JPH0231095B2 - YOJUIHOSEIHOKOZOKUHORIESUTERUOYOBISONOSEIZOHOHO - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a melt anisotropic aromatic polyester and a method for producing the same. More specifically, the present invention uses a substituted hydroquinone whose nucleus is substituted with a specific tertiary alkyl group as the main diol component, and produces a melt-molded product that is low in polymer production cost, easy to melt-mold, and has a high Young's modulus. The present invention relates to a melt anisotropic aromatic polyester that can be formed and a method for producing the same. (Prior art) In recent years, fully aromatic copolyesters (hereinafter referred to as aromatic polyesters) consisting of aromatic compound components such as P-oxybenzoic acid, hydroquinone, terephthalic acid, and isophthalic acid, which give molded articles with a high Young's modulus, and fibers thereof have been developed. has been proposed (Japanese Patent Laid-Open No. 1973-
Publication No. 43223). However, even in this case, the aromatic polyester using terephthalic acid as the dicarboxylic acid component has an extremely high melting point, and even if a polymer with a high degree of polymerization is produced, it can be melt-molded, such as by melt-spinning, to achieve high strength and high elasticity. It is difficult to industrially and efficiently produce molded articles, such as fibers, with a high yield. In addition, fully aromatic polyesters using isophthalic acid as the dicarboxylic acid component can be melt-molded, and have the advantage that their melt viscosity is significantly lower than that of terephthalic acid-based aromatic polyesters. The disadvantage is that fibers with a high Young's modulus, which have long been awaited, cannot be produced by spinning alone because they do not have any properties. On the other hand, the softening point of aromatic polyamide is lower than the melting point.
In order to lower the temperature by more than 100℃, aromatic polyesters using an aromatic diol in which two benzene nuclei are directly bonded, such as phenylhydroquinone, instead of the diol component hydroquinone, have also been proposed (Special Features). (Sho 55-500215). However, such special aromatic diols are complicated to synthesize, have low yields, and do not necessarily have good polymerizability, so they are not suitable for industrial production. (Problems to be Solved by the Invention) The present invention solves the various drawbacks of conventionally known aromatic polyesters, makes it easy to produce polymers including the synthesis of raw materials, and is easy to melt mold and have a high young strength. An object of the present invention is to provide an aromatic polyester that can form molded articles with high strength and high strength, such as fibers and films, only by melt molding, and a method for industrially producing the polyester. (Means for Solving the Problems) As a result of intensive research in order to solve the above-mentioned problems of conventionally known aromatic polyesters, the present inventors discovered that the aromatic diol component was nuclear-substituted with a specific tertiary alkyl group. The inventors have discovered that the objects of the present invention can be achieved by using substituted hydroquinones, and have arrived at the present invention. That is, in the present invention, (1) the polyester structural unit is substantially the following []
A linear aromatic polyester consisting of (However, Ar in the above [][] formula,
Ar′ is an aromatic group oriented in the para position,
These may be the same or different from each other. R in the above formula [ ] is an alkyl group having 2 to 7 carbon atoms. ) and the above [] in the polyester
The molar ratio of and [] is 100:0 to 25:75,
and contains 10 mol% or more of polyester repeating units derived from [] and [],
A fiber-forming or film-forming melting agent characterized in that the intrinsic viscosity of the polymer (calculated from the relative viscosity measured at 50°C in a 1/1 mixed solvent of phenol/tetrachloroethane) is 0.8 or more. Directional aromatic polyester, and (2) (A) An aryl ester of an aromatic dicarboxylic acid in which a carboxyl group is bonded to the para position, or an aromatic acid in which this and a hydroxyl group and a carboxyl group are bonded to the para position. A mixture of a group oxycarboxylic acid with an aryl ester and (B) general formula -C
(CH ₃ ) ₂ R (where R is an alkyl group having 2 to 7 carbon atoms) and a monosubstituted hydroquinone whose nucleus is substituted with a group represented by (CH 3 ) 2 R (where R is an alkyl group having 2 to 7 carbon atoms).
The molar ratio (a/b) of the aromatic dicarboxylic acid or its aryl ester (a) and the aromatic oxycarboxylic acid or its aryl ester (b), which accounts for 70 mol% or more and is in component (A).
The ratio is 100:0 to 25:75 and melt polymerized to form a polymer with an intrinsic viscosity (calculated from the relative viscosity measured at 50℃ in a 1/1 mixed solvent of phenol/tetrachloroethane) of 0.8 or more. A method for producing a melt anisotropic aromatic polyester, characterized by: The diol component constituting the melt anisotropic aromatic polyester of the present invention mainly consists of monosubstituted hydroquinone (hereinafter sometimes referred to as substituted hydroquinone) whose nucleus is substituted with a specific tertiary alkyl group. This tertiary alkyl group is -C
It is a tertiary alkyl group represented by (CH ₃ ) ₂ -R (where R is an alkyl group having 2 to 7 carbon atoms), and preferred specific examples of the above R include -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , −CH ₂ CH ₂ CH ₂ CH ₃ , −CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , −CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ C ₃ , −CH ₂ CH _{2 Examples} include C( _{CH3 ) 2.CH3} , _-CH2CH2CH2C ( _CH3 ) _2.CH3 , and _{the like} . Preferred specific examples of the substituted hydroquinone include the following compounds. In the present invention, in addition to the substituted hydroquinone,
Other aromatic diols and/or aliphatic diols can also be used in combination as long as the properties of the resulting polyester are not essentially changed. Such aromatic diols include hydroquinone, resorcinol, bisphenol A, bisphenol S, bisphenol Z, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether,
Examples include tertiary butylhydroquinone, tertiary amylhydroquinone, tertiary octylhydroquinone, tertiary nonylhydroquinone, methylhydroquinone, chlorohydroquinone, tertiary butylhydroquinone, and 4-tertiary butyl resorcinol. , and as an aliphatic diol,
Ethylene glycol, neopentylene glycol, cyclohexane dimethylol, bis-β-hydroxybisphenols (especially bis-β-hydroxybisphenol A, bis-β-hydroxybisphenol S, bis-β-hydroxybisphenol Z, etc.) ) and the like can be mentioned. Among these, the above aromatic diols are more preferred. The proportion of the substituted hydroquinone in the total diol component should be at least 70 mol% or more, preferably 80 mol% or more, particularly 90 mol% or more. On the other hand, the acid component constituting the melt anisotropic aromatic polyester of the present invention is an aromatic dicarboxylic acid in which two ester-forming functional groups are bonded to the para position and/or a combination of this and an aromatic oxycarboxylic acid. Become the Lord over both. Here, para positions refer to positions 1 and 4 in a benzene nucleus, positions 2 and 6 or positions 1 and 5 in a naphthalene nucleus, and positions 4 and 4 in a diphenyl nucleus. ′ represents the position. The two ester-forming functional groups herein mean two carboxyl groups, or one carboxyl group and one hydroxyl group. Examples of aromatic dicarboxylic acids in which an ester-forming functional group is bonded to the para position include terephthalic acid, chlorterephthalic acid, bromiterephthalic acid,
2,5-dibromoterephthalic acid, methylterephthalic acid, 2,6-naphthalene dicarboxylic acid, 4,
Examples include 4'-diphenyldicarboxylic acid and 3,3'-dibromo-4,4'-diphenyldicarboxylic acid. Among these, terephthalic acids, particularly terephthalic acid, are preferred. Further, as aromatic oxycarboxylic acids in which an ester-forming functional group is bonded to the para position, P-oxybenzoic acid is typical, but 3-chloro-4-
Oxybenzoic acid, 3-bromo-4-oxybenzoic acid, 3,5-dichloro-4-oxybenzoic acid, 3
-Tertiary butyl-4-oxybenzoic acid and the like are used. Among these, P-oxybenzoic acid is particularly preferred. In addition to the above-mentioned aromatic dicarboxylic acids and aromatic oxycarboxylic acids, other dicarboxylic acids or oxycarboxylic acids can also be used in small proportions that do not essentially impair the properties of the polymer from which the oxycarboxylic acids are obtained.
Examples of such dicarboxylic acids include isophthalic acid, 1,4-naphthalene dicarboxylic acid, 1,
Examples of oxycarboxylic acids include 6-naphthalene dicarboxylic acid, succinic acid, adipic acid, etc.
m-oxybenzoic acid, p-(β-hydroxyethoxy)benzoic acid, m-(β-hydroxyethoxy)
Benzoic acid, p-(4-hydroxyphenoxy)benzoic acid, m-(4-hydroxyphenoxy)benzoic acid, P-(3-hydroxyphenoxy)benzoic acid, m-(3-hydroxyphenoxy)benzoic acid C) Benzoic acid,
Mention may be made of dicarboxylic acids and oxycarboxylic acids such as 4-hydroxy-1-naphthoic acid, 6-hydroxy-1-naphthoic acid, 8-oxy-2-naphthoic acid and the like. The proportion of the above-mentioned aromatic dicarboxylic acids and aromatic oxycarboxylic acids in which two ester-forming functional groups are bonded at the para position in the total acid component should be 70 mol% or more, and 80 mol % or more, particularly preferably 90 mol% or more. Furthermore, when using a mixture of aromatic dicarboxylic acid and aromatic oxycarboxylic acid, the molar ratio is 100:0 to 75:25.
within the range of In the present invention, at least 10 mol% of the total repeating units of the aromatic polyester must be ester units derived from the aromatic dicarboxylic acid and the substituted hydroquinone (i.e., ester units consisting of [] and []). There is. Therefore, when using a mixture of aromatic dicarboxylic acid and aromatic oxycarboxylic acid, it is necessary to consider the proportion of aromatic dicarboxylic acid in the total acid component. When producing the melt anisotropic aromatic polyester of the present invention, it is preferable that the diol component and the dicarboxylic acid component be used in an approximately equimolar or higher proportion. The ratio of the diol component and dicarboxylic acid component in the aromatic polyester is preferably approximately equimolar. For example, in the case of an aromatic polyester consisting of a terephthalic acid component, a P-oxybenzoic acid component, and a tertiary amyl monosubstituted hydroquinone component, when the molar ratio of the terephthalic acid component and the P-oxybenzoic acid component is 1:1, the tertiary
The amyl monosubstituted hydroquinone component may be used in an approximately equimolar ratio to the terephthalic acid component; in other words, the diol component may be used in an amount approximately 1/2 times the mole of the total acid component. The aromatic polyester of the present invention as described above is (A)1
an aryl ester (a) of an aromatic dicarboxylic acid in which four carboxyl groups are bonded to the para position, or
A mixture of the above aryl ester (a) and an aryl ester of an aromatic oxycarboxylic acid (b) in which one hydroxyl group and one carboxyl group are bonded to the para position, and (B) the general formula -C(CH ₃ ) Substituted hydroquinone whose nucleus is substituted with a tertiary alkyl group represented by _2R (where R is an alkyl group having 2 to 7 carbon atoms) is charged in a predetermined molar ratio and melt-polymerized. can be advantageously manufactured. In this method, there are few impurities mixed into the raw materials, and the purity of the starting materials can be increased, so the quality of the obtained polyester is high, and it is an industrially preferred method. Although the polycondensation reaction proceeds substantially without a catalyst, it is preferably carried out using a conventionally known transesterification catalyst. Among these transesterification catalysts, calcium, magnesium, strontium, barium, lanthanum, cerium, manganese, cobalt, zinc, germanium, tin,
Examples include compounds containing metals such as lead, antimony, and bismuth, and specific examples include magnesium acetate, calcium benzoate, strontium acetate, barium propionate, lanthanum carbonate, cerium oxide, manganese acetate, cobalt acetate, zinc acetate, and oxide. germanium, stannous acetate, lead oxide,
Examples include antimony trioxide and bismuth trioxide. It is also preferred to use stabilizers with these transesterification (polycondensation) catalysts. Examples of preferred stabilizers are conventionally known trivalent or pentavalent phosphorus compounds or esters thereof, such as phosphorous acid, phosphoric acid, phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid,
Butylphosphonic acid, benzylphosphonic acid, trimethylphosphite, trimethylphosphate, triethylphosphate, tributylphosphate, triphenylphosphite, triphenylphosphate, diethylphenylphosphonate, dimethyl-(methyl)phosphonate, dimethyl-(ethyl ) phosphonate, dimethyl(benzyl)phosphonate, and the like. Such stabilizers improve the melt stability and color tone of the polymer, but depending on the type of catalyst, they may inactivate the polycondensation catalyst. Therefore, when the catalyst is made non-condensing, it is preferable to add the stabilizer after the polycondensation reaction is completed. Polycondensation catalysts containing antimony or germanium are difficult to be inactivated by stabilizers, so when such catalysts are used, stabilizers can be added from the beginning of the polycondensation reaction. The amount of these catalysts to be used is 0.005 to 0.5 mol%, more preferably 0.01 to 0.1 mol% of the total number of moles of aromatic dicarboxylic acid such as terephthalic acid and aromatic oxycarboxylic acid such as P-oxybenzoic acid. Preferably, the amount (P) of the stabilizer is 0.8<P/N<1.5 (where P: mole of stabilizer) based on the amount (N moles) of the polycondensation catalyst used. After adding such an amount of catalyst, stabilizer in some cases, and tertiary alkyl monosubstituted hydroquinone to the reaction system, the reaction system is heated to, for example, 250 to 300°C, and the reaction is carried out under normal pressure to produce phenol, that is, monohydroxy. The aromatic compound is distilled out of the system and polycondensation is allowed to proceed. The polycondensation reaction is first carried out under normal pressure and then under reduced pressure, and the resulting monohydroxy aromatic compound is distilled out of the system to proceed. In the reaction under normal pressure, it is preferable that the reaction temperature is gradually increased as the amount of aromatic monohydroxy compound distilled out. Such reaction under normal pressure is preferably carried out at a reaction temperature as low as possible so long as the aromatic monohydroxy compound can be distilled out. for example
At temperatures below 250°C, the polycondensation reaction proceeds slowly, but the reaction soon reaches equilibrium because very little of the aromatic monohydroxy compound produced is distilled out of the reaction system. Therefore, it is preferable to substantially start the reaction temperature at about 260°C and gradually increase the temperature to reach a reaction temperature of about 290°C at about 35 to 60% of the theoretical distillation amount of the aromatic monohydroxy compound. If the reaction temperature is set at a high temperature of 290°C or higher from the beginning and the reaction is allowed to proceed, undesirable side reactions such as gelation may occur. Once such an amount of aromatic monohydroxy compound has been distilled out of the system, the reaction system is reduced in pressure, and while the aromatic monohydroxy compound produced is further distilled out of the system, the degree of vacuum and reaction temperature are gradually increased to reach the final stage. It is preferable to carry out the reaction under a pressure of about 1 mmHg or less and at a reaction temperature of 320 to 340°C to obtain a polymer having a predetermined degree of polymerization. The melt anisotropic aromatic polyester of the present invention has fiber-forming or film-forming properties. The term "fiber-forming property" or "film-forming property" does not mean fiber or film use, but is understood to have the ability to be made into fibers or films by melt molding. Should. Therefore, the aromatic polyester of the present invention can be used not only for fibers and films, but also for plastics and other uses. The aromatic polyester is preferably a polymer having an intrinsic viscosity of 0.8 or more, more preferably 1 or more, particularly 1.5 or more. By using this polymer, molded articles having high Young's modulus and high strength can be obtained industrially efficiently and easily. (Effect of the invention) The melt anisotropic aromatic polyester of the present invention has a substituted hydroquinone component whose nucleus is substituted with a tertiary alkyl group having a total number of carbon atoms of 5 to 10, and two ester-forming groups in the para position. Because it is mainly composed of a bonded aromatic bifunctional carboxylic acid component,
It has excellent linearity (symmetry) of polymer molecules (molecular structure), excellent thermal stability, low melting temperature, low flow start temperature, etc. Furthermore, the melt anisotropic aromatic polyester is characterized by having a relatively low specific gravity and excellent hydrolysis resistance. Conventionally, it has been believed that when the linearity of polymer molecules increases, the melting temperature, flow start temperature, etc. become significantly higher.
Although fully aromatic polyesters with such characteristics are known, the aromatic polyester of the present invention has
It exhibits characteristics completely different from those described above. This is due to the use of the above-mentioned substituted hydroquinone. Therefore, the aromatic polyester of the present invention can be melt-molded at lower temperatures, and deterioration during molding, especially oxidative deterioration under heating and temperature rise, is suppressed to a low level, making it possible to produce molded products of excellent quality. can be formed. Furthermore, since the production temperature of the aromatic polyester can be kept low, it has the advantage that products with a high degree of polymerization, which is difficult to produce with conventional polymers, can be produced by melt polymerization. Furthermore, since the aromatic polyester exhibits melt anisotropy, a molded article with a high Young's modulus and high strength can be formed simply by melt molding. Furthermore, the above-mentioned substituted hydroquinone is extremely easy to synthesize and has good reactivity compared to hydroquinone in which a benzene nucleus is directly bonded to another benzene nucleus, so it has the advantage of lowering the manufacturing cost of polyester. . The melt anisotropic aromatic polyester according to the present invention has a melting point below its decomposition temperature, for example 240 to 400
A polyester molded article can be obtained by melt extrusion molding at ℃. For example, polyester fibers can be obtained by melting aromatic polyester at 240 to 400°C, extruding it from a spinneret, and winding it at a draft rate of 5 to 500 and a winding speed of 10 to 500 m/min. At that time, polyester fibers do not necessarily require heat treatment, and can be melt-spun and wound to achieve a strength of 5 g/de or more and a Young's modulus of 2500.
It can be made with high strength of Kg/mm ² or more and high Young's modulus. This fiber can be advantageously used for tire cords, rubber reinforcing materials, fillers, and other heat-resistant industrial materials. Further, a polyester film can be obtained by melt-extruding it through a die at 240 to 400°C and winding it around a drum. The draft during extrusion is 1-50, preferably 1-10. At this time, the film extruded onto the drum may be left to cool at room temperature, or may be rapidly cooled in water. The polyester film obtained in this way has a sufficiently high Young's modulus (more than 700 kg/ ^mm2 ) and tensile strength (30
Kg/mm ² or more). This film can be advantageously used as an industrial material. Molded articles using the polyester of the present invention have sufficient strength even without heat treatment as described in JP-A No. 50-43223, but it is possible to further increase the strength by heat treatment. Can be done.
For example, heat treatment at 200 to 300°C for about 10 hours improves the above properties several times. Molded products using the aromatic polyester of the present invention have a high Young's modulus and excellent hydrolysis resistance, so they can be advantageously used as industrial materials such as tire cords, rubber reinforcing materials, fillers, and films. . (Example) The present invention will be explained below with reference to Examples. In addition, all "parts" in the examples are "parts by weight."
It is. In addition, the intrinsic viscosity in the present invention is determined by dissolving 50 mg of polyester in 10 ml of a mixed solvent (phenol/tetrachloroethane = 1/1 vol/vol mixture).
The relative viscosity (ηr) was determined at 50° C. using an Ostwald viscometer and calculated using the following formula. Intrinsic viscosity = lnηr / 0.5 In addition, the flow start temperature is
The sample was placed in a high-performance flow tester equipped with a nozzle of 0.5 mm and 4 mm in length, and heated at a rate of about 2° C. per minute under a pressure of 60 kg/cm ² to determine the temperature at which polyester started flowing out from the nozzle. The specific gravity was determined by heat-treating the polymer at 200° C. for 3 hours to crystallize it and using a pycnometer using a mixed solvent of carbon tetrachloride and n-hexane. Furthermore, the hydrolysis resistance of 1.0g of polymer at 240℃
After treatment for 15 hours _at a temperature of (ηinh) was calculated using the following formula. Hydrolysis resistance (%) = {(ηinh) / (ηinh) ₀ }×1
00 Example 1 214 parts of phenyl P-oxybenzoate, 318 parts of diphenyl terephthalate, 198 parts of tertiary amylhydroquinone, and 0.1 part of antimony trioxide were added at 260 parts under normal pressure.
℃/30 minutes, 270℃/30 minutes, 290℃/30 minutes to react while distilling off phenol, then gradually increasing the temperature and increasing the degree of vacuum by 100 mmHg every 20 minutes to distill off phenol. The polycondensation reaction was then carried out, and finally the reaction was carried out for 20 minutes at 330° C. under a high vacuum of about 1 mmHg to carry out the polycondensation reaction. The flow onset temperature of the obtained polyester is 265℃,
The intrinsic viscosity was 3.551. This polyester
It was melted at 350℃ and extruded using a spinning machine with a pore diameter of 0.3m/m, with a draft of 20 at a speed of 50m/min.
I rolled it up. The fineness of the obtained fiber is 40 denier.
The tensile strength was 7 g/de, the Young's modulus was 5000 Kg/mm ² and the elongation was 2%. Examples 2 to 4 Using raw materials having the composition shown in Table 1 below, Example 1
A polyester was produced in the same manner as above and further melt-spun.

[Table] The flow initiation temperature, intrinsic viscosity, and physical properties of the yarn of the obtained polyester were as shown in Table 2 below.

[Table] Examples 5 to 7 Using raw materials with the composition shown in Table 3 below, Example 1
Polyester was produced and spun in the same manner as above.

[Table] In Example 5, tertiary peptylhydroquinone was used as the tertiary alkyl-substituted hydroquinone, and in Examples 6 and 7, tertiary octylhydroquinone was used. The physical properties of the obtained polyester and the physical properties of the yarn spun in the same manner as in Example 1 are shown in Table 4 below.

[Table] Examples 8 to 10 Diphenyl terephthalate (), diphenyl isophthalate () and tertiary amylhydroquinone () or tertiary peptylhydroquinone () were used as shown in Table 5, and the same procedure as in Example 1 was carried out. Polyester was produced and spun.

[Table] Table 6 shows the physical properties of the obtained polyester and the physical properties of a yarn spun in the same manner as in Example 1. However, Example 8 was spun at 380°C, and Examples 9 and 10 were spun at 350°C.

[Table] Examples 11-12 Into a reactor equipped with a stirrer and a distillation system, predetermined amounts of the compounds shown in Table 7, 21.4 parts of phenyl P-oxybenzoate, 2.4 mg of stannous acetate, and triphenylphosphine were added. 2.6 mg was charged, and the temperature was gradually raised from 260° C. to 290° C. over 90 minutes under normal pressure, and the reaction was carried out while distilling the phenol produced by the reaction out of the system. Next, the degree of vacuum in the system was increased by 100 mmHg every 20 minutes, and at the same time the reaction temperature was raised to 330°C to allow the reaction to occur.Finally, the temperature was reduced to 330°C under a reduced pressure of 1 mmHg or less.
The mixture was allowed to react for 30 minutes. Table 7 shows the intrinsic viscosity and flow onset temperature of the obtained polymer.

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Claims (1)

[Claims] 1. The polyester constituent units are substantially the following []
and [] or a substantially linear aromatic polyester consisting of the following [], [] and [], -CO-Ar-CO- ...[] -O-Ar'-CO- ...[] (However, Ar in the above [][] formula,
Ar' is an aromatic group oriented at the para position, and these groups may be the same or different from each other. R in the above formula [ ] is an alkyl group having 2 to 7 carbon atoms. ) and the molar ratio of the above [] and [] in the polyester is 100:0 to 25:75, and contains 10 mol% or more of polyester repeating units derived from [] and []. and the intrinsic viscosity of the polymer (calculated from the relative viscosity measured at 50°C in a 1/1 mixed solvent of phenol/tetrachloroethane) is 0.8 or more,
Fiber-forming or film-forming melt anisotropic aromatic polyester. 2 (A) An aryl ester of an aromatic dicarboxylic acid in which a carboxyl group is bonded to the para position, or a mixture of this and an aryl ester of an aromatic oxycarboxylic acid in which a hydroxyl group and a carboxyl group are bonded to the para position. and (B) general formula -C( _CH3 ) _2R
(However, R is an alkyl group having 2 to 7 carbon atoms.) A monosubstituted hydroquinone whose nucleus is substituted with a group represented by R is an alkyl group having 2 to 7 carbon atoms. ) The aromatic dicarboxylic acid or aryl ester thereof (a) and the aromatic oxycarboxylic acid or aryl ester thereof (b) in component
and the molar ratio (a/b) of 100:0 to 25:75.
A method for producing a melt anisotropic aromatic polyester, characterized by forming a polymer having a relative viscosity (calculated from relative viscosity measured at 50°C) of 0.8 or more.