JP2755822B2 - Melt-processable liquid crystal polyester, process for producing the same, and products manufactured from the polyester - Google Patents

Description

The present invention relates to a liquid crystal polyester which is optically anisotropic in a molten phase and has a molecular weight suitable for melt processing. The invention also relates to methods for making such polyesters and products made from the polyesters.

Liquid crystalline polyesters, that is, polyesters that are optically anisotropic in the molten state, are known. Liquid crystalline polyesters are described in many patent publications, some of which are described, for example, in the following documents: Jackson, WJJ
r.), Liquid Crystal Polymers
stal polymers), XI, Liquid Crystal Aromatic Polyesters
esters): Early History and Future Trends
s), Mol.Cryst.Li
Cryst.), 169 (1989) 23-49, and Noel C. (Nol, C.) and Navard P. (Narvard, P.),
Liquid Crystal P
olymers), Prog.Polym.Sc
i.), 16 (1991) 55-110. Prior art is also described in U.S. Patent Nos. 4,600,764, 4,599,395 and 4,083,829.

The strength and stiffness of many thermoplastics can be significantly improved by mixing liquid crystal polymers.
Liquid crystal polymers form fibers that align in the melt flow direction of the thermoplastic polymer matrix, thus improving mechanical properties such as tensile strength and modulus in this direction. By adding a liquid crystal polymer,
It is often possible to improve the heat resistance and dimensional stability of thermoplastic materials and to facilitate their processing.

However, known liquid crystalline aromatic polyesters have the problem that their melt processing temperatures are too high to process with thermoplastic materials and cannot be used in blends with these polymers. This is the case in the aromatic polyesters described in the aforementioned U.S. Patent and in Vectra [Hoechs-Celanese.
This is true of the thermotropic polyesters marketed as "T-Celanese" and "Xydar" (commercially available from Amco).

Polymers prepared by the transesterification process are described in U.S. Pat. No. 3,804,805 and in J. Polym. Sci. Polym. Chem. Ed., 1
Jackson, WJJr. On 4 (1976) 2043
And in the literature by Kuhfuss, HF. The polymer forms an anisotropic mesophase at temperatures above 220 ° C. A disadvantage of these known polymers is their low glass transition temperature. The glass transition temperature limits the maximum temperature at which the polymer can be used (this temperature is about 30-40 ° C. below the glass transition temperature), so a low glass transition temperature, as far as the use of the polymer is concerned, and its As far as compounds and blends are concerned, it is not convenient.

SUMMARY OF THE INVENTION It is an object of the present invention to solve the problems in the prior art and to provide a completely new liquid crystal polyester which can be used in injection-molded and blow-molded products requiring extremely high strength, rigidity and toughness and dimensional stability. Is to do.

The present invention provides a compound of formula (I): Wherein R ₁ is t-butyl; R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are hydrogen; n is an integer of 0-5. ] The liquid crystal polymer which has a repeating unit shown by these is provided.

The polyester of the present invention has the formula (II): [Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are as defined above. ] It is preferable to have the structural unit represented by these.

In the formula (I), each of R ₁ , R ₂ , R ₃ and R ₄ is preferably hydrogen, phenyl, benzyl, 1,1-dimethylethyl, methyl, methoxy, chloro, bromo or ethylphenyl, Preferably, R ₅ and R ₆ are hydrogen or a phenyl, benzyl or alkyl group. R ₁ is preferably lower alkyl,
R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are preferably hydrogen,
n is preferably 0.

The polyesters of the invention are then converted to monomers of formula (III): HO—R ₇ —OH (III) and formula (IV): HOOC—R ₈ —COOH (IV) and / or formula (V): HOOC— It is copolymerized with the monomer represented by R ₉ -OH (V).

Thus, the polymer has the formula (IIIa): —O—R ₇ —O— (IIIa) and the formula (IVa): —OC—R ₈ —CO— (IVa) and / or the formula (Va): —OC—R It has a repeating unit represented by _9- O- (Va).

Formulas (III), (IIIa), (IV), (IVa) and (V)
And in (Va), R ₇ is a substituted arylene or naphthenylene group, or a compound of the formula R ₁₀ -A-R ₁₀ [wherein R ₁₀
Is a phenylene group, A is _{-CH 2 -, - C (CH} 3)
_2- , -O-, -S (O) _2- or -S-. A substituted biphenylene group represented by the formula: wherein R ₈ and R ₉ are
The same or different, unsubstituted or substituted arylene or naphthenylene group, or a compound of the formula R ₁₀ -A-R
_{10 wherein} R ₁₀ is a phenylene group, and A is -CH ₂ -,-
_{C (CH 3) 2 -,} - O -, - S (O) 2 - or -S-. And an unsubstituted or substituted biphenylene group represented by the formula:

Alternatively, the polymer of the present invention, at least partially replacing structural units (III) and (IV), may be poly (ethylene terephthalate) (PET), poly (butylene terephthalate (PBT), poly (ethylene naphthalate) (PEN), Poly (butylene naphthalate) (PBN) or poly ((dimethylol) cyclohexyl) naphthalate) (PCT)
May be included.

In a preferred embodiment, the polyester has, in addition to the structural units of formula (I), 0-49.5% of the structural units -O
-R ₇ -O- (IIIa), and contains from 0 to 49.5% of the structural unit -OC-R ₈ -CO- (IVa) or 0 to 99.9% of the structural unit -OC-R ₉ -O- (Va) You can go out.

In another particularly preferred embodiment, the polyester is substituted with 0-99.9% of poly (ethylene terephthalate) (PE) instead of structural units (IIIa) and (IVa).
T), poly (butylene terephthalate) (PBT), poly (ethylene naphthalate) (PEN), poly (butylene naphthalate) (PBN) or poly ((dimethylol) cyclohexyl) terephthalate (PCT).

In particular, the polyesters of the invention contain 2 to 60% of monomer (I), 10 to 49% of monomer (III), 10 to 49% of monomer (IV) and 20 to 70% of monomer (V). . A preferable amount ratio of the structural unit is 5 to 40% of (I), 20
-40% (III), 20-40% (IV) and 30-60% (V). Or structural units (III) and (IV)
Is 10 to 80%, preferably 20 to 60% of poly (ethylene terephthalate) (PET), poly (butylene terephthalate) (PBT), poly (ethylene naphthalate) (PEN),
Poly (butylene naphthalate) (PBN) or poly ((dimethylol) cyclohexyl) terephthalate)
(PCT).

In the present invention, "halogen" refers to fluorine, chlorine,
Bromine or iodine, preferably chlorine or bromine. “Lower alkyl” means a straight-chain or branched saturated hydrocarbon having 1 to 6, preferably 1 to 4 carbon atoms. The following are exemplified: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t
-Butyl (1,1-dimethylethyl) and 2-methylbutyl. "Lower alkoxy" refers to C 1 -C such as methoxy, ethoxy and propoxy, and t-butoxy.
6, preferably 1-4 alkoxy. “Arylene” is a divalent aromatic group such as phenylene and biphenylene, wherein the arylene, naphtenylene, or biphenylene group may be substituted by a halogen, lower alkyl, or phenyl group. The substituent may be a phenyl group or a 1,1-dimethylethyl-, methyl-, chloro-, bromo-, or ethyl-substituted phenyl group.

In the present invention, the terms "structural unit" and "monomer" refer to repeating units of a polymer that are linked to each other via an ester bond.

Having the groups of the formulas (I) and (II) and, if necessary, the groups of the formulas (IIIa) and (IVa) and / or (Va), or at least partly of the structural units (IIIa) Poly (ethylene terephthalate) (PET), poly (butylene terephthalate) (PBT), poly (ethylene naphthalate) (PE
N), poly (butylene naphthalate) (PBN) or poly ((dimethylol) cyclohexyl) terephthalate)
The polymer of the present invention having (PCT) is formed by reacting a polyester-forming precursor having the group under polyester-forming conditions.

Thus, according to the present invention, formula (VI): [Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are as defined above. A hydroxyphenylalkanoic acid represented by the formula (VI) or a monomer represented by the formula (III): HO—R ₇ —OH (III) and a compound represented by the formula (IV): ): HOOC-R ₈ -COOH (IV) and / or formula (V): HOOC-R ₉ -OH (V) [wherein R ₇ , R ₈ and R ₉ are as defined above. ] Or a reactive derivative thereof is subjected to an esterification reaction. Alternatively, the hydroxyphenylalkanoic acid (VI) may be replaced with poly (ethylene terephthalate), poly (butylene terephthalate), poly (ethylene naphthalate), poly (ethylene naphthalate), at least partially instead of reacting with monomers (III) and (IV). (Butylene naphthalate) or poly ((dimethylol) cyclohexyl) terephthalate).

The reactive derivative of the acid is selected, for example, from the group consisting of acid anhydrides, acid chlorides and esters.

The esterification reaction may be based on conventionally known methods, for example, the acetate method, the "in situ" acetylation method and the transesterification method. The reactants used in these reactions are:
a) diacids and acetylated hydroxy compounds, b) diacids, diols and acetylating agents, and c) diacid esters and diols or polyesters.

Polyesters can also be prepared by known esterification reactions of aromatic acid chlorides with diols. But,
Only low molecular weight polyesters can be produced by this reaction. In addition, acid chlorides are expensive and removal of the solvent from the polymer is complicated. Post-polymerization of the product is required.

According to a preferred embodiment of the present invention, formula (I) or (I
When the groups I) and (III) and (IV) and / or (V) are used in the preparation process, the molar amounts of terminal hydroxyl groups (-OH) and terminal carboxyl groups (-COOH) should be equal. Choose the molar ratio. Polymers having stoichiometrically equal amounts of repeating units (IIIa) and (IVa) are produced. It is preferred to use an excess of acetoanhydride in the "in situ" acetylation method. A suitable excess is 1.1 to 1.5 equivalents based on the amount of hydroxyl groups. According to another preferred embodiment of the invention, the amounts of terminal hydroxyl groups and terminal carboxyl groups are not equal. It becomes possible to provide a polyester having a desired terminal group. By using more terminal carboxyl groups than the abundance of terminal hydrosyl groups, the terminal groups necessarily become carboxyl groups.

The product is in the solid state and can be produced by melt, solution or emulsion polymerization, which is a preferred method of producing polyesters suitable for melt processing.

Polyester production by melt polymerization is hampered by the high viscosity of the polymer and the sticking of the polymer to the reactor. Sticking can be reduced by performing the polymerization in a solution, slurry or solid phase. The problem with solution polymerization lies in the reaction of the reactants and products with the solvent and the difficult removal of high boiling organic solvents. In the solid phase, the polymerization is slow. The products often form networks and their mechanical properties are poor.

According to a preferred embodiment of the present invention, the polymer can be synthesized using a two-stage melt polymerization based on the acetate method. The advantages of a two-stage melt polymerization are its low processing cost, a fairly short polymerization time and good mechanical and rheological properties of the product. The reactants used can be selected from the group consisting of aromatic dicarboxylic acids, diols and hydroxy acids. Esterification can be performed before or with the polymerization, using an excess of the anhydride in the reaction mixture.

Polymerization is usually carried out in a nitrogen or argon atmosphere.
Performed in the molten phase at a temperature of 250-350 ° C. The reaction between monomers is a condensation reaction that produces and separates small molecular products, generally acetic acid. Condensation products must be removed from the reaction mixture. In the first stage of the reaction, the temperature is gradually increased. By increasing the temperature,
Distillation of the condensation product is facilitated, and the progress of the reaction is promoted. The second stage of the polymerization is performed at high vacuum and standard temperature. The reaction time is generally between 3 and 6 hours.
Further post-polymerization sometimes takes place over several days under high vacuum at a temperature just below the melting point of the polymer.

As far as the reaction is concerned, it is preferred to use a catalyst to promote the reaction. Catalysts suitable for catalyzing transesterification include those commonly used in condensation, transesterification and polycondensation reactions. These catalysts
As is generally known, Lewis acids and hydrohalides; oxides, hydrides, hydroxides,
They are represented by halides, alcoholates, phenolates, salts and organic and inorganic salts (especially carboxylate salts), alkali metal salt complexes or salt mixtures (eg magnesium and calcium salts). Other examples are tin, lead, antimony, alkali and alkaline earth metals themselves, especially sodium, sodium hydroxide, lithium, sodium, calcium, magnesium, cobalt and zinc acetate, calcium benzoate, magnesium and zinc acetyl. Acetonates, titanium alkoxyls, such as titanium tetrabutylate, titanium tetrapropylate, alkoxytitanium silicate, zirconium propylate and zirconium butyrate, antimony trioxide, dialkyl and diaryl stannic oxides, dibutylstannic diacetate and i-butyl Dimethoxyl tin. Particularly preferred catalysts are acetates of magnesium, magnesium, sodium, potassium and zinc and dibutylstannic oxide, tetra-n-butyltitanate and titanium (IV) isopropylate.

 If desired, the reaction may be performed without the presence of a catalyst.

According to the invention, considerable advantages are obtained. The glass transition temperature of the polyesters of the present invention is substantially higher than the known polymers obtained by transesterification. Typically, the glass transition temperature is above 90 ° C. Polyesters are optically anisotropic in the melt phase and have a glass transition temperature below 300C, typically about 200-300C.

The polymers of the present invention are suitable for use in thermoplastic materials, especially blends with polyolefins and copolymers thereof, and with polyesters.
Examples of suitable polyolefins are: those including polyethylene, polypropylene, polybutylene, polyisobutylene, poly (4-methyl-1-pentylene), copolymers of ethene and propene (EPM, EPDM), and chlorination And chlorosulfonated polyethylene. If they contain styrene, acrylic, vinyl and fluoroethyl groups, the corresponding polyalkanes are also possible as matrix polymers. The matrix polymer may further consist of various polyesters, for example, poly (ethylene terephthalate), poly (butylene terephthalate) and polycarbonate. In addition to the above polymers, the polyesters of the present invention may also be blended with polyamides and polyethers.

The thermoplastic material / liquid crystalline polymer blend of the present invention can be produced by a conventionally known method. The mixing method is
It is a batch method or a continuous method. Examples of typical batch mixers include Banbury mixers and heated roll machines. As a continuous mixer, for example, Farrell
el) Mixers and single and twin screw extruders are exemplified. Preferably, a single or twin screw extruder is used to mix the liquid crystal polymer with the thermoplastic. The liquid crystal polymer is first premixed with the thermoplastic material in a twin screw extruder and then processed in an injection molding machine or by injection molding or extrusion without premixing. It can be mixed with a thermoplastic material.

The polyesters of the present invention can be used to prepare reinforcement for polymeric materials. By blending the polyester of the present invention with a polymer matrix, a reinforcing thermoplastic material can be produced, the advantage of which is that it is not reused (since it does not contain reinforcing fibers made of different materials such as glass). It is possible. At the same time, device wear is reduced.

Fibrous polyesters can be used in industrial products and consumables that require high strength and light weight and product recycling. The polymers and their blends can be used, inter alia, in injection molded, blow molded, extruded, and deep drawn products. Examples of these products include yarns, films, pipes, tubes, sheets, as well as formed and deep drawn products. Another application is the structural parts and sheaths of cables. Polyesters can also be used in manufacturing processes as processing agents to reduce the viscosity of the polymer melt.

The present invention will now be described in more detail with reference to the attached drawings and the following non-limiting examples.

The figures show the results of the thermal analysis of the polyesters according to Examples 1, 1A, 2, 3, 4, 5 and 6.

FIG. 1 shows the DSC of the polyester prepared according to Example 1.
The curve is shown.

 FIG. 2 shows a TGA curve of the above example.

FIG. 3 shows a DSC curve of the copolymer prepared in Comparative Example 1A, and FIG. 4 shows a TGA curve of the compound.

FIG. 5 shows the DSC curve of the polyester prepared in Example 2, and FIG. 6 shows the corresponding TGA curve.

7 and 8 show the DS of the polyester according to Example 3.
C and TGA curves are shown.

9 and 10 show DS of polyester according to Example 4.
C and TGA curves are shown.

11 and 12 show DS of polyester according to Example 5.
C and TGA curves are shown.

13 and 14 show DS of polyester according to Example 6.
C and TGA curves are shown.

Example 1 Terephthalic acid, 3-tert-butylhydroquinone, 4-hydroxybenzoic acid and 3- (4-hydroxy-3-te
Preparation of a copolymer composed of (rt-butylphenyl) propionic acid by an acetate method: terephthalic acid 0.25 mol, 3-tert-butyl-1,4-diacetoxyphenyl 0.25 mol, 4-acetoxybenzoic acid
0.30 mol and 0.20 mol of 3- (4-acetoxy-3-tert-butylphenyl) propionic acid and 0.003 mol of sodium acetate were weighed into a reactor equipped with a stirrer, distillation apparatus and nitrogen inlet. The reactants were dried at + 110 ° C. by repeating the nitrogen supply / vacuum cycle three times. Raise the temperature of the heating bath to 210 ° C within 10 minutes,
The temperature was further increased to 275 ° C in 60 minutes, at which
At 0 minutes, the first stage of the reaction was performed under a nitrogen atmosphere. Finally, the temperature was raised to 300 ° C. within 30 minutes, and the reaction was carried out at that temperature for 90 minutes.

After first reducing the pressure to 560 mbar, until reaching 0.5 mbar
The vacuum was applied every 10 minutes and the second stage of the reaction was performed under that vacuum. The reaction time was 90 minutes under this reduced pressure.

The amorphous polyester prepared by this method was fibrous and formed an anisotropic mesophase at temperatures above 260 ° C. The glass transition temperature of the polymer based on differential scanning calorimetry was 146 ° C. (see FIG. 1), and the decomposition temperature by thermogravimetric analysis was 390 ° C. (see FIG. 2). The logarithmic viscosity number of the polymer at 45 ° C. in a 4-chlorophenol / 1,1,2,2-tetrachloroethane solution was 1.25 dL / g at a concentration of 0.5 g / 100 mL.

Example 1A (Comparative Example) Terephthalic acid, 3-tert-butylhydroquinone and 4
Preparation of Copolymer of -Hydroxybenzoic Acid by Acetate Method: 0.20 mol of terephthalic acid, 0.20 mol of 3-tert-butyl-1,4-diacetoxybenzene, 4-acetoxybenzoic acid
0.60 mole and 0.003 mole of sodium acetate were prepared according to Example 1.
Weighed into a reactor similar to that described above. The reactants were dried and reacted as in Example 1, except that the final temperature of the first reaction stage was 340 ° C. and the reaction time was 60 minutes at that temperature. This was necessary because the melting point of the formed polyester was much higher than the melting point of the polymer containing 3- (4-acetoxy-3-tert-butylphenyl) propionic acid prepared in Example 1.

The polyester prepared by the above method is fibrous, 31
At temperatures above 1 ° C., an anisotropic mesophase was formed. Glass transition temperature of polymer is 185.2 ° C based on differential scanning calorimetry
(See FIG. 3) and the decomposition temperature by thermogravimetric analysis was 440.
° C (see Figure 4). 4-chlorophenol / 1,1,
The logarithmic viscosity number of the polymer at 45 ° C. in a 2,2-tetrachloroethane solution was 1.25 dL / g at a concentration of 0.5 g / 100 mL.
However, the melting point of the polymer was too high for use in mixing with thermoplastic materials.

Example 2 Terephthalic acid, 3-tert-butylhydroquinone, 4-hydroxybenzoic acid and 3- (4-hydroxy-3-te
(rt-butylphenyl) propionic acid
Preparation by in situ method: terephthalic acid 0.290 mol, 3-tert-butylhydroquinone 0.290 mol, 4-hydroxybenzoic acid 0.520 mol, 3
0.058 mol of-(4-hydroxy-3-tert-butylphenyl) propionic acid, 1.04 mol of acetic anhydride and 0.003 mol of sodium acetate were weighed into a reactor similar to that described in Example 1. The temperature of the reaction mixture is 17
The temperature was raised to 0 ° C. At the end of the acetic acid distillation (after about 1 hour), the temperature is raised to 275 ° C. in 60 minutes, the reaction is carried out at that temperature for 60 minutes, and finally the temperature is raised to 300 ° C. within 30 minutes and the temperature is further increased. Hold for 90 minutes.

 The second stage of the reaction was carried out as in Example 1.

The polyester prepared by this method was fibrous and formed an anisotropic mesophase at a temperature of 280 ° C or higher. Glass transition temperature of polymer is 159 ℃, pyrolysis temperature is 420 ℃
(See FIGS. 5 and 6). The logarithmic viscosity number of the polymer was 1.08 dL / g.

Example 3 Preparation of a copolymer consisting of polyethylene terephthalate, 4-hydroxybenzoic acid and 3- (4-hydroxy-3-tert-butylphenyl) propionic acid by a transesterification method: polyethylene terephthalate 0.180 mol, 4-acetoxybenzoate 0.090 mol of acid and 3- (4-acetoxy-
0.03 mol of 3-tert-butylphenyl) propionic acid
Weighed into a reactor similar to that described in Example 1. The reactants were dried as in Example 1. Heating bath temperature 275
The temperature was raised to ° C. and allowed to react at that temperature for 180 minutes, or the reaction was continued until the acetic acid distillation was completed, and the first stage of the reaction was performed under a nitrogen atmosphere.

The pressure was first reduced to 560 mbar and then every 10 minutes until about 0.5 mbar was reached, and the second stage of the reaction was carried out under that reduced pressure. The reaction time under reduced pressure is 180 minutes at 275 ° C and
30 minutes at 295 ° C.

The amorphous polymer prepared by the method described above was pale and fibrous. As analyzed by the method described in Examples 1 and 2, it formed an anisotropic mesophase at temperatures above 280 ° C. The glass transition temperature of the polymer is 92.6
° C (see Fig. 7) and the thermal decomposition temperature was 390 ° C (see Fig. 8). The logarithmic viscosity number of the polymer was 1.13 dL / g.

Example 3A (Comparative Example) Preparation of a Copolymer of Polyethylene Terephthalate and 4-Hydroxybenzoic Acid by a Transesterification Method: Jackson W. Jr.
nWJ, Jr) and Kuhfus
sHF) "Journal of Polymer Science (J.Polym.Sci.) Polymer Chemistry (Polym.Ch)
em., Ed.) "(Vol. 14 , p. 2043, 1976) and U.S. Pat. No. 3,804,805.

0.073 mol of polyethylene terephthalate and 0.109 mol of 4-acetoxybenzoic acid were weighed into a reactor similar to that described in Example 1. The reactants were dried according to Example 1. The temperature of the heating bath was raised to 275 ° C., and the reaction was performed at that temperature for 180 minutes, or the reaction was continued until the distillation of acetic acid was completed, and the first stage of the reaction was performed under a nitrogen atmosphere.

The pressure was first reduced to 560 mbar and then every 10 minutes until about 0.5 mbar was reached, and the second stage of the reaction was carried out under that reduced pressure. The reaction time at that pressure was 275 ° C. for 240 minutes.

The polymer prepared by the method described above was pale and fibrous. When analyzed by the method set forth in Examples 1 and 2, it formed an anisotropic mesophase at temperatures above 220 ° C., but the glass transition temperature of the polymer was low, ie 61. The logarithmic viscosity number of the polymer was 0.71 dL / g.

A low polymer glass transition temperature indicates that the low polymer glass transition point is not favored and limits the maximum service temperature.

Examples 4 to 10 below show the preparation of copolymers of general formula (I) from different derivatives of hydroxyphenylalkanoic acid.

Example 4 0.25 mol of terephthalic acid, 0.25 mol of 3-tert-butyl-1,4-diacetoxybenzene, 4-acetoxybenzoic acid
0.30 mol, 0.20 mol of 3- (4-acetoxyphenyl) -propionic acid and 0.003 mol of sodium acetate were weighed into a reactor similar to that described in Example 1. The polymer was prepared according to Example 1.

The polymer prepared by the method described above was pale and fibrous. As analyzed by the method described in Examples 1 and 2, it formed an anisotropic mesophase at temperatures above 225 ° C. The glass transition temperature of the polymer was 129 ° C. and the thermal decomposition temperature was 400 ° C. (see FIGS. 9 and 10). The logarithmic viscosity number of the polymer was 0.58 dL / g.

Example 5 0.25 mol of terephthalic acid, 0.25 mol of 3-tert-butyl-1,4-diacetoxybenzene, 4-acetoxybenzoic acid
0.30 mol, 0.20 mol of 3- (4-acetoxy-3-methoxyphenyl) -propionic acid and 0.00 of sodium acetate
3 moles were weighed into the same reactor as in Example 1. The polymer was prepared according to Example 1.

The polymer prepared by this method was pale and fibrous, which formed an anisotropic mesophase at temperatures above 240 ° C. The glass transition point of the polymer is 122 ° C based on differential scanning calorimetry, and the decomposition temperature by thermogravimetric analysis is 390 ° C.
(See FIGS. 11 and 12). 4-chlorophenol
The logarithmic viscosity number of the polymer at 45 ° C. in a / 1,1,2,2-tetrachloroethane solution was 1.16 dL / g at a concentration of 0.5 g / 100 mL.

Example 6 0.25 mol of terephthalic acid, 0.25 mol of 3-tert-butyl-1,4-diacetoxybenzene, 4-acetoxybenzoic acid
0.30 mol, 0.20 mol of 3- (4-acetoxy-3-chlorophenyl) -propionic acid and 0.00 of sodium acetate
Three moles were weighed into a reactor similar to that described in Example 1. The polymer was prepared according to Example 1.

The polymer prepared by the method described above was pale and fibrous. As analyzed by the method described in Examples 1 and 2, it formed an anisotropic mesophase at temperatures above 220 ° C. The glass transition temperature of the polymer was 126 ° C. and the pyrolysis temperature was 380 ° C. (see FIGS. 13 and 14). The logarithmic viscosity number of the polymer was 0.65 dL / g.

Example 7 0.25 mol of terephthalic acid, 0.25 mol of 3-tert-butyl-1,4-diacetoxybenzene, 4-acetoxybenzoic acid
0.30 mol, 0.20 mol of 3- (4-acetoxy-3-benzylphenyl) -propionic acid and 0.00 of sodium acetate
Three moles were weighed into a reactor similar to that described in Example 1. Polymers were prepared according to Example 1 or Example 2, using acetate as the polymer precursor instead of the hydroxylated compound.

Example 8 0.25 mol of terephthalic acid, 0.25 mol of 3-tert-butyl-1,4-diacetoxybenzene, 4-acetoxybenzoic acid
0.30 mol, 0.20 mol of 3- (4-acetoxy-3-butylphenyl) -pentanoic acid and 0.003% of sodium acetate
The moles were metered into a reactor similar to that described in Example 1. Polymers were prepared according to Example 1 or Example 2, using acetate as the polymer precursor instead of the hydroxylated compound.

Example 9 0.25 mol of terephthalic acid, 0.25 mol of 3-tert-butyl-1,4-diacetoxybenzene, 4-acetoxybenzoic acid
0.30 mol, 0.20 mol of 3- (4-acetoxy-3-tert-butylphenyl) -3-methylpropionic acid and 0.003 mol of sodium acetate were weighed into a reactor similar to that described in Example 1. Polymers were prepared according to Example 1 or Example 2, using acetate as the polymer precursor instead of the hydroxylated compound.

Example 10 0.25 mol of terephthalic acid, 0.25 mol of 3-tert-butyl-1,4-diacetoxybenzene, 4-acetoxybenzoic acid
0.30 mole, 0.20 mole of 3- (4-acetoxy-3-tert-butylphenyl) -3-phenylpropionic acid and 0.003 mole of sodium acetate were weighed into a reactor similar to that described in Example 1. Polymers were prepared according to Example 1 or Example 2, using acetate as the polymer precursor instead of the hydroxylated compound.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Lahatinen, Leila Finland EFIEN-00320 Helsinki, Curatier 28a No. 12 (72) Inventor Payunen, Esco Finland EFIEN-06450 Porvoo, Pellavapolk 4se 21 (56 ) References JP-A-2-160826 (JP, A)

Claims (5)

(57) [Claims] (1) Formula (I): Wherein R ₁ is t-butyl; R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are hydrogen; n is an integer of 0-5. And formula (IIIa): —O—R ₇ —O— (IIIa) and formula (IVa): —OC—R ₈ —CO— (IVa) and / or formula (Va): —OC—R ₉ —O -(Va) [wherein R ₇ is a substituted arylene or naphthenylene group, or a formula R ₁₀ -A-R ₁₀ (where R ₁₀ is a phenylene group, and A is -CH _2- , -C ( CH ₃ ) _2- , -O
—, S (O) ₂ — or —S—. And R ₈ and R ₉ are the same or different and are an unsubstituted or substituted arylene or naphthenylene group;
R ₁₀ -A-R ₁₀ (where R ₁₀ is a phenylene group;
Is _{-CH 2 -, - C (CH} 3) 2 -, - O -, - S (O) 2 - or -S-. ) Is an unsubstituted or substituted biphenylene group. ] Having or at least partially replacing the structural units (IIIa) and (IVa) with: poly (ethylene terephthalate) (PET), poly (butylene terephthalate) (PBT), poly (ethylene naphthalene) Phthalate) (PEN), poly (butylene naphthalate) (PBN) or poly ((dimethylol) cyclohexyl) terephthalate) (PCT) (IVa), (2) Structural unit (I) + (IIIa) + (IVa) + (Va), (3) Structural unit (I) + (IIIa) + (IVa) + PET, PBT, P
EN, PBN or PCT, (4) Structural unit (I) + (Va) + PET, PBT, PEN, PBN or PCT, (5) Structural unit (I) + (IIIa) + (IVa) + (Va) + P
ET, PBT, PEN, PBN or PCT, or (6) a liquid crystal polymer comprising the structural unit (I) + PET, PBT, PEN, PBN or PCT. 2. Formula (VI): Wherein R ₁ is t-butyl; R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are hydrogen; n is an integer of 0-5. A hydroxyphenylalkanoic acid represented by the formula (VI) or a monomer represented by the formula (III): HO—R ₇ —OH (III) and a compound represented by the formula (IV): _{): HOOC-R 8 -COOH (} IV) and / or formula (V): in _{HOOC-R 9 -OH (V)} [ the above formulas, R ₇ is a substituted arylene or Nafuteniren group, or a group of the formula R ₁₀ -A, —R ₁₀ (where R ₁₀ is a phenylene group, and A is —CH ₂ —, —C (CH ₃ ) ₂ —, —O
—, S (O) ₂ — or —S—. And R ₈ and R ₉ are the same or different and are an unsubstituted or substituted arylene or naphthenylene group;
R ₁₀ -A-R ₁₀ (where R ₁₀ is a phenylene group;
Is _{-CH 2 -, - C (CH} 3) 2 -, - O -, - S (O) 2 - or -S-. ) Is an unsubstituted or substituted biphenylene group. Or hydroxyphenylalkanoic acid (VI) is converted to poly (ethylene terephthalate) (or at least partially instead of being subjected to an esterification reaction with a monomer represented by the following formula (III) or (IV)). PE
T), poly (butylene terephthalate) (PBT), poly (ethylene naphthalate) (PEN), poly (butylene naphthalate) (PBN) or poly ((dimethylol) cyclohexyl) terephthalate) (PCT) A method for producing a liquid crystal polymer according to claim 1, wherein 3. A polymer blend containing a thermoplastic material blended with a liquid crystal plastic, wherein the liquid crystal plastic comprises the liquid crystal polymer according to claim 1. 4. A polymer product containing the liquid crystal polymer according to claim 1, which can be mixed with another polymer and formed into a product. 5. A polymer melt viscosity reducing agent comprising the liquid crystal polymer according to claim 1.