JP2000281795A - Apparatus for polymerizing liquid crystal resin and preparation of liquid crystal resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization apparatus capable of giving, with improved productivity, a liquid crystal resin having high qualities, excellent in heat resistance in particular by effecting efficient agitation in the polymerization of a liquid crystal resin, and to provide a method for the preparation thereof. SOLUTION: There is provided an apparatus for polymerizing a liquid crystal resin comprising a reactor 11 equipped with a feed port of a raw material, a transporting port, a stirring apparatus and a jacket, a reactor equipped with a transporting port, a polymer delivery port, a stirring apparatus and a jacket, a transporting pipe connecting these and a baffle plate 2 on the sidewall inside a reactor, the baffle being 5-30% in size based on the inside diameter of the reactor in the direction of the inside diameter of the reactor. The method for preparing the liquid crystal resin utilizes the above apparatus.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for polymerizing a liquid crystal resin and a method for producing a liquid crystal resin using the same. The present invention relates to an apparatus for polymerizing a liquid crystalline resin having high quality, especially excellent heat resistance, and a method for producing a liquid crystalline resin using the same.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and a number of polymers having various new properties have been developed and marketed. Among them, a polymer is characterized by a parallel arrangement of molecular chains. Optically anisotropic liquid crystalline resins are attracting attention because of their excellent fluidity and mechanical properties, and particularly because of their high rigidity, the demand for small molded products in the fields of electric / electronics and office equipment has increased. Is coming.

As liquid crystal resins, liquid crystal resins obtained by copolymerizing p-hydroxybenzoic acid and polyethylene terephthalate (Japanese Patent Publication No. 56-18016) and p-hydroxybenzoic acid and polyethylene terephthalate, and
A liquid crystalline resin having improved fluidity and heat resistance by adding an aromatic diol such as 4'-dihydroxybiphenyl and a copolymer component such as an aromatic dicarboxylic acid (JP-A-63-3
0523), p-hydroxybenzoic acid has 4,4 ′
-Liquid crystalline resin obtained by copolymerizing dihydroxybiphenyl, t-butylhydroquinone and terephthalic acid
164719), p-hydroxybenzoic acid has 4,
Liquid crystalline resin obtained by copolymerizing 4'-dihydroxybiphenyl, isophthalic acid and terephthalic acid (Japanese Patent Publication No. 57-2440)
No. 7, JP-A-60-25046), a liquid crystalline resin obtained by copolymerizing p-hydroxybenzoic acid with 6-hydroxy-2-naphthoic acid (JP-A-54-77691).
Etc. are known.

As a method for producing a liquid crystalline resin, as disclosed in Japanese Patent Application Laid-Open No. 1-149825, when the viscosity increases, the number of stirring is decreased to control the polymerization reaction temperature. As disclosed in JP-A-225023, the shear rate at the can wall surface is 10 to
It is known that polymerization is carried out at 100 (1 / second) while stirring in a direction in which the reactant is scraped.

[0005]

However, the conventional polymerization method can produce a liquid crystalline resin having excellent quality, but when the polymerization is carried out for about 10 to 20 batches, the monomers and oligomers remaining in the can are repeatedly discharged. Due to the heat history due to polymerization, it becomes a foreign substance that does not melt even at a temperature equal to or higher than the melting point of the normal polymer, mixes into the polymer when discharged from the can after the polymerization, and adversely affects the physical properties of the resulting liquid crystalline resin It was found that the inside of the can had to be periodically cleaned to release the water.

Accordingly, an object of the present invention is to improve the productivity by reducing the amount of monomers and oligomers remaining in the can and lengthen the cleaning cycle in the can, and to improve the quality of the liquid crystal, especially the heat resistance. An object of the present invention is to provide an apparatus and a method for manufacturing a conductive resin.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the following present invention.

That is, the present invention relates to (1) an apparatus for polymerizing a liquid crystalline resin, which comprises a raw material input port, a transfer port, a stirrer, a reaction vessel having a jacket, a transfer port, a polymer discharge port, and a stirrer. A polymerization vessel having an apparatus and a jacket, a transfer pipe connecting them, and a baffle on a side wall inside the reaction vessel, wherein the size of the baffle in the vessel inner diameter direction is 5% to 30% of the reaction vessel inner diameter. Liquid crystal resin polymerization equipment.

(2) The diameter of the stirring blade of the reactor is 2 times the inner diameter of the reactor.
The polymerization apparatus for a liquid crystalline resin according to (1), wherein the content is 0 to 85%. (3) Using the polymerization apparatus described in (1) or (2), the raw material of the liquid crystalline resin is reacted at a peripheral speed of the stirring blade in the reaction vessel of 1.5 m / s or more and 30 m / s or less. A method for producing a liquid crystalline resin, comprising transferring a substance to a polymerization can and polymerizing the same.

(4) After the acetylation reaction of the hydroxyl group in the raw material monomer with acetic anhydride, when producing a liquid crystalline resin by deacetic acid polycondensation, a distillate represented by the following formula (1) is produced in a reaction vessel. (3) The method for producing a liquid crystalline resin according to (3), wherein after reacting until the rate becomes 80% or more, the reactant is transferred to a polymerization vessel and polymerized. Distillation rate (%) = Distillate amount (g) / [[mol number of acetic anhydride charged-mol number of hydroxyl group in raw material monomer] × molecular weight of acetic anhydride + mol number of hydroxyl group in raw material monomer × 2 × Acetic acid molecular weight + mol number of acetyl group in raw material monomer × acetic acid molecular weight] (g) × 100 (%) (1) (5) The liquid crystal resin is composed of the following structural units (I), (II), (III),
The method for producing a liquid crystalline resin according to any one of (3) and (4), which comprises (IV).

[0011]

Embedded image (However, R1 in the formula is

[0012]

Embedded image R2 represents one or more groups selected from

[0013]

Embedded image R3 represents one or more groups selected from

[0014]

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. )

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystalline resin produced in the present invention is a resin capable of forming an anisotropic molten phase upon melting, and includes liquid crystalline polyester and liquid crystalline polyesteramide. Examples of the liquid crystalline polyester include an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic dicarbonyl unit, and a polyester that forms an anisotropic molten phase composed of structural units selected from ethylene dioxy units, and the like. Examples of the liquid crystalline polyesteramide include a polyesteramide that forms a fusible anisotropic phase composed of the above structural unit and a structural unit selected from an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit, and the like. The production method of the present invention is used when producing such a liquid crystalline resin.

In the above, the raw materials that can constitute the structural units of the liquid crystalline polyester or the liquid crystalline polyester amide include aromatic hydroxycarboxylic acids, dihydroxy compounds, aromatic dicarboxylic acids, polyesters comprising dioxy units and dicarbonyl units, and aromatic polyesters. Aromatic aminohydroxy compounds, aromatic aminocarboxylic acids, and derivatives thereof, and the like, may be mentioned, and these are obtained by appropriately combining these types and compositions so that the resulting polymer exhibits liquid crystallinity.

In the above, as the aromatic hydroxycarboxylic acid, p-hydroxybenzoic acid, 6-hydroxy-
2-naphthoic acid and the like, and examples of the aromatic dihydroxy compound include 4,4′-dihydroxybiphenyl,
3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, 2-bis (4-hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl ether. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and diphenyl ether dicarboxylic acid. Examples of the polyester comprising a dioxy unit and a dicarbonyl unit include polyethylene terephthalate and oligomers thereof. Examples of the aromatic aminohydroxy compound include p-aminophenol, and examples of the aromatic aminocarboxylic acid include p-aminobenzoic acid. And the like.

An aromatic oxycarboxylic acid or a derivative thereof, a diol or a derivative thereof, or an aromatic dicarboxylic acid or a derivative thereof, which can be a raw material that can constitute a structural unit of a liquid crystalline resin, is often solid at ordinary temperature, It is preferably used as a powder. Further, the polyester comprising a dioxy unit and a dicarbonyl unit is solid at room temperature, but is usually used in the form of pellets or powder obtained by pulverizing it.

In the present invention, the reaction for producing the liquid crystalline polyester can be carried out, for example, by subjecting the liquid crystalline polyester to deacetic acid polymerization.
In this case, a case where deacetic acid polymerization is carried out using a raw material in which a hydroxyl group is acetylated in advance, and a case where a hydroxyl group-containing monomer is used together with an acetylating agent as a raw material constituting a liquid crystalline polyester, and acetylation in which the hydroxyl group is acetylated. In some cases, a polymerization reaction and a deacetic acid polymerization reaction are performed, but the latter method is preferred.

In the present invention, 12 as an acetylating agent is used.
It is preferable that the acetylating agent can be liquid at a temperature of 0 ° C. or lower, and specifically, acetic anhydride is preferable. Also,
The acetylating agent is preferably used in a molar ratio of 0.9 or more and 1.5 or less, more preferably 0.95 or more and 1.3 or less with respect to the number of moles of the hydroxyl group of the monomer.

As a specific method, for example, the following (1)
Alternatively, the hydroxyl group is acetylated using a hydroxyl group-containing compound, a carboxylic acid group-containing compound and an acetylating agent such as acetic anhydride as represented by the method (2), and then the temperature is increased and the acetic acid is removed under reduced pressure. A method of performing polycondensation,
In this method, there is a method in which a part of the hydroxyl group-containing compound is replaced with an acetylated compound, and the following method is particularly preferable.

In the following method, the production method (1) is preferred when a polyester comprising a dioxy unit and a dicarbonyl unit is not used as a raw material, and the production method (2) is used when the polyester is used. (1) After reacting acetic anhydride with an aromatic dihydroxy compound such as p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl or hydroquinone, or an aromatic dicarboxylic acid such as terephthalic acid to acetylate a phenolic hydroxyl group, A method for producing a liquid crystalline polyester by deacetic acid polycondensation reaction under reduced pressure at elevated temperature.

(2) Polyester polymers such as polyethylene terephthalate, oligomers or bis (β-
A method for producing a liquid crystalline polyester by the method (1) in the presence of bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as (hydroxyethyl) terephthalate.

Although these polycondensation reactions proceed without a catalyst, a metal compound such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide and metal magnesium is used as a catalyst or a catalyst and a color tone improver. Sodium hypophosphite, which is effective as
It may be preferable to add a compound such as potassium hypophosphite.

Although these polycondensation reactions can be carried out in one reaction vessel, they are preferably carried out in two reaction vessels. Usually, the acetylation reaction and the initial deacetic acid polycondensation reaction are carried out in the second half of the reaction vessel. Is preferably carried out in a reaction vessel called a polymerization vessel. In general, these reactors are generally provided with nothing on the wall of the reactor or the polymerization vessel in order to increase the shear rate by the stirring blade.

However, in the case of using the above-mentioned production apparatus in which nothing is provided on the reaction vessel wall, when about 10 to 20 batches are polymerized, the monomers and oligomers remaining in the vessel undergo heat history due to repeated batch polymerization, It becomes foreign matter that does not melt even at a temperature higher than the melting point of the normal polymer.It mixes into the polymer when it is discharged from the can after the polymerization is completed, and the inside of the can is periodically cleaned to adversely affect the physical properties of the obtained liquid crystalline resin. This will inevitably lead to reduced productivity.

Therefore, in order to achieve the object of the present invention, an apparatus for polymerizing a liquid crystalline resin includes a raw material inlet, a transfer port, a stirrer, a reactor having a jacket and a transfer port, a polymer discharge port, a stirrer. And a polymerization vessel having a jacket, a transition pipe connecting them, and a baffle on a side wall inside the reaction vessel, and it is essential that the size of the baffle in the vessel inside diameter direction be 5% to 30% of the inside diameter of the reaction vessel. The size of the baffle in the inner diameter direction of the can is preferably 7 to 28%, preferably 10 to 28%.
~ 26% is more preferred.

The term "reactor" refers to a vessel in which the reaction is carried out at least up to the initial stage of the polycondensation reaction of the liquid crystalline resin, and the term "polymerization vessel" refers to the reaction product obtained by reacting the liquid crystalline resin in the reactor in the final step. A can that performs polycondensation up to

If the reactor has no baffle, or if the size of the baffle in the inner diameter direction of the reactor is too small relative to the inner diameter of the reactor, the stirring efficiency at the time of stirring decreases, so that the composition is partially uneven in composition. The monomers and oligomers reacted in the state receive a thermal history due to repeated batch polymerization, and a high melting point material is easily generated. In addition, if the size of the baffle in the direction of the inner diameter of the can is too large, the stirring load is increased, and the reactant adheres to the inner wall surface of the can due to splashing and tends to stay.

Here, the inner diameter of the can is the diameter of the inside of the reactor, and the size of the baffle in the inner diameter direction of the baffle is the distance between the longest part in the inner diameter direction of the can and the side wall of the reactor when the baffle is attached to the reactor. .

The shape of the baffle is not particularly limited, and any known shape can be used as long as it has the function of causing the reactants to flow up and down during stirring. Specific examples include a plate-shaped or rod-shaped member that is in contact with the side wall of the reactor or via a support rod, and examples thereof include those illustrated in FIGS. 1 to 3. In FIG. 1, a baffle 2 is provided in contact with a can wall (side wall of the reaction vessel) 1, and in FIGS.
Is provided with a baffle 2.

The mounting position is preferably such that all or at least 20% of the baffle is immersed in the reactant. Further, it is preferable to attach two or more baffles, and in that case, it is preferable to attach the baffles symmetrically with respect to the stirring shaft.

Further, the diameter of the stirring blade of the reactor is preferably 20 to 85%, more preferably 30 to 80%, and most preferably 40 to 75% of the inner diameter of the reactor. Here, the stirring blade diameter is obtained by multiplying the distance between the tip of the stirring blade and the center of the stirring shaft during stirring.

The stirring blades of the reaction vessel are not particularly limited, but include a bullmarble stirring blade, a Faudler stirring blade, a fan turbine stirring blade, a propeller stirring blade, a disk turbine stirring blade, a paddle stirring blade, Examples include a full zone type stirring blade. When (the diameter of the stirring blade + the size of the baffle in the can inner diameter direction × 2) is equal to or more than the inner diameter of the reaction vessel, the position of the baffle is set so that the stirring blade does not contact the baffle.
It is necessary to consider the shape of the stirring blade. In the above case, it is preferable that the stirring blade exists below the baffle. The polymerization can is not particularly limited, but preferably has a structure without baffles.

The preferred reactor for producing the liquid crystalline resin is as described above, and the method for producing the liquid crystalline resin is such that the peripheral speed of the stirring blade in the reactor during the reaction is from 1.5 m / s to 30 m / s. It is essential to set the peripheral speed to not more than 1.8 m / s, preferably not more than 20 m / s, more preferably not less than 2 m / s and not more than 15 m / s. If the peripheral speed of the stirring blade is too slow, sufficient stirring efficiency tends not to be obtained, and if too fast, the rising of the liquid surface due to stirring becomes severe, or the reactant tends to stay on the inner wall of the can due to splashing and scattering. It is in. Here, the peripheral speed of the stirring blade is the speed of the tip of the stirring blade during stirring, and is generally the diameter of the stirring blade × 3.14.
It can be obtained by (pi) × number of rotations per unit time.

Further, after a hydroxyl group in the raw material monomer is subjected to an acetylation reaction with acetic anhydride and then a liquid crystalline resin is produced by deacetic acid polycondensation, a distillation rate represented by the following formula (1) is obtained in a reaction vessel. Is preferably 80% or more, and then the reaction product is transferred to a polymerization vessel to produce a liquid crystalline resin.

Distillation rate (%) = Distilled liquid amount (g) / [[mol number of acetic anhydride-mol number of hydroxyl group in raw material monomer] × molecular weight of acetic anhydride + mol number of hydroxyl group in raw material monomer] × 2 × acetic acid molecular weight + mol number of acetyl group in raw material monomer × acetic acid molecular weight] (g) × 100 (%) (1)

As a specific production method, a raw material slurried in advance using a raw material monomer and an acetylating agent is charged into a reaction vessel, and the temperature is increased, and acetylation is performed at 130 to 150 ° C. for 1 hour or more. The temperature is raised to ° C. to distill off the product formed by acetylation and unreacted acetylating agent. Next, transfer to a polymerization can, and
A method of raising the temperature to ° C and performing polycondensation under reduced pressure.

The method for producing the liquid crystalline resin of the present invention is selected from 6-hydroxy-2-naphthoic acid, aromatic diol, aromatic dicarboxylic acid, polyester comprising ethylenedioxy unit and aromatic dicarbonyl unit, and the like. It is effective when one or more monomers and p-hydroxybenzoic acid are subjected to acetylation reaction and deacetic acid polymerization using an acetylating agent such as acetic anhydride.

In particular, a liquid crystalline polyester composed of the following structural units (I) or a liquid crystalline polyester composed of the structural units (I), (II) and (IV) or composed of the structural units (I), (III) and (IV) Liquid crystalline polyester or structural units (I), (II), (II
And liquid crystalline polyesters consisting of (I) and (IV), among which structural units (I), (III), (IV) and structural units
It is effective when producing a liquid crystalline polyester comprising (I), (II), (III) and (IV), and has structural units (I), (II) and (I).
It is most effective when producing a liquid crystalline polyester composed of II) and (IV).

[0041]

Embedded image (However, R1 in the formula is

[0042]

Embedded image R2 represents one or more groups selected from

[0043]

Embedded image R3 represents one or more groups selected from

[0044]

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. )

The structural unit (I) is a structural unit formed from p-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid, and the structural unit (II) is 4,4'-dihydroxybiphenyl, 3,3 ', 5,5'-Tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4 ′
-A structural unit formed from an aromatic dihydroxy compound selected from dihydroxy diphenyl ether,
(III) is a structural unit formed from ethylene glycol,
Structural unit (IV) is terephthalic acid, isophthalic acid, 4,4 ′
-Diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4 '
-Dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, and a structural unit formed from an aromatic dicarboxylic acid selected from diphenyl ether dicarboxylic acid.

Preferred examples of the liquid crystalline polyesteramide include 6-hydroxy-2-naphthoic acid and p-
Liquid crystalline polyesteramide formed from aminophenol and terephthalic acid, p-hydroxybenzoic acid, 4,4 ′
Liquid crystalline polyesteramides formed from dihydroxybiphenyl and terephthalic acid, p-aminobenzoic acid and polyethylene terephthalate (JP-A-64-33123)
Publication).

Among these, in the case of the liquid crystal polyester comprising the above structural unit (I), the structural unit (I-1) composed of p-hydroxybenzoic acid and the structural unit (I-2) composed of 6-hydroxy-2-naphthoic acid Is preferred. Also,
In the case of a liquid crystal polyester comprising the above structural units (I), (II) and (IV), R1 is

[0048]

Embedded image And R2 is

[0049]

Embedded image R3 represents one or more groups selected from

[0050]

Embedded image And preferably one or more groups selected from the following: In the case of the structural units (I), (III) and (IV), R1 is

[0051]

Embedded image And R3 is

[0052]

Embedded image Particularly preferred are those which are one or more groups selected from
In the case of a liquid crystal polyester comprising the structural units (I), (II), (III), and (IV), R1 is

[0053]

Embedded image And R2 is

[0054]

Embedded image And R3 is

[0055]

Embedded image Is particularly preferred. Further, the above structural unit (I),
The copolymerization amount of (II), (III) and (IV) is optional. However, the following copolymerization amount is preferred from the viewpoint of fluidity.

That is, in the case of the copolymer comprising the above structural unit (I), the structural unit (I-1) comprising p-hydroxybenzoic acid and the structural unit (I-2) comprising 6-hydroxy-2-naphthoic acid ) When the respective molar ratios are [I-1] and [I-2], [I-1] / [I-2] is preferably 60/40 to 90/10,
65/35 to 85/15 is more preferred.

In the case of a copolymer comprising the above structural units (I), (II) and (IV), the structural unit (I) is replaced by the structural unit (I)
It is preferably from 15 to 90 mol%, more preferably from 30 to 88 mol%, most preferably from 50 to 85 mol%, based on the total of (II) and (II). The structural unit (IV) is the structural unit (II)
And preferably substantially equimolar.

In the case of a copolymer comprising the structural units (I), (III) and (IV), the structural unit (I) is
The amount is preferably from 30 to 95 mol%, more preferably from 40 to 95 mol%, based on the total of (III) and (III). Also, structural units
(IV) is preferably substantially equimolar to the structural unit (III).

Further, the structural units (I), (II), (III),
In the case of the copolymer consisting of (IV), the total of the above structural units (I) and (II) is structural units (I), (II) and (III) from the viewpoint of heat resistance, flame retardancy and mechanical properties. 60) to the sum of
95 mol% is preferable, and 80 to 92 mol% is more preferable. Structural units (III) are structural units (I), (II) and (I
It is preferably from 40 to 5 mol% based on the total of II), and
8 mol% is more preferred. The molar ratio [(I) / (II)] of the structural units (I) and (II) is preferably 75/25 to 95/5, more preferably 78 from the viewpoint of the balance between heat resistance and fluidity. / 22 to 93/7. The structural unit (I
V) is preferably substantially equimolar to the sum of the structural units (II) and (III).

The term "substantially" used herein means that, if necessary, the number of the terminal groups of the polyester can be increased at either the carboxyl group end or the hydroxyl group end. In such a case, the structural unit (IV) This is because the number of moles is not completely equal to the total number of moles of the structural units (II) and (III).

As the liquid crystal polyester amide resin, p-aminopheno-phenol may be used in addition to the above structural units (I) to (IV).
Polyester amides which form an anisotropic molten phase containing p-iminophenoxy units formed from phenols are preferred.

The preferred liquid crystalline polyester or liquid crystalline polyester amide includes, in addition to the components constituting the above structural units (I) to (IV), 3,3′-diphenyldicarboxylic acid,
Aromatic dicarboxylic acids such as 2,2'-diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecandioic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid; chlorohydroquinone; 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide,
Aromatic diols such as 4,4'-dihydroxybenzophenone, 3,4'-dihydroxybiphenyl, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol,
Aliphatic, alicyclic diols such as 4-cyclohexanedimethanol and the like, m-hydroxybenzoic acid, aromatic hydroxycarboxylic acids such as 2,6-hydroxynaphthoic acid, p-aminobenzoic acid, and the like are in a range that does not impair the liquid crystallinity. Further, they can be copolymerized.

Some liquid crystal resins produced in the present invention can be measured for logarithmic viscosity in pentafluorophenol. In this case, the structure is determined by the value measured at 60 ° C. at a concentration of 0.1 g / dl. 1.0 when unit (III) is not included
dl / g or more is preferable and 3.0-15.0 dl / g is more preferable. On the other hand, when the structural unit (III) is contained, the content is 0.1.
It is preferably at least 3 dl / g, particularly preferably from 0.5 to 3.0 dl / g.

In the present invention, the liquid crystalline resin is
20,000 poises are preferred, and especially 20,000 to 10,000.
0 poise is more preferred. The melt viscosity was measured at a melting point (Tm) + 10 ° C. and a shear rate of 1,000 (1/1).
Second) under the conditions of the Koka type flow tester.

Here, the melting point (Tm) refers to an endothermic peak temperature (Tm) observed when a polymer having undergone polymerization is measured from room temperature under a heating condition of 20 ° C./min.
After observation at m1), the temperature is maintained at a temperature of Tm1 + 20 ° C. for 5 minutes, cooled once to room temperature at a temperature lowering condition of 20 ° C./min, and then measured again at a temperature rising condition of 20 ° C./min. Refers to the endothermic peak temperature (Tm2).

Further, the liquid crystalline resin obtained by using the polymerization apparatus of the present invention or by the polymerization method is further improved in mechanical properties and heat resistance by adding various fillers or additives according to the purpose. An improved liquid crystal resin composition can be obtained.

When a filler is added, the amount is usually 1 to 200 parts by weight, preferably 15 to 150 parts by weight, based on 100 parts by weight of the liquid crystalline resin, and is preferably glass fiber, carbon fiber, aromatic resin or the like. Polyamide fiber, potassium titanate fiber, aluminum borate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, asbestos fiber, graphite, mica, talc, silica, calcium carbonate, glass beads,
Fibrous, powdery, granular or plate-like inorganic fillers such as glass flakes, glass microballoons, clay, wollastenite, titanium oxide, molybdenum disulfide, and the like. These fillers may be those treated with a silane-based, titanate-based coupling agent, or another surface treatment agent.

The method of adding these is preferably melt kneading, and a known method can be used for melt kneading. For example, Banbury mixer, rubber roll machine,
Using a kneader, single screw or twin screw extruder, etc.
The composition can be melt-kneaded at a temperature of from about 370 ° C. to a composition.

For the purpose of imparting flame retardancy, an organic bromine compound, a phosphorus compound, red phosphorus and the like can be further added. Of these, organic bromine compounds and / or red phosphorus are preferred. The organic bromine compound has a bromine atom in the molecule, and particularly preferably has a bromine content of 20% by weight or more. Specifically, low molecular weight organic bromine compounds such as decabromodiphenyl ether, ethylene bis- (tetrabromophthalimide), and brominated polycarbonate (for example,
Polycarbonate oligomers produced from brominated bisphenol A or copolymers thereof with bisphenol A), brominated epoxy compounds (for example, diepoxy compounds and brominated phenols produced by the reaction of brominated bisphenol A with epichlorohydrin) Monoepoxy compound obtained by the reaction of chlorobenzene with epichlorohydrin), poly (brominated benzyl acrylate),
Halogenated polymers and oligomers such as brominated polyphenylene ether, brominated bisphenol A, condensates of cyanuric chloride and brominated phenol, brominated polystyrene, cross-linked brominated polystyrene, cross-linked brominated poly α-methylstyrene, or these. Mixtures,
Among them, ethylene bis- (tetrabromophthalimide), brominated epoxy oligomer or polymer, brominated polystyrene, cross-linked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are preferable, and ethylene bis- (tetrabromophthalimide) and brominated polystyrene are preferable. And brominated polycarbonate can be particularly preferably used.

As the red phosphorus, it is possible to use red phosphorus powder as it is, but usually, it is preferable to use modified red phosphorus in which the surface of red phosphorus particles is coated with an inert substance. As an inert substance as a coating agent, for example, aluminum, iron,
Examples thereof include metal hydroxides such as chromium, nickel, copper, antimony, zirconium, and titanium, and thermosetting resins such as phenolic resins, urea resins, and melamine resins. Among them, red phosphorus having an average particle diameter of 100 μm or less and coated with a phenolic resin is preferable because of its high thermal stability and excellent flame retardant effect.

The content of the flame retardant is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the liquid crystalline resin. The content of the organic bromide is based on 100 parts by weight of the liquid crystalline resin.
The amount is preferably 0.5 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. Further, the content of red phosphorus is preferably from 0.01 to 10 parts by weight, particularly preferably from 0.05 to 1 part by weight.

The method of adding these is preferably melt kneading, and a known method can be used for melt kneading. For example, Banbury mixer, rubber roll machine,
Using a kneader, single screw or twin screw extruder, etc.
The composition can be melt-kneaded at a temperature of from about 370 ° C. to a composition.

Further, an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and substituted substances thereof) and an ultraviolet absorber (additive) are added to the liquid crystalline resin of the present invention as additives. For example, resorcinol, salicylate, benzotriazole, benzophenone and the like), lubricants and release agents (montanic acid and its salts, esters, half esters thereof, stearyl alcohol, stearamide, polyethylene and polyethylene wax and the like), dyes (for example, nitrosine and the like) ) And pigments (eg, cadmium sulfide, phthalocyanine, carbon black, etc.), plasticizers,
Ordinary additives such as an antistatic agent and other thermoplastic resins can be added to impart predetermined characteristics.

The method of adding these is preferably melt kneading, and a known method can be used for melt kneading. For example, using a Banbury mixer, a rubber roll machine, a kneader, a single screw or twin screw extruder,
The composition can be melt-kneaded at a temperature of 370 ° C. to obtain a composition.

The liquid crystalline resin obtained by the production method of the present invention or the liquid crystalline resin composition obtained therefrom has excellent melt fluidity, moldability and optical anisotropy,
It is possible to process into three-dimensional molded products, sheets, container pipes, etc. having excellent heat resistance, chemical resistance, hydrolysis resistance, and mechanical properties by ordinary molding methods, for example, various gears, various Cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones Electrical and electronic parts such as headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage, FDD chassis, HDD parts, motor brush holder, parabolic antenna, computer related parts; VTR Goods, TV parts, iron,
Home and office represented by hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, washing jigs, oilless bearings, stern bearings, underwater bearings, etc., various bearings, motor parts, lighters, typewriters, etc. Optical components such as microscopes, binoculars, cameras, clocks, etc., precision machinery-related components; alternator terminals, alternator connectors, IC regulators, potentiometer bases for light drier, exhaust gas valves, etc. Seed valves, fuel-related / exhaust / intake pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle Position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust tribute Starter switch, starter relay, transmission wire harness,
Window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, lamp reflector,
It is useful for automotive and vehicle related parts such as lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, and various other uses.

[0076]

The present invention will be described in more detail with reference to the following examples. Example 1 The size of the baffle in the direction of the inner diameter of the baffle was 0.3 m (reaction) symmetrically with respect to the raw material input port, the transfer port, the condenser for condensing the vapor distilled from the reaction vessel, the condensate receiving tank and the inner wall surface of the vessel. Two baffles 2 (25% of the inner diameter of the can) as shown in FIG. 2 were installed so as not to come into contact with the stirring blade 10 at the time of stirring, the inner volume was 1.6 m3, the inner diameter of the can was 1.2 m, and the diameter of the stirring blade was 0.8 m.
(67% of the inner diameter of the reactor), a reactor 11 having a Faudler stirring blade, an inner volume of 0.8 m3, an inner diameter of the can of 1.1 m,
Using two polymerization cans of a double helical blade stirrer without a center axis having a bottom blade, polymerization was performed as follows.

In a reaction vessel 11, p-hydroxybenzoic acid 22
1.0 kg, 4,4'-dihydroxybiphenyl
8 kg, polyethylene terephthalate 47.8 kg, terephthalic acid 24.8 kg and acetic anhydride 211.8 kg
After stirring at 60 revolutions / minute (peripheral speed 2.5 m / s) for 5 minutes, heating was started, and after reaching 130 ° C. in 0.75 hours, the reaction was carried out at 130 ° C. to 250 ° C. for 5 hours. Was. The distillation rate in the reactor 11 was 85%. Thereafter, the mixture is transferred to a polymerization vessel, and the stirring speed is increased to 250 ° C. to 320 ° C. over 2 hours while stirring at 30 rpm, and the pressure in the polymerization vessel is reduced to 1 Torr, and stirring is continued at 320 ° C. for 2 hours to continue the polycondensation reaction. Completed. Then, the inside of the polymerization can is pressurized to 2 kg / cm2,
The polymer was discharged in the form of a strand through a die and formed into pellets.

When the polymer having the above composition was repeatedly batch-polymerized by the above-mentioned method, 35 batches were repeatedly polymerized. The phenomenon that a substance having a melting point equal to or higher than that of the normal polymer was mixed into the discharged polymer after the completion of the reaction to become a foreign substance was observed. I didn't see it.

Comparative Example 1 A material inlet and a transfer port were provided, the inner volume was 1.6 m3, the inner diameter of the can was 1.2 m, and the diameter of the stirring blade was 1.18 m (98 of the inner diameter of the reactor).
%) And a polymerization vessel of a double helical blade stirrer having an inner volume of 0.8 m 3, an inner diameter of the can of 1.1 m, and a central axis having a bottom blade without a baffle. Batch polymerization was repeated in the same manner as in Example 1 except that the polymer was used. In the 20th batch, a substance having a melting point higher than the melting point of the normal polymer was mixed into the discharged polymer after the reaction and became a foreign substance. Was interrupted and the inside of the can was washed.

[0080]

As described above, according to the present invention, a high quality liquid crystalline resin can be manufactured with high productivity.

[Brief description of the drawings]

FIG. 1 is an explanatory side view showing an example of a main part of a reaction can in the present invention.

FIG. 2 is an explanatory side view showing another example of a main part of the reaction can in the present invention.

FIG. 3 is an explanatory side view showing another example of the main part of the reaction can in the present invention.

FIG. 4 is an explanatory longitudinal sectional view showing an example of a reaction vessel according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Can wall 2 Baffle 3 Support rod 10 Stirrer blade 11 Reactor

Continued on the front page F-term (reference) 4J029 AA06 AB04 BB05A BB05B BB10A BB10B BB13A BC05A BC06A BF14A BF25 BH01 CB05A CB06A CB10A CC06A CF08 CF15 CG25X EB05A EC06A FB16 CG04 CG034

Claims (5)

[Claims] An apparatus for polymerizing a liquid crystalline resin, comprising: a reaction vessel having a material input port, a transfer port, a stirrer, and a jacket; and a transfer port, a polymer discharge port, a stirrer, and a jacket. A liquid crystal resin, comprising: a polymerization can, a transfer pipe connecting them, and a baffle on a side wall inside the reaction can, wherein the size of the baffle in the can inner diameter direction is 5% to 30% of the inner diameter of the reaction can. Polymerization equipment. 2. The stirring blade diameter of the reaction vessel is 20 to the inner diameter of the reaction vessel.
2. The apparatus for polymerizing a liquid crystalline resin according to claim 1, wherein the amount is 85%. 3. The reactor according to claim 1, wherein the peripheral speed of the stirring blade in the reactor is 1.5 m / s or more and 30 m or more.
A method for producing a liquid crystalline resin, comprising reacting a raw material of a liquid crystalline resin at a rate of not more than / s, and then transferring the reactant to a polymerization vessel and polymerizing. 4. An acetylation reaction of a hydroxyl group in a raw material monomer with acetic anhydride, and then, when producing a liquid crystalline resin by deacetic acid polycondensation, a distillation rate represented by the following formula (1) in a reaction vessel. 4. The method according to claim 3, wherein the reaction product is transferred to a polymerization vessel and polymerized after the reaction is carried out until the content becomes 80% or more. 5. Distillation rate (%) = Distillate amount (g) / [[mol number of acetic anhydride charged-mol number of hydroxyl group in raw material monomer] × molecular weight of acetic anhydride + mol number of hydroxyl group in raw material monomer × 2 × Acetic acid molecular weight + mol number of acetyl group in raw material monomer × acetic acid molecular weight] (g) × 100 (%) (1) 5. The liquid crystalline resin comprises the following structural units (I), (II),
The method for producing a liquid crystalline resin according to any one of claims 3 and 4, which comprises (III) and (IV). Embedded image (However, R1 in the formula is R2 represents one or more groups selected from R3 represents one or more groups selected from Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. )