JPS58215420A - Production of aromatic polyester - Google Patents

Abstract

PURPOSE:To produce a high-quality polyarylate in good productivity without fear of equipment corrosion, by employing conventional polyester copolymerization equipment as such and using inexpensive, readily available starting materials. CONSTITUTION:In the first stage, an inexpensive, readily available dicarboxylic acid dialkyl ester (e.g., methyl terephthalate) is transesterified with an inexpensive, readily available aliphatic carboxylic acid aryl ester (e.g., m-tolyl ester of a lower aliphatic carboxylic acid) in the presence of a transesterification catalyst comprising a compound containing tin or lead. In the second stage, the desired aromatic polyester is obtained by polycondensing the above produced aromatic dicarboxylic acid diaryl ester with an aromatic dihydroxy compound, e.g., 2,2- (4,4'-dihydroxydiphenyl)propane(bisphenol A).

Description

[Detailed description of the invention]

The present invention is directed to a method for activating aromatic polyester. More specifically, we will turn to a method for producing an aromatic polyester comprising an aromatic dicarboxylic acid component and a bisphenol component. Dark aromatic polyester (j:J, referred to as lower polyarylate) has excellent air insulation properties, abrasion resistance, high melting point, etc., and is used as a molding material 44. It is used as a film material. Conventionally, as a manufacturing method for such a Borea relay 1, a 4″1
1 (a number of proposals have been made 1), for example, the Special Public Interest Publication Act 1977-1.
959 V, the publication describes a so-called interfacial polymerization method in which an apricot group dicarbonyl chloride dissolved in an organic solvent incompatible with water and an alkali metal salt of bisphenol dissolved in water are mixed and reacted. Tetj+1 X
'4! Publication No. 37-5599 describes a solution polymerization method in which aromatic dicarboxylic acid chloride and bisphenol are reacted in an organic solvent, and also J, Polym, 5.
science, 2B (1958) P, 179~
184 contains aromatic dicarboxylic acid and bisphenol 1J-
Touch the vinegar ester from step 111. (A melt polymerization method in which diaryl ester of an aromatic dicarboxylic acid and a bisphenol carbonate are heated in the presence of However, each of the above-mentioned i% f' methods has drawbacks that impede industrialization.The method using aromatic dicarbonate chloride and bisphenols as raw materials has low polymerization production efficiency, and chlorine Impurities such as ions may be mixed into the polymer, causing a decrease in the polymer product 1'f, requiring complex processes such as polymer and organic solvent molecules, washing W, and consideration must also be given to waste water issues. The method using aromatic dicarboxylic acids and acetate esters of bisphenols has a high production efficiency, but at high temperatures 1. This is a fatal defect especially when using existing polyester polymerization equipment.Also, in the method using diaryl ester of aromatic dicarboxylic acid and bisphenol, the aromatic dicarboxylic acid used as raw material Since the diaryl ester of -y'J aromatic dicarboxylic acid is expensive, it is an important issue how to easily obtain the diaryl ester.Many proposals have been made regarding the synthesis method of the diaryl ester of -y'J aromatic dicarboxylic acid. Ori,, (S
Taking terephthalic acid as an example of an aromatic dicarboxylic acid, (a) reaction of terephthalic acid dichloride and phenol; (b) reaction of benzoic acid ester of terephthalic acid tophenol; (c) terephthalic acid Methods such as the direct esterification reaction of phenol and the reaction of button dimedyl terephthalate and rlI+acid phenyl are known. Among these processes, the most economical method is the direct synthesis method from aromatic dicarboxylic acids and phenol; In addition, the polymerization product must be used after being purified, so it is not satisfactory in terms of production efficiency. The present invention was discovered through intensive research.In other words, the object of the present invention is to be able to use existing polyester copolymerization equipment, and to
(i'If!!i f')It is an attempt to provide an M7=2 method for polyarylates that does not have the concern of ``It''. The present invention aims to provide a method for producing high-quality polyarylate with high production efficiency. The object of the present invention is, as described in the claims, to transesterify dialkyl esters of aromatic dicarboxylic acids and aryl esters of aliphatic carboxylic acids.
1.: Aromatic polyester polymerization in which the diaryl ester of an aromatic dicarboxylic acid obtained and an aromatic dihydroxy compound are condensed after carrying out an ester cross-reaction reaction in the presence of a compound containing lead or lead as a catalyst. This can be achieved through equipment and methods. In the misfire 1i-1, the first stage reaction was transesterification of dialkyl esters of aromatic dicarboxylic acids, which are inexpensive and easily available, and aryl esters of aliphatic carboxylic acids, and transesterification in the presence of a catalyst. k l1f
f1. However, as the aromatic dicarboxylic component cm, terephthalic acid, isophthalic acid/l/i', 8.2.
6-naphthalene dicarboxylic acid, 217-naphthalene dicarboxylic acid, chloroisophthalic acid, methyl terephthalic acid
, 414'-or 3,3'-diphenylsulfone dicarbone ffi, 4,4'-diphenyl dicarbone r1
Dialkyl esters such as 1'9, tetrahydroterephthalic acid, and l+2-ethylenediogysyphenyl-4,4'-dicarboxylic acid are mentioned, but are not limited to these. . As the sialicyl ester contained in the dialkyl ester of aromatic dicarboxylic acid, lower alkyl ester, propyl ester, etc. are used. These aromatic dicarbons r1! Sialyl ester of honey can be mixed with 2 parts (1 J!).Furthermore, it is also possible to mix and use argyl esters of aromatic oxycarbon 11I.Also, the characteristics of polyarylate may be impaired. - Aliphatic and alicyclic dicarboxylic acids such as adipic acid, sebacic acid, dodecamethylene dicarboxylic acid, azelaic acid, and cyclohegysanedicarboxylic acid, as well as ethyl glycol, propanediol, butanediol, and hexanediol. A mixture of aliphatic and alicyclic diols such as , cyclohexane dimetatool, etc. may be used. 1. Aryl esters of 1. Examples include esters of phenols in a broad sense such as fatty V-phenol, m-cresol, p-cresol, 0-cresol, 3,5-xylenol, and naphthol.Phenyl esters of lower aliphatic carboxylic acids and lower aliphatic carboxylic acids are preferred. The m-tolyl ester of acetic acid is used.
- The use of tolyl esters makes the process even more practical for the following reasons. In other words, the dim − ) of the aromatic dicarboxylic carbon f + ) obtained in the first stage reaction
The distillate that is produced in the gap where the J-lester is reacted with the aromatic dihydroxy compound in the second stage's synthesis process is m-cresol (freezing point: 11°C), and there is no concern that the distillation circuit will be clogged. It is a point. By the way, the residues j1 and 1j4 are phenol (freezing point 41τ
]), p-cresol (freezing point 35°C), 〇-cresol (freezing point 30τ゛), etc.
lliX',! i'li output is necessary. Of course, a mixture of aliphatic carboxylic acid esters may be used. As the aromatic dihydroxy compound used in the second 191ii1rσ)Iri condensation compound 1 of the present invention
Examples include compounds represented by the following general formula. H O - A r - 0 1 [
(I) are busy, A r +1 4'ft 11? Benzene ring, naphthalene ring, diphenyl J that can have a substituent
'14, X is -0-, 3-, -So, -+ -
Coo(OH,)no00-p19 is an alkylene group, and n is an integer of 2 to 6. R1, R1
+ Rs l R4 1 R1'', R,', R
'l. R+' is hydrogen j

[; (Selected from the group consisting of a child, a bar, a 1.tK child, a hydrocarbon group, an alkoxy group, and a nitro ring.) As a specific example of the compound represented by the formula (1), number 1 Examples include hydroquinone, chlorohydroquinone, methylhydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 2,6-hydroxynaphthalene tC, etc.Specific examples of compounds represented by the formula (TI) include:
(4.4'-dihydroxydiphenyl)methane, (4
．． 4'-dihydroxytriphenyl)methane, 2. 2
- (4,4'-dihydroxydiphenyl)propane (bisphenol A), 1,,1 - (4,4'
-dihydroxydiphenyl)cyclohexane, L 1
- (4.4'-dihydroxy-3, idimethyldiphenyl)cyclohexane, 2,2-(4.4'-dihydroxydiphenyl)pentane, 2,2 - (4.
4'-dihydroxydiphenyl)hexane, 2.2-
(4,4'-dihydroxy-3,3'-dimethyldiphenyl)propane, 2,2 (4,''-dihydroxydiphenyl)3-methylbutane, ?,2-(4,4
″-dihydroxy-3.5,3,′5,′-tetramethyldiphenyl)propane and 2.2-(4
．． 4'-dihydroxy-3. 5, 3: 5'-
(4I4'-dihydroxydiphenyl)ether, (4,4'-dihydroxydiphenyl)thionidel, (4,4'-dihydroxydiphenyl)sulfone and (4,4-dihydroxy-3.3') -dimethyldiphenylsulfone), ethylene-di-P-hydroxybenzoate, hydroquinone, chlorhydroquinone, 2, 2-(
Examples include 4,4'-dihydroxydiphenyl)propane (bisphenol A) and (4,4'-dihydroxydiphenyl)sulpon. Unexploded 11) 1 is +jtl The raw material marked in the molten state is anti-1;
1. However, the reaction is preferably carried out in an inert atmosphere. The feature of the present invention is that the 11th floor transesterification reaction
:, : Regarding the use of tin←semi-tin or lead-containing compounds as catalysts). By using this tin←10- or lead-containing compound as a catalyst, the first stage of transesterification can be carried out.
It not only smoothly promotes the reaction but also the polycondensation reaction between the aromatic dihydroxy compound and the aromatic dicarboxylic acid diaryl ester containing the aliphatic carbon 11-tired diaryl ester of h'jf)idl obtained by this transesterification reaction. , item 1. This forms a high polymerization degree polymer with excellent j7. These catalysts include gold with 1 (single substance, 1' with 4'M salts such as compounds, hydroxides, hydrochlorides, and stannic chloride, organic acid salts such as acetic acid and stearic acid) -1 , complex 98 salts, alcoholades, phenolates, alkyl compounds, and other modified tin compounds are used, and modified tin compounds represented by the following general formula are used. jl, II: A oxide, monobutyltin monoaji I, monobutyl multi-monobutyrate, T: 7-butylene monopropylate, monobutyl mono-sub-cutylate, monobutyltin ethylene glycol
1., monomethyltin laurate, mozupdelf easy slurry 1., monooctyl 6, easy oxide, moabutyltin triacetate, monobutyl anchor tri-2-ethylhenyl 1-sa*-to, methylphenyl:QA Agilide,
Dibutyl oxide, didodecyl: lW + oxidide, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dioctylate, dibutyltin distearate, dibutyltin dibutyrate, dibutyltin dibropyre-1, dibutyldibutylthioglycol, Dibutyl (tin dimalleide I, dibutyl ethylene chloride I', syl'A ctyltin bis(in-octyl thioglycolic acid ester), sea n-octyl tin malei I, di-n-octyl tin laurate, di-n- Octyl maleate polymer, di-n-octyl tin maleate base, diphenyl dilaurate, tributyl tin maleate, tributyl tin fumarate, tributyl; 1
Oleate, tributyltin sulfamate, tributyl acetate, tributyltin phthalate, triisobutyl acetate, dibutyltin dilaurate, monooctyltin trichloride, dibutyltin dichloride, monoethyl, I"4) Lychloride, tributyl also easily fluoride, tributyl Monobutyltin sulfide, dibutyltin sulfide trimer, di-n-octyl mercaptoacetate, S'-bis(in-octylmercaptoacetate), diacetoxytetrabutyldistannoxane, diacetoxytetrabutyldistannoxane, tri- Examples include phenyltin hydroxide, triethyl anchor hydroxide, and tetraethyl.These various catalysts may be used alone or in combination with 2N (or more).Transesterification/lli /Ijl addition 1t1 is 0005 to 1.0% by weight, preferably 0.01 to ('1.5'ili ii( %. Of course, a known transesterification catalyst may be used in combination with the resistant medium described in 1. As such a catalyst, f, t, I
'z: i Harikotsu 13, manganese, magnesium, calcium, cobalt, titanium, 71k lead, Si/l/
:1Nium and other compounds are listed. Examples of these compounds include metal oxides such as lithium hydride, magnesium oxide, 111i oxide, cobalt oxide,
Examples include lower aliphatic carboxylates such as lead acetate + li lead acid, calcium manganate acetate, tetrabutyl titanate, and tetrabutyl zirconate. The amount of the aryl ester of the aliphatic carbon used in the first stage transesterification reaction 5 is 2 to 1 mole of the dialkyl ester of the aromatic dicarboxylic acid.
~10 moles are preferred, and 2 to 4 moles are particularly preferred. If the aryl ester of the aliphatic carboxylic acid is used in the first step, the transesterification reaction will not be completed. It gets bigger and I don't like it. In order for the transesterification reaction to proceed smoothly, it is desirable to carry out the reaction without distilling off the by-produced alkyl ester of aliphatic carboxylic acid from the system. After the distillation to the outside is completed and the first step of the reaction is completed, the mixture of the diaryl ester of the aromatic dicarboxylic acid and the aryl ester of the aliphatic carboxylic acid of 11. The reaction proceeds to a two-step reaction. In this step, hl of the aryl ester of aliphatic carboxylic acid is replaced with aromatic dicarbonate f'r.
It is preferable that the amount of the diaryl ester is within a certain range of 315, and if the ratio of both is in the range of 1 to 4 moles, the reaction can proceed directly to step 202. When there is an excess of aliphatic carboxylic acid aryl ester exceeding this range, it is desirable to distill it off until it reaches this range and then proceed to the second stage reaction. The amount of aryl ester of aliphatic carboxylic acid exceeds 4 times the amount of aromatic dicarboxylic acid ester by mole: LI, G4, and the degree of polycondensation after being subjected to the second stage reaction. 1+i,, an undesirable side reaction occurs,
Polymer color: vrh is 1. jl, j. In the transesterification reaction of the present invention, equipment 1, such as acetic acid,
Since it does not produce anything that corrodes 1', it can be used in a normal polyester transesterification reactor (JtJ).The reaction temperature for the transesterification is about 160~
300 r: is preferable, and the reaction pressure may be any pressure, but is usually carried out at normal pressure. Next, in the In condensation reaction step of 2nd jp,; The 'l' of the present invention is that the polycondensation reaction between the diaryl ester of the aromatic dicarboxylic tP and the aromatic dididroxy compound can be carried out without Fpl+ medium! It's been a long time. In other words, r'fi 11-<, a compound containing tin or a ship used in the reaction of 2, or a heavy compound that is the reaction of the second step of the first step, 1.11-1 is also effective in J11. Therefore, the reaction in the 21st bar 2 proceeds smoothly even without adding a new catalyst. Of course, a known polymerization catalyst may also be added in order to make the reaction proceed more smoothly. Such catalysts include, for example, lithium, sodium, potassium, calcium, magnesium, zinc, manganese, cobalt, titanium, tin, copper, lead, antimony, germanium nanometals and their compounds (for example, oxides, hydrides, hydroxides, etc.). substances, halides, alcoholados,
Phenolate, organic 1 mist salt, none, torrate, complex salt, double salt)
For example, two or more buildings may be used in combination fIJ,'. The amount of addition L1 of polymerization F and all medium is 0.005 to 1.0% by weight, preferably 0.01 to 0.3% by weight, based on the weight of the final polymer. The amount of the aromatic dihydroxy compound used as a reaction raw material in the polycondensation step is basically preferably equimolar to the diaryl ester of the aromatic dicarboxylic acid, but some increase or decrease is acceptable. For the polycondensation degree + IC of the present invention, a conventional polyester polymerization apparatus I/tt can be used;
*There is no concern about li. Polycondensation reaction 1'llA lj'
j:ha] 8o to 4o. °C, reaction pressure 4:1: (The pressure may be set to 61 °C as the polycondensation reaction progresses, but it is preferable to set it to 61 °C. zl can be converted into an aryl ester of an aliphatic carboxylic acid with water-saving acetic acid and an aliphatic carboxylic acid in another step, for example, and reused as the reaction FX PI in the step]. In the process, the TRT polymer can be further made into a high-to-medium polymer by solid-phase polymerization reaction, if necessary.In the present invention, various additives such as antioxidants (hindered phenol stabilizers, amine stabilizers, etc.) are used. , ultraviolet 11
ii + i absorbent, representative Salel M (Q
, 11N +1. l”ill, rat l'l, what f
Mole 1. It is also possible to add reinforcing agents such as ll, if lath R, various fillers, and the like. 5Ba polyethylene terephthalate due to unexploded 1111,
Existing polyesters (7) such as polybutylene door lids 1) to 1) can be used in heavy use, and inexpensive raw materials that are easy to handle can be used as starting materials. This is advantageous in terms of the cost per original.Also, it has excellent bioactivity and allows high-quality polyarylates to be obtained.
Ill do it. The logarithmic viscosity (ηjnh) in the present invention is measured at 25° C. at a concentration of 0.5 g of polymer in 0-chlorophenol]-0Ome. V) Vi'i i (+ is defined by the following formula (however, in the formula, ηrel is the relative viscosity + h, and c is the concentration.) In addition, in this example, 3 + j Akishit h1u is a representative of the aryl ester of aliphatic carbon □ Vinegar r1 used as an example
The m-cresol ester of □φ (vinegar r'lQm-tolyl) was isolated by the following method. In an aqueous solution of 180 g of sodium hydroxide and 200 g of water, m
- Add 324 g of cresol, add 1500 g of ice, and cool. Furthermore, 387 g of acid anhydride r'm was added, and after stirring well, the mixture was left to stand for one hour. The organic layer is separated from the water and washed with an aqueous solution of IJum (hydroxide), then washed with water and dried over calcium chloride. 9
0 ++ 1 l It was steamed under reduced pressure 1:360 g of m-l-lyl acetate (141°C fraction) as a product. Example J 58.3 g (0.3 mol) of dimethyl terephthalate, 523.3 g (0.3 mol) of dimethyl isophthalate, 216.3 g (1.44 mol) of m-tolyl, and 216.3 g (1.44 mol) of m-tolyl, and monophthyltin 0.62 g of acetic acid was added, and the temperature was gradually raised from 160°C to 250°C while distilling methyl acetate, and the reaction was continued until the distillation of methyl acetate was completed.Then, the reaction mixture (D-m-tolyl terephthalate, di-m-tolyl isophthalate, m-tolyl acetate 0.5:0.5:0.3 mol each)
2.2-(4,4'-dihydrochloride) was charged into a polycondensation reactor, heated for 1 hour, heated to 250°C, then the pressure was reduced throughout the system, and after 30 minutes the absolute The pressure was set to 0.5 mHg or less. After heating at 250°C for an hour, the temperature was raised to 290°C, and the polycondensation reaction was continued for 2 hours. After the reaction was completed, the polymer was immersed in water and rapidly cooled. ηh
A polyarylate polymer having a melting point of 250° C. and a melting point of 250° C. was obtained. The color tone of the polymer was pale yellow and transparent. Example 2 245.2 g (1.8%/l) of dimethyl isophthalate vinegar (rg phenyl) was charged into a three-layer flask equipped with a stirrer and a rectification column, and 0.62 g of dibutyltin oxide was added.
The temperature was gradually raised from 60°C to 250°C while distilling methyl, and the reaction was continued until the distillation of methyl acetate was completed. Then, the reaction mixture (1 mol of diphenyl isophthalate to 08 phenyl vinegar)
) was charged into the polycondensation reactor, and (4,4″
-dihydroxydiphenyl)sulfone 150 g (0
, 6 moles) and 0.23 g of antimony trioxide were added and heated at 200°C for 1 hour in a nitrogen atmosphere, then the temperature was raised to 250°C, and the pressure inside the system was gradually reduced until the absolute pressure reached 0 after 30 minutes. .5, Hg or less. After heating at 250° C. for 1 hour, the temperature was raised to 290° C. and the polycondensation reaction was continued for 2 hours. After the reaction is completed, the polymer is immersed in water to be rapidly cooled, and η1. n
h 0.57, f^11 (point) A pale yellow transparent polyarylate polymer at 250°C was prepared. Example 3 Dimethyl terephthalate was added to a three-hole flask equipped with a PdP machine and a distillation column. 1-163.0g (0.84 mol), dimethyl isophthalate 69.ag (o, a 6 mol) and Nibinishi acid m-tolyl 7 mixed qf4 were charged, and 1'ilN lead (hydrated salt) 08g was added. The temperature was gradually raised from 160'T" to 265 Y: while distilling methyl acetate, and the reaction was continued until the distillation of methyl acetate was completed. After the reaction was completed. The reaction mixture was charged into a polycondensation reactor, and the volume was gradually reduced to remove excess m-tolyl acetate.The system was vortexed at a ratio of 1:11 to 1:1 to 1:1. -Tolyl terephthalate/isophthalate ratio is 01:]
It was a mole. After returning the reaction system to normal pressure with nitrogen gas, 273.6 g of bisphenol A (],, 2
Add 2 moles of antimony oxide and 0.5 g of antimony oxide, heat for 1 hour at 200°C under nitrogen atmosphere, and then heat to 250°C.
The temperature was raised to 1, and the pressure inside the system was gradually reduced to reach an absolute pressure of 5 mHg or less after 30 minutes. In this state, heat for 1 hour at 4°C, raise the temperature to 290°C, and carry out the polycondensation reaction for 2 hours.
I went. After the reaction is completed, the polymer is rapidly cooled in water, and η1nh=058
A pale yellow transparent polyarylate polymer with a melting point of 265° C. was obtained. Implementation θS4 In Example 13'l11, dimethyl terephthalate (D
MT), dimethyl isophthalate (DMT) and vinegar g
The molar ratio of the mixture of IJL was set as shown in Table 1, and monobutyltin triacetate was used as the transesterification reaction catalyst. The results are shown in Table 1. The above experiment i1a 1 ?j was completed and the transesterification reaction was completed at 4" θ), and the experiment was stopped at Il, 1 . ^14 acid m- at the start
) The ratio of lyl/diallyl tere(iso)phthalate is 1lllll hinoki in gas chromatograph 7! did. Patent issued by KiCj Co., Ltd. (24 completed)

Claims (1)

[Claims] (1) "Jt dialkyl ester of aromatic dicarboxylic acid, aryl ester of aliphatic carboxylic acid, transesterification reaction in the presence of a compound containing tin or lead as a catalyst, and the resulting aroma I (A method for producing an aromatic polyester, characterized by polycondensing a diaryl ester of a dicarboxylic acid and an aromatic dihydroxy compound. (2) In claim 1, the aryl ester of an aliphatic carbon N is a lower aliphatic carboxylic acid m-)
Made of aromatic polyester, which is characterized by being a relay ester. k method.