.
- Example 15 The amount was changed to 8.89 kg (76.5 mol) of 1,6-hexamethylenediamine and 150 g (2.5 mol) of acetic acid, and vacuum drying was performed in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), reaction was carried out in an environment of 235 ° C. and a vacuum degree of 0.07 KPa for 12 hours to obtain a semi-aromatic polyamide resin.
- Comparative Example 1 The amount was changed to 8.72 kg (75.0 mol) of 1,6-hexamethylenediamine and 32 g (0.5 mol) of acetic acid as a terminal blocking agent, followed by vacuum drying in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), the reaction was carried out in an environment of 180 ° C. and a vacuum degree of 0.07 KPa for 5 hours to obtain a semi-aromatic polyamide resin.
- Comparative Example 3 The amount was changed to 8.67 kg (74.6 mol) of 1,6-hexamethylenediamine and 183 g (3.1 mol) of acetic acid as an end-blocking agent, followed by vacuum drying in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), the reaction was carried out in an environment of 240 ° C. and a vacuum degree of 0.07 KPa for 9 hours to obtain a semi-aromatic polyamide resin.
- Comparative Example 4 The amount was changed to 8.67 kg (74.6 mol) of 1,6-hexamethylenediamine and 183 g (3.1 mol) of acetic acid as an end-blocking agent, followed by vacuum drying in the same manner as in Example 1 to obtain a low-order condensate. Next, using a blender (capacity 0.1 m 3 ), the reaction was carried out in an environment of 240 ° C. and a vacuum degree of 0.07 KPa for 5 hours to obtain a semi-aromatic polyamide resin.
- reaction mixture was supplied to a pressure reaction can, heated to 290 ° C., and a part of water was distilled off so as to maintain the internal pressure of the can at 3 MPa to obtain a low-order condensate (end blockage of 0). %).
- the polycondensation proceeded under melting while the resin temperature was 335 ° C. and water was extracted from three vents to obtain a semi-aromatic polyamide resin.
- Table 1 shows the details of the characteristics of the semi-aromatic polyamide resin obtained in each example and each comparative example.
- Comparative Example 1 it is found that AEG + CEG> 140 eq / t, the residual amount of AEG and CEG is large, and the resin is easily gelled. Moreover, it is (AEG + CEG) / (AEG + CEG + EC)> 0.50, and it turns out that it is resin which has few amounts of terminal blockers and is easy to gelatinize. In Comparative Examples 2 to 4, (AEG + CEG) / (AEG + CEG + EC)> 0.50, and the amide exchange reaction progresses due to the excessive acid component at the carboxyl group terminal, and the outgas component derived from the terminal blockage increases. Recognize.
- a semi-aromatic polyamide resin suitable for the above resin composition can be provided, and is expected to greatly contribute to the industrial world.
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Abstract
Description
すなわち、本発明は、以下の構成からなる。
1.95≦RV≦3.50 ・・ (1)
10eq/t≦AEG+CEG≦140eq/t ・・ (2)
(AEG+CEG)/(AEG+CEG+EC)≦0.50 ・・ (3)
原料水溶液を管状反応装置に連続的に導入する原料導入工程と、
導入された原料を管状反応装置内を通過させアミド化を行いアミド化物と縮合水とを含む反応混合物を得るアミド化工程と、
反応混合物を水分離除去可能な連続式反応装置に導入して溶融重合を行う工程と、
真空下または窒素気流下で固相重合を行う工程を含む、[1]~[4]のいずれかに記載の半芳香族ポリアミド樹脂の製造方法。
共重合可能なジアミン成分としては、1,2-エチレンジアミン、1,3-トリメチレンジアミン、1,4-テトラメチレンジアミン、1,5-ペンタメチレンジアミン、2-メチル-1,5-ペンタメチレンジアミン、1,7-ヘプタメチレンジアミン、1,8-オクタメチレンジアミン、1、9-ノナメチレンジアミン、2-メチル―1,8-オクタメチレンジアミン、1,10-デカメチレンジアミン、1,11-ウンデカメチレンジアミン、1,12-ドデカメチレンジアミン、1,13-トリデカメチレンジアミン、1,16-ヘキサデカメチレンジアミン、1,18-オクタデカメチレンジアミン、2,2,4(または2,4,4)-トリメチルヘキサメチレンジアミンのような脂肪族ジアミン、ピペラジン、シクロヘキサンジアミン、ビス(3-メチル-4-アミノヘキシル)メタン、ビス-(4,4’-アミノシクロヘキシル)メタン、イソホロンジアミンのような脂環式ジアミン、メタキシリレンジアミン、パラキシリレンジアミン、パラフェニレンジアミン、メタフェニレンジアミンなどの芳香族ジアミンおよびこれらの水添物等が挙げられ、これらを単独もしくは複数使用することが可能である。
共重合可能なジカルボン酸成分としては、イソフタル酸、オルソフタル酸、1,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボンル酸、4,4’-ジフェニルジカルボン酸、2,2’-ジフェニルジカルボン酸、4,4’-ジフェニルエーテルジカルボン酸、5-スルホン酸ナトリウムイソフタル酸、5-ヒドロキシイソフタル酸等の芳香族ジカルボン酸、フマル酸、マレイン酸、コハク酸、イタコン酸、アジピン酸、アゼライン酸、セバシン酸、1,11-ウンデカン二酸、1,12-ドデカン二酸、1,14-テトラデカン二酸、1,18-オクタデカン二酸、1,4-シクロヘキサンジカルボン酸、1,3-シクロヘキサンジカルボン酸、1,2-シクロヘキサンジカルボン酸、4-メチル-1,2-シクロヘキサンジカルボン酸、ダイマー酸等の脂肪族や脂環族ジカルボン酸等が挙げられる。また、ε-カプロラクタム、12-アミノドデカン酸、12-ラウリルラクタムなどのラクタムおよびこれらが開環した構造であるアミノカルボン酸などが挙げられる。
なお、便宜上、アミノ基末端、カルボキシル基末端、及びモノカルボン酸又は/及びモノアミンで封鎖した末端を、それぞれAEG、CEG、及びECと称することもある。
残存する全リン原子量に対してP3が10%未満の場合は、重合時の熱履歴による熱ダメージを受けている場合や重合系内に残存する酸素と反応し酸化劣化が進行していることを意味しており、着色しやすくゲル化しやすい樹脂となってしまう。残存する全リン原子量に対してP3の比率の上限は特に定めないが、本発明においては50%程度である。
P3が30ppm以上であり、且つ残存する全リン原子量に対してP3が10%以上とするには貯蔵層の酸素濃度を10ppm以下とし、重縮合工程を低温で重合した低次縮合物を得た後、熱履歴の少ない固相重合により所定の粘度まで調整することで達成できる。
残存する全リン原子量に対してP3が30ppm以上とするため、半芳香族ポリアミド樹脂中に残存する全リン原子量は、200~400ppmが好ましい。
耐圧反応缶に、ヘキサメチレンジアミンとテレフタル酸と、11-アミノウンデカン酸又はウンデカンラクタムをそれぞれ所定量、投入する。同時に、原料濃度が30~90重量%となるように水を加え、重合触媒であるリン化合物、末端封鎖剤であるモノカルボン酸を仕込む。また、後工程で発泡するものには、発泡抑制剤を投入する。
原料調合工程において調整された塩水溶液を、管路を通じて供給ポンプによってアミド化工程の管状反応装置の入口に連続的に導入する。
アミド化工程では、管状反応装置の入口に連続的に導入された塩水溶液を、管状反応装置内を通過させアミド化を行い、低重合度のアミド化生成物と縮合水とを含む反応混合物を得る。管状反応装置内では、水の分離除去は行われない。
初期重合工程における反応条件は、内圧は0~5MPaであり、平均滞留時間は10~150分であり、内温は缶内の残存水分率によるFloryの融点降下式に従い決定される。望ましい反応条件は、内温は230~285℃であり、内圧は0.5~4.5MPaであり、平均滞留時間は15~140分であり、さらに望ましい反応条件は、内温は235~280℃であり、内圧は1.0~4.0MPaであり、平均滞留時間は20~130分である。反応条件が上記範囲の下限から外れると到達重合度が低すぎたり、缶内で樹脂が固化してしまうなど好ましくない。反応条件が上記範囲の上限から外れると、P3成分の分解や副反応が併発し、P3が30ppm未満となるため、耐熱黄変性やゲル化特性に不利である。
本発明でいう固相重合は、半芳香族ポリアミド樹脂が溶融しない範囲の任意の温度で、真空下または窒素気流下で重合反応を進める工程をいう。固相重合を行う設備は、特に限定はされないが、ブレンダーや真空乾燥機が例として挙げられる。望ましい反応条件は、内温は200~260℃であり、内圧は0.7KPa以下であり、さらに望ましい反応条件は、内温は210~250℃であり、内圧は0.4KPa以下である。
ポリアミド樹脂3mgを秤量し、熱分解GC/MS(Shimadzu製PY-2020iD)を用いて330℃×20分間のHe下で発生するガスの量を測定した。定量値は標準物質にジメチルシロキサン環状4量体を用いて換算した。カラム:Rxi-5ms、注入口圧力:80KPa、スプリット比:30、カラムオーブン温度:40℃(2分)-300℃(15分)、昇温速度:10分/℃、質量測定範囲:m/z30-550。
試料0.25gを96%硫酸25mlに溶解し、この溶液10mlをオストワルド粘度管に入れ20℃で測定、下式より求めた。
RV=t/t0
(但し、t0:溶媒の落下秒数 t:試料溶液の落下秒数)
半芳香族ポリアミド樹脂20mgを重水素化クロロホルム(CDCl3)/ヘキサフルオロイソプロパノール(HFIP)=1/1(Vol比)の混合溶媒0.6mlに溶解し、重蟻酸を滴下後、500MHzフーリエ変換核磁気共鳴装置(BRUKER社製AVANCE500)を用いて、1H-NMR分析を行い、その積分比より決定した。
サンプル5mgをアルミニウム製サンプルパンに入れて密封し、ティー・エイ・インスツルメント・ジャパン(株)製示差走査熱量分析計(DSC)DSC-Q100を用いて、350℃まで、昇温速度20℃/分にて測定し、融解熱の最大ピーク温度を結晶融点として求めた。
試料を硝酸イットリウム法により溶液化し、ICP(日立ハイテクサイエンス製 SPECTROBLUE)で分析した。白金るつぼに試料0.1gを秤量し、5%の硝酸イットリウムのエタノール溶液を5mL添加し、硝酸塩灰化処理を実施した。灰化残渣に1.2Nの塩酸を20mL添加し、一晩浸漬した。完全溶解を確認したのち、溶液をICP発光分析装置にかけ、214nmの波長のリンの発光強度を測定し、溶液中のリン濃度を定量後、試料中のリン含有量に換算した。
試料340~350mgを重水素化クロロホルム(CDCl3)/ヘキサフルオロイソプロパノール(HFIP)=1/1(Vol比)の混合溶媒2.5mlに室温で溶解させ、トリ(t-ブチルフェニール)リン酸(以下、TBPPAと略称)をPとしてポリアミド樹脂に対して100ppm添加し、さらに室温でトリフロロ酢酸を0.1ml加え、30分後にフーリエ変換核磁気共鳴装置(BRUKER社製AVANCE500)にて31P-NMR分析を行った。なお、31P共鳴周波数は202.5MHz、検出パルスのフリップ角は45°、データ取り込み時間は1.5秒、遅延時間は1.0秒、積算回数は1000~20000回、測定温度は室温、プロトン完全デカップリングの条件で分析を行い、その積分比により構造式(P1)で表されるリン化合物と構造式(P2)で表されるリン化合物とのモル比を求めた。
上記、ICPで求めたP化合物量と31P-NMRで求めたP1、P2のモル比からP1、P2の量をそれぞれ算出し、その合計をP3とした。
ポリアミド樹脂10gを液体窒素により冷凍凍結後、粉砕機(大阪ケミカル製 ABLOLUTE 3)にて15000rpmで3分間粉砕し、粉末とした。カラーメーター(日本電色社製 ZE 2000)を用いて粉砕したポリアミド樹脂のCo-bを測定した。ポリアミド樹脂をシャーレ上に薄く敷き、260℃に加温されたギアオーブン(TABAI製 GEER OVEN GHPS-222)中に入れ、大気下で10分間熱処理した樹脂のCo-b値を測定し、熱処理前後の差をΔCo-bとした。
ポリアミド樹脂3gをアンプル管に入れ、330℃に加温されたイナートオーブン(TAMATO製 DN4101)に10l/min窒素気流下で所定の時間熱処理を行った。熱処理した樹脂0.25gを96%硫酸25mlに溶解し、不溶物が出てくる熱処理時間をゲル化時間とした。
1,6-ヘキサメチレンジアミン9.13kg(78.6モル)、テレフタル酸12.24kg(73.7モル)、11-アミノウンデカン酸7.99kg(39.7モル)、触媒として次亜リン酸ナトリウム30.4g、末端封鎖剤として酢酸354g(5.9モル)および窒素バブリングし溶存酸素を0.5ppm以下に調整したイオン交換水16.20kgを50リットルのオートクレーブに仕込み、常圧から0.05MPaまでN2で加圧し、放圧させ、常圧に戻した。この操作を10回行い、N2置換を行った後、攪拌下135℃、0.3MPaにて均一溶解させた。その後、溶解液を送液ポンプにより、連続的に供給し、加熱配管で260℃まで昇温させ、0.5時間、熱を加えた。その後、加圧反応缶に反応混合物が供給され、270℃に加熱され、缶内圧を3MPaで維持するように、水の一部を留出させ、低次縮合物を得た。その後、この低次縮合物を大気中、常温、常圧の容器に取り出した後、真空乾燥機を用いて、70℃、真空度0.07KPa以下の環境下で乾燥した。乾燥後、低次縮合物をブレンダー(容量0.1m3)を用いて、225℃、真空度0.07KPaの環境で8時間反応させ、半芳香族ポリアミド樹脂を得た。得られた半芳香族ポリアミド樹脂の特性の詳細を表1に示す。
1,6-ヘキサメチレンジアミン9.07kg(78.1モル)、末端封鎖剤として酢酸286g(4.8モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、240℃、真空度0.07KPaの環境で8時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン9.10kg(78.3モル)、末端封鎖剤として酢酸301g(5.0モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、240℃、真空度0.07KPaの環境で8時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン8.93kg(76.9モル)、末端封鎖剤として酢酸197g(3.3モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、245℃、真空度0.07KPaの環境で15時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン8.84kg(76.1モル)、末端封鎖剤として酢酸286g(4.8モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、230℃、真空度0.07KPaの環境で8時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン9.21kg(79.3モル)、末端封鎖剤として酢酸315g(5.2モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、240℃、真空度0.07KPaの環境で8時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン9.11kg(78.4モル)、末端封鎖剤として安息香酸612g(5.0モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、240℃、真空度0.07KPaの環境で8時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン8.00kg(68.8モル)、テレフタル酸10.82kg(65.2モル)、11-アミノウンデカン酸10.31kg(51.2モル)、末端封鎖剤として酢酸280g(4.7モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、240℃、真空度0.07KPaの環境で8時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン9.67kg(83.2モル)、テレフタル酸13.00kg(78.3モル)、11-アミノウンデカン酸6.75kg(33.6モル)、末端封鎖剤として酢酸284g(4.7モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、240℃、真空度0.07KPaの環境で8時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン6.69kg(57.6モル)、テレフタル酸8.98kg(54.1モル)、11-アミノウンデカン酸13.3kg(66.1モル)、末端封鎖剤として酢酸296g(4.9モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、230℃、真空度0.07KPaの環境で6時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン10.8kg(92.6モル)、テレフタル酸14.5kg(87.3モル)、11-アミノウンデカン酸4.38kg(21.8モル)、末端封鎖剤として酢酸310g(5.2モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、230℃、真空度0.07KPaの環境で6時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン8.96kg(77.1モル)、次亜リン酸ナトリウム9g、酢酸223g(3.7モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、230℃、真空度0.07KPaの環境で6時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン9.00kg(77.4モル)、テレフタル酸12.24kg(73.7モル)、11-アミノウンデカン酸7.99kg(39.7モル)、触媒として次亜リン酸ナトリウム30.4g、末端封鎖剤として酢酸226g(3.8モル)および窒素バブリングし溶存酸素を0.5ppm以下に調整したイオン交換水16.20kgを50リットルのオートクレーブに仕込み、常圧から0.05MPaまでN2で加圧し、放圧させ、常圧に戻した。この操作を10回行い、N2置換を行った後、攪拌下135℃、0.3MPaにて均一溶解させた。その後、溶解液を送液ポンプにより、連続的に供給し、加熱配管で260℃まで昇温させ、0.5時間、熱を加えた。その後、加圧反応缶に反応混合物が供給され、290℃に加熱され、缶内圧を3MPaで維持するように、水の一部を留出させ、低次縮合物を得た。その後、この低次縮合物を大気中、常温、常圧の容器に取り出した後、真空乾燥機を用いて、70℃、真空度0.07KPa以下の環境下で乾燥した。乾燥後、低次縮合物をブレンダー(容量0.1m3)を用いて、230℃、真空度0.07KPaの環境で6時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン8.87kg(76.3モル)、酢酸114g(1.9モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、210℃、真空度0.07KPaの環境で10時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン8.89kg(76.5モル)、酢酸150g(2.5モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、235℃、真空度0.07KPaの環境で12時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン8.72kg(75.0モル)、末端封鎖剤として酢酸32g(0.5モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、180℃、真空度0.07KPaの環境で5時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン8.57kg(73.8モル)、末端封鎖剤として酢酸150g(4.4モル)、触媒として次亜リン酸ナトリウム9gに変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、220℃、真空度0.07KPaの環境で4時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン8.67kg(74.6モル)、末端封鎖剤として酢酸183g(3.1モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、240℃、真空度0.07KPaの環境で9時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン8.67kg(74.6モル)、末端封鎖剤として酢酸183g(3.1モル)に変更し、実施例1同様に真空乾燥まで行い低次縮合物を得た。次いでブレンダー(容量0.1m3)を用いて、240℃、真空度0.07KPaの環境で5時間反応させ、半芳香族ポリアミド樹脂を得た。
1,6-ヘキサメチレンジアミン7.54kg(65.0モル)、テレフタル酸10.79kg(65.0モル)、11-アミノウンデカン酸7.04kg(35.0モル)、触媒として次亜リン酸ナトリウム9g、イオン交換水17.52kgを50リットルのオートクレーブに仕込み、常圧から0.05MPaまでN2で加圧し、放圧させ、常圧に戻した。この操作を3回行い、N2置換を行った後、攪拌下135℃、0.3MPaにて均一溶解させた。その後、溶解液を送液ポンプにより、連続的に供給し、加熱配管で240℃まで昇温させ、1時間、熱を加えた。その後、加圧反応缶に反応混合物が供給され、290℃に加熱され、缶内圧を3MPaで維持するように、水の一部を留出させ、低次縮合物を得た(末端封鎖率0%)。その後、この低次縮合物を、溶融状態を維持したまま直接二軸押出し機(スクリュー径37mm、L/D=60)に供給し、末端封鎖剤として酢酸107g(1.8モル)を添加しながら、樹脂温度を335℃、3箇所のベントから水を抜きながら溶融下で重縮合を進め、半芳香族ポリアミド樹脂を得た。
各実施例、各比較例で得られた半芳香族ポリアミド樹脂の特性の詳細を表1に示す。
比較例2~4は、(AEG+CEG)/(AEG+CEG+EC)>0.50であり、カルボキシル基末端の過剰な酸成分によりアミド交換反応が進行し、末端封鎖由来のアウトガス成分が増加していることがわかる。また、着色反応が併発し色調安定性に劣り、またゲル化しやすい樹脂となっている。
比較例5は、二軸押し出し機で溶融重合し所定のRVまで増粘させているためP3成分が残存しておらず、アウトガス、ΔCo-b、ゲル化時間が悪化していることがわかる。
Claims (5)
- ヘキサメチレンジアミンとテレフタル酸から得られる構成単位、及び11-アミノウンデカン酸又はウンデカンラクタムから得られる構成単位を含有し、相対粘度(RV)が式(1)の範囲であり、アミノ基末端濃度(AEG)、カルボキシ基末端濃度(CEG)及びモノカルボン酸でアミノ基末端を封鎖した末端濃度(EC)の関係が式(2)及び(3)を満たす半芳香族ポリアミド樹脂。
1.95≦RV≦3.50 ・・ (1)
10eq/t≦AEG+CEG≦140eq/t ・・ (2)
(AEG+CEG)/(AEG+CEG+EC)≦0.50 ・・ (3) - ヘキサメチレンジアミンとテレフタル酸から得られる構成単位が55~75モル%、11-アミノウンデカン酸又はウンデカンラクタムから得られる構成単位が45~25モル%であり、融点が280~330℃である請求項1に記載の半芳香族ポリアミド樹脂。
- 半芳香族ポリアミド樹脂を、330℃、20分間熱分解した際に発生するガス量(アウトガス)が500ppm以下である請求項1~3のいずれかに記載の半芳香族ポリアミド樹脂。
- 半芳香族ポリアミド樹脂を構成する原料水溶液を調合する工程と、
原料水溶液を管状反応装置に連続的に導入する原料導入工程と、
導入された原料を管状反応装置内を通過させアミド化を行いアミド化物と縮合水とを含む反応混合物を得るアミド化工程と、
反応混合物を水分離除去可能な連続式反応装置に導入して溶融重合を行う工程と、
真空下または窒素気流下で固相重合を行う工程を含む、請求項1~4のいずれかに記載の半芳香族ポリアミド樹脂の製造方法。
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