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WO2021241607A1 - Procédé de production de résine cristalline liquide - Google Patents

Procédé de production de résine cristalline liquide Download PDF

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Publication number
WO2021241607A1
WO2021241607A1 PCT/JP2021/019894 JP2021019894W WO2021241607A1 WO 2021241607 A1 WO2021241607 A1 WO 2021241607A1 JP 2021019894 W JP2021019894 W JP 2021019894W WO 2021241607 A1 WO2021241607 A1 WO 2021241607A1
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Prior art keywords
acid
liquid crystal
crystal resin
salt
raw material
Prior art date
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PCT/JP2021/019894
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English (en)
Japanese (ja)
Inventor
浩一 齊藤
智之 多田
桂一 加中
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Polyplastics Co Ltd
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Polyplastics Co Ltd
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Priority to JP2021556780A priority Critical patent/JP7072733B1/ja
Publication of WO2021241607A1 publication Critical patent/WO2021241607A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C08G63/87—Non-metals or inter-compounds thereof
    • 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

Definitions

  • the present invention relates to a method for producing a liquid crystal resin.
  • Liquid crystal resins represented by liquid crystal polyester resins and liquid crystal polyester amide resins are widely used in various fields because they are excellent in high fluidity, low burr property, reflow resistance and the like.
  • the liquid crystal resin is obtained by appropriately combining and selecting raw material monomers such as aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, and aromatic diol so as to obtain a liquid crystal resin having desired physical properties, and polycondensing them. Be done.
  • a mixture of raw material monomers is pre-acylated with an acylating agent (acetic anhydride or the like), and then the acylated raw material monomers are subjected to a polycondensation reaction (for example, Patent Documents 1 and 2).
  • Japanese Unexamined Patent Publication No. 2020-19866 International Publication No. 2020/026746 Japanese Unexamined Patent Publication No. 2020-19866 International Publication No. 2020/026746
  • the present inventor conducts a polycondensation reaction with at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic having one or more nitrogen atoms. It has been found that the reduction of gas generation and the improvement of the polycondensation rate can be achieved at the same time and the decrease in the brightness of the liquid crystal resin can be suppressed by carrying out in the presence of a salt with the basic compound.
  • an acid anhydride such as acetic anhydride
  • Patent Documents 1 and 2 an acid anhydride
  • acid anhydrides are expensive, there is a demand for a method for producing a liquid crystal resin at a lower cost.
  • a carboxylic acid such as acetic acid is generally cheaper than an acid anhydride, and if it can be used as an acylating agent, a liquid crystal resin can be produced at low cost.
  • the acylation reaction of the raw material monomer does not proceed sufficiently.
  • the present inventor performs the acylation reaction in the presence of a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms. It has been found that the acylation reaction rate of the raw material monomer can be increased even when a carboxylic acid is used as the agent.
  • a common object of the present invention is to provide a method for producing a liquid crystal resin using a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms. That is.
  • a further problem in the first aspect of the present invention is the production of a liquid crystal resin capable of increasing the reaction rate, suppressing the generation of gas when the liquid crystal resin is melted, and obtaining a liquid crystal resin having high brightness.
  • a further object of the second aspect of the present invention is to provide a method for producing a liquid crystal resin at a lower cost than before.
  • a liquid crystal resin comprising reacting a raw material monomer in the presence of a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms.
  • Manufacturing method comprises (A) acylating the raw material monomer, (B) polycondensing the acylated raw material monomer, and (A) acidifying the raw material monomer and the carboxylic acid.
  • a method for producing a liquid crystal resin which comprises reacting at least one acidic compound having a dissociation constant pKa of 1 or less with at least one organic base compound having 1 or more nitrogen atoms in the presence of a salt (a1).
  • the first aspect of the present invention relates to the following.
  • a liquid crystal resin comprising reacting a raw material monomer in the presence of a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms. Manufacturing method.
  • [3] The method for producing a liquid crystal resin according to [1] or [2], wherein the organic base compound constituting the salt has an amino group.
  • [4] The method for producing a liquid crystal resin according to any one of [1] to [3], wherein the acid dissociation constant pKa of the acidic compound constituting the salt is 0.65 or less.
  • [5] The method for producing a liquid crystal resin according to any one of [1] to [4], wherein the acid dissociation constant pKa of the conjugate acid of the organic base compound constituting the salt is less than 13.0.
  • [6] The method for producing a liquid crystal resin according to any one of [1] to [5], wherein the acidic compound constituting the salt contains a halogenated alkyl sulfonic acid.
  • [7] The method for producing a liquid crystal resin according to any one of [1] to [6], wherein the organic base compound constituting the salt contains a halogenated aromatic amine.
  • the second aspect of the present invention relates to the following.
  • Acylation comprises (A) acylating the raw material monomer, (B) polycondensing the acylated raw material monomer, and (A) acidifying the raw material monomer and the carboxylic acid.
  • a method for producing a liquid crystal resin which comprises reacting at least one acidic compound having a dissociation constant pKa of 1 or less with at least one organic base compound having 1 or more nitrogen atoms in the presence of a salt (a1).
  • Acylation (A) causes the reaction of the raw material monomer and the carboxylic acid (a1), and then the acid anhydride is added to the reaction solution to react the unreacted raw material monomer with the acid anhydride.
  • [3] The method for producing a liquid crystal resin according to [1] or [2], wherein the polycondensation (B) comprises polycondensing the acylated raw material monomer in the presence of the salt.
  • the amount of the acid anhydride added in (a2) of adding the acid anhydride and reacting the unreacted raw material monomer with the acid anhydride is 0.01 to 0.
  • a method for producing a liquid crystal resin using a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms. can.
  • a method for producing a liquid crystal resin which can increase the reaction rate, suppress the generation of gas when the liquid crystal resin is melted, and can obtain a liquid crystal resin having high brightness.
  • the raw material monomer is in the presence of a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms. Including reacting with. More specifically, as described in Examples described later, the method for producing a liquid crystal resin according to an embodiment uses a raw material monomer, at least one acidic compound having an acid dissociation constant pKa of 1 or less, and a nitrogen atom. It comprises performing an acylation reaction and / or a polycondensation reaction in the presence of a salt with at least one organic base compound having one or more.
  • the polycondensation reaction preferably the acylation reaction and the polycondensation reaction
  • at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base having one or more nitrogen atoms It describes what to do in the presence of a salt with the compound.
  • the acylation reaction preferably the acylation reaction and the polycondensation reaction
  • the raw material monomer is in the presence of a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms. Including reacting with.
  • the polycondensation rate can be increased and gas such as carbon dioxide is generated when the liquid crystal resin is melted. Can be further reduced than before.
  • the liquid crystal resin can be produced in a shorter time than before, and the cost can be reduced. Since the generation of gas when the liquid crystal resin is melted can be further reduced, the swelling (blister) of the molded product due to the generated gas can be suppressed. Since it is possible to prevent a decrease in the brightness of the liquid crystal resin, it is possible to produce a liquid crystal resin that gives a molded product having an excellent appearance.
  • Liquid crystal means having a property of being able to form an optically anisotropic molten phase.
  • the properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizing element. More specifically, the confirmation of the anisotropic molten phase can be carried out by observing the molten sample placed on the Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope.
  • a resin having liquid crystallinity normally transmits polarized light even in a molten stationary state when inspected between orthogonal polarizing elements, and exhibits optical anisotropy.
  • the raw material monomer preferably contains at least one compound selected from the group consisting of aromatic hydroxycarboxylic acids and polymerizable derivatives thereof.
  • the aromatic hydroxycarboxylic acid and its polymerizable derivative are not particularly limited, and are, for example, p-hydroxybenzoic acid (4-hydroxybenzoic acid: HBA), 6-hydroxy-2-naphthoic acid, m-hydroxybenzoic acid.
  • the raw material monomer further preferably satisfies the following (1) or (2).
  • the alicyclic dicarboxylic acid is not particularly limited, and examples thereof include 1,4-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid.
  • the polymerizable derivative is not particularly limited, and examples thereof include an alkyl ester (about 1 to 4 carbon atoms) of the above compound, a halide and the like.
  • the aromatic diol is not particularly limited, and is, for example, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl (BP), hydroquinone, resorcin, represented by the following general formula (II). Examples thereof include compounds represented by the following general formula (III).
  • 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 an alkyl ester (about 1 to 4 carbon atoms) of the above compound, a halide and the like.
  • the aromatic hydroxyamine is not particularly limited, and examples thereof include p-aminophenol and m-aminophenol.
  • the alicyclic hydroxyamine is not particularly limited, and examples thereof include 4-hydroxycyclohexanecarboxylic acid and 3-hydroxycyclopentanecarboxylic acid.
  • the polymerizable derivative is not particularly limited, and examples thereof include an alkyl ester (about 1 to 4 carbon atoms) of the above compound, a halide and the like.
  • 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 and 1,3-cyclopentanediamine.
  • the polymerizable derivative is not particularly limited, and examples thereof include an alkyl ester (about 1 to 4 carbon atoms) of the above compound, a halide and the like.
  • raw material monomers include, for example, (I) (a) Containing or containing at least one compound selected from the group consisting of aromatic hydroxycarboxylic acids and polymerizable derivatives thereof. (II) A group consisting of at least one compound selected from the group consisting of (a) aromatic hydroxycarboxylic acid and a polymerizable derivative thereof, and (b) a group consisting of an aromatic or alicyclic dicarboxylic acid and a polymerizable derivative thereof. At least one compound selected from, and (c) at least one compound selected from the group consisting of aromatic or alicyclic diols, aromatic hydroxyamines, aromatic diamines, and polymerizable derivatives thereof. Can be a combination including. Further, a molecular weight adjusting agent may be used in combination with the above-mentioned constituent components, if necessary.
  • the above-mentioned raw material monomer is preferably subjected to an acylation reaction described later, and then referred to as at least one acidic compound having an acid dissociation constant pKa of 1 or less (hereinafter, also simply referred to as “acid compound”).
  • a polycondensation reaction is carried out by melt polymerization in the presence of a salt with at least one organic base compound having one or more nitrogen atoms (hereinafter, also simply referred to as “organic base compound”).
  • organic base compound organic base compound having one or more nitrogen atoms
  • the salt of the acidic compound and the organic base compound is composed of an anion of the acidic compound and a cation of the organic base compound.
  • the salt in addition to using the salt itself, the salt may be formed by coexisting the acidic compound and the organic base compound in the reaction system.
  • the acidic compound and the organic base compound can form a salt by an acid-base reaction in the reaction system.
  • the acidic compound (anionic component) has an acid dissociation constant pKa of 1 or less, preferably 0.65 or less, more preferably -14.0 to 0.65, and further preferably -14.0 to-. It is 2.0. If the acid dissociation constant pKa of the acidic compound exceeds 1, the effect of improving the polycondensation reaction rate may decrease, which is not preferable.
  • the above pKa means pKa in an aqueous solution at 25 ° C.
  • the acidic compounds, organic acid compounds include, for example, a sulfonic acid group (-SO 3 H), a sulfonyl group (-SO 2 -) organic acid compounds having at least one one or more functional groups selected from the listed , One or more selected from these can be used. That is, the salt preferably contains one or more anion components selected from sulfonic acid anions and sulfonylimide anions. In one embodiment, the acidic compound has a sulfonic acid group.
  • the acidic compound preferably contains a sulfonic acid in terms of acidity or ease of handling at room temperature.
  • the sulfonic acid include an alkyl sulfonic acid which may have a substituent and an aryl sulfonic acid which may have a substituent.
  • the alkyl sulfonic acid include methane sulfonic acid (pKa: -2.6) and the like.
  • aryl sulfonic acid examples include benzene sulfonic acid (pKa: 0.7), p-toluene sulfonic acid (pKa: -2.8), naphthalene sulfonic acid (pKa: 0.17), and dodecylbenzene sulfonic acid (pKa). : -0.45), 1.3-benzenedisulfonic acid (pKa: -1.4) and the like.
  • the acidic compound preferably contains a halogenated sulfonic acid and / or a halogenated alkyl sulfonic acid in terms of adjusting the acidity or lowering the boiling point.
  • halogenated sulfonic acid and / or the halogenated alkyl sulfonic acid examples include fluorosulfonic acid (pKa: -10), difluoromethanesulfonic acid (pKa: -2.0), and trifluoromethanesulfonic acid (pKa: -14.0).
  • fluorosulfonic acid pKa: -10
  • difluoromethanesulfonic acid pKa: -2.0
  • trifluoromethanesulfonic acid pKa: -14.0
  • Perfluorobutane sulfonic acid pKa: -13.2
  • perfluorohexane sulfonic acid pKa: -12.3
  • trifluoromethanesulfonic acid is most preferable.
  • the acidic compound comprises a halogenated alkyl sulfonic acid.
  • a compound capable of generating the acidic compound anion in the reaction system in addition to using the acidic compound as it is (or using the salt of the acidic compound and an organic base compound described later as it is), a compound capable of generating the acidic compound anion in the reaction system. Can be used. By generating the acidic compound in the reaction system, the same effect as the effect when the acidic compound (or the salt of the acidic compound and the organic base compound) can be obtained can be obtained.
  • Compounds that can generate an organic acid compound having at least one sulfonic acid group in the reaction system include mono, di or trifluoromethanesulfonic acid trimethylsilyl, mono, di or trifluoromethanesulfonic acid tert-butylsilyl, mono, di or trifluo. Examples thereof include lomethanesulfonyl halide and trifluoromethanesulfonic acid metal salt. These compounds can generate mono, di or trifluoromethanesulfonic acid anions in the reaction system due to the presence of carboxylic acid or heating.
  • the organic base compound is a compound that generates an organic onium cation and has one or more nitrogen atoms. That is, the salt contains at least a nitrogen cation.
  • the organic base compound (cationic component) preferably has an acid dissociation constant pKa of the conjugate acid of less than 13.0, preferably -10.0 to 8.0, in terms of the basicity of the organic base compound. Is more preferable, and ⁇ 8.0 to 6.0 is even more preferable.
  • the acid dissociation constant pKa of the conjugate acid of the organic base compound means pKa in an aqueous solution at 25 ° C.
  • Examples of the organic base compound having one or more nitrogen atoms include alkylamines, aromatic amines, alicyclic amines, nitrogen-containing heterocyclic compounds and the like, which may have a substituent. That is, the salt has an alkylammonium cation that may have a substituent, an aromatic ammonium cation that may have a substituent, an alicyclic ammonium cation that may have a substituent, and a substituent.
  • a nitrogen-containing heterocyclic compound may contain one or more selected from cations.
  • alkylamine examples include N, N-diisopropylethylamine (acid dissociation constant of conjugated acid pKa: 11.0), trimethylamine (acid dissociation constant of conjugated acid pKa: 9.8), and triethylamine (acid dissociation constant of conjugated acid pKa:: 10.8) and the like.
  • aromatic amine examples include diphenylamine (acid dissociation constant of conjugated acid pKa: 0.7), aniline (acid dissociation constant of conjugated acid pKa: 4.6), and triphenylamine (acid dissociation constant of conjugated acid pKa: -3). .0) and the like.
  • Examples of the alicyclic amine include cyclopentylamine (acid dissociation constant of conjugated acid pKa: 10.7), cyclohexylamine (acid dissociation constant of conjugated acid pKa: 10.7) and the like.
  • Examples of the nitrogen-containing heterocyclic compound include 2,5-dimethylpyrrolidine (acid dissociation constant of conjugated acid pKa: 11.4), N, N-dimethylpiperazine (acid dissociation constant of conjugated acid pKa: 4.6), N-.
  • Methylmorpholin (acid dissociation constant of conjugated acid pKa: 7.38), N-acetylmorpholin (acid dissociation constant of conjugated acid pKa: -0.7), dimethylaminopyridine-N-oxide / hydrate (of conjugated acid) Acid dissociation constant pKa: 3.9), N, N-dimethyl-4-aminopyridine (DMAP, acid dissociation constant of conjugated acid pKa: 9.7), 4-methoxypyridine-N-oxide (MPO, (conjugated acid) Acid dissociation constant pKa: 2.3) and the like.
  • DMAP acid dissociation constant of conjugated acid pKa: 9.7
  • MPO 4-methoxypyridine-N-oxide
  • the organic base compound preferably has an amino group in terms of basicity, and more preferably contains a halogenated aromatic amine in terms of adjusting the acid dissociation constant pKa of the conjugate acid or lowering the boiling point.
  • the halogenated aromatic amine include pentafluoroaniline (acid dissociation constant of conjugated acid pKa: ⁇ 0.16), 2-fluoropyridine (acid dissociation constant of conjugated acid pKa: ⁇ 0.44) and the like.
  • the organic base compound preferably contains one or more selected from diphenylamine and pentafluoroaniline. That is, the salt preferably contains one or more selected from a diphenylammonium cation, a pentafluoroanillium cation, and a 2-fluorodimethylaminopyridinium cation.
  • salt of the acidic compound and the organic base compound include, for example, the following compounds:
  • the salts of the acidic compound and the organic base compound are the above-mentioned (pentafluorophenyl) ammonium trifluoromethanesulfonate (PFBAT), (pentafluorophenyl) ammonium bis (trifluoromethanesulfonyl) imide and diphenylammonium trifluoromethanesulfonate (DPAT). It is preferable to include 1 or more selected from. It is preferable to use the above-mentioned salt of the acidic compound and the organic base compound as a catalyst in the polycondensation reaction step.
  • the amount of the salt added to the acidic compound and the organic base compound is not particularly limited as long as it does not adversely affect acylation or polycondensation, but is generally based on the theoretical yield of the liquid liquid resin obtained. It is preferably 50 to 5000 ppm, more preferably 100 to 3000 ppm.
  • the amount of the acidic compound and the organic base compound added when the salt of the acidic compound and the organic base compound is generated by coexisting the acidic compound and the organic base compound in the reaction system is, for example, the acidic compound (or in the reaction system).
  • the addition amount of (a compound capable of generating an acidic compound) is [(molecular weight of acidic compound / molecular weight of produced salt) ⁇ 50] to [(molecular weight of acidic compound / molecular weight of produced salt) ⁇ 5000] ppm.
  • the amount of the organic base compound added is preferably 0.8 to 1.2 equivalents with respect to the acid moiety of the acidic compound, and 0.9 to 1 with respect to the acid moiety of the acidic compound. More preferably, it is 1 equivalent.
  • the temperature for polycondensation is preferably, for example, 200 to 400 ° C, more preferably 240 to 380 ° C.
  • the reaction time is not particularly limited, and is preferably, for example, 4 to 14 hours, more preferably 6 to 10 hours.
  • the number average degree of polymerization at 260 ° C. is preferably 2.5 or more, and more preferably 3.0 or more.
  • the reaction rate (polycondensation rate) is increased and the liquid crystal resin can be produced in a short time.
  • the number average degree of polymerization is a value calculated from the amount of distillate of acetic acid produced as a by-product in the polycondensation reaction process.
  • acylation reaction step In the production method of the present embodiment, a step of acylating the raw material monomer with an acylating agent can be provided before the polycondensation reaction described above.
  • the acylation is characterized in that a liquid crystal resin is produced in a shorter time, and the above-mentioned catalyst (at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms) is used. It is preferable to carry out in the presence of (salt) with.
  • acylating agent examples include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric acid anhydride, pivalic anhydride, 2-ethylhexanoic acid anhydride, monochloroacetic anhydride, dichloroacetic acid anhydride, trichloracetic anhydride, and monobromoacetic acid anhydride.
  • the amount of the acylating agent used is preferably 1.0 to 1.1 equivalents, preferably 1.01 to 1.05 equivalents, based on the total amount of hydroxyl groups of the substance used in the reaction, in terms of ease of reaction control. Is more preferable.
  • Acylation can be performed by a known method.
  • the raw material monomer is mixed with an acylating agent and heated in a temperature range of 120 to 160 ° C. for about 0.5 to 5 hours for an acylation reaction to obtain a reaction product containing an acylated product.
  • the production method of the present embodiment may further include a step of solid-phase polymerization of the resin obtained in the melt polymerization step (the above-mentioned polycondensation reaction step).
  • the molecular weight of the raw material resin can be increased, and a liquid crystal resin having excellent strength and heat resistance can be obtained.
  • Solid phase polymerization For solid phase polymerization, a conventionally known method can be used. For example, it can be carried out by heating under reduced pressure or vacuum in an inert gas stream such as nitrogen gas at a temperature 10 to 120 ° C. lower than the liquid crystal forming temperature of the raw material resin. Since the melting point of the liquid crystal resin increases as the solid phase polymerization progresses, it is possible to carry out the solid phase polymerization at a temperature equal to or higher than the original melting point of the raw material resin.
  • the solid phase polymerization may be carried out at a constant temperature or may be gradually heated to a high temperature.
  • the heating method is not particularly limited, and microwave heating, heater heating, or the like can be used.
  • the liquid crystal resin obtained by the production method of the present embodiment preferably contains at least one selected from liquid crystal polyester and liquid crystal polyester amide.
  • the liquid crystal polyester and the liquid crystal polyester amide are not particularly limited, but are preferably aromatic polyester or aromatic polyester amide, and are repeating units derived from one or more of aromatic hydroxycarboxylic acid and its derivatives. It is particularly preferable that it is an aromatic polyester or an aromatic polyester amide having the above as a constituent component. Further, it may be a polyester which partially contains an aromatic polyester or an aromatic polyester amide in the same molecular chain.
  • Polyester mainly composed of (a) one or more kinds of aromatic hydroxycarboxylic acids and derivatives thereof; (2) Mainly (a) one or more of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives. Polyester consisting of; (3) Mainly (a) one or more of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or more of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof.
  • a polyester amide consisting of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and one or more of their derivatives; (5) Mainly (a) one or more kinds of aromatic hydroxycarboxylic acids and their derivatives, and (b) one or more kinds of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives. , (C1) one or more of aromatic hydroxyamines, aromatic diamines, and their derivatives, and (c2) one or more of aromatic diols, alicyclic diols, and their derivatives. Examples thereof include a polyester amide composed of.
  • the molecular weight (number average molecular weight Mn) of the liquid crystal resin is not particularly limited, and the resin obtained in the melt polymerization step (polycondensation reaction step) is preferably 10,000 to 100,000, preferably 15,000 to 80,000. Is more preferable.
  • the resin obtained in the solid phase polymerization step is preferably 12,000 to 120,000, more preferably 15,000 to 100,000.
  • the number average molecular weight Mn can be measured by gel permeation chromatography.
  • the melting point of the liquid crystal resin is not particularly limited and can be 250 to 380 ° C.
  • the melt viscosity of the liquid crystal resin is not particularly limited, and the resin obtained by melt polymerization (polycondensation reaction step) has a cylinder temperature 10 to 30 ° C. higher than the melting point of the liquid crystal resin and a shear rate of 1000 sec -1 .
  • the measured melt viscosity is preferably 5 Pa ⁇ s or more and 150 Pa ⁇ s or less, and more preferably 10 Pa ⁇ s or more and 100 Pa ⁇ s or less.
  • the resin obtained by performing the solid phase polymerization step has a melt viscosity of 5 Pa ⁇ s or more and 200 Pa ⁇ s or less measured at a cylinder temperature 10 to 30 ° C. higher than the melting point of the liquid crystal resin and a shear rate of 1000 sec -1. It is preferable, and more preferably, it is 10 Pa ⁇ s or more and 150 Pa ⁇ s or less.
  • “Cylinder temperature 10 to 30 ° C higher than the melting point of the liquid crystal resin” means the cylinder temperature at which the liquid crystal resin can be melted to the extent that the melt viscosity can be measured, and is several degrees Celsius higher than the melting point. Whether to set the cylinder temperature high depends on the type of raw material resin in the range of 10 to 30 ° C.
  • the liquid crystal resin can be in the form of a powder or granular material mixture, or can be in the form of a melt mixture (melt kneaded product) such as pellets.
  • Mass%) is preferably 1.2% by mass or less, more preferably 1.0% by mass or less, and further preferably 0.8% by mass or less.
  • the weight reduction amount (mass%) is 1.2% by mass or less, the amount of gas generated at the time of melting is small, so that the swelling (blister) of the molded product due to the generated gas can be suppressed.
  • the liquid crystal resin preferably has an L * value of 70 or more, preferably 80 or more, of the powdery granular liquid crystal resin (size: 100 to 200 ⁇ m) measured by a spectrocolorimeter so as not to impair the appearance of the molded product. Is more preferable.
  • Second Embodiment in the second embodiment, particularly in the acylation reaction step, in the presence of a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms. It is essential to do it in.
  • the polycondensation reaction step is also preferably carried out in the presence of a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having 1 or more nitrogen atoms.
  • the method for producing a liquid crystal resin includes (A) acylating a raw material monomer, (B) polycondensing the acylated raw material monomer, and (A) acylating.
  • the reaction of the raw material monomer and the carboxylic acid in the presence of a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms (a1). include.
  • "Liquid crystallinity" is as described in the first embodiment. Since the raw material monomer is the same as that in the first embodiment, the description thereof is omitted here.
  • acylation reaction step (A) In the production method of the present embodiment, a step of acylating the raw material monomer is provided before the polycondensation reaction step of polycondensing the raw material monomer.
  • the raw material monomer and the carboxylic acid have at least one acidic compound having an acid dissociation constant pKa of 1 or less (hereinafter, also simply referred to as “acidic compound”) and one or more nitrogen atoms.
  • it comprises a step (a1) of reacting with at least one organic base compound (hereinafter, also simply referred to as “organic base compound”) in the presence of a salt (hereinafter, also simply referred to as “step (a1)”).
  • the acylation reaction step (A) includes the step (a1) of using the salt of the acidic compound and the organic base compound described above. It was found that the acylation reaction rate of the raw material monomer can be increased even when a carboxylic acid such as the above is used. As a result, at least a part of the acid anhydride conventionally used as an acylating agent can be changed to a carboxylic acid, and a liquid crystal resin can be produced at a lower cost than the conventional one.
  • the salt of the acidic compound and the organic base compound is considered to have an action as a catalyst for the acylation reaction.
  • carboxylic acid examples include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, 2-ethylhexanoic acid, monochloroacetic acid, dichloroacetic acid, trichloracetic acid, monobromoacetic acid, dibromoacetic acid, tribromoacetic acid, and monofluoroacetic acid.
  • Difluoroacetic acid, trifluoroacetic acid, glutaric acid, maleic acid, succinic acid, ⁇ -bromopropionic acid and the like are not particularly limited. At least one selected from these can be used.
  • carboxylic acids selected from acetic acid, propionic acid, butyric acid, isobutyric acid and the like. Above all, it is more preferable to contain acetic acid in terms of easy availability.
  • the amount of the carboxylic acid added in the step (a1) of reacting the raw material monomer with the carboxylic acid is preferably 0.01 to 1000 equivalents, preferably 0.1 to 500 equivalents, relative to the hydroxyl group of the raw material monomer. Is more preferable, and it is further preferable that the amount is 1 to 100 equivalents.
  • the acylation method is a known method except that a catalyst described later (a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms) is used. Can be done based on.
  • the raw material monomer is mixed with a carboxylic acid and a catalyst described later, and heated in a temperature range of 120 to 160 ° C. for about 0.5 to 5 hours for an acylation reaction to obtain a reaction product containing an acylated product.
  • step (a2) (hereinafter, also simply referred to as “step (a2)”. ”In step (a2), the unreacted raw material monomer is acylated after the reaction of step (a1).
  • the step (a1) of reacting the raw material monomer with the carboxylic acid is referred to as a "first acylation reaction step”
  • an acid anhydride is added to react the unreacted raw material monomer with the acid anhydride.
  • A2) can be referred to as a "second acylation reaction step”.
  • the acylation of the raw material monomer can be achieved more efficiently than in the case of only the first acylation reaction step (step (a1)).
  • the carboxylic acid used in the first acylation reaction step (step (a1)) the amount thereof added, and the acylation method are as described above, the description thereof is omitted here.
  • anhydrous acetic acid anhydrous propionic acid, anhydrous butyric acid, anhydrous isobutyric acid, anhydrous valeric acid, anhydrous pivalic acid, anhydrous 2-ethylhexanoic acid, anhydrous monochloroacetic acid, anhydrous dichloracetic acid, anhydrous Trichloracetic acid, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, ⁇ -bromopropionic anhydride, etc.
  • At least one selected from these can be used. From the viewpoint of price and handleability, it is preferable to contain one or more anhydrous carboxylic acids selected from acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride and the like. Above all, it is more preferable to contain acetic anhydride from the viewpoint of easy availability.
  • the amount of the acid anhydride added in the step (a2) is preferably 0.01 to 0.99 equivalents, more preferably 0.01 to 0.90 equivalents, relative to the hydroxyl group of the raw material monomer. It is more preferably 0.01 to 0.85 equivalent.
  • the amount is larger than the amount used in the conventional acylation reaction step (for example, 1.00 to 1.10 equivalents).
  • the amount of acid anhydride added can be reduced. As a result, the liquid crystal resin can be manufactured at a lower cost than before.
  • the acylation in the step (a2) is performed by using a catalyst described later (a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms). It can be performed based on a known method. For example, an acid anhydride is added to the reaction solution (including the catalyst) of the first acylation reaction step (a1), and the reaction is not reacted by further heating in a temperature range of 120 to 160 ° C. for about 0.5 to 5 hours. The raw material monomer of the above is acylated to obtain a reaction product containing an acylated product.
  • a catalyst described later a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms. It can be performed based on a known method. For example, an acid anhydride is added to the reaction solution (including the catalyst) of the first acylation reaction step (a1),
  • the acylation reaction rate of the raw material monomer after the step (a1) is preferably 5% or more, and more preferably 10% or more. When the acylation reaction rate is 5% or more, the liquid crystal resin can be produced more efficiently.
  • the acylation reaction rate of the raw material monomer after the step (a2) is preferably 90% or more, more preferably 95% or more.
  • the acylation reaction rate shall be a value measured by a nuclear magnetic resonance apparatus (1 H-NMR).
  • the salt of the acidic compound and the organic base compound is composed of an anion of the acidic compound and a cation of the organic base compound.
  • the salt of the acidic compound and the organic base compound in addition to using the salt itself, the salt may be formed by coexisting the acidic compound and the organic base compound in the reaction system.
  • the acidic compound and the organic base compound can form a salt by an acid-base reaction in the reaction system.
  • the acidic compound (anionic component) has an acid dissociation constant pKa of 1 or less, preferably 0.65 or less, more preferably -14.0 to 0.65, and further preferably -14.0 to-. It is 2.0. If the acid dissociation constant pKa of the acidic compound exceeds 1, the effect of improving the acylation reaction rate may decrease, or the effect of improving the polycondensation reaction rate in the polycondensation reaction step described later may decrease, which is not preferable.
  • the above pKa means pKa in an aqueous solution at 25 ° C. Since the example of the acidic compound is the same as the compound described in the first embodiment, the description thereof is omitted here.
  • the organic base compound is a compound that generates an organic onium cation and has one or more nitrogen atoms. That is, the salt contains at least a nitrogen cation.
  • the organic base compound (cationic component) preferably has an acid dissociation constant pKa of the conjugate acid of less than 13.0, preferably -10.0 to 8.0, in terms of the basicity of the organic base compound. Is more preferable, and ⁇ 8.0 to 6.0 is even more preferable.
  • the acid dissociation constant pKa of the conjugate acid of the organic base compound means pKa in an aqueous solution at 25 ° C.
  • the examples of the "organic base compound” and the examples of “salt of an acidic compound and an organic base compound” are the same as the compounds and salts described in the first embodiment, the description thereof will be omitted here. It is preferable to use the above-mentioned salt of the acidic compound and the organic base compound as a catalyst in the acylation reaction step, preferably as a catalyst in the acylation reaction step and the polycondensation reaction step.
  • the amount of the salt added to the acidic compound and the organic base compound is not particularly limited as long as it does not adversely affect acylation and polycondensation described later, but is generally based on the theoretical yield of a liquid liquid resin obtained. It is preferably 50 to 5000 ppm, and more preferably 100 to 3000 ppm.
  • the amount of the acidic compound and the organic base compound added when the salt of the acidic compound and the organic base compound is generated by coexisting the acidic compound and the organic base compound in the reaction system is, for example, the acidic compound (or in the reaction system).
  • the addition amount of (a compound capable of generating an acidic compound) is [(molecular weight of acidic compound / molecular weight of produced salt) ⁇ 50] to [(molecular weight of acidic compound / molecular weight of produced salt) ⁇ 5000] ppm.
  • the amount of the organic base compound (or the compound capable of generating the organic base compound in the reaction system) is preferably 0.8 to 1.2 equivalents of the base moiety with respect to the acid moiety of the acidic compound, and the acidic compound. It is more preferable that the base moiety is 0.9 to 1.1 equivalents with respect to the acid moiety of.
  • the acylated raw material monomer is preferably the catalyst used in the acylation reaction step (A) (at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one having one or more nitrogen atoms.
  • a polycondensation reaction is carried out by melt polymerization.
  • the temperature for polycondensation is preferably, for example, 200 to 400 ° C, more preferably 240 to 380 ° C.
  • the reaction time is not particularly limited, and is preferably, for example, 4 to 14 hours, more preferably 6 to 10 hours.
  • the liquid crystal resin can be produced in high yield even if the amount of acid anhydride is reduced. That is, the liquid crystal resin can be produced in a high yield of 90% or more, 95% or more, or 98% or more at low cost.
  • the production method of the present embodiment may further include a step of solid-phase polymerization of the resin obtained in the melt polymerization step (the above-mentioned polycondensation reaction step).
  • the molecular weight of the raw material resin can be increased, and a liquid crystal resin having excellent strength and heat resistance can be obtained. Since the method of solid-phase polymerization is the same as that of the first embodiment, the description thereof is omitted here.
  • the liquid crystal resin obtained by the production method of the present embodiment preferably contains at least one selected from liquid crystal polyester and liquid crystal polyester amide.
  • the liquid crystal polyester and the liquid crystal polyester amide include the same as those exemplified in the first embodiment.
  • the molecular weight (number average molecular weight Mn) and melting point of the liquid crystal resin are the same as those in the first embodiment.
  • Mass% is preferably 0.8% by mass or less, and more preferably 0.6% by mass or less.
  • mass reduction amount is 0.8% by mass or less, the amount of gas generated at the time of melting is small, so that the swelling (blister) of the molded product due to the generated gas can be suppressed.
  • a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms is used as a catalyst in the polycondensation reaction. Therefore, it is possible to increase the reaction rate, suppress the generation of gas when the liquid crystal resin is melted, and obtain a liquid crystal resin having high brightness.
  • a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having one or more nitrogen atoms is used as a catalyst in the acylation reaction. Therefore, it is possible to provide a method for producing a liquid crystal resin at a lower cost than before.
  • Example 1 After charging the following raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 3 hours (acyllation reaction step). Then, the temperature is further raised to 360 ° C. over 4.5 hours, and then the pressure is reduced to 10 Torr (that is, 1330 Pa) over 15 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Polycondensation was performed (polycondensation reaction step).
  • Liquid crystal resin pellets were obtained in the same manner as in Example 1 except that 45 mg (150 ppm) of potassium acetate (manufactured by Kanto Chemical Co., Inc.) was used instead of PFBAT.
  • Liquid crystal resin pellets were obtained in the same manner as in Example 1 except that 81 mg (270 ppm) of pentafluoroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of PFBAT.
  • the production method of the examples can achieve both improvement of the reaction rate and suppression of the amount of gas generated when the liquid crystal resin is melted, and can obtain a liquid crystal resin having high brightness. Understandable.
  • Comparative Example 1 using potassium acetate as a catalyst has the same number average degree of polymerization at 260 ° C. as that of Comparative Example 2 having no catalyst, so that the effect of improving the reaction rate is not observed and the liquid crystal resin has no effect.
  • the amount of gas generated during melting was large.
  • Comparative Example 3 in which the acidic compound was used alone as the catalyst, the reaction rate was increased, but the amount of gas generated when the liquid crystal resin was melted was larger than that in the example, and the brightness of the liquid crystal resin was higher. It was low.
  • Comparative Example 4 In Comparative Example 4 in which the organic base compound was used alone as the catalyst, the amount of gas generated when the liquid crystal resin was melted and the decrease in the brightness of the liquid crystal resin could be suppressed, but the reaction rate could not be improved. could not.
  • Comparative Example 5 in which an acidic compound having a pKa greater than 1 and a basic compound were used as catalysts, the amount of gas generated when the liquid crystal resin was melted could be suppressed, but the effect of improving the reaction rate was not observed, and the effect of improving the reaction rate was not observed. The brightness of the liquid crystal resin was low.
  • Example 2-1 After charging the following raw materials excluding acetic anhydride into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 3 hours (first acylation reaction step). Then, acetic anhydride was added while maintaining the temperature at 140 ° C., and the mixture was reacted for 1 hour (second acylation reaction step). Further, the temperature was raised to 325 ° C. over 3.5 hours, and then the pressure was reduced to 10 Torr (that is, 1330 Pa) over 15 minutes, and polycondensation was performed while distilling acetic acid and other low boiling points (heavy). Condensation reaction step).
  • Example 2-1 Liquid crystal resin pellets were obtained in the same manner as in Example 2-1 except that 37 mg (740 ppm) of potassium acetate (manufactured by Kanto Chemical Co., Inc.) was used instead of PFBAT. The yield of the obtained liquid crystal resin was 86%.
  • [Acylation (acetylation) reaction rate] 0.5 mL of DMSO-d 6 was added to 10 mg of the sample sampled during the acylation reaction in the first acylation reaction step and the second acylation reaction step to dissolve the sample.
  • the obtained solution was transferred to a glass sample tube, 1 H-NMR measurement was performed with a nuclear magnetic resonance apparatus (NMR, manufactured by Bluker), and the aromatic ring 3-position proton of the unreacted monomer and the acylated (acetylated) monomer were performed.
  • the integrated value of the proton at the 3-position of the aromatic ring was obtained, and the acylation reaction rate was calculated by the following formula.
  • Acetylation reaction rate (%) [(integral value of protons of acetylated monomer) / ((integrated value of protons of unreacted monomer) + (integrated value of protons of acetylated monomer))] ⁇ 100
  • acylation performed using a salt of at least one acidic compound having an acid dissociation constant pKa of 1 or less and at least one organic base compound having 1 or more nitrogen atoms as a catalyst.
  • the acylation (acetylation) reaction rate of the step (a1) using acetic acid as an acylating agent is high, and the acylation reaction rate of the raw material monomer is reduced even if the amount of anhydrous acetic acid used in the step (a2) is reduced.
  • a liquid crystal resin could be produced in a high yield.
  • Comparative Example 2-1 using potassium acetate as a catalyst has a low acylation reaction rate in the step (a1) using acetic acid as an acylating agent, and the amount of acetic anhydride used in the step (a2).
  • the amount was reduced from the conventional amount, the acylation reaction rate of the raw material monomer was not sufficient, and the liquid crystal resin could not be produced in high yield.
  • the amount of gas generated when the liquid crystal resin was melted was large.
  • Comparative Example 2-2 in which no catalyst was used although the amount of gas generated when the liquid crystal resin was melted was small, the acylation reaction rate in the step (a1) using acetic anhydride as the acylating agent was high. It was low, and when the amount of acetic anhydride used in the step (a2) was reduced from the conventional amount, the acylation reaction rate of the raw material monomer was not sufficient, and the liquid crystal resin could not be produced in high yield.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polyamides (AREA)

Abstract

L'invention concerne un procédé de production d'une résine cristalline liquide, ledit procédé utilisant un sel d'au moins un composé acide présentant une constante de dissociation acide pKa de 1 ou inférieure et au moins un composé de base organique contenant au moins un atome d'azote. Le premier mode de réalisation de l'invention concerne également un procédé de production d'une résine cristalline liquide, ledit procédé étant apte à augmenter la vitesse de réaction, tout en supprimant la génération d'un gaz pendant la fusion d'une résine cristalline liquide, et permettant d'obtenir une résine cristalline liquide dotée d'une luminosité élevée. Le deuxième mode de réalisation de l'invention concerne un procédé par lequel une résine cristalline liquide est produite à un coût plus bas que jamais auparavant. Le procédé de production de résine cristalline liquide selon l'invention consiste à mettre en réaction un monomère de matériau de départ en présence d'un sel d'au moins un composé acide présentant une constante de dissociation acide pKa de 1 ou inférieure et au moins un composé de base organique contenant au moins un atome d'azote.
PCT/JP2021/019894 2020-05-29 2021-05-26 Procédé de production de résine cristalline liquide Ceased WO2021241607A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395536A (en) * 1981-11-17 1983-07-26 Celanese Corporation Preparation of aromatic copolyesters via in situ esterification with isopropenyl esters of an alkyl acid
JP2003171449A (ja) * 2001-12-05 2003-06-20 Daicel Chem Ind Ltd 新規サーモトロピック液晶ポリエステル及びその製造方法
WO2007116818A1 (fr) * 2006-03-30 2007-10-18 Toray Industries, Inc. Polyester dendritique, procédé pour le produire, et composition de résine thermoplastique
WO2009087910A1 (fr) * 2008-01-09 2009-07-16 National University Corporation Kyoto Institute Of Technology Procédé de fabrication de polymère biodégradable
JP2012532951A (ja) * 2009-07-09 2012-12-20 インビスタ テクノロジーズ エス エイ アール エル ポリアミドの製造
CN111072936A (zh) * 2019-12-23 2020-04-28 上海普利特化工新材料有限公司 一种全芳香族液晶聚酯树脂及其应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395536A (en) * 1981-11-17 1983-07-26 Celanese Corporation Preparation of aromatic copolyesters via in situ esterification with isopropenyl esters of an alkyl acid
JP2003171449A (ja) * 2001-12-05 2003-06-20 Daicel Chem Ind Ltd 新規サーモトロピック液晶ポリエステル及びその製造方法
WO2007116818A1 (fr) * 2006-03-30 2007-10-18 Toray Industries, Inc. Polyester dendritique, procédé pour le produire, et composition de résine thermoplastique
WO2009087910A1 (fr) * 2008-01-09 2009-07-16 National University Corporation Kyoto Institute Of Technology Procédé de fabrication de polymère biodégradable
JP2012532951A (ja) * 2009-07-09 2012-12-20 インビスタ テクノロジーズ エス エイ アール エル ポリアミドの製造
CN111072936A (zh) * 2019-12-23 2020-04-28 上海普利特化工新材料有限公司 一种全芳香族液晶聚酯树脂及其应用

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