Patent Application
20210301084
The present invention relates to a method for producing an amorphous polyamide resin.
Polyamide resins obtained by polycondensation reaction of a diamine and a dicarboxylic acid have been researched for many years, and resins with various chemical structures have been used in various fields. Typical examples include polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, and polyamide MXD6, named by the type of raw material monomers that are used.
Meanwhile, in recent years, amorphous polyamide resins have been synthesized, and research of such resins has been advancing. Amorphous polyamide resins exhibit a high level of transparency, and through the use of this characteristic, such amorphous resins are beginning to be used in a wide range of applications from daily necessities such as various packaging containers, switch covers, and frames for lenses and eyeglasses, to industrial products and applications requiring design properties.
Patent Document 1 discloses, as such an amorphous polyamide resin, an amorphous polyamide resin that contains a constituent unit derived from a diamine and a constituent unit derived from a dicarboxylic acid, and is substantially free of constituent units derived from terephthalic acid, wherein at least 70 mol % of the constituent unit derived from a diamine is derived from 1,3-bis(aminomethyl)cyclohexane, and of the constituent unit derived from a dicarboxylic acid, from 10 to 90 mol % is derived from isophthalic acid and from 90 to 10 mol % is derived from a linear aliphatic dicarboxylic acid having from 8 to 12 carbons.
Patent Document 1: WO 2016/208272
Here, the applicant of the present invention is developing, as amorphous polyamide resins, resins having a constituent unit derived from isophoronediamine, a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons, and a constituent unit derived from an aromatic dicarboxylic acid.
Furthermore, through further examinations conducted by the present inventors, it was discovered that in the amorphous polyamide resins developed by the applicant, minute foreign matter may be produced in the resins. The foreign matter is not of a level that is particularly problematic in ordinary products, but depending on the application such as films, thin-walled molded articles, and products requiring exceptionally high exterior appearance characteristics, improvements over foreign matter are desirable.
Thus, an object of the present invention is to solve such problems by providing a method for producing an amorphous polyamide resin that can suppress or prevent the generation of foreign matter in resin when producing an amorphous polyamide resin having a constituent unit derived from isophoronediamine, a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons, and a constituent unit derived from an aromatic dicarboxylic acid.
The present inventors conducted examinations on the basis of the above problems, and as a result, discovered that the above object can be achieved by adding, as an aqueous solution, a phosphorus atom-containing compound that is used as a catalyst when synthesizing a specific amorphous polyamide resin. Specifically, the problems described above are solved by the following means <1>, and preferably by the following means <2>to <11>.
<1>An method for producing an amorphous polyamide resin including subjecting a diamine component and a dicarboxylic acid component to melt polycondensation reaction in presence of a phosphorus atom-containing compound, the diamine component including 70 mol % or more of isophoronediamine, and the dicarboxylic acid component including an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons and an aromatic dicarboxylic acid; wherein a thermal decomposition temperature of the phosphorus-atom containing compound is equal to or above a maximum attainable temperature reached in the melt polycondensation reaction; and the melt polycondensation reaction is conducted by adding an aqueous solution of the phosphorus atom-containing compound, and the diamine component to the dicarboxylic acid component in a molten state.
<2>The method for producing an amorphous polyamide resin according to <1>, wherein the phosphorus atom-containing compound is at least one selected of an alkali metal salt of hypophosphorous acid, an alkaline earth metal salt of hypophosphorous acid, an alkali metal salt of phosphorous acid, an alkaline earth metal salt of phosphorous acid, an alkali metal salt of phosphoric acid, an alkaline earth metal salt of phosphoric acid, an alkali metal salt of pyrophosphoric acid, an alkaline earth metal salt of pyrophosphoric acid, an alkali metal salt of metaphosphoric acid, and an alkaline earth metal salt of metaphosphoric acid.
<3>The method for producing an amorphous polyamide resin according to <1>, wherein the phosphorus atom-containing compound is at least one selected of an alkali metal salt of hypophosphorous acid, an alkaline earth metal salt of hypophosphorous acid, an alkali metal salt of phosphorous acid, an alkaline earth metal salt of phosphorous acid, an alkali metal salt of metaphosphoric acid, and an alkaline earth metal salt of metaphosphoric acid.
<4>The method for producing an amorphous polyamide resin according to any one of <1>to <3>, further including performing the melt polycondensation reaction in presence of a polymerization rate modifier.
<5>The method for producing an amorphous polyamide resin according to <4>, wherein the polymerization rate modifier is at least one selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal acetates, and alkaline earth metal acetates.
<6>The method for producing an amorphous polyamide resin according to any one of <1>to <5>, wherein the maximum attainable temperature reached in the melt polycondensation reaction is from 200° C. to 300° C.
<7>The method for producing an amorphous polyamide resin according to any one of <1>to <6>, wherein the thermal decomposition temperature of the phosphorus atom-containing compound is 200° C. or higher.
<8>The method for producing an amorphous polyamide resin according to any one of <1>to <7>, wherein the amorphous polyamide resin includes a constituent unit derived from a diamine and a constituent unit derived from a dicarboxylic acid, and of the constituent unit derived from a diamine, from 30 to 80 mol % is a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons, and from 70 to 20 mol % is a constituent unit derived from an aromatic dicarboxylic acid.
<9>The method for producing an amorphous polyamide resin according to <8>, wherein in the amorphous polyamide resin, the constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons includes at least one of a constituent unit derived from sebacic acid and a constituent unit derived from dodecanedioic acid.
<10>The method for producing an amorphous polyamide resin according to <8>or <9>, wherein in the amorphous polyamide resin, the constituent unit derived from an aromatic dicarboxylic acid includes at least one of a constituent unit derived from 2,6-naphthalene dicarboxylic acid and a constituent unit derived from isophthalic acid.
<11>The method for producing an amorphous polyamide resin according to any one of <1>to <7>, wherein the amorphous polyamide resin includes a constituent unit derived from a diamine and a constituent unit derived from a dicarboxylic acid; at least 90 mol % of the constituent unit derived from a diamine is a constituent unit derived from isophoronediamine; of the constituent unit derived from a dicarboxylic acid, from 30 to 80 mol % is a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons, and from 70 to 20 mol % is a constituent unit derived from an aromatic dicarboxylic acid; the constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons includes at least one of a constituent unit derived from sebacic acid and a constituent unit derived from dodecanedioic acid; and the constituent unit derived from an aromatic dicarboxylic acid includes at least one of a constituent unit derived from 2,6-naphthalene dicarboxylic acid and a constituent unit derived from isophthalic acid.
According to the present invention, when producing an amorphous polyamide resin having a constituent unit derived from isophoronediamine, a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons, and a constituent unit derived from an aromatic dicarboxylic acid, the generation of foreign matter in the resin can be suppressed or prevented.
The contents of the present invention will be described in detail below. Note that in the present specification, “from . . . to . . . ” is used to mean that the given numerical values are included as the lower limit and the upper limit, respectively.
The method for producing an amorphous polyamide resin of the present invention is characterized in that a diamine component and a dicarboxylic acid component are subjected to melt polycondensation reaction in the presence of a phosphorus atom-containing compound, the diamine component including 70 mol % or more of isophoronediamine, and the dicarboxylic acid component including an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons; a thermal decomposition temperature of the phosphorus-atom containing compound is equal to or above a maximum attainable temperature reached in the melt polycondensation reaction; and the melt polycondensation reaction is conducted by adding an aqueous solution of the phosphorus atom-containing compound, and the diamine component to the dicarboxylic acid component in a molten state. According to the present production method, foreign matter generated in the obtained amorphous polyamide resin can be suppressed or prevented.
The amorphous polyamide resin in the present invention is a polyamide resin that does not have a definite melting point, and specifically, it is a polyamide resin having a crystal melting enthalpy ΔHm of less than 5 J/g, preferably 3 J/g or less, and more preferably 1 J/g or less. The crystal melting enthalpy ΔHm is measured in accordance with a method described in the examples below.
The amorphous polyamide resin produced by the production method of the present invention is such that at least 70 mol % of the constituent unit derived from a diamine is a constituent unit derived from isophoronediamine, and preferably at least 80 mol %, more preferably at least 90 mol %, even more preferably at least 95 mol %, and yet even more preferably at least 99 mol % of the constituent unit derived from a diamine is a constituent unit derived from isophoronediamine. By adding isophoronediamine at a ratio greater than or equal to the lower limit described above, a higher transparency can be imparted to the molded article with less haze, which is preferable.
In the amorphous polyamide resin obtained by the production method according to the present invention, preferably, the constituent unit derived from a dicarboxylic acid includes a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons and a constituent unit derived from an aromatic dicarboxylic acid, and of the constituent unit derived from a dicarboxylic acid, from 30 to 80 mol % is a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons, and from 70 to 20 mol % is a constituent unit derived from an aromatic dicarboxylic acid (provided that the total does not exceed 100 mol %).
Preferably from 30 to 80 mol %, more preferably from 45 to 80 mol %, further preferably from 50 to 80 mol %, even more preferably from 60 to 80 mol %, and yet even more preferably 65 to 80 mol % of the constituent unit derived from a dicarboxylic acid is a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons.
In the present invention, it is preferable that the number of carbons of the constituent unit derived from the linear aliphatic dicarboxylic acid forms an appropriate length in terms of the various performance aspects of the obtained amorphous polyamide. From this perspective, the number of carbons of the α,ω-linear aliphatic dicarboxylic acid is more preferably from 10 to 12.
Furthermore, preferably from 70 to 20 mol %, more preferably from 55 to 20 mol %, further preferably from 50 to 20 mol %, even more preferably from 40 to 20 mol %, and yet even more preferably from 35 to 20 mol % of the constituent unit derived from a dicarboxylic acid is a constituent unit derived from an aromatic dicarboxylic acid.
In the amorphous polyamide resin, for each of the α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons and the aromatic dicarboxylic acid, one type, or two or more types may each be used. When two or more types are used, the total amount is preferably within the range described above.
In the present invention, of the constituent unit derived from a dicarboxylic acid, the total amount of the constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons and the constituent unit derived from an aromatic dicarboxylic acid accounts for preferably at least 90 mol %, more preferably at least 95 mol %, and even more preferably at least 99 mol %.
The α,ω-linear aliphatic dicarboxylic acid having 8 to 14 carbons is preferably an α,ω-linear aliphatic dicarboxylic acid having from 8 to 12 carbons. Examples of the α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons include suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and dodecanedioic acid, and at least one of sebacic acid and dodecanedioic acid is preferable.
Examples of the aromatic dicarboxylic acid include isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. At least one type of isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, or 2,6-naphthalenedicarboxylic acid is preferable, and at least one of 2,6-naphthalenedicarboxylic acid or isophthalic acid is more preferable. As an example of an embodiment of the amorphous polyamide resin, a form substantially free of constituent units derived from terephthalic acid is presented. “Substantially free” means that the proportion of the constituent unit derived from terephthalic acid is 5 mol % or less, preferably 3 mol % or less, and more preferably 1 mol % or less, of the constituent unit derived from a dicarboxylic acid constituting the amorphous polyamide resin.
Examples of dicarboxylic acids (other dicarboxylic acids) besides the α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons and the aromatic dicarboxylic acid, include α,ω-linear aliphatic dicarboxylic acids having less than 8 carbons (e.g., adipic acid and pimelic acid), and alicyclic dicarboxylic acids (e.g., 1,3-cyclohexanedicarboxylic acid). One or more types of the other dicarboxylic acids may be used.
In the amorphous polyamide resin, of the constituent unit derived from a dicarboxylic acid, the molar ratio of the constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons to the constituent unit derived from an aromatic dicarboxylic acid ((constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons)/(constituent unit derived from an aromatic dicarboxylic acid)) is preferably from 0.5 to 3.5, more preferably from 0.8 to 3.2, and even more preferably from 2.0 to 3.1. Within such a range, an amorphous polyamide resin better excelling in various performance aspects can be obtained.
Embodiments of preferred amorphous polyamide resins of the present invention are described below. Of course, the present invention is not limited to these embodiments.
A first embodiment of the amorphous polyamide resin is an amorphous polyamide resin in which not less than 90 mol % of the constituent unit derived from a diamine is a constituent unit derived from isophoronediamine; of the constituent unit derived from a dicarboxylic acid, from 30 to 80 mol % is a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons and from 70 to 20 mol % is a constituent unit derived from an aromatic dicarboxylic acid; the constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons includes at least one of a constituent unit derived from sebacic acid and a constituent unit derived from dodecanedioic acid; and the constituent unit derived from an aromatic dicarboxylic acid includes at least one of a constituent unit derived from 2,6-naphthalenedicarboxylic acid and a constituent unit derived from isophthalic acid. The first embodiment includes an aspect in which the constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons includes the constituent unit derived from sebacic acid or the constituent unit derived from dodecanedioic acid, and an aspect in which the constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons includes both the constituent unit derived from sebacic acid and the constituent unit derived from dodecanedioic acid. Furthermore, the first embodiment includes an aspect containing a constituent unit derived from 2,6-naphthalenedicarboxylic acid or a constituent unit derived from isophthalic acid, and an aspect containing both of these constituent units.
A second embodiment of the amorphous polyamide resin is an aspect in which, of the constituent unit derived from a dicarboxylic acid of the first embodiment, from 30 to 80 mol % is a constituent unit derived from dodecanedioic acid and from 70 to 20 mol % is a constituent unit derived from an aromatic dicarboxylic acid. In the second embodiment, the molar ratio of (the constituent unit derived from dodecanedioic acid)/(the constituent unit derived from an aromatic dicarboxylic acid) is preferably from 2.3 to 4.0, and more preferably from 2.8 to 3.2.
A third embodiment of the amorphous polyamide resin is an aspect in which of the constituent unit derived from a dicarboxylic acid of the first embodiment, from 30 to 80 mol % is a constituent unit derived from sebacic acid and from 70 to 20 mol % is a constituent unit derived from an aromatic dicarboxylic acid. In the third embodiment, the molar ratio of (the constituent unit derived from sebacic acid)/(the constituent unit derived from an aromatic dicarboxylic acid) is preferably from 2.3 to 4.0, and more preferably from 2.8 to 3.2.
A fourth embodiment of the amorphous polyamide resin is an aspect in which, of the constituent unit derived from a dicarboxylic acid of the first embodiment, from 30 to 80 mol % is a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons and from 70 to 20 mol % is a constituent unit derived from 2,6-naphthalene dicarboxylic acid. In the fourth embodiment, the molar ratio of (the constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons)/(the constituent unit derived from 2,6-naphthalene) is preferably from 2.3 to 4.0, and more preferably from 2.8 to 3.2.
A fifth embodiment of the amorphous polyamide resin is an aspect in which, of the constituent unit derived from a dicarboxylic acid of the first embodiment, from 30 to 80 mol % is a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons and from 70 to 20 mol % is a constituent unit derived from isophthalic acid. In the fifth embodiment, the molar ratio of (the constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons)/(the constituent unit derived from isophthalic acid) is preferably from 2.3 to 4.0, and more preferably from 2.8 to 3.2.
Note that the amorphous polyamide resin is constituted from the constituent unit derived from a dicarboxylic acid and the constituent unit derived from a diamine, but may also include a constituent unit besides the constituent unit derived from a dicarboxylic acid and the constituent unit derived from a diamine, or other moieties such as terminal groups. Examples of other constituent units include, but are not limited to, constituent units derived from lactams such as ε-caprolactam, valerolactam, laurolactam, and undecalactam; and from aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid. Furthermore, the amorphous polyamide resin used in the present invention may include trace components such as additives used for synthesis.
Of the amorphous polyamide resin used in the present invention, typically 95 mass % or more, preferably 98 mass % or more, and more preferably 99 mass % or more is the constituent unit derived from a dicarboxylic acid or the constituent unit derived from a diamine.
In the production method of the present invention, the melt polycondensation reaction is conducted by adding an aqueous solution of a phosphorus atom-containing compound, and the diamine component to dicarboxylic acid component in a molten state. By adding the phosphorus atom-containing compound to the reaction system for melt polycondensation reaction, amidation can be promoted, and coloration of the polyamide resin due to oxygen present in the polycondensation reaction system can also be prevented. In the present invention, by adding, in the form of an aqueous solution, a phosphorus atom-containing compound having such an effect to molten dicarboxylic acid, the generation of foreign matter in the resulting resin can be effectively suppressed and prevented. While based on also an assumption, it is thought that by forming the phosphorus atom-containing compound into an aqueous solution and adding the aqueous solution thereof to the molten dicarboxylic acid, dispersibility of the phosphorus atom-containing compound in the molten dicarboxylic acid becomes extremely favorable, and the generation of foreign matter can be suppressed. In other words, in the present invention, the diamine component is preferably added after an aqueous solution of the phosphorus atom-containing compound has been added to and dispersed in the molten dicarboxylic acid component.
“Molten dicarboxylic acid component” means that at least one type of dicarboxylic acid that is a raw material of the polyamide resin has been melted and formed into a liquid state. However, in the present invention, in addition to a case where all (100 mass %) of at least one type of dicarboxylic acid serving as the raw material melts and is formed into a liquid state, a case where 80 mass % or more (preferably, 90 mass % or more) of at least one type of dicarboxylic acid serving as the raw material is formed into a liquid state is also included.
In the present invention, preferably at least one of the α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons and the aromatic dicarboxylic acid is in a molten state, and more preferably, at least the α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons is in a molten state.
When an aqueous solution of a phosphorus atom-containing compound is added, and the temperature of the dicarboxylic acid is sufficiently high with respect to the boiling point of water, the water soon evaporates once the aqueous solution reaches the molten dicarboxylic acid. If water evaporates after the aqueous solution is dispersed in the dicarboxylic acid, the phosphorus atom-containing compound uniformly disperses in the aqueous solution. Even if the water evaporates before the aqueous solution is dispersed, it is assumed that through the formation into fine powder of the phosphorus-atom containing compound precipitated in association with the evaporation of water, the phosphorus atom-containing compound with a reduced particle size is uniformly dispersed in the dicarboxylic acid. This action is believed to lead to the effect of suppressing or preventing the production of foreign matter in the resin.
In the production method of the present invention, the thermal decomposition temperature (Td) of the phosphorus atom-containing compound is equal to or more than the maximum attainable temperature (Tp) that is reached in the melt polycondensation reaction (Td ≥Tp).
The decomposition temperature (Td) of the phosphorus atom-containing compound is preferably at least 230° C., more preferably at least 245° C., and even more preferably at least 270° C. An upper limit of not greater than 1000° C. is practical, and the upper limit may further be not greater than 800° C., not greater than 700° C., or not greater than 630° C.
When water is introduced into a liquid at the boiling point thereof or higher, the volume expands, and the pressure inside the reaction chamber tends to increase. Alternatively, significant scattering of dicarboxylic acid may occur as the water evaporates. From the perspective of controlling the reaction, it is usually preferable to avoid the addition of an aqueous solution to dicarboxylic acid in a molten state. However, in the present invention, the abovementioned excellent effect is exhibited by adding the phosphorus atom-containing compound to the reaction chamber in the form of an aqueous solution. From this perspective, in the present invention, a phosphorus atom-containing compound that is highly soluble in water is preferably used.
The phosphorus atom-containing compound is preferably an alkali metal salt or an alkaline earth metal salt, is more preferably a sodium salt, a potassium salt, a calcium salt, or a magnesium salt, and is further preferably a sodium salt, a calcium salt, or a magnesium salt.
The alkaline earth metal salt in the present invention includes beryllium and magnesium in addition to calcium, strontium, barium, and radium. Calcium or magnesium is preferable.
Examples of the phosphorus atom-containing compound also include hypophosphites, phosphites, phosphates, and pyrophosphates. Hypophosphites, phosphites, and phosphates are preferable, and hypophosphites are more preferable.
That is, the phosphorus atom-containing compound is preferably selected from an alkali metal salt of hypophosphorous acid, an alkaline earth metal salt of hypophosphorous acid, an alkali metal salt of phosphorous acid, an alkaline earth metal salt of phosphorous acid, an alkali metal salt of phosphoric acid, an alkaline earth metal salt of phosphoric acid, an alkali metal salt of pyrophosphoric acid, an alkaline earth metal salt of pyrophosphoric acid, an alkali metal salt of metaphosphoric acid, and an alkaline earth metal salt of metaphosphoric acid; and is more preferably selected from an alkali metal salt of hypophosphorous acid, an alkaline earth metal salt of hypophosphorous acid, an alkali metal salt of phosphorous acid, an alkaline earth metal salt of phosphorous acid, an alkali metal salt of phosphoric acid, an alkaline earth metal salt of phosphoric acid, an alkali metal salt of metaphosphoric acid, and an alkaline earth metal salt of metaphosphoric acid.
In the present invention, in particular, the phosphorus atom-containing compound is more preferably at least one of an alkali metal salt of hypophosphorous acid, an alkaline earth metal salt of hypophosphorous acid, an alkali metal salt of phosphorous acid, an alkaline earth metal salt of phosphorous acid, an alkali metal salt of metaphosphoric acid, or an alkaline earth metal salt of metaphosphoric acid, and is even more preferably at least one of an alkaline earth metal salt of hypophosphorous acid and an alkali metal salt of metaphosphoric acid, and is yet even more preferably calcium hypophosphite.
Specific examples of alkali metal salts of hypophosphorous acid include sodium hypophosphite and potassium hypophosphite. Specific examples of alkaline earth metal salts of hypophosphorous acid include calcium hypophosphite and magnesium hypophosphite. Specific examples of alkali metal salts of phosphorous acid include sodium phosphite, sodium hydrogen phosphite, potassium phosphite, potassium hydrogen phosphite, lithium phosphite, and lithium hydrogen phosphite. Specific examples of alkaline earth metal salts of phosphorous acid include magnesium phosphite, magnesium hydrogen phosphite, calcium phosphite, and calcium hydrogen phosphite. Specific examples of alkali metal salts of phosphoric acid include sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, lithium phosphate, lithium hydrogen phosphate, and lithium dihydrogen phosphate. Specific examples of the alkaline earth metal salt of phosphoric acid include magnesium phosphate, dimagnesium hydrogen phosphate, magnesium dihydrogen phosphate, calcium phosphate, dicalcium hydrogen phosphate, and calcium dihydrogen phosphate. Specific examples of alkali metal salts of pyrophosphoric acid include sodium pyrophosphate, potassium pyrophosphate, and lithium pyrophosphate. Specific examples of the alkaline earth metal salts of pyrophosphoric acid include magnesium pyrophosphate and calcium pyrophosphate. Specific examples of alkali metal salts of metaphosphoric acid include sodium metaphosphate, potassium metaphosphate, and lithium metaphosphate. Specific examples of alkaline earth metal salts of metaphosphoric acid include magnesium metaphosphate and calcium metaphosphate.
The maximum attainable temperature (Tp) reached in melt polycondensation reaction of the diamine and the dicarboxylic acid varies depending on the type of reaction substrate that is used, the reaction device, and the reaction conditions, but from the perspectives of reaction yield and reaction rate, the maximum attainable temperature (Tp) is preferably 200° C. or higher, more preferably 230° C. or higher, even more preferably 245° C. or higher, yet even more preferably 260° C. or higher, and still even more preferably 265° C. or higher. The upper limit may be, for example, not higher than 300° C., and may be not higher than 280° C. The method for measuring the maximum attainable temperature (Tp) reached in the melt polycondensation reaction may be determined in accordance with details that are common for this type of reaction, such as the structure of the device and the characteristics of the temperature measuring instrument. An example when carrying out the reaction in a batch-type reaction vessel having a sufficient stirring function is an aspect in which the tip of a thermocouple or thermometer is sufficiently immersed in the molten dicarboxylic acid component and is sufficiently separated from a wall surface of the reaction vessel. Through this, the temperature of the molten raw material at which the reaction proceeds can be accurately determined.
The maximum attainable temperature (Tp) reached in the melt polycondensation reaction is determined, for example, by inserting a thermocouple through a thermocouple-insertion opening provided in an upper side of the reaction vessel, and positioning the tip end of the thermocouple at a height of approximately 10 mm from the bottom of the reaction vessel. The opening is preferably sealed by a heat-resistant plug or the like so that a sealed state is maintained. A thermocouple that can support measurements of temperatures from 0° C. to 400° C. is preferably selected.
In the measurement, the dicarboxylic acid is heated to a molten state, the reaction is initiated by adding an aqueous solution of a phosphorus atom-containing compound, and a diamine component (and a reaction rate modifier or the like, as necessary), after which the maximum attainable temperature (Tp) is measured over time. In this measurement, the temperature when the maximum temperature is indicated is used as the maximum attainable temperature (Tp). However, the temperature is read premised on the condition that the temperature was maintained for 3 continuous seconds.
In the present invention, a melting point (Tm) of the phosphorus atom-containing compound is not particularly limited, but from the perspective of remarkably exhibiting the effect of the present invention, the melting point (Tm) of the phosphorus atom-containing compound can be higher than the maximum attainable temperature (Tp) reached in the melt polycondensation reaction.
The addition amount of the phosphorus atom-containing compound added to the polycondensation reaction system of the polyamide resin is an amount such that the phosphorus atom concentration (by mass) in the polyamide resin is preferably at least 1 ppm, more preferably at least 15 ppm, and even more preferably at least 20 ppm. Furthermore, the upper limit of the addition amount of the phosphorus atom-containing compound is an amount such that the phosphorus atom concentration (by mass) in the polyamide resin is preferably 1000 ppm or less, more preferably 400 ppm or less, even more preferably 350 ppm or less, and yet even more preferably 300 ppm or less.
If the phosphorus atom concentration in the polyamide resin is greater than or equal to the lower limit described above, an effect as an antioxidant can be sufficiently obtained, and coloration of the polyamide resin can be prevented. On the other hand, if the phosphorus atom concentration in the polyamide resin is less than or equal to the upper limit described above, the occurrence of foreign matter thought to be caused by the phosphorus atom-containing compound can be suppressed, and a molded article with excellent appearance can be obtained.
In view of the addition of excess water into the reaction system, the concentration of the aqueous solution of the phosphorus atom-containing compound is preferably not less than 1 mass %, more preferably not less than 2 mass %, and even more preferably not less than 5 mass %. However, from the perspective of precipitation of the phosphorus atom-containing compound, based on solubility in water at 25° C., the concentration of the aqueous solution of the phosphorus atom-containing compound is preferably not greater than 90 mass % of the solubility, more preferably not greater than 70 mass % of the solubility, and even more preferably not greater than 50 mass % of the solubility.
The solubility of the phosphorus atom-containing compound in water is preferably high. In the present invention, the solubility of the phosphorus atom-containing compound in water at 25° C. is preferably not less than 5%, more preferably not less than 10%, even more preferably not less than 15%, and yet even more preferably not less than 20%. The upper limit is preferably not greater than 100%. By increasing the solubility of the phosphorus atom-containing compound in water, the melt polycondensation reaction can proceed more effectively with the addition of a smaller amount of aqueous solution.
The temperature of the aqueous solution when adding the aqueous solution of the phosphorus atom-containing compound is preferably from 10 to 80° C., more preferably from 15 to 60° C., and even more preferably from 20 to 35° C.
The addition rate of the aqueous solution of the phosphorus atom-containing compound is preferably an addition rate equal to or less than the production rate of condensed water that is produced in the polycondensation reaction between the dicarboxylic acid component and the diamine component. Moreover, when the aqueous solution of the phosphorus atom-containing compound flows in an aqueous solution addition line, the addition rate of the aqueous solution of the phosphorus atom-containing compound is preferably a rate such that the aqueous solution passes through the addition line without the water being vaporized by heat transfer from the reaction chamber. Therefore, when the aqueous solution of the phosphorus atom-containing compound is to be added, the addition rate v/V (v: dripping rate [ml/s], V: reaction chamber volume [ml]) of the aqueous solution of the phosphorus atom-containing compound to the reaction chamber volume is preferably from 1.0×106 to 1.0×10−3 [1/s], more preferably from 5.0×10−6 to 7.0×10−4 [1/s], and even more preferably from 2.0×10−5 to 5.0×10−4 [1/s].
In the production method of the present invention, from the perspective of preventing gelling of the polyamide resin, preferably, a polymerization rate modifier is further added, and melt polycondensation reaction is performed in the presence of the phosphorus atom-containing compound and the polymerization rate modifier. That is, the method of producing an amorphous polyamide resin of the present invention preferably further includes carrying out melt polycondensation reaction in the presence of a polymerization rate modifier.
The polymerization rate modifier is preferably added before starting the reaction of the raw material monomers, and is more preferably added to the molten dicarboxylic acid component.
Examples of the polymerization rate modifier include at least one type selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal acetates, and alkaline earth metal acetates. Alkali metal hydroxides and alkali metal acetates are preferable.
Specific examples of the alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Specific examples of the alkaline earth metal hydroxides include magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. Specific examples of the alkali metal acetates include lithium acetate, sodium acetate, potassium acetate, rubidium acetate, and cesium acetate. Specific examples of the alkaline earth metal acetates include magnesium acetate, calcium acetate, strontium acetate, and barium acetate.
Among these, the polymerization rate modifier is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium acetate, and potassium acetate, is more preferably at least one selected from the group consisting of sodium hydroxide, sodium acetate, and potassium acetate, and is even more preferably sodium acetate.
When the polymerization rate modifier is added to the polycondensation reaction system, the molar ratio of the phosphorus atoms of the phosphorus atom-containing compound to the polymerization rate modifier ((phosphorus atom-containing compound)/(polymerization rate modifier)) is preferably not less than 0.10, more preferably not less than 0.30, and even more preferably not less than 0.40 from the perspective of achieving a balance between promoting and suppressing an amidation reaction. The molar ratio thereof is preferably 0.95 or less, more preferably 0.93 or less, and even more preferably 0.91 or less, and may be 0.90 or less.
The polymerization rate modifier may be added to the polycondensation reaction system separately from the phosphorus atom-containing compound, or may be added to the polycondensation reaction system as an aqueous solution of the phosphorus atom-containing compound and the polymerization rate modifier.
A small amount of a monofunctional compound that is reactive with the terminal amino group or terminal carboxyl group of the polyamide resin may be added as a molecular weight modifier. Examples of monofunctional compounds include, but are not limited to, aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, and pivalic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, and naphthalene carboxylic acid; aliphatic monoamines such as butylamine, amylamine, isoamylamine, hexylamine, heptylamine, and octylamine; aromatic aliphatic monoamines such as benzylamine and methylbenzylamine; or mixtures thereof.
When a molecular weight modifier is used in the polycondensation reaction system, the suitable usage amount thereof varies depending on factors such as the reaction conditions and the reactivity and boiling point of the molecular weight modifier, but ordinarily, the usage amount is approximately from 0.002 to 1 mass % with respect to the total of the diamine component and the dicarboxylic acid component of the raw materials.
Examples of the method for polycondensing the polyamide resin include a reaction extrusion method, a pressurized salt method, a normal pressure dripping method, and a pressurized dripping method. However, in the present invention, the normal pressure dripping method or pressurized dripping method in which a diamine component is continuously added dropwise to a molten dicarboxylic acid component in a reaction chamber, and the mixture is subjected to polycondensation reaction is preferably adopted, and adoption of the pressurized dripping method is particularly preferable.
In the normal pressure dripping method, the diamine component and the aqueous solution of the phosphorus atom-containing compound are continuously added dropwise to the molten dicarboxylic acid component in a reaction chamber under normal pressure, and polycondensation reaction is performed while removing the condensed water. Note that the polycondensation reaction is preferably performed while increasing the temperature of the reaction system so that the polycondensation reaction of the produced polyamide resin is accelerated and the upper torque limit of the polymerization vessel that is used is not exceeded.
With the pressurized dripping method, the diamine component and the aqueous solution of the phosphorus atom-containing compound are continuously added dropwise to the molten dicarboxylic acid component while pressurizing the inside of the reaction chamber to approximately from 0.4 to 0.5 MPa (Abs), and polycondensation reaction is performed while removing the condensed water. At this time, the polycondensation reaction is performed while increasing the temperature of the reaction system so that the polycondensation reaction of the produced polyamide resin is accelerated and the upper torque limit of the polymerization vessel that is used is not exceeded. When the molar ratio setting is reached, the dropwise addition of the diamine component is ended, and while the inside of the reaction chamber is gradually returned to normal pressure, polycondensation reaction of the polyamide resin is promoted, and the inside of the reaction chamber is maintained at a temperature such that the upper torque limit of the polymerization vessel that is used is not exceeded, after which the temperature thereof is maintained while gradually depressurizing the inside of the reaction chamber to 0.08 MPa (Abs), and polycondensation reaction is continued. Once the stifling torque reaches a certain level, the inside of the reaction chamber is pressurized to approximately 0.3 MPa (Abs) with nitrogen, and the polyamide resin is recovered.
The addition time of the diamine component is not particularly limited, but if the addition rate is too fast, the heating rate of the reaction system may be slowed due to insufficient heating capacity. While dependent also on factors such as the volume of the reaction device and the heating capacity of the heater, the addition time of the diamine component is preferably from 30 minutes to 5 hours, and more preferably from 30 minutes to 4 hours.
The condensed water that is produced as the reaction progresses is passed through a partial condenser and a total condenser (cooler) and distilled and removed from the reaction system. The diamine component that is distilled to outside of the reaction system as steam together with the condensed water, the dicarboxylic acid that is distilled away as steam, and the like are preferably separated from water vapor by the partial condenser and once again returned to the reaction chamber. [0044]
Furthermore, immediately after the addition of the diamine component is ended, preferably the temperature of the reaction mixture is kept constant, and stirring is continued for approximately 10 to 30 minutes.
Subsequently, the pressure is reduced to approximately from 40 to 90 kPa (Abs) at a rate of preferably from 0.005 to 0.03 MPa/minute, and stirring is continued for approximately 5 to 40 minutes, and thereby a polyamide resin can be obtained.
Once the obtained polyamide resin is removed, it can be pelletized, dried, and then used. Also, in order to further increase the degree of polymerization, the pelletized polyamide resin may be solid phase polymerized.
The lower limit of a number average molecular weight of the amorphous polyamide resin is preferably 8000 or higher, and more preferably 10000 or higher. The upper limit of the number average molecular weight is preferably 25000 or less, and more preferably 20000 or less. The number average molecular weight is measured in accordance with the method described in the examples below.
The molecular weight distribution ((weight average molecular weight)/(number average molecular weight)=Mw/Mn) of the amorphous polyamide resin of the present invention is preferably from 1.5 to 5.0, and more preferably from 1.5 to 3.5. By setting the molecular weight distribution to be within the range described above, fluidity and melt viscosity stability during melting increase, and melt-kneading and melt molding processability become favorable. Furthermore, toughness is favorable, and physical properties such as water absorption resistance, chemical resistance, and thermal aging resistance also become favorable.
The glass transition temperature (Tg) of the amorphous polyamide resin is preferably 130° C. or higher, more preferably 140° C. or higher, and even more preferably 145° C. or higher. In the present invention, such a high Tg can be achieved, and thus an advantage of the present invention is that physical properties are hardly reduced even under high-temperature conditions. That is, the value of the amorphous polyamide resin obtained by the present invention is high in that the resin can be configured with a low melt viscosity while maintaining a high glass transition temperature. The upper limit of the glass transition temperature is not particularly limited and, for example, is preferably 220° C. or lower or may be 200° C., and even a glass transition temperature of 170° C. or lower is a sufficiently practical level. The glass transition temperature is measured in accordance with the method described in the examples described below.
The amorphous polyamide resin of the present invention has a notched Charpy impact strength in accordance with JIS K 7111-1 of preferably 4.0 kJ/m2 or more, and more preferably 4.3 kJ/m2 or more. The upper limit thereof is not particularly limited and, for example, an upper limit of 9.0 kJ/m2 or less or even 8.7 kJ/m2 or less is a sufficiently practical level. In the measurements, an ISO test piece of 4 mm×10 mm×80 mm is used, unless otherwise specified. An improvement in this impact strength is another merit according to the present invention.
The amorphous polyamide resin of the present invention has a unnotched Charpy impact strength in accordance with JIS K 7111-1 of preferably 70 kJ/m2 or more, more preferably 90 kJ/m2 or more, even more preferably 100 kJ/m2 or more, and yet even more preferably 110 kJ/m2 or more. The upper limit thereof is not particularly defined, and for example, an upper limit of 160 kJ/m2 or less or even 155 kJ/m2 or less is a sufficiently practical level. In the measurements, an ISO test piece of 4 mm×10 mm×80 mm is used, unless otherwise specified. Another merit according to the present invention is an improvement in this impact strength.
The unnotched Charpy impact strength is measured by the method described in the examples below.
When the amorphous polyamide resin of the present invention is molded to a thickness of 2 mm, a measured haze value is preferably 2.0% or less, more preferably 1.7% or less, even more preferably 1.6% or less, and yet even more preferably 1.5% or less. The lower limit of the haze value is ideally 0%, but even a haze value of 1.0% or more is a sufficiently practical level.
The yellowness index (YI) value in a color difference test in accordance with JIS K7373 of the amorphous polyamide resin obtained through the method of the present invention is preferably not greater than 10, more preferably not greater than 6, and even more preferably not greater than 5. If the YI value of the polyamide resin is not greater than 10, yellowing of a molded article obtained through subsequent processing can be prevented, and thus a molded article with high product value can be obtained.
The amorphous polyamide resin obtained by the production method of the present invention can be blended with reinforcing fibers to thereby form a fiber-reinforced resin composition. Examples of reinforcing fibers include carbon fibers and glass fibers. Examples of the fiber-reinforced resin composition include pellets obtained by melt-kneading a composition including the polyamide resin and reinforcing fibers, and a prepreg in which the polyamide resin is impregnated into or brought into proximity with reinforcing fibers.
The amorphous polyamide resin obtained by the production method of the present invention may also be blended and used with other amorphous polyamide resins, crystalline polyamide resins, other thermoplastic resins, and additives, such as fillers, matting agents, heat-resistance stabilizers, weather-resistance stabilizers, ultraviolet absorbents, plasticizers, flame retardants, antistatic agents, anti-coloration agents, anti-gelling agents, impact-resistance modifiers, lubricants, colorants, and conductive additives. One or more types of each of these resins and additives may be used.
The amorphous polyamide resin according to the present invention can be molded by a known molding method such as injection molding, blow molding, extrusion molding, compression molding, stretching, and vacuum molding.
As molded articles formed using the amorphous polyamide resin according to the present invention, the amorphous polyamide resin according to the present can be used in various molded articles including films, sheets, thin-walled molded articles, hollow molded articles, fibers, hoses, and tubes.
The amorphous polyamide resin according to the present invention is preferably used in engineering plastic applications. Examples of fields of use of such molded articles include transportation equipment components for automobiles, etc., general mechanical parts, precision mechanical parts, electronic and electrical equipment components, OA device parts, building materials and resident related components, medical devices, optical products, industrial materials, leisure sporting goods, amusement equipment, medical products, articles for daily use such as food packaging films, and defense and aerospace products. Examples of embodiments of molded articles according to the present invention include housings for electronic and electrical devices, and sunglasses.
Another example of an embodiment of a molded article formed using the amorphous resin composition according to the present invention is a single layer or multi-layer container.
The present invention will be described in greater detail below through examples. The following materials, usage amounts, proportions, processing details, processing procedures, and the like described in the examples may be changed, as appropriate, as long as there is no deviation from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below.
Calcium hypophosphite, magnesium hypophosphite, and sodium pyrophosphate were used as phosphorus atom-containing compounds. The decomposition temperatures were as follows. Calcium hypophosphate decomposition temperature: 320° C., magnesium hypophosphate decomposition temperature: 340° C., and sodium pyrophosphate decomposition temperature: 628° C. A phosphorus atom-containing compound having a thermal decomposition temperature higher than the maximum temperature of polymerization was selected.
A pressure-resistant reaction vessel having an internal volume of 50 L and equipped with a stirrer, a partial condenser, a total condenser, a pressure regulator, a thermometer, a dropping funnel and pump, an aspirator, a nitrogen introduction tube, a bottom drain valve, and a strand die was charged with precisely weighed materials including 9500 g (40.89 mol) of dodecanedioic acid (dodecane dicarboxylic acid: DDA, available from Laiyang Himount Bio-Products Technology Co., Ltd.), 2267 g (13.63 mol) of isophthalic acid (PIA, available from Mitsubishi Gas Chemical Co., Inc.), and 1.14 g (0.0139 mol) of sodium acetate (available from Kanto Chemical Co., Inc.), and then sufficiently purged with nitrogen, after which the inside of the reaction vessel was sealed, and the temperature was raised to 180° C. under stirring while the pressure in the vessel was maintained at 0.4 MPa. After the temperature reached 180° C., a 25° C. aqueous solution adjusted by dissolving 2.63 g (0.00154 mol) of calcium hypophosphate (available from Kanto Chemical Co., Inc.) in 50 mL of water was continuously added to the dodecanedioic acid/isophthalic acid, which were in a molten state, in the reaction vessel at an addition rate of 1.5 mL/s. Dropwise addition of 9475 g (55.53 mol) of isophoronediamine (IPDA, available from BASF SE) stored in a dropping funnel, into the raw materials in the reaction vessel was then initiated, and the temperature in the reaction chamber was raised to 250° C. while condensed water that was produced was removed from the system and the pressure in the vessel was maintained at 0.4 MPa. After the completion of dropwise addition of IPDA, the pressure in the reaction vessel was gradually returned to normal pressure while the temperature was gradually raised to 270° C., and then an aspirator was used to reduce the pressure inside the reaction chamber to 80 kPa and remove the condensed water. Agitation torque of the stirrer was observed under a reduced pressure, and agitation was terminated when a predetermined torque was reached. Then, the inside of the reaction chamber was pressurized with nitrogen, the bottom drain valve was opened, and the polymer was extruded from the strand die to form a strand and then cooled and pelletized by using a pelletizer to obtain a polyamide resin.
The glass transition temperature of the obtained polyamide resin was 146° C., and the number average molecular weight was 13300.
The crystal melting enthalpy ΔHm was 1 J/g or less.
Using a differential scanning calorimeter (DSC), the glass transition temperature was measured when heating was performed at a temperature increase rate of 10° C./min from room temperature to 250° C., then cooling was immediately performed to room temperature or lower, and then heating was performed again at the temperature increase rate of 10° C./min from room temperature to 250° C. in a nitrogen stream. In the present example, the DSC-60 available from Shimadzu Corporation was used as the differential scanning calorimeter. Furthermore, the crystal melting enthalpy ΔHm of the polyamide resin was measured during the temperature increase process in accordance with JIS K 7121 and JIS K 7122.
The number average molecular weight of the amorphous polyamide resin was determined as follows.
An amount of 0.3 g of the amorphous polyamide resin was inserted into a 4/1 mixed solvent of phenol/ethanol (volume ratio), the mixture was stirred at 25° C. until completely dissolved, after which under agitation, the inner wall of a container was rinsed with 5 mL of methanol, and neutralization titration was performed with a 0.01 mol/L hydrochloric acid aqueous solution to determine the terminal amino group concentration [NH2]. Furthermore, 0.3 g of the polyamide resin was added to benzyl alcohol and stirred at 170° C. in a nitrogen stream until completely dissolved. Next, the mixture was cooled to 80° C. or lower in a nitrogen stream, after which the inner wall of the container was rinsed with 10 mL of methanol while stirring, and neutralization titration was performed with a 0.01 mol/L sodium hydroxide aqueous solution to determine the terminal carboxyl group concentration [COOH]. The number average molecular weight was determined from the measured terminal amino group concentration [NH2] (unit: μeq/g) and the measured terminal carboxyl group concentration [COOH] (unit: μeq/g) by the following equation.
Number average molecular weight (Mn)=2000000/([COOH]+[NH2])
The obtained pellets were vacuum-dried at 120° C. (dew point: −40° C.) for 24 hours, and then molded with an injection molding machine (SE130DU-HP, available from Sumitomo Heavy Industries, Ltd.) to form ISO test pieces of 2 mm×10 mm×10 mm at a molding temperature of 100° C. and a cylinder temperature of 280° C.
Each test piece described above was observed using a microscope (Digital Microscope VHX-1000, available from Keyence Corporation), and the number of pieces of foreign matter was measured. Three test pieces were measured in each case, and the average value was used. Foreign matter of a size from 50 to 200 μm was targeted.
A: The foreign matter quantity was 0.
B: The foreign matter quantity was from 1 to less than 30.
C: The foreign matter quantity was 30 or more.
The obtained polyamide resin pellets were vacuum-dried at 120° C. (dew point: -40° C.) for 24 hours, and then 4 mm×10 mm×80 mm test pieces were prepared using an injection molding machine (SE130DU-HP, available from Sumitomo Heavy Industries, Ltd.) at a mold temperature of 100° C. and a cylinder temperature of 280° C.
The unnotched Charpy impact strength of each of the obtained test pieces was measured in accordance with JIS K 7111-1. The units were shown in kJ/m2.
The SE130DU-HP available from Sumitomo Heavy Industrial Co., Ltd. was used as the injection molding machine.
A pressure-resistant reaction vessel having an internal volume of 50 L and equipped with a stirrer, a partial condenser, a total condenser, a pressure regulator, a thermometer, a dropping funnel and pump, an aspirator, a nitrogen introduction tube, a bottom drain valve, and a strand die was charged with precisely weighed materials including 9500 g (40.89 mol) of dodecanedioic acid (dodecane dicarboxylic acid: DDA, available from Laiyang Himount Bio-Products Technology Co., Ltd.), 2267 g (13.63 mol) of isophthalic acid (PIA, available from Mitsubishi Gas Chemical Co., Inc.), 2.63 g (0.00154 mol) of calcium hypophosphite (available from Kanto Chemical Co., Inc.), and 1.14 g (0.0139 mol) of sodium acetate (available from Kanto Chemical Co., Inc.), and then sufficiently purged with nitrogen, after which the inside of the reaction vessel was sealed, and the temperature was raised to 180° C. under stirring while the pressure in the vessel was maintained at 0.4 MPa. After the temperature reached 180° C., dropwise addition of 9475 g (55.53 mol) of isophoronediamine (IPDA, available from BASF SE) stored in a dropping funnel, into the raw materials in the reaction vessel was then initiated, and the temperature in the reaction chamber was raised to 250° C. while condensed water that was produced was removed from the system and the pressure in the vessel was maintained at 0.4 MPa. After the completion of dropwise addition of IPDA, the pressure in the reaction vessel was gradually returned to normal pressure while the temperature was gradually raised to 270° C., and then an aspirator was used to reduce the pressure inside the reaction chamber to 80 kPa and remove the condensed water. Agitation torque of the stirrer was observed under a reduced pressure, and agitation was terminated when a predetermined torque was reached. Then, the inside of the reaction chamber was pressurized with nitrogen, the bottom drain valve was opened, and the polymer was extruded from the strand die to form a strand and then cooled and pelletized by using a pelletizer to obtain a polyamide resin.
The glass transition temperature of the obtained polyamide resin was 146° C., and the number average molecular weight was 12900.
The crystal melting enthalpy ΔHm was 1 J/g or less.
The appearance of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
The Charpy impact strength of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
A pressure-resistant reaction vessel having an internal volume of 50 L and equipped with a stirrer, a partial condenser, a total condenser, a pressure regulator, a thermometer, a dropping funnel and pump, an aspirator, a nitrogen introduction tube, a bottom drain valve, and a strand die was charged with precisely weighed materials including 9500 g (40.89 mol) of dodecanedioic acid (dodecane dicarboxylic acid: DDA, available from Laiyang Himount Bio-Products Technology Co., Ltd.), 2267 g (13.63 mol) of isophthalic acid (PIA, available from Mitsubishi Gas Chemical Co., Ltd.), and 1.14 g (0.0139 mol) of sodium acetate (available from Kanto Chemical Co., Inc.), and then sufficiently purged with nitrogen, after which the inside of the reaction vessel was sealed, and the temperature was raised to 180° C. under stirring while the pressure in the vessel was maintained at 0.4 MPa. After the temperature reached 180° C., a 25° C. aqueous solution adjusted by dissolving 4.11 g (0.00154 mol) of sodium pyrophosphate (available from Junsei Chemical Co., Ltd.) in 50 mL of water was continuously added to the dodecanedioic acid/isophthalic acid, which were in a molten state, in the reaction vessel at an addition rate of 1.5 mL/s. Dropwise addition of 9475 g (55.53 mol) of isophoronediamine (IPDA, available from BASF SE) stored in a dropping funnel, into the raw materials in the reaction vessel was then initiated, and the temperature in the reaction chamber was raised to 250° C. while condensed water that was produced was removed from the system and the pressure in the vessel was maintained at 0.4 MPa. After the completion of dropwise addition of IPDA, the pressure in the reaction vessel was gradually returned to normal pressure while the temperature was gradually raised to 270° C., and then an aspirator was used to reduce the pressure inside the reaction chamber to 80 kPa and remove the condensed water. Agitation torque of the stirrer was observed under a reduced pressure, and agitation was terminated when a predetermined torque was reached. Then, the inside of the reaction chamber was pressurized with nitrogen, the bottom drain valve was opened, and the polymer was extruded from the strand die to form a strand and then cooled and pelletized by using a pelletizer to obtain a polyamide resin.
The glass transition temperature of the obtained polyamide resin was 146° C., and the number average molecular weight was 12100.
The crystal melting enthalpy ΔHm was 1 J/g or less.
The appearance of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
The Charpy impact strength of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
A pressure-resistant reaction vessel having an internal volume of 50 L and equipped with a stirrer, a partial condenser, a total condenser, a pressure regulator, a thermometer, a dropping funnel and pump, an aspirator, a nitrogen introduction tube, a bottom drain valve, and a strand die was charged with precisely weighed materials including 9500 g (40.89 mol) of dodecanedioic acid (dodecane dicarboxylic acid: DDA, available from Laiyang Himount Bio-Products Technology Co., Ltd.), 2266.8 g (13.63 mol) of isophthalic acid (PIA, available from Mitsubishi Gas Chemical Co., Inc.), 4.11 g (0.00154 mol) of sodium pyrophosphate (available from Junsei Chemical Co., Ltd.), and 1.14 g (0.0139 mol) of sodium acetate (available from Kanto Chemical Co., Inc.), and then sufficiently purged with nitrogen, after which the inside of the reaction vessel was sealed, and the temperature was raised to 180° C. under stirring while the pressure in the vessel was maintained at 0.4 MPa. After the temperature reached 180° C., dropwise addition of 9475 g (55.53 mol) of isophoronediamine (IPDA, available from BASF SE) stored in a dropping funnel, into the raw materials in the reaction vessel was then initiated, and the temperature in the reaction chamber was raised to 250° C. while condensed water that was produced was removed from the system and the pressure in the vessel was maintained at 0.4 MPa. After the completion of dropwise addition of IPDA, the pressure in the reaction vessel was gradually returned to normal pressure while the temperature was gradually raised to 270° C., and then an aspirator was used to reduce the pressure inside the reaction chamber to 80 kPa and remove the condensed water. Agitation torque of the stirrer was observed under a reduced pressure, and agitation was terminated when a predetermined torque was reached. Then, the inside of the reaction chamber was pressurized with nitrogen, the bottom drain valve was opened, and the polymer was extruded from the strand die to form a strand and then cooled and pelletized by using a pelletizer to obtain a polyamide resin.
The glass transition temperature of the obtained polyamide resin was 146° C., and the number average molecular weight was 11600.
The crystal melting enthalpy ΔHm was 1 J/g or less.
The appearance of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
The Charpy impact strength of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
A pressure-resistant reaction vessel having an internal volume of 50 L and equipped with a stirrer, a partial condenser, a total condenser, a pressure regulator, a thermometer, a dropping funnel and pump, an aspirator, a nitrogen introduction tube, a bottom drain valve, and a strand die was charged with precisely weighed materials including 9500 g (40.89 mol) of dodecanedioic acid (dodecane dicarboxylic acid: DDA, available from Laiyang Himount Bio-Products Technology Co., Ltd.), 2267 g (13.63 mol) of isophthalic acid (PIA, available from Mitsubishi Gas Chemical Co., Ltd.), and 1.14 g (0.0139 mol) of sodium acetate (available from Kanto Chemical Co., Inc.), and then sufficiently purged with nitrogen, after which the inside of the reaction vessel was sealed, and the temperature was raised to 180° C. under stirring while the pressure in the vessel was maintained at 0.4 MPa. After the temperature reached 180° C., a 25° C. aqueous solution adjusted by dissolving 3.99 g (0.00154 mol) of magnesium hypophosphate hexahydrate (available from Junsei Chemical Co., Ltd.) in 50 mL of water was continuously added to the dodecanedioic acid/isophthalic acid, which were in a molten state, in the reaction vessel at an addition rate of 1.5 mL/s. Dropwise addition of 9475 g (55.53 mol) of isophoronediamine (IPDA, available from BASF SE) stored in a dropping funnel, into the raw materials in the reaction vessel was then initiated, and the temperature in the reaction chamber was raised to 250° C. while condensed water that was produced was removed from the system and the pressure in the vessel was maintained at 0.4 MPa. After the completion of dropwise addition of IPDA, the pressure in the reaction vessel was gradually returned to normal pressure while the temperature was gradually raised to 270° C., and then an aspirator was used to reduce the pressure inside the reaction chamber to 80 kPa and remove the condensed water. Agitation torque of the stirrer was observed under a reduced pressure, and agitation was terminated when a predetermined torque was reached. Then, the inside of the reaction chamber was pressurized with nitrogen, the bottom drain valve was opened, and the polymer was extruded from the strand die to form a strand and then cooled and pelletized by using a pelletizer to obtain a polyamide resin.
The glass transition temperature of the obtained polyamide resin was 146° C., and the number average molecular weight was 12800.
The crystal melting enthalpy ΔHm was 1 J/g or less.
The appearance of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
The Charpy impact strength of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
A pressure-resistant reaction vessel having an internal volume of 50 L and equipped with a stirrer, a partial condenser, a total condenser, a pressure regulator, a thermometer, a dropping funnel and pump, an aspirator, a nitrogen introduction tube, a bottom drain valve, and a strand die was charged with precisely weighed materials including 9500 g (40.89 mol) of dodecanedioic acid (dodecane dicarboxylic acid: DDA, available from Laiyang Himount Bio-Products Technology Co., Ltd.), 2267 g (13.63 mol) of isophthalic acid (PIA, available from Mitsubishi Gas Chemical Co., Inc.), 3.99 g (0.00154 mol) of magnesium hypophosphite hexahydrate (available from Junsei Chemical Co., Ltd.), and 1.14 g (0.0139 mol) of sodium acetate (available from Kanto Chemical Co., Inc.), and then sufficiently purged with nitrogen, after which the inside of the reaction vessel was sealed, and the temperature was raised to 180° C. under stirring while the pressure in the vessel was maintained at 0.4 MPa. After the temperature reached 180° C., dropwise addition of 9475 g (55.53 mol) of isophoronediamine (IPDA, available from BASF SE) stored in a dropping funnel, into the raw materials in the reaction vessel was then initiated, and the temperature in the reaction chamber was raised to 250° C. while condensed water that was produced was removed from the system and the pressure in the vessel was maintained at 0.4 MPa. After the completion of dropwise addition of IPDA, the pressure in the reaction vessel was gradually returned to normal pressure while the temperature was gradually raised to 270° C., and then an aspirator was used to reduce the pressure inside the reaction chamber to 80 kPa and remove the condensed water. Agitation torque of the stirrer was observed under a reduced pressure, and agitation was terminated when a predetermined torque was reached. Then, the inside of the reaction chamber was pressurized with nitrogen, the bottom drain valve was opened, and the polymer was extruded from the strand die to form a strand and then cooled and pelletized by using a pelletizer to obtain a polyamide resin.
The glass transition temperature of the obtained polyamide resin was 146° C., and the number average molecular weight was 11900.
The crystal melting enthalpy ΔHm was 1 J/g or less.
The appearance of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
The Charpy impact strength of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
A pressure-resistant reaction vessel having an internal volume of 50 L and equipped with a stirrer, a partial condenser, a total condenser, a pressure regulator, a thermometer, a dropping funnel and pump, an aspirator, a nitrogen introduction tube, a bottom drain valve, and a strand die was charged with precisely weighed materials including 9500 g (40.89 mol) of dodecanedioic acid (dodecane dicarboxylic acid: DDA, available from Laiyang Himount Bio-Products Technology Co., Ltd.), 2947 g (13.63 mol) of 2,6-naphthalene dicarboxylic acid (2,6-NDCA, available from BP plc), and 0.27 g (0.0154 mol) of sodium acetate (available from Kanto Chemical Co., Inc.), and then sufficiently purged with nitrogen, after which the inside of the reaction vessel was sealed, and the temperature was raised to 180° C. under stirring while the pressure in the vessel was maintained at 0.4 MPa. After the temperature reached 180° C., a 25° C. aqueous solution adjusted by dissolving 4.43 g (0.0172 mol) of calcium hypophosphate (available from Kanto Chemical Co., Inc.) in 50 mL of water was continuously added to the dodecanedioic acid/naphthalene dicarboxylic acid, which were in a molten state, in the reaction vessel at an addition rate of 1.5 mL/s. Dropwise addition of 9476 g (55.53 mol) of IPDA (available from BASF SE) stored in a dropping funnel, into the raw materials in the reaction vessel was then initiated, and the temperature in the reaction chamber was raised to 250° C. while condensed water that was produced was removed from the system and the pressure in the vessel was maintained at 0.4 MPa. After the completion of dropwise addition of IPDA (available from BASF SE), the pressure in the reaction vessel was gradually returned to normal pressure while the temperature was gradually raised to 270° C., and then an aspirator was used to reduce the pressure inside the reaction chamber to 80 kPa and remove the condensed water. Agitation torque of the stirrer was observed under a reduced pressure, and agitation was terminated when a predetermined torque was reached. Then, the inside of the reaction chamber was pressurized with nitrogen, the bottom drain valve was opened, and the polymer was extruded from the strand die to form a strand and then cooled and pelletized by using a pelletizer to obtain a polyamide resin.
The glass transition temperature of the formed polyamide resin was 150° C., and the number average molecular weight was 17000.
The crystal melting enthalpy ΔHm was 1 J/g or less.
The appearance of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
The Charpy impact strength of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
A pressure-resistant reaction vessel having an internal volume of 50 L and equipped with a stirrer, a partial condenser, a total condenser, a pressure regulator, a thermometer, a dropping funnel and pump, an aspirator, a nitrogen introduction tube, a bottom drain valve, and a strand die was charged with precisely weighed materials including 9500 g (40.89 mol) of dodecanedioic acid (dodecane dicarboxylic acid: DDA, available from Laiyang Himount Bio-Products Technology Co., Ltd.), 2947 g (13.63 mol) of 2,6-naphthalene dicarboxylic acid (2,6-NDCA, available from BP plc), 4.43 g (0.0172 mol) of calcium hypophosphate (available from Kanto Chemical Co., Inc), and 0.27 g (0.0154 mol) of sodium acetate (available from Kanto Chemical Co., Inc.), and then sufficiently purged with nitrogen, after which the inside of the reaction vessel was sealed, and the temperature was raised to 180° C. under stirring while the pressure in the vessel was maintained at 0.4 MPa. After the temperature reached 180° C., dropwise addition of 9476 g (55.53 mol) of IPDA (available from BASF SE) stored in the dropping funnel, into the raw materials in the reaction vessel was initiated, and the temperature in a reaction chamber was raised to 250° C. while condensed water that was produced was removed from the system and while the pressure in the vessel was maintained at 0.4 MPa. After the completion of dropwise addition of IPDA, the pressure in the reaction vessel was gradually returned to normal pressure while the temperature was gradually raised to 270° C., and then an aspirator was used to reduce the pressure inside the reaction chamber to 80 kPa and remove the condensed water. Agitation torque of the stirrer was observed under a reduced pressure, and agitation was terminated when a predetermined torque was reached. Then, the inside of the reaction chamber was pressurized with nitrogen, the bottom drain valve was opened, and the polymer was extruded from the strand die to form a strand and then cooled and pelletized by using a pelletizer to obtain a polyamide resin.
The glass transition temperature of the formed polyamide resin was 150° C., and the number average molecular weight was 15300.
The crystal melting enthalpy ΔHm was 1 J/g or less.
The appearance of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
The Charpy impact strength of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
A pressure-resistant reaction vessel having an internal volume of 50 L and equipped with a stirrer, a partial condenser, a total condenser, a pressure regulator, a thermometer, a dropping funnel and pump, an aspirator, a nitrogen introduction tube, a bottom drain valve, and a strand die was charged with precisely weighed materials including 9500 g (46.51 mol) of sebacic acid (1,8-octane dicarboxylic acid: SA (available from CASDA)), 2578 g (15.50 mol) of isophthalic acid (PIA, available from Mitsubishi Gas Chemical Co., Inc.), and 1.22 g (0.0149 mol) of sodium acetate (available from Kanto Chemical Co., Inc.), and then sufficiently purged with nitrogen, after which the inside of the reaction vessel was sealed, and the temperature was raised to 180° C. under stirring while the pressure in the vessel was maintained at 0.4 MPa. After the temperature reached 180° C., a 25° C. aqueous solution adjusted by dissolving 5.62 g (0.0331 mol) of calcium hypophosphate (available from Kanto Chemical Co., Inc.) in 50 mL of water was continuously added to the dodecanedioic acid/isophthalic acid, which were in a molten state, in the reaction vessel at an addition rate of 1.5 mL/s. Dropwise addition of 9475 g (55.53 mol) of isophoronediamine (IPDA, available from BASF SE) stored in a dropping funnel, into the raw materials in the reaction vessel was then initiated, and the temperature in the reaction chamber was raised to 250° C. while condensed water that was produced was removed from the system and the pressure in the vessel was maintained at 0.4 MPa. After the completion of dropwise addition of IPDA, the pressure in the reaction vessel was gradually returned to normal pressure while the temperature was gradually raised to 270° C., and then an aspirator was used to reduce the pressure inside the reaction chamber to 80 kPa and remove the condensed water. Agitation torque of the stirrer was observed under a reduced pressure, and agitation was terminated when a predetermined torque was reached. Then, the inside of the reaction chamber was pressurized with nitrogen, the bottom drain valve was opened, and the polymer was extruded from the strand die to form a strand and then cooled and pelletized by using a pelletizer to obtain a polyamide resin.
The glass transition temperature of the formed polyamide resin was 161° C., and the number average molecular weight was 14800.
The crystal melting enthalpy ΔHm was 1 J/g or less.
The appearance of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
The Charpy impact strength of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
A pressure-resistant reaction vessel having an internal volume of 50 L and equipped with a stirrer, a partial condenser, a total condenser, a pressure regulator, a thermometer, a dropping funnel and pump, an aspirator, a nitrogen introduction tube, a bottom drain valve, and a strand die was charged with precisely weighed materials including 9500 g (46.51 mol) of sebacic acid (1,8-octane dicarboxylic acid: SA (available from CASDA)), 2578 g (15.50 mol) of isophthalic acid (PIA, available from Mitsubishi Gas Chemical Co., Inc.), 5.62 g (0.0331 mol) of calcium hypophosphite (available from Kanto Chemical Co., Inc.), and 1.22 g (0.0149 mol) of sodium acetate (available from Kanto Chemical Co., Inc.), and then sufficiently purged with nitrogen, after which the inside of the reaction vessel was sealed, and the temperature was raised to 180° C. under stirring while the pressure in the vessel was maintained at 0.4 MPa. After the temperature reached 180° C., dropwise addition of 9475 g (55.53 mol) of isophoronediamine (IPDA, available from BASF SE) stored in a dropping funnel, into the raw materials in the reaction vessel was then initiated, and the temperature in the reaction chamber was raised to 250° C. while condensed water that was produced was removed from the system and the pressure in the vessel was maintained at 0.4 MPa. After the completion of dropwise addition of IPDA, the pressure in the reaction vessel was gradually returned to normal pressure while the temperature was gradually raised to 270° C., and then an aspirator was used to reduce the pressure inside the reaction chamber to 80 kPa and remove the condensed water. Agitation torque of the stirrer was observed under a reduced pressure, and agitation was terminated when a predetermined torque was reached. Then, the inside of the reaction chamber was pressurized with nitrogen, the bottom drain valve was opened, and the polymer was extruded from the strand die to form a strand and then cooled and pelletized by using a pelletizer to obtain a polyamide resin.
The glass transition temperature of the formed polyamide resin was 161° C., and the number average molecular weight was 14000.
The crystal melting enthalpy ΔHm was 1 J/g or less.
The appearance of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
The Charpy impact strength of the obtained amorphous polyamide resin was evaluated in the same manner as in Example 1.
As is clear from the above results, it was found that when producing an amorphous polyamide resin having a constituent unit derived from isophoronediamine, a constituent unit derived from an α,ω-linear aliphatic dicarboxylic acid having from 8 to 14 carbons, and a constituent unit derived from an aromatic dicarboxylic acid, the production of foreign matter in the resin can be suppressed or prevented, and a good appearance when formed into a molded article can be obtained by adding a phosphorus atom-containing compound as an aqueous solution into a dicarboxylic acid that is in a molten state.
In contrast, when the phosphorus atom-containing compound is added without being formed into an aqueous solution, the appearance was inferior.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-154373 | Aug 2018 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2019/031888 | 8/13/2019 | WO | 00 |
