JPH0543670A - Polyarylate and its production - Google Patents

Abstract

PURPOSE:To obtain a polyarylate improved in heat resistance, etc., by bringing an alkaline aqueous solution of a bisphenol into contact with a solution of terephthaloyl dihalide and/or isophthaloyl dihalide in a hydrophobic organic solvent in the presence of a specified phase transfer catalyst. CONSTITUTION:An alkaline aqueous solution of a bisphenol of formula I (wherein R1 to R4 are each methyl, ethyl or halogen; and Y is a 1-20C hydrocarbon group, O, S, SO2 or CO) is brought into contact with a solution of terephthaloyl dihalide and/or isophthaloyl dihalide in a hydrophobic organic solvent in the presence of a quat. salt phase transfer catalyst of formula II (wherein R5 is a 4-12C hydrocarbon group; and Z is N or P; and X is halogen or HSO3) to obtain a polyarylate comprising residues of a bisphenol of formula I and residues of terephthalic acid and/or residues of isophthalic acid and having relative viscosities of formulas II and IV [wherein etainhA is measured in tetrachloroethane at 25 deg.C, 1g/dl, and etainhB is measured in a mixture (40/60 by weight) of tetrachloroethane containing 0.01mol/l of sodium acetate with phenol at 25 deg.C, 1g/dl].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylate excellent in various properties as an engineering plastic and a method for producing the same.

[0002]

2. Description of the Related Art Polyarylates consisting of residues of bisphenols, especially 2,2-bis (4-hydroxyphenyl) propane and terephthalic acid and / or isophthalic acid are already well known as engineering plastics. .. It is also well known that such polyarylate has high heat resistance, excellent mechanical strength and dimensional stability, and is transparent, so that its molded product is widely applied to the fields of electric / electronic, automobile, machine, etc. ing.

In recent years, improvement of fuel efficiency of automobiles has become one of the major problems in the automobile industry. Therefore, in order to reduce the weight of constituent materials of automobiles, plastics of low specific gravity are replaced by plastics of low specific gravity instead of metals having high specific gravity. Attempts are being made to apply the technology to automobiles, and the material for lamp covers and lenses mounted on automobiles is also being changed from glass to plastic. Among these lamp covers and lenses, acrylic resin is used for parts with relatively low heat resistance requirements, and polycarbonate is used for parts with relatively high heat resistance requirements. However, for headlight lenses, inner lenses, fog light lenses, etc., which have higher heat resistance requirements, these acrylic resins and polycarbonates do not have sufficient heat resistance.

Under these circumstances, application of polyarylate having higher heat resistance has been expected. However, polyarylate, which is composed of the most typical residue of 2,2-bis (4-hydroxyphenyl) propane and the residue of terephthalic acid and / or isophthalic acid, has high heat resistance and excellent transparency. Its application has been greatly limited due to the significant discoloration.

As an attempt to prevent such discoloration of polyarylate by ultraviolet rays, for example, JP-A-49-2245 is used.
No. 1, gazette 50-83446 gazette, same 52
As disclosed in Japanese Patent Publication No. -16558, a method of blending a so-called ultraviolet absorber, an antioxidant and the like is known. However, these methods were not sufficiently effective and could not substantially prevent discoloration of polyarylate by ultraviolet rays.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, an object of the present invention is to provide a transparent and high heat resistance, mechanical strength,
Not to mention excellent dimensional stability, discoloration due to ultraviolet rays is substantially suppressed, and polyarylate having improved heat aging resistance and wet heat aging resistance and polyarylate having such excellent properties It is to provide a manufacturing method.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have introduced a specific substituent at a position ortho to a hydroxy group as bisphenol constituting polyarylate. Polyarylate, which uses bisphenol and satisfies certain conditions, is transparent, has high heat resistance, and has excellent mechanical strength and dimensional stability.
Moreover, it was found that discoloration due to ultraviolet rays was substantially suppressed, and that it was also excellent in heat resistance and heat resistance under heat and humidity. Moreover, such polyarylate was obtained by the interfacial polymerization method using a specific phase transfer catalyst. The present invention has been achieved by finding that it can be manufactured.

That is, the first gist of the present invention is the formula [1]
It is a polyarylate which comprises the residue of bisphenol represented by and the residue of terephthalic acid and / or isophthalic acid and satisfies the formulas [2] and [3].

[0009]

[Chemical 4]

0.4 ≤ ηinh (A) ≤ 1.7 [2] 0.9 ≤ ηinh (B) / ηinh (A) [3] (In the formula [1], R _{1 to} R ₄ are methyl. Group _,
It represents _an ethyl group or a halogen atom, which may be the same or different, and Y is selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, O, S, SO ₂ and CO. In the formula [2], ηinh (A) uses tetrachloroethane as a solvent, the temperature is 25 ° C., and the concentration is 1 g /
It is the logarithmic viscosity obtained under the condition of dl. In the formula [3], ηinh (B) is 0.0% sodium acetate as a solvent.
Tetrachloroethane / phenol containing 1 mol / l = 40
It is the logarithmic viscosity obtained by using a mixed solvent of / 60 (weight ratio) at a temperature of 25 ° C. and a concentration of 1 g / dl. Note that ηin
In h (A) and η inh (B), the logarithmic viscosity is defined by the formula [4]. ηinh = ln ηr / C [4] where ln is the natural logarithm, ηr is the relative viscosity, and C is the concentration (g / dl). )

The second gist is to bring an alkaline aqueous solution in which the bisphenol represented by the formula [1] is dissolved into contact with a hydrophobic organic solvent solution in which an acid halide of terephthalic acid and / or isophthalic acid is dissolved. In producing polyarylate, a quaternary salt represented by the formula [5] is used as a phase transfer catalyst, which is a method for producing polyarylate.

[0012]

[Chemical 5]

[0013]

[Chemical 6]

(However, in the formula [1], R _{1 to} R ₄
Represents a methyl _group, ethyl group or halogen _atom, or different an each identical, Y is C 1 -C
To 20 hydrocarbon groups, O, S, SO ₂ , and CO. In the formula [5], R ₅ is a hydrocarbon group having 4 to 12 carbon atoms, Z is a nitrogen atom or a phosphorus atom, and X is a halogen atom or HSO ₄ . + And-indicate positive and negative charges, respectively. )

The present invention will be described in more detail. First, the process of obtaining the polyarylate of the present invention will be described. That is, as a result of earnest studies by the present inventors, as a bisphenol constituting a polyarylate, a bisphenol in which a specific substituent is introduced at the ortho position with respect to a hydroxy group (represented by the formula [1]) is used. It was found that polyarylate satisfying [2] is transparent, has high heat resistance, is excellent in mechanical strength and dimensional stability, and can substantially prevent discoloration due to ultraviolet rays. However, as it is, heat aging resistance and wet heat aging resistance were not sufficient. Therefore, as a result of further study, the formula [3]
It was found that the polyarylate satisfying the requirements is excellent in heat aging resistance and wet heat aging resistance.

Also in the production of polyarylate,
Even when a polyarylate satisfying the formula [2] was produced by the melt polymerization method using the bisphenol represented by the formula [1], the transparency was poor and the desired polyarylate could not be obtained. In addition, when a similar polyarylate is produced by the interfacial polymerization method using a phase transfer catalyst that has been commonly used in the past, it has high heat resistance, excellent mechanical strength and dimensional stability, and is discolored by ultraviolet rays. However, those having sufficient heat aging resistance and wet heat aging resistance were not obtained. Therefore, it was found that when a quaternary salt represented by the formula [5] is used as the phase transfer catalyst, polyarylate having excellent heat aging resistance and wet heat aging resistance can be obtained.

The polyarylate of the present invention comprises a residue of bisphenol represented by the formula [1], terephthalic acid and / or
Alternatively, it is a polyarylate composed of a residue of isophthalic acid and satisfying the formulas [2] and [3]. With polyarylate using bisphenol other than bisphenol represented by the formula [1], discoloration due to ultraviolet rays cannot be suppressed. Further, when the value of ηinh (A) is less than 0.4, the mechanical properties, particularly toughness, is significantly deteriorated, and when it exceeds 1.7, the workability during melt molding is deteriorated.
Further, if the value of ηinh (B) / ηinh (A) is less than 0.9, the heat aging resistance and the wet heat aging resistance are deteriorated. Therefore, when used as an engineering plastic, it is necessary to satisfy the formula [3].

Although the meaning of the formula [3] is not always clear, ηinh (B) is a logarithmic viscosity measured using a solvent containing an alkaline substance such as sodium acetate as a solvent. The value of B) is considered to correspond to the molecular weight after alkaline decomposition of the structural defects of polyarylate. On the other hand, ηinh
(A) is a value measured with a solvent that does not contain such an alkaline substance, and is judged to correspond to the molecular weight of the polyarylate including structural defects.

Therefore, a large value of ηinh (B) / ηinh (A) is considered to mean that the nucleophilic substance typified by an alkaline substance has excellent resistance to attack. In fact, the polyarylate satisfying the formula [3] had a very small decrease in the molecular weight represented by ηinh (A) due to the aging treatment at high temperature or high humidity, and the deterioration of the physical properties was also greatly suppressed. On the other hand, polyarylate that does not satisfy Eq. [3] has a ηin value after aging treatment at high temperature or high humidity.
The decrease in the molecular weight represented by h (A) was extremely large, and the physical properties were also significantly deteriorated, making it unsuitable for use as an engineering plastic.

Examples of typical bisphenols represented by the formula [1] are bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-diethyl-4-hydroxyphenyl) methane and bis. (3,5-dibromo-
4-hydroxyphenyl) methane, 1,1-bis (3,3
5-dimethyl-4-hydroxyphenyl) ethane, 1,
1-bis (3,5-diethyl-4-hydroxyphenyl) ethane, bis (3,5-dibromo-4-hydroxyphenyl) ethane, 1,1-bis (3,5-dimethyl-
4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (3,5-diethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-Diethyl-4-hydroxyphenyl) propane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) Propane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) butane, 1,1-bis (3,5- Diethyl-4-hydroxyphenyl) butane, 2,2-bis (3,5-diethyl-
4-hydroxyphenyl) butane, 1,1-bis (3,3
5-dibromo-4-hydroxyphenyl) butane, 2,
2-bis (3,5-dibromo-4-hydroxyphenyl) butane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-diethyl-4-) Hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) cyclohexane, bis (3,5-dimethyl-4-hydroxyphenyl) phenylmethane, bis (3,5-diethyl-4-) Hydroxyphenyl) phenylmethane, bis (3,5-dibromo-4-hydroxyphenyl) phenylmethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-diethyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,3
5-dibromo-4-hydroxyphenyl) -1-phenylethane, bis (3,5-dimethyl-4-hydroxy)
Diphenylmethane, bis (3,5-diethyl-4-hydroxy) diphenylmethane, bis (3,5-dibromo-
4-hydroxy) diphenylmethane, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-diethyl-4-hydroxyphenyl) ether, bis (3,5-dibromo-4-hydroxyphenyl) ether , Bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-diethyl-
4-hydroxyphenyl) sulfide, bis (3,5)
-Dibromo-4-hydroxyphenyl) sulfide,
Bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-diethyl-4-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (3,5 -Dimethyl-4
-Hydroxyphenyl) ketone, bis (3,5-diethyl-4-hydroxyphenyl) ketone, bis (3,5-
Dibromo-4-hydroxyphenyl) ketone etc. are mentioned. Among them, the most preferable bisphenols are bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (3,5-). Dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-
Bis (3,5-dimethyl-4-hydroxyphenyl)-
1-phenylethane, bis (3,5-dimethyl-4-hydroxyphenyl) phenylmethane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) ether , Bis (3,5-dimethyl-4-hydroxyphenyl) ketone, and the like. Further, of the above bisphenols, polyarylate using halogen-substituted bisphenol becomes excellent in flame retardancy.

In the polyarylate of the present invention, part of the bisphenol represented by the formula [1] may be replaced with other bisphenols as long as the characteristics are not substantially impaired. Such bisphenols include hydroquinone, resorcinol, dihydroxybiphenyl, bis (hydroxyphenyl) alkane, bis (hydroxyphenyl) cycloalkane, bis (hydroxyphenyl) sulfide, bis (hydroxyphenyl) sulfone, bis (hydroxyphenyl) ether, Included are bis (hydroxyphenyl) ketones and their nuclear halides.

The ratio of the residues of terephthalic acid and / or isophthalic acid constituting the polyarylate of the present invention is not particularly limited, and the constituents may be used alone or in combination according to the purpose. May be. In that case, the more terephthalic acid residues are, the more polyarylate having high heat resistance can be obtained. In addition, the toughness of the polyarylate containing 10 mol% or more of the residue of isophthalic acid is improved. Therefore, when used as an engineering plastic, it is preferable to determine the ratio of the residues of terephthalic acid and isophthalic acid according to the required properties.

In the polyarylate of the present invention, a part of terephthalic acid and / or isophthalic acid may be replaced with other dicarboxylic acid as long as the characteristics thereof are not substantially impaired. Examples of the dicarboxylic acid include naphthalenedicarboxylic acid, bis (p-carboxyphenyl) alkane, aromatic dicarboxylic acid such as 4,4′-dicarboxydiphenyl ether, cycloaliphatic dicarboxylic acid, adipic acid, sebacic acid, glutaric acid, and the like. Alternatively, aliphatic dicarboxylic acids and their halides are included.

The physical properties of the polyarylate of the present invention may be affected by the presence of impurities. In particular, the presence of an alkali salt which is a by-product in the interfacial polymerization is not preferable. The amount of such alkali salt contained in the polyarylate of the present invention is preferably 500 ppm or less, more preferably 200 ppm or less.

Next, the method for producing the polyarylate of the present invention will be described. The polyarylate of the present invention has the formula [1]
It is obtained by bringing an alkaline aqueous solution in which bisphenol is dissolved and a solution in a hydrophobic organic solvent in which an acid halide of terephthalic acid and / or isophthalic acid is dissolved into contact with each other, and preferably mixing and stirring. At this time, a specific quaternary salt represented by the formula [5] is used as the phase transfer catalyst. In this interfacial polymerization method, the relative volume ratio of the alkaline aqueous solution and the hydrophobic organic solvent solution is preferably in the range of 5: 1 to 1: 5, but it is not absolute.

Bisphenol is used by dissolving it in an alkaline aqueous solution, and as such alkali, sodium hydroxide and potassium hydroxide are generally used. The amount of alkali necessary to dissolve bisphenol varies depending on the type of phenol used, but it is usually preferable to use it in an equimolar amount or a 2.0-fold molar amount with respect to bisphenol.
At this time, it is not necessary to completely dissolve the bisphenol in the alkaline aqueous solution, and the polymerization may be started in the suspended state of the bisphenol. This is because the bisphenol that had been suspended as the polymerization proceeded was rapidly dissolved in alkaline water and provided for the polymerization reaction. At this time, since the acid halide of terephthalic acid and / or isophthalic acid may be hydrolyzed, the amount of alkali used is preferably as small as possible. Since the alkaline aqueous solution of bisphenols may be colored by oxidation when left in the air for a long time, it is preferably adjusted and stored in an atmosphere shielded from air and ultraviolet rays. It is also preferable to add a small amount of an antioxidant such as sodium hydrosulfite. The concentration of bisphenols dissolved in alkaline water is not particularly limited, but usually 1
-20% by weight is preferably used.

Examples of the acid halide of terephthalic acid and / or isophthalic acid include terephthalic acid chloride, terephthalic acid bromide, isophthalic acid chloride, isophthalic acid bromide, and the like, and the acid halide of terephthalic acid and / or isophthalic acid is used. The hydrophobic organic solvent used for dissolution is preferably one that is incompatible with water and dissolves the resulting polyarylate. However, depending on the case, an organic solvent that does not dissolve the generated polyarylate can be used, and in this case, when the polyarylate has a molecular weight of a certain level or higher, it precipitates out of the system.

Specific examples of the hydrophobic organic solvent used for dissolving the acid halide of terephthalic acid and / or isophthalic acid and capable of dissolving polyarylate are dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane. , 1,1,2-Trichloroethane, 1,
Examples thereof include 1,2,2-tetrachloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, xylene, ethylbenzene, anisole, acetophenone and nitrobenzene. These may be used alone or in combination. Among them, a general and preferable hydrophobic organic solvent is a halogenated hydrocarbon having 1 to 6 carbon atoms, and the most preferable one is dichloromethane. The concentration of the acid halide of terephthalic acid and / or isophthalic acid which is soluble in the hydrophobic organic solvent is not particularly limited, but it is usually preferably 0.5 to 40% by weight.

When the polyarylate is produced by the interfacial polymerization method, the phase transfer catalyst transfers the phenoxide ion dissolved in the aqueous phase to the organic solvent phase in which the polymerization reaction takes place, and the halogen ion generated as a result of the reaction is transferred to the aqueous phase. Play the role of transport. The phase transfer catalyst is a quaternary salt represented by the general formula [5].

Among the phase transfer catalysts represented by the formula [5], preferred phase transfer catalysts include, for example, tetra-n-butylammonium halide (ie tetra-n-butylammonium chloride, tetra-n-butylammonium bromide). And tetra-n-butylammonium iodide), tetra-n-butylammonium hydrogensulfate, tri-n-butylbenzylammonium halide, tri-n-butylbenzylammonium hydrogensulfate, tetra-n-butylphosphonium halide, tetra -N-butyl phosphonium hydrogen sulfate, tri-n-butyl benzyl phosphonium halide, tri-n-butyl benzyl phosphonium hydrogen sulfate, etc. are mentioned. The amount of the phase transfer catalyst used in the present invention can be arbitrarily selected, but is generally 0.001 to 10 mol%, particularly 0.01 to 5 mol% based on bisphenol.
Is preferred.

Conventionally, in the interfacial polymerization method of polyarylate, a quaternary ammonium salt, especially trimethylbenzylammonium chloride, a quaternary phosphonium salt or crown ether has been known as a phase transfer catalyst. However, as in the present invention, such a general phase transfer catalyst is not effective for the polymerization reaction of polyarylate using the bisphenol having the specific structure represented by the formula [1]. That is, when bisphenol having a specific structure is used, not only a high molecular weight polyarylate cannot be obtained, but also the obtained polyarylate has extremely poor heat aging resistance and wet heat aging resistance. On the other hand, the use of the phase transfer catalyst represented by the formula [5] shows a remarkable effect that the effect is specifically high for the polyarylate having a specific chemical structure as in the present invention.

That is, to enumerate those effects (A)
The polymerization reaction rate is remarkably increased, (B) a high molecular weight polyarylate is obtained, and (C) a polyarylate having excellent heat aging resistance and wet heat aging resistance is obtained. (D) The fact that the phase separation property between the aqueous phase and the organic solvent phase at the end of the polymerization is extremely excellent. These remarkable effects could not be realized at all with conventional conventional phase transfer catalysts.

In the interfacial polymerization, the polymerization reaction proceeds near the interface of the hydrophobic organic solvent phase, but the phase transfer catalyst plays an extremely important role of promoting the diffusion of phenoxide ions into the organic phase. When the effect of the phase transfer catalyst is low, not only the polymerization reaction does not proceed due to the slow diffusion rate of phenoxide ions into the organic phase, but also the hydrolysis of the acid halide occurs during that time. Therefore, an acid anhydride structure, which is thought to be the result of the reaction of carboxylic acid generated by hydrolysis with acid chloride, is formed in the molecular chain of polyarylate, which significantly improves the heat and wet heat aging resistance of polyarylate. It seems that it is decreasing. The acid anhydride bond in the main chain is cleaved during the measurement of ηinh (B) as described above.

When the polyarylate of the present invention is produced by the interfacial polymerization method, a known method can be used as a method for controlling the molecular weight. The most general method is a method of polymerizing by adding a certain amount of a compound having a monovalent reactive functional group. Such compounds include monohydric alcohols,
There are monovalent carboxylic acids and phenols. When a monovalent carboxylic acid is used for this purpose, it is generally added to the polymerization system as an acid halide.

In the present invention, alcohols that can be used as a molecular weight control agent include, for example, methanol, ethanol, isopropanol, n-butanol, isobutanol, 1-butanol, n-pentanol, neopentanol, n-. Hexanol, cyclohexanol, octanol, nonyl alcohol, decyl alcohol, benzyl alcohol, phenethyl alcohol and the like can be mentioned. Examples of monovalent carboxylic acids include acetic acid, propionic acid, octylic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid and p-methoxyphenylacetic acid. You can Furthermore, examples of phenols include phenol and p-ter.
t-butylphenol, 2,6-xylenol, 2,6
-Dichlorophenol, 2,4,6-tribromophenol, isooctylphenol, p-methoxyphenol and the like can be mentioned.

The production method of the present invention will be described more specifically. For example, an aqueous alkaline solution in which bis (3,5-dimethyl-4-hydroxyphenyl) propane is dissolved, dichloromethane in which acid chloride of terephthalic acid and / or isophthalic acid is dissolved, a phase transfer catalyst, a molecular weight control agent and other additives are added. Mix and stir vigorously. When mixing and stirring, a general stirrer can be used,
For example, a homomixer, a propeller mixer, a line mixer, etc. can be used.

The polymerization reaction temperature is often selected in the range of -15 ° C to 30 ° C when the hydrophobic organic solvent is dichloromethane. At this time, the upper limit temperature depends on the boiling points of the aqueous solution and the hydrophobic organic solvent used. In general, a lower reaction temperature is preferable in order to prevent hydrolysis of the acid halide, but on the contrary, the polymerization reaction rate becomes slower. When dichloroethane is used, the reaction temperature is preferably 0 ° C to 50 ° C.

In the method of the present invention, the rate of the polymerization reaction is extremely fast, and a reaction time of 5 minutes is sufficient depending on the efficiency of mixing and stirring. Generally, a reaction time of 10 minutes to 10 hours is suitable. The polyarylate produced by the polymerization reaction is dissolved in a hydrophobic organic solvent. Therefore, the viscosity of the organic solvent increases with the formation of polyarylate and the increase of the molecular weight. Since the viscosity of this organic phase also depends on the initial concentration of the monomeric acid chloride, the most suitable initial concentration for the isolation of polyarylate should be selected.

After the polymerization reaction, the alkaline aqueous solution phase and the hydrophobic organic solvent solution phase are separated. At this time, generally, the addition of a mineral acid or an organic acid facilitates the separation. When the phase transfer catalyst of the present invention is used, phase separation is extremely easy and it is not necessary to add a mineral acid or an organic acid, but it is preferable in the sense of neutralizing the alkaline aqueous solution. The aqueous phase and the organic solvent phase can be separated by allowing them to stand, or can be separated by a centrifugal separation method in a shorter time. The separated organic phase is preferably extracted and washed with water or another detergent. If necessary, filtration is performed.

The polyarylate is isolated from the thus washed organic phase. A known method can be appropriately selected for the isolation method. For example, there is a method of adding an organic solvent which is a non-solvent of the polymer. In the case of dichloromethane, acetone and methyl alcohol are suitable. There is also a method of isolating polyarylate by vaporizing an organic solvent. For example, it is a method of isolating polyarylate while concentrating an organic solvent solution containing polyarylate with a kneader or the like.

The polyarylate of the present invention may be added with a pigment, a heat stabilizer, an antioxidant, a weathering agent, a flame retardant, a plasticizer, a release agent, a reinforcing material, etc., as long as the characteristics are not significantly impaired. Is. These additives may be added at the time of polymerization, and the polyarylate may be added after isolation. Examples of the heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds and mixtures thereof, and phosphorus compounds are most effective. Examples of such phosphorus compounds include phosphorous acid, phosphorous acid ester, orthophosphoric acid, orthophosphoric acid ester. Further, as a reinforcing material, clay, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, asbestos, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, water Aluminum oxide, calcium hydroxide, barium sulfate, potassium alum, sodium alum, iron alum, glass balloon, carbon black, zinc oxide, antimony trioxide, boric acid, borax, zinc borate, zeolite, hydrotalcide, metal Fiber, metal whiskers, ceramic whiskers, potassium titanate, ticker boron, mica, graphite, glass fibers and the like can be mentioned.

Furthermore, if necessary, other polymers can be blended with the polyarylate of the present invention. Examples of the polymer include polybutadiene, butylene-styrene copolymer, acrylic rubber, ethylene-propylene copolymer, EPDM, natural rubber, chlorinated butyl rubber, chlorinated polyethylene rubber-like copolymer, and styrene-butadiene block. Elastomers such as copolymers, styrene-butadiene block copolymers, butadiene-styrene radial tereblock copolymers, styrene-maleic anhydride copolymers, styrene-phenylmaleimide copolymers, nylon 6, nylon 66, nylon 46 , Nylon 1
2, polyamide such as nylon 610, polypropylene, butadiene-acrylonitrile copolymer, polyvinyl chloride, PET, PBT, polyacetal, polyvinylidene fluoride, polysulfone, PPS, polyether sulfone, phenoxy resin, PPO, PMMA, polyether ketone, Examples include polycarbonate.

The polyarylate of the present invention can be made into a desired molded product by a usual molding processing method. For example, hot melt molding methods such as injection molding, extrusion molding, blow molding, and sintering molding can be applied. Further, a film can be prepared from an organic solvent solution by a casting method.

[0044]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
The measurement methods used for evaluation of the following examples and comparative examples are as follows.

(1) Logarithmic viscosity ηinh (A) uses tetrachloroethane as a solvent,
The temperature was 25 ° C. and the concentration was 1 g / dl. ηinh
(B) is 0.01 mol / l of sodium acetate as a solvent
Containing tetrachloroethane / phenol / = 40/60
(Weight ratio) mixed solvent, temperature 25 ℃, concentration 1g /
It was determined under the condition of dl.

(2) Total Light Transmittance The obtained polyarylate was vacuum dried at 120 ° C. for 16 hours and then injection-molded at a cylinder temperature of 380 ° C. and a mold temperature of 130 ° C. to obtain a thickness of 3 mm and a side of 5 cm. A square test piece was prepared. The molding machine is 125 manufactured by Mitsubishi Heavy Industries, Ltd.
A / 75 MST type molding machine was used. Using this test piece, the total light transmittance was measured according to ASTM D1003. The measurement was performed using SZ-Σ80 type colorimeter manufactured by Nippon Denshoku Co., Ltd.

(3) Yellowness Index (YI) A rectangular test piece having a thickness of 3 mm and a side of 5 cm was prepared under the same injection molding conditions as in the above (2), and JIS K7103 was prepared.
YI was measured based on (Irradiation conditions: dominant wavelength 270
(nm, 120 W / cm ² , 5 minutes) The measurement was performed using a Nippon Denshoku Co., Ltd. SZ-Σ80 type colorimeter.

(4) Bending strength A 1/8 inch bending test piece was prepared under the same injection molding conditions as in (2) above. ASTM D for the obtained test piece
Bending strength was measured based on 790.

(5) Izod Impact Test An Izod impact test was conducted using the test piece obtained in the same manner as in (4) above. The measurement was performed based on ASTM D256.

(6) Deflection temperature under heat load (HDT) Deflection temperature under heat load (HDT) using the test piece of (4) above.
T) was measured. The measurement was performed based on ASTM D648. The load was 18.6 kg / cm ² .

(7) Glass transition temperature Differential thermal analyzer (manufactured by Perkin-Elmer, DSC
7 type) at a temperature rising rate of 20 ° C./min.

(8) Thermal aging treatment A test piece obtained in the same manner as in (4) above was subjected to 360 ° C. at 170 ° C.
The sample was treated in an air oven for a period of time and used for performance measurement after treatment.

(9) Wet heat aging treatment A test piece obtained in the same manner as in (4) above was treated at 80 ° C. and 95% R.
The treatment was performed under the condition of H for 360 hours, and the performance was measured after the treatment.

(10) Ultraviolet irradiation The thickness obtained in the same manner as in (2) above is 3 mm and 5 cm on a side.
UV irradiation on the rectangular test piece (irradiation condition: main wavelength 270
nm, 120 W / cm ² , 20 minutes) and subjected to YI measurement after the treatment.

Example 1 In a reaction vessel equipped with a stirrer, 6.0 mol of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane (TMbisA), sodium hydroxide 790
g, 10 g of sodium hydrosulfite, 11.2 g of tri-n-butylbenzylammonium chloride (TBBAC) as a phase transfer catalyst, and 0.12 mol of p-tert-butylphenol as a terminal stopper so that the total amount becomes 20 liters. Dissolved in water (aqueous phase). Separately, 3.0 mol of terephthalic acid chloride (TPC) and 3.0 mol of isophthalic acid chloride (IPC) were dissolved in dichloromethane so that the total amount was 10 liters (organic phase). The reaction vessel was kept at 20 ° C., and the organic phase was immediately added to the aqueous phase under strong stirring. After reacting for 4 hours under a nitrogen atmosphere, acetic acid was added to neutralize the aqueous phase and the stirring was stopped. The reaction solution rapidly separated into a water phase and a viscous organic phase containing a polymer. The aqueous phase was removed, the organic phase was washed with a large amount of water, and then dropped into methanol to isolate the polymer. The isolated polymer solid is further added to 80
After washing with hot water of ° C, vacuum drying was further performed at 120 ° C for 16 hours. Various performances were evaluated using the obtained polyarylate.

Example 2 Polyarylate was obtained in the same manner as in Example 1 except that 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) methane (TMbisF) was used as bisphenol.
Various performance evaluations were performed.

Example 3 Polyarylate was obtained in the same manner as in Example 1 except that 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane (TMbisZ) was used as bisphenol, and various performances were obtained. An evaluation was made.

Example 4 Polyarylate was obtained in the same manner as in Example 1 except that bis (3,5-dimethyl-4-hydroxyphenyl) ether (TMbis EH) was used as the bisphenol, and various performance evaluations were performed. ..

Example 5 Polyarylate was obtained in the same manner as in Example 1 except that bis (3,5-dimethyl-4-hydroxyphenyl) sulfone (TMbisS) was used as the bisphenol, and various performance evaluations were performed. ..

Example 6 As bisphenol, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -1-phenylethane (T
Polyarylate was obtained in the same manner as in Example 1 except that Mbis AP) was used, and various performance evaluations were performed.

Example 7 Polyarylate was obtained in the same manner as in Example 1 except that 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (TB bisA) was used as bisphenol, and various performances were obtained. An evaluation was made.

Example 8 Polyarylate was obtained in the same manner as in Example 1 except that 5 mol of terephthalic acid chloride and 1 mol of isophthalic acid chloride were used, and various performance evaluations were performed.

Example 9 Polyarylate was obtained in the same manner as in Example 1 except that 0 mol of terephthalic acid chloride and 6 mol of isophthalic acid chloride were used, and various performance evaluations were performed.

Example 10 Polyarylate was obtained in the same manner as in Example 1 except that tetra-n-butylammonium chloride (TBAC) was used as the phase transfer catalyst, and various performance evaluations were performed.

Example 11 Polyarylate was obtained in the same manner as in Example 1 except that tri-n-butylbenzylammonium hydrogen sulfate (TBBHS) was used as a phase transfer catalyst, and various performance evaluations were performed.

Example 12 Polyarylate was obtained in the same manner as in Example 1 except that tetra-n-butylphosphonium chloride (TBPC) was used as the phase transfer catalyst, and various performance evaluations were performed.

Example 13 Polyarylate was obtained in the same manner as in Example 1 except that 6 mol of terephthalic acid chloride and 0 mol of isophthalic acid chloride were used, and various performance evaluations were performed.

Comparative Example 1 Polyarylate was obtained in the same manner as in Example 1 except that 2,2-bis (4-hydroxyphenyl) propane (bisA) was used as bisphenol, and various performance evaluations were performed.

Comparative Example 2 Polyarylate was obtained in the same manner as in Example 1 except that trimethylbenzylammonium chloride (TMBAC) was used as the phase transfer catalyst, and various performance evaluations were performed.

Comparative Example 3 Polyarylate was obtained in the same manner as in Example 1 except that tetramethylammonium chloride (TMAC) was used as the phase transfer catalyst, and various performance evaluations were performed.

Comparative Example 4 Polyarylate was obtained in the same manner as in Example 1 except that tetraethylammonium chloride (TEAC) was used as the phase transfer catalyst, and various performance evaluations were performed.

Comparative Example 5 18-crown-6-ether (1
8C6E) was used and polyarylate was obtained in the same manner as in Example 1, and various performance evaluations were performed.

Comparative Example 6 Polyarylate was obtained in the same manner as in Example 1 except that 0.65 mol of P-tert-butylphenol was used as an end terminating agent, and various performances were evaluated.

Comparative Example 7 A polyarylate was obtained in the same manner as in Example 1 except that 0.01 mol of P-tert-butylphenol was used as a terminal stopper, and various performance evaluations were performed. The above measurement results are shown in Tables 1 to 5.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

[Table 4]

[0079]

[Table 5]

[0080]

Since the polyarylate of the present invention is transparent and has high heat resistance, it has excellent mechanical strength and dimensional stability, and its discoloration due to ultraviolet rays is substantially suppressed. Moreover, it exhibits extremely excellent heat aging resistance and wet heat aging resistance. Therefore, the polyarylate of the present invention can be effectively used as an engineering plastic in the fields of electric / electronics, automobiles, machines and the like. In particular, it is expected to find applications in automotive optical parts such as lamp covers and lenses, taking advantage of its transparency, heat resistance, suppression of discoloration due to ultraviolet rays, and heat and aging resistance. Further, the polyarylate having such excellent properties can be produced by an interfacial polymerization method by using a specific quaternary salt as a phase transfer catalyst.

Front page continued (72) Inventor Naomi Takai 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Ltd. Central Research Laboratory

Claims (2)

[Claims] 1. A polyarylate comprising a bisphenol residue represented by the formula [1] and a terephthalic acid and / or isophthalic acid residue, and satisfying the formulas [2] and [3]. [Chemical 1] 0.4 ≤ ηinh (A) ≤ 1.7 [2] 0.9 ≤ ηinh (B) / ηinh (A) [3] (In the formula [1], R _{1 to} R ₄ are methyl groups _,
It represents _an ethyl group or a halogen atom, which may be the same or different, and Y is selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, O, S, SO ₂ and CO. In equations [2] and [3], ηinh
(A) uses tetrachloroethane as a solvent and has a temperature of 2
It is a logarithmic viscosity obtained under the conditions of 5 ° C. and a concentration of 1 g / dl.
In the formula [3], ηinh (B) is a mixed solvent of tetrachloroethane / phenol = 40/60 (weight ratio) containing 0.01 mol / l of sodium acetate as a solvent, the temperature is 25 ° C., the concentration is 1 g / dl. It is the logarithmic viscosity obtained under the condition of. In addition, in ηinh (A) and ηinh (B),
The logarithmic viscosity is defined by the formula [4]. ηinh = ln ηr / C [4] where ln is the natural logarithm, ηr is the relative viscosity, and C is the concentration (g / dl). ) 2. To obtain a polyarylate by contacting an alkaline aqueous solution in which the bisphenol represented by the formula [1] is dissolved with a hydrophobic organic solvent solution in which an acid halide of terephthalic acid and / or isophthalic acid is dissolved. A method for producing polyarylate, which comprises using a quaternary salt represented by the formula [5] as a phase transfer catalyst. [Chemical 2] [Chemical 3] (However, in the formula [1], R _{1 to} R ₄ are methyl groups _,
It represents _an ethyl group or a halogen atom, which may be the same or different, and Y is selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, O, S, SO ₂ and CO. In the formula [5], R ₅ has 4 to 1 carbon atoms.
2 is a hydrocarbon group, Z is a nitrogen atom or a phosphorus atom, and X is a halogen atom or HSO ₄ . + And-indicate positive and negative charges, respectively. )