CN112334508B - Method for producing liquid crystalline resin - Google Patents
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- CN112334508B CN112334508B CN201980042346.9A CN201980042346A CN112334508B CN 112334508 B CN112334508 B CN 112334508B CN 201980042346 A CN201980042346 A CN 201980042346A CN 112334508 B CN112334508 B CN 112334508B
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
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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
- C08G69/44—Polyester-amides
Abstract
The present invention provides a method for producing a liquid crystalline resin, which comprises reacting a raw material monomer comprising at least 1 selected from an aromatic hydroxycarboxylic acid and a polymerizable derivative thereof to produce the liquid crystalline resin, wherein the method for producing the liquid crystalline resin comprises a step of polycondensing the raw material monomer in the presence of an acidic compound having a B-O (boron-oxygen) bond or a compound capable of producing an acidic compound in the reaction system.
Description
Technical Field
The present invention relates to a method for producing a liquid crystalline resin.
Background
Liquid crystalline resins represented by liquid crystalline polyester resins are excellent in high flowability, low burr property, resistance to reflow, and the like, and thus can be widely used in various fields. Such a liquid crystalline resin is obtained by appropriately combining and selecting raw material monomers such as an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and an aromatic diol, and polycondensing them to obtain desired physical properties. In practice, the polycondensation reaction is usually carried out after the mixture of the raw material monomers is acylated in advance with an acylating agent (acetic anhydride or the like).
In order to increase the rate of the polycondensation reaction in the production of the liquid crystalline resin, various catalysts can be used, for example. Among them, when potassium acetate is used as a catalyst, the generation of gas during the reaction tends to increase. This is considered to be due to the presence of potassium acetate as a baseThe carboxyl group (-COOH) at the end of the liquid crystalline resin is converted into a carboxylate ion (-COO)-) And is activated and easily released as carbon dioxide. In order to suppress the generation of carbon dioxide, it is conceivable that the polycondensation reaction is performed under acidic conditions using an acid catalyst. Examples of the acid catalyst include aliphatic sulfonic acids and aromatic sulfonic acids (see patent document 1).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2015/016141
Disclosure of Invention
Problems to be solved by the invention
However, the inventors have studied and found that the polycondensation rate cannot be sufficiently increased although the generation of carbon dioxide can be suppressed by using an acid catalyst such as an aliphatic sulfonic acid or an aromatic sulfonic acid. It is considered that when the acid catalyst as described above is used, the terminal carboxyl group of the liquid crystalline resin is stably present, and the generation of carbon dioxide due to the terminal carboxyl group is reduced, but parahydroxybenzoic acid which is difficult to be distilled off from the system is generated, and it takes time to perform polycondensation.
On the other hand, if only suppression of the generation of carbon dioxide is considered, the polycondensation reaction may be carried out without using a catalyst, but it is needless to say that the polycondensation rate cannot be increased without using a catalyst.
From the above, it is useful if the production of a liquid crystalline resin can be suppressed and the polycondensation rate can be increased by using an acid catalyst.
The present invention has been made in view of the above-described conventional problems, and an object thereof is to provide a method for producing a liquid crystalline resin, which can reduce the generation of carbon dioxide and increase the polycondensation rate at the same time.
Means for solving the problems
The present inventors have found that when a polycondensation reaction for obtaining a liquid crystalline resin is carried out in the presence of an acidic compound having a B — O (boron-oxygen) bond or a compound capable of generating the acidic compound in the reaction system, the rate of the polycondensation reaction can be increased and the generation of gas can be reduced, and have completed the present invention.
An aspect of the present invention to solve the above problems is as follows.
(1) A method for producing a liquid crystalline resin by reacting a raw material monomer comprising at least 1 selected from the group consisting of an aromatic hydroxycarboxylic acid and a polymerizable derivative thereof,
the method comprises a step of polycondensing the raw material monomer in the presence of an acidic compound having a B-O (boron-oxygen) bond or a compound capable of forming the acidic compound in the reaction system.
(2) The method for producing a liquid crystalline resin according to item (1) above, further comprising a step of acylating the raw material monomer in the presence of an acidic compound having a B-O (boron-oxygen) bond or a compound capable of producing the compound in a reaction system, prior to the polycondensation step.
(3) The method for producing a liquid crystalline resin according to the above (1) or (2), wherein a compound having a tertiary amine or an oxide thereof is further present in the polycondensation step.
(4) The method for producing a liquid crystalline resin according to any one of (1) to (3), wherein the acidic compound having a B-O (boron-oxygen) bond is an arylboronic acid having at least 1 electron-withdrawing group in an aryl group.
Effects of the invention
According to the present invention, it is possible to provide a method for producing a liquid crystalline resin which can reduce the generation of carbon dioxide and increase the polycondensation rate at the same time.
Detailed Description
The method for producing a liquid crystalline resin according to the present embodiment is a method for producing a liquid crystalline resin by reacting a raw material monomer including at least 1 selected from an aromatic hydroxycarboxylic acid and a polymerizable derivative thereof. And is characterized by comprising a step of polycondensing a raw material monomer in the presence of an acidic compound having a B-O (boron-oxygen) bond (hereinafter, also referred to as "B-O bond-containing compound") or a compound capable of forming the acidic compound in a reaction system (hereinafter, also referred to as "B-O bond-containing compound" or the like ").
In the method for producing a liquid crystalline resin according to the present embodiment, since the raw material monomers are polycondensed in the presence of a B — O bond-containing compound or the like as a catalyst, the production of carbon dioxide can be reduced and the polymerization rate can be increased. That is, since the production can be performed in a shorter time than the conventional one while suppressing the side reaction accompanying the polycondensation reaction, the cost can be reduced. More preferably, the step of acylation reaction is carried out in the presence of the above-mentioned compound having a B-O bond or the like. The acylation step and the polycondensation step are both carried out in the presence of the above-mentioned compound containing a B-O bond, etc., whereby a liquid crystalline resin can be produced in a shorter time.
The term "liquid-crystalline" in the liquid-crystalline resin of the present embodiment means that the liquid-crystalline resin has a property of forming an optically anisotropic melt phase. The properties of the anisotropic molten phase can be confirmed by a common polarization examination method using crossed polarizers. More specifically, the anisotropic molten phase was confirmed by observing a molten sample placed on a Leitz hot stage at a magnification of 40 times in a nitrogen atmosphere using a Leitz polarized light microscope. When a resin having liquid crystallinity is inspected between crossed polarizers, the polarized light generally penetrates and optically exhibits anisotropy even in a molten static state.
(raw Material monomer)
The raw material monomer includes at least 1 compound selected from the group consisting of aromatic hydroxycarboxylic acids and polymerizable derivatives thereof. The aromatic hydroxycarboxylic acid and the polymerizable derivative thereof are not particularly limited, and examples thereof include p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, m-hydroxybenzoic acid, 6-hydroxy-3-naphthoic acid, 6-hydroxy-4-naphthoic acid, 4-hydroxy-4 '-carboxydiphenyl ether, 2, 6-dichloro-p-hydroxybenzoic acid, 2-chloro-p-hydroxybenzoic acid, 2, 6-dimethyl-p-hydroxybenzoic acid, 2, 6-difluoro-p-hydroxybenzoic acid, 4-hydroxy-4' -biphenylcarboxylic acid, vanillic acid and the like. At least 1 compound selected therefrom may be used. Among them, it is preferable to use at least 1 selected from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid in terms of the ease of acquisition.
The raw material monomer further preferably satisfies the following (1) or (2).
(1) Comprising at least 1 compound selected from aromatic or alicyclic dicarboxylic acids and polymerizable derivatives thereof, or,
(2) a compound comprising at least 1 member selected from the group consisting of aromatic or alicyclic dicarboxylic acids and polymerizable derivatives thereof, and
at least 1 compound selected from the group consisting of aromatic or alicyclic diols, aromatic or alicyclic hydroxyamines, aromatic or alicyclic diamines, and polymerizable derivatives thereof.
The aromatic dicarboxylic acid is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, 4' -diphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (I).
[ chemical formula 1]
(Y: is selected from- (CH)2)n- (n-1-4) and-O (CH)2)nAnd (1-4) O- (n). )
The alicyclic dicarboxylic acid is not particularly limited, and examples thereof include 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, and the like. The polymerizable derivative is not particularly limited, and examples thereof include alkyl esters (having about 1 to 4 carbon atoms) and halides of the above compounds.
The aromatic diol is not particularly limited, and examples thereof include 2, 6-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 4' -dihydroxybiphenyl, hydroquinone, resorcinol, a compound represented by the following general formula (II), a compound represented by the following general formula (III), and the like.
[ chemical formula 2]
(X: is selected from alkylene (C)1～C 4) Alkylene, -O-, -SO-, -SO2-, -S-, and-CO-. )
[ chemical formula 3]
The alicyclic diol is not particularly limited, and examples thereof include 1, 4-cyclohexanedimethanol and 1, 4-cyclohexanediol. The polymerizable derivative is not particularly limited, and examples thereof include alkyl esters (having about 1 to 4 carbon atoms) and halides of the above compounds.
The aromatic hydroxylamine is not particularly limited, and examples thereof include p-aminophenol and (m-aminophenol). The alicyclic hydroxylamine is not particularly limited, and examples thereof include (4-hydroxycyclohexanecarboxylic acid, 3-hydroxycyclopentanecarboxylic acid) and the like. The polymerizable derivative is not particularly limited, and examples thereof include alkyl esters (having about 1 to 4 carbon atoms) and halides of the above compounds.
Examples of the aromatic diamine include p-phenylenediamine and the like. The alicyclic diamine is not particularly limited, and examples thereof include 1, 4-cyclohexanediamine, 1, 3-cyclopentanediamine, and the like. The polymerizable derivative is not particularly limited, and examples thereof include alkyl esters (having about 1 to 4 carbon atoms) and halides of the above compounds.
As a specific combination of the raw material monomers, for example,
(I) (a) comprises at least 1 compound selected from the group consisting of aromatic hydroxycarboxylic acids and polymerizable derivatives thereof, or,
(II) (a) at least 1 compound selected from the group consisting of aromatic hydroxycarboxylic acids and polymerizable derivatives thereof, (b) at least 1 compound selected from the group consisting of aromatic or alicyclic dicarboxylic acids and polymerizable derivatives thereof, and (c) at least 1 compound selected from the group consisting of aromatic or alicyclic diols, aromatic hydroxyamines, aromatic diamines, and polymerizable derivatives thereof. If necessary, a molecular weight regulator may be used in combination with the above-mentioned components.
[ acylation ]
In the production method of the present embodiment, the step of acylating the raw material monomer with an acylating agent may be performed before the polycondensation described later. The acylation is preferably carried out in the presence of the above-mentioned compound having a B-O bond or the like. Examples of the acylating agent include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, β -bromopropionic anhydride, and the like, but are not particularly limited. At least 1 selected therefrom may be used. Examples of the preferable substance from the viewpoint of cost and operability include carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride and isobutyric anhydride. Among them, acetic anhydride is preferable in terms of ease of acquisition. In terms of ease of reaction control, the amount of the acylating agent used in the total amount of hydroxyl groups of the substance used for the reaction is preferably 1.0 to 1.1 equivalents, and more preferably 1.01 to 1.05 equivalents.
The acylation may be carried out by a known method. For example, a raw material monomer is mixed with an acylating agent, and the mixture is heated at a temperature of 120 to 160 ℃ for about 0.5 to 5 hours to carry out an acylation reaction, thereby obtaining a reaction product including an acylated product.
[ condensation polymerization ]
The raw material monomers are subjected to polycondensation in the presence of a compound containing a B-O bond or the like. In the case where the acylation step is designed as described above, and the compound containing a B-O bond or the like is used in the step, the compound containing a B-O bond or the like used in the polycondensation may be the same as or different from that used in the acylation.
(acidic Compound having B-O bond)
In the production method of the present embodiment, an acidic compound having a B — O bond is used as a catalyst when a raw material monomer is subjected to polycondensation, and reduction in the production of carbon dioxide and increase in the rate of polycondensation can be simultaneously achieved by using a compound containing a B-O bond. Even if a compound having a B-O bond is present in the polycondensation reaction, the compound having a B-O bond is weakly acidic, so that the polymerization system tends to be weakly acidic, and thus the terminal carboxyl group can be stably present. Thus resulting in a reduction in carbon dioxide generation. In addition, the terminal carboxyl group reacts with a compound having a B-O bond to form a borate ester, thereby enhancing electron withdrawing properties. Therefore, the hydroxyl group of the raw material monomer is attracted, so that the polycondensation speed is increased.
On the other hand, when a general acid catalyst such as an aromatic sulfonic acid is used, the ester group is preferably activated rather than the terminal carboxyl group, and thus a side reaction due to strong activation of the ester group is likely to occur. In contrast, since the B — O bond-containing compound used in the present embodiment mainly activates the terminal carboxyl group, a polycondensation reaction proceeds from the terminal carboxyl group as an origin, and a side reaction is less likely to occur.
Examples of the compound having a B-O bond include boric acid derivatives such as boronic acid, arylboronic acid and fluoroboronic acid, and boric acid, and among these, arylboronic acid and boric acid are preferable.
The compound having a B-O bond is preferably used in that the electron-withdrawing property is improved and the polycondensation rate is further improved when an arylboronic acid having at least 1 electron-withdrawing group in the aryl group is used. Examples of the electron-withdrawing group include halogens such as trifluoromethyl, fluoro and chloro, nitro, cyano and keto groups.
Alternatively, in the present embodiment, a compound capable of generating a compound having a B-O bond in the reaction system is used in addition to the compound having a B-O bond directly used. By forming the compound having a B-O bond in the reaction system, the same effect as that obtained when the compound having a B-O bond is used can be obtained. Examples of the compound include boric anhydride compounds. These compounds can generate the above-mentioned acid in the reaction system by the presence of a carboxylic acid and heating.
The acid dissociation constant pKa of the B-O bond-containing compound is preferably 14 or less, more preferably-1.0 to 13, and further preferably 0to 12. The pKa is a pKa in an aqueous solution at 25 ℃.
In the present embodiment, the amount of the compound having a B-O bond or the compound capable of forming a compound having a B-O bond in the reaction system is not particularly limited as long as it does not adversely affect the acylation or the polycondensation. The amount of the compound is preferably 50 to 2000ppm, more preferably 100 to 1000ppm, based on the theoretical yield of a liquid crystalline resin to be obtained. The temperature during polycondensation is preferably 300 to 400 ℃.
In the step of polycondensation, it is more preferable that a compound having a tertiary amine or an oxide thereof is present. As described above, in the polycondensation reaction in the present embodiment, first, although the terminal carboxyl group is dehydration-condensed with the B — O bond-containing compound to form a boric acid ester, when a compound having a tertiary amine or an oxide thereof is present, the boric acid moiety is substituted by the compound and converted into a more active ester. That is, the electrophilicity of the terminal carboxyl group is further improved, and thus the polycondensation rate is further improved.
Examples of the compound having a tertiary amine or an oxide thereof include dimethylaminopyridine oxide (DMAPO), N-dimethyl-4-aminopyridine (DMAP), 4-methoxypyridine-N-oxide (MPO), 4-pyrrolidinylpyridine-N-oxide (PPYO), N-isopropylethylamine, trimethylamine, and triethylamine. Among them, preferred is trimethylaminopyridine oxide having a stronger nucleophilicity.
In the present embodiment, the amount of the compound having a tertiary amine or an oxide thereof added is preferably 50 to 2000ppm, more preferably 100 to 1000ppm, based on the theoretical yield of a liquid crystalline resin to be obtained in general.
(solid-phase polymerization Process)
The method for producing a liquid crystalline resin according to the present embodiment may further include a step of solid-phase polymerizing the resin obtained in the melt polymerization step (the polycondensation step). The solid-phase polymerization can increase the molecular weight of the raw material resin, and thus a liquid crystalline resin having excellent strength and heat resistance can be obtained.
The solid-phase polymerization may be carried out by a conventionally known method. For example, the heating may be performed by heating the raw material resin in a gas flow of an inert gas such as nitrogen at a temperature 10to 120 ℃ lower than the liquid crystal forming temperature of the raw material resin under reduced pressure or vacuum. Further, since the melting point of the liquid crystalline resin also increases as the solid-phase polymerization proceeds, the liquid crystalline resin may be solid-phase polymerized at the melting point of the raw material resin or higher. The solid-phase polymerization may be carried out at a constant temperature or may be carried out by raising the temperature in stages. The heating method is not particularly limited, and microwave heating, heater heating, or the like can be used.
[ liquid Crystal resin ]
The liquid crystalline resin obtained by the production method of the present embodiment preferably contains at least 1 selected from the group consisting of a liquid crystalline polyester and a liquid crystalline polyester amide. The liquid crystalline polyester and the liquid crystalline polyester amide are not particularly limited, but are preferably an aromatic polyester or an aromatic polyester amide. Further, a polyester partially containing an aromatic polyester or an aromatic polyester amide in the same molecular chain may be used.
More specifically, the aromatic polyester or aromatic polyester amide includes:
(1) a polyester mainly comprising (a) 1 or 2 or more species of aromatic hydroxycarboxylic acids and derivatives thereof;
(2) a polyester mainly comprising (a) 1 or 2 or more species of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) 1 or 2 or more species of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof;
(3) a polyester mainly comprising (a) 1 or 2 or more species of aromatic hydroxycarboxylic acids and derivatives thereof, (b) 1 or 2 or more species of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, and (c) 1 or 2 or more species of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof;
(4) polyesteramides consisting essentially of (a) 1 or 2 or more species of aromatic hydroxycarboxylic acids and derivatives thereof, (c1) 1 or 2 or more species of aromatic hydroxyamines, aromatic diamines, and derivatives thereof, (c2) 1 or 2 or more species of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof;
(5) polyesteramides mainly comprising (a) 1 or 2 or more species of aromatic hydroxycarboxylic acids and derivatives thereof, (b) 1 or 2 or more species of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, (c1) 1 or 2 or more species of aromatic hydroxyamines, aromatic diamines, and derivatives thereof, and (c2) 1 or 2 or more species of aromatic diols, alicyclic diols, and derivatives thereof, and the like.
The molecular weight (number average molecular weight Mn) of the liquid crystalline resin is not particularly limited, and the resin obtained in the melt polymerization step is preferably 10000 to 100000, more preferably 15000 to 80000. The resin obtained in the solid-phase bonding step で is preferably 12000 to 120000, more preferably 15000 to 100000. In addition, the number average molecular weight Mn can be determined by gel permeation chromatography.
The melting point of the liquid crystalline resin is not particularly limited, and may be 250 to 380 ℃. The melt viscosity of the liquid crystalline resin is not particularly limited, and the resin obtained by melt polymerization has a cylinder temperature 10to 30 ℃ higher than the melting point of the liquid crystalline resin and a shear rate of 1000sec-1The melt viscosity measured is preferably 5 pas to 150 pas, more preferably 10 pas to 100 pas. The resin is further subjected to a solid-phase polymerization step at a cylinder temperature 10to 30 ℃ higher than the melting point of the liquid crystalline resin and a shear rate of 1000sec-1The melt viscosity measured is preferably 5 pas to 200 pas, more preferably 10 pas to 150 pas.
The "cylinder temperature 10to 30 ℃ higher than the melting point of the liquid crystalline resin" means a cylinder temperature at which the liquid crystalline resin is melted to such an extent that the melt viscosity can be measured, and the cylinder temperature of several ℃ higher than the melting point is used, and varies depending on the kind of the raw material resin. The liquid crystalline resin may be in the form of a powder-granule mixture or a molten mixture (melt-kneaded product) of particles or the like.
The present embodiment will be described in more detail below with reference to examples, but the present embodiment is not limited to the following examples.
[ example 1]
After charging the following raw materials into a polymerization vessel, the temperature of the reaction system was raised to 140 ℃ and the reaction was carried out at 140 ℃ for 3 hours (acylation). Then, the temperature was raised to 360 ℃ for a further 4.5 hours, and then the pressure was reduced to 10Torr (1330 Pa) for 15 minutes to perform polycondensation while leaving acetic acid, an excessive amount of acetic anhydride, and other low boiling points. The time from the start of the depressurization to the time when the stirring torque reached the predetermined value was 20 minutes. After the stirring torque reached a predetermined value, nitrogen was introduced, the pressure was increased from a reduced pressure state to a pressurized state through an ordinary pressure, and the polymer was discharged from the lower portion of the polymerization vessel. Then, the strand was pelletized to obtain liquid crystalline resin pellets.
(raw materials)
4-Hydroxybenzoic acid (HBA): 184g (60 mol%)
Terephthalic Acid (TA): 52g (14 mol%)
Isophthalic Acid (IA): 22g (6 mol%)
4, 4' -dihydroxybiphenyl (BP): 83g (20 mol%)
Phenyl boronic acid: 54mg (180ppm) (catalyst; compound containing a B-O bond)
Acylating agent (acetic anhydride): 233g
[ example 2]
Liquid crystalline resin particles were obtained in the same manner as in example 1, except that dimethylaminopyridine oxide was added. The amount of dimethylaminopyridine oxide used is shown in Table 1.
[ example 3]
Liquid crystalline resin particles were obtained in the same manner as in example 1, except that the compound having a B — O bond was changed to 3, 5-bis (trifluoromethyl) phenylboronic acid. The amount of 3, 5-bis (trifluoromethyl) phenylboronic acid used is shown in table 1.
[ example 4]
Liquid crystalline resin particles were obtained in the same manner as in example 1, except that the compound having a B — O bond was changed to boric acid. The amount of boric acid used is shown in table 1.
Comparative example 1
Liquid crystalline resin particles were obtained in the same manner as in example 1, except that the phenylboronic acid was changed to potassium acetate. The amount of potassium acetate used is shown in table 1.
Comparative example 2
Liquid crystalline resin particles were obtained in the same manner as in example 1, except that phenylboronic acid was not used, that is, a catalyst was not used.
[ polycondensation time ]
In each of the examples and comparative examples, the time from the start of the depressurization to the time when the stirring torque reached the predetermined value was confirmed. The results are shown in Table 1. The torque value indicated when the target melt viscosity is reached is set to a predetermined value. The polymers of examples 1 to 4 and comparative examples 1 and 2 had a cylinder temperature of 360 ℃ and a shear rate of 1000sec as target melt viscosities-1The melt viscosity was 15 pas.
The melt viscosity was measured by measuring the apparent melt viscosity according to ISO 11443 with a capillary rheometer (capillary rheometer 1D manufactured by Toyo Seiki Seisaku-Sho Ltd.: piston diameter: 10mm) at the above cylinder temperature and shear rate. The measurement was carried out using a port (orifice) having an inner diameter of 0.5mm and a length of 30 mm.
[ melting Point ]
In each of examples and comparative examples, the endothermic peak temperature (Tm1) observed when the liquid crystalline resin was heated from room temperature at a temperature increase rate of 20 ℃/min was measured using a differential scanning calorimeter (DSC, manufactured by hitachi hei). Next, the temperature was maintained at (Tm1+ 40). degree.C.for 2 minutes. Then, the temperature was once cooled to room temperature at a cooling rate of 20 ℃/min, and then the endothermic peak temperature (Tm2) observed when the sample was heated again at a heating rate of 20 ℃/min was measured as the melting point.
[ amount of carbon dioxide produced ]
In each of examples and comparative examples, the amount of weight loss of 10mg of the liquid crystalline resin when it was held at a temperature higher than the melting point of the liquid crystalline resin by 25 ℃ (Tm2+25 ℃) for 30 minutes under a nitrogen stream was measured by a thermogravimetric apparatus (manufactured by TGA, TA instruments Co., Ltd.), and the amount was evaluated as the amount of carbon dioxide generated.
[ Table 1]
From Table 1, the examples are shown
The time from the start of depressurization to the time when the predetermined torque is reached is short, and the amount of carbon dioxide generated is small. Namely, in the examples
It was shown that the reduction of the generation of carbon dioxide and the increase of the polycondensation rate can be simultaneously achieved.
In contrast, in the comparative example
In (2), it is not possible to obtain a result satisfying both reduction of carbon dioxide generation and improvement of polycondensation rate.
Claims (4)
1. A method for producing a liquid crystalline resin, which comprises reacting a raw material monomer comprising at least 1 selected from an aromatic hydroxycarboxylic acid and a polymerizable derivative thereof to produce a liquid crystalline resin,
the method for producing the liquid crystalline resin includes: and a step of polycondensing the raw material monomer using an acidic compound selected from the group consisting of an arylboronic acid, a boronic acid and a boric acid, or a compound capable of producing the acidic compound in a reaction system as a catalyst.
2. The method for producing a liquid crystalline resin according to claim 1,
further comprising: before the polycondensation step, acylating the raw material monomer in the presence of an acidic compound selected from an arylboronic acid, a boronic acid and a boric acid, or a compound capable of producing the compound in the reaction system.
3. The method for producing a liquid crystalline resin according to claim 1 or 2,
in the polycondensation step, a compound having a tertiary amine or an oxide thereof is also present.
4. The method for producing a liquid crystalline resin according to claim 1 or 2,
the aryl boronic acid is an aryl boronic acid having at least 1 electron withdrawing group on the aryl group.
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| JP2018143824 | 2018-07-31 | ||
| JP2018-143824 | 2018-07-31 | ||
| PCT/JP2019/027482 WO2020026746A1 (en) | 2018-07-31 | 2019-07-11 | Method for producing liquid-crystalline resin |
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| CN112334508A CN112334508A (en) | 2021-02-05 |
| CN112334508B true CN112334508B (en) | 2022-04-15 |
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| JP (1) | JP6695012B1 (en) |
| CN (1) | CN112334508B (en) |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5286834A (en) * | 1991-10-29 | 1994-02-15 | Ge Plastics Japan, Ltd. | Melt preparation of copolycarbonate with alkaline compound catalyst and boric acid compound catalyst |
| JPH10330466A (en) * | 1997-06-04 | 1998-12-15 | Polyplastics Co | Production of polyester resin |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS4641033B1 (en) * | 1968-03-15 | 1971-12-03 | ||
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- 2019-07-11 CN CN201980042346.9A patent/CN112334508B/en active Active
- 2019-07-11 WO PCT/JP2019/027482 patent/WO2020026746A1/en active Application Filing
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| US5286834A (en) * | 1991-10-29 | 1994-02-15 | Ge Plastics Japan, Ltd. | Melt preparation of copolycarbonate with alkaline compound catalyst and boric acid compound catalyst |
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| JPWO2020026746A1 (en) | 2020-08-06 |
| TWI789540B (en) | 2023-01-11 |
| CN112334508A (en) | 2021-02-05 |
| JP6695012B1 (en) | 2020-05-20 |
| WO2020026746A1 (en) | 2020-02-06 |
| TW202012488A (en) | 2020-04-01 |
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