JPS59187022A - Improved aromatic polyester and its manufacture - Google Patents

Abstract

PURPOSE:To obtain titled polymer with high heat resistance and moldability, capable of affording molded product of high impact resistance, by the polycondensation, in a sepecific way, between an acid dichloride mixture, two kinds of dihydric phenols, and a specific monohydric phenol. CONSTITUTION:(A) an alkaline aqueous solution of two kinds of dihydric phenols of formula I (X is 1-10C alkylene, 5-15C cycloalkylene, etc.) and formula II(R1 and R2 are each 2-20C alkyl, allyl, etc.; p and q are each integer satisfying equation p+q=1-8; m and n are each 0 or 1), respectively, also with the molar ratio of the former to the latter being 95/5-5/95, and (B) an organic solvent solution incompatible with water, prepared by dissolving in the solvent (i) a mixture of terephthalic dichloride and isophthalic dichloride with the molar ratio of terephthalic acid to isophthalic acid being 9/1-2/8 and (ii) a monohydric phenol of formula III (R is 1-7C alkyl, alkenyl, etc.; r is 0-5) are added to an aqueous solution and/or said incompatible organic solvent solution of catalyst followed by carrying out an interfacial polycondensation, thus obtaining the objective polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to aromatic polyesters with improved quality and processes for their production.Aromatic polyester compounds have long been known. The first method for producing it is to mix interfacial beating water, aromatic cyclocarphonic acid cybaride dissolved in an organic solvent that does not dissolve in water, and bisphenols dissolved in an alkaline water bath (8). Special Public Service Showa 4O-1959)
The second method is the M-liquid method, which is a method in which aromatic dicarboxylic acid halides and bisphenols are reacted together in an organic solvent (Japanese Patent Publication No. 87-5599), and the third method is the method of reacting aromatic dicarboxylic acid halide and bisphenol together in an organic solvent (Japanese Patent Publication No. 87-5599), and the third method is the method of reacting aromatic dicarboxylic acid halide and bisphenol together in an organic solvent. (Special Publication No. 88-15247゜Special Publication No. 4)
Several methods are known, such as 8-28119) or a method using a phase transfer catalyst. Excellent qualities in? The aromatic polyester polymer consisting of terephthalic acid and 21-benzene phenols is an aromatic polyester polymer composed of terephthalic acid and 21-benzene phenols, which has a wide range of uses such as molded products, films, and fibers either as a single polymer or as a resin composition. It is known to have higher heat resistance (e.g. glass transition point) than those made of acid and inphthalic acid (Tele/Iso = 7/3 to 3/7) and divalent phenol/L/. There is. However, at the same time, when terephthalic acid is the main component (tere/iso = 1010 to 9/l) as the hydrochloric acid component that crystallizes, when two or more specific dihydric phenols are used in combination, the crystallinity becomes crystallized.
We have already proposed that it is possible to obtain a transparent molded body with a low degree of bioactivity and high heat resistance. However, the impact resistance, which is an important property for practical use as a molded body, is not necessarily sufficient. In addition, due to the low melt flowability, there were drawbacks such as the need for a non-electrolytic high degree of heat and pressure during extrusion or injection molding.

More specifically, the present invention solves the drawbacks listed in L by setting the molar ratio of terephthalic acid and inphthalic acid to 9/1 to 2/8, and using two or more types of bisphenols and a specific monophenol as constituent components. This invention relates to an aromatic polyester/V-vehicle composite that maintains high heat resistance and chemical resistance such as alkali resistance, has improved moldability, and has improved impact resistance of the resulting molded product. .

Furthermore, as a manufacturing method, monophenol-I dichloride, which is a terminal capping agent, is simultaneously added to a solution containing a catalyst and an alkaline aqueous solution of 211III phenols as an organic bath solution that is substantially incompatible with water. It is characterized by the fact that it is added in a specific manner.

Conventionally, in the production method of aromatic polyester polymers by interfacial disarmament method, monophenols and molecular regulators have been used. Although their use was known, they were all dissolved together with a catalyst in an alkaline aqueous solution of dihydric phenols.

However, with this method, when the dihydric phenol solution and the acid dichloride solution are charged into the reaction vessel at the same time, the reaction between the two is extremely fast, so a slight deviation in the molar rate ratio of the charged polymer molecules may occur. It affected the number and molecular weight distribution, and lacked combination reproducibility and stability.

According to the method of the present inventors, phenols that can be dissolved in an alkaline aqueous solution can also be used. Since monophenol is used after being dissolved together with acid dichloride, the molar ratio of monophenol acid dichloride is always kept constant during the preparation time, which not only exerts a stable molecular weight adjustment effect but also improves the molecular weight distribution. It has been found that narrow polymers are obtained and fc5 The acid component used in the present invention is a mixture of terephthalic acid dichloride and isophthalic acid dichloride in a molar ratio of 9/1 to 2/8.

Preferably, it is a 9/1 to 7/8 mixture.

The divalent pheno-tv component used in the present invention is represented by the following general formulas (I) and (B). However, (I)=9515 to 5/95 (molar ratio).

HO+X+OK (■) (wherein, L...
R2; 7 having 1 to 20111 carbon atoms /lz ki A/, allyl, afurkyl, aflecoxyl, allyloxyl and ant! A monovalent group selected from a realcoquine group, a substituted product thereof, a halogen, and a mixture thereof.

P, q: P 10 q = integer from 1 to 8, m, n; 0
In addition, when m=1, n~0 is shown. ) For convenience, the above (II) is a 21-piece phenol represented by the general formula (IV).

(In the formula, R, ~R6 are the same as ILl, 1't2,
, m are the same as above) Examples of such dihydric phenols (I) include 4.4-dihydroxydiphenyl and 4.4-dihydroxydipheny! Remethane, ■,■-Bis(4-hydroquinphenylacetate)ethane, 2,2-bis(4-hydroxyphenyl)propane, l,l-bis(4-hydroquinphenyl)cyclohexane, 4.4-/hydroxydiphenyl ether /
L', 4,4-dihydroxydiphenylthioether,
Examples include 4,4-dihydroxydiphenylsulfone and 4,4-dihydroquinediphenylrekatone.

In addition, specific examples of 21+lti phenol ■ include a,
a'.

5.5-tetramethyl-4,4-dihydroxydiphenyl, 8,8.5.5-tetraphenyl-4,4-dihydroxydiphenyl, bis(3,5-dimethyl-4-hydroxyphenylene/L/)methane , bis(8,5-diphenyl-4-hydroxyphenyl)methane, bis(8,5-
dichloro-4-hydroxyphenyl)methane, bis(R
3,5-dibromo-4-hydroxyphenyl)methane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(a,5-diphenyl-
4-hydroquinphenyl)propane, 2,2-bis(3
, 5-Diclofre4-hydroxyphenyl)propane, 2,2-bis(8,5-difurome-4-hydroxyphenyl)furopane, 1,■-bis(3,5-dimethyl-
4-hydroxyphenyl)-7chlorohexane, 1.1-
Bis(8,5-diphenyl-4-hydroxyphenyl)
-Cyclohexane, bis(8,5-dimethy-4-hydroxyphenyl)thlephon, bis(8,5-diphenyl-4-hydroxyphenyl)thlephone, bis(3-diphenyl-4-hydroxyphenyl)thlephon,
゜5-dimethyl-4-hydroxyphenyl)ether,
Bis(8,5-dimethyl-4-hydroxyphenyl)thioether, bis(3,5-diphenyl-4-hydroxyphenyl)ketone, 2,2-bis(8,5-dimethyl-4-hydroxyphenyl)-hexane Fluoropropane, 1. Examples include l-bis(3,5-dimethyl-4-hydroxyphenyl)-2,2,2-trichloroethane.

Other condensed polycyclic bisphenols such as dihydroquinaphthalene and dihydroxyanthracene; alizarin, phenolphthalein, and ph! Leorescein, naftophthalein, chimo! Bisphenolic pigments such as lephthalein, ollin, phenolsulfophthalein, dibromophenolsulfophthalein; 2,2-dihydroxy-
1,1-sinaphthyl 7 remethane, 4,4-dihydroxydinaphthyl-1゜■, 2,2-dihydroxysinaphthyl 1.1%l, 1-bis(4-hydroxynaphthyl)
-2,2,2-Trichloroethane, dinaphthyl compounds such as 2,2'-dihydroxysinaphthifurephenyl-methane, etc., and can also be used as part of bisphenols.

The monophenol used in the present invention is
It is expressed by the formula.

(R; anolekylene group having 1 to 7 carbon atoms, alkylene group, alkoxyl group, cyano group, phenyl group, nitro group,
halogen atom, r; integer of 0 to 5) Preferred specific examples are:
Phenol and cresol.

xylenol, ethyl leueno-7, i-7” lobbyv
Examples include phenol, t-butylphenol, i-butylphenol, hydroxystyrene, allylphenol, methoxyphenol, etquinphenol, cyanophenol, phenylphenol, nitrophenol, chlorofuthino-I, and bromophenol. These compounds are used in amounts of 0.5 to 10 molar based on the total dihydric phenol.

The method for producing aromatic polyester polymers of the present invention is an improved interfacial polycondensation method. In other words, a catalyst? The aqueous phase and/or the organic solvent substantially immiscible with water are stirred and cooled.

On the one hand, 211III phenols are dissolved in aqueous sodium hydroxide or potassium hydroxide solution, and on the other hand, acid dichlorides and monophenols are dissolved in water-insoluble organic agents, and each is cooled. While vigorously stirring the previous catalyst solution, add the latter two liquids to the solution so that bisphenol and acid dichloride are maintained in approximately equimolar amounts, and then add the terminal capping agent to the solution. Since the molar ratio of monophenol to acid dichloride is always maintained at a certain mole ratio during the preparation time, a stable molecular weight adjustment effect can be exerted. Fourth, for example, JP-A-56-57
As disclosed in No. 822, when this acid cyclolide solution is added to an aqueous solution containing an alkaline aqueous solution and a catalyst, the molecular weight distribution becomes extremely large (for example, the weight average molecular weight ttMw ,!: Expressed as the ratio of number average molecular weight Rv1n, Mw/M, 9)
As mentioned above, when two liquids are added to the catalyst solution at the same time, the molecular weight distribution becomes narrower (for example, ΔIw).
/Mn2), it has been found that very favorable polymers are obtained when molded.

As the catalyst used in the present invention, quaternary ammonium salts, pyridinium u, quaternary phosphonium salts, arsonium salts, etc. of 21 tll + 0.1-10 mol of phenol are used. For example, benzy7retrimethylammonium chloride, benzyltriethylammonium chloride, tetraethylammonium chloride, trioctylmethylammonium chloride, benzyltributylammonium chloride, N-laurylpyridinium chloride, tetrabutylphosphonium bromide, tetraethyloctadecylphosphonium bromide. , Te.

As the solvent used in the present invention, any solvent that is substantially incompatible with water can be used, but it is preferably a solvent for the polymer to be produced. Specifically, salt (hymethylene,
Lower halogens such as chloroform and ethylene dichloride
Examples include arsenic carbon (arsenic hydrogen; chlorobenzene, O-dichlorobenzene, etc.).

The solution concentration of acid dichloride is not particularly limited, but is 2 to 3.
Polymerization (4) of the present invention, in which a range of 0 weight range is preferable, can be carried out by a method known in the art, such as contacting a polymer solution with a non-solvent such as acetone or methanol to precipitate the polymer solution, which can be separated from the solvent using a bed. The polymer of the present invention can be prepared by concentrating the entire polymer solution and pulverizing it, or by bringing it into contact with hot water and distilling off the solvent Ik.
Reduced viscosity η /C in chloroform at 2°C (concentration 0.
821t'/dn) of 0.3 to 2.0dl/9, is the strength lower than 0.8 sufficient? If the melt viscosity is higher than 2.0, the melt viscosity is too high to be practical.

These polymers can be used in combination with stabilizers such as acid inhibitors and UV absorbers, lubricants, mold release agents, plasticizers, etc. :
, or can be colored with pigments, dyes, etc., or mixed with inorganic fillers. Alternatively, it may be used in conjunction with commonly known reinforcing materials such as glass fiber, inorganic silicate, silica, quartz, carbon fiber, asbestos, clay, etc. Also, vinyl polymers such as polystyrene, polyethylene, polypropylene, polymethyfurene methacrylate, etc.
Polycarbonate, Polyether Resulfone, Polysulfone, Boliete! It can also be used in combination with thermoplastic polymers such as Reimide and polyphenylene oxide, rubber, and thermo-i5J plastic elastomers.

As shown in the examples below, the polymer of the present invention has improved melt flowability and a single molded product while maintaining heat resistance and chemical resistance at the same level as the polymer containing terephthalic acid. impact strength has been significantly improved. Is this the polymer of the present invention which has great limitations from a practical standpoint? It can also be used for electrical insulation films, sheets, connectors, switch covers, etc., and can also be used for mechanical applications such as sliding parts, gears, etc. Alternatively, it may be a heat-resistant fiber.

Examples of the present invention are shown below, but the present invention is not limited thereto.

Example 1 Benzyltrimethyl-l-reammmonium chloride 4.1 was added as a catalyst to an 81 separable flask under N2 atmosphere FM.
8 f, 500 g of water7. Salt (500tttl
While stirring and cooling, add 5 g under N2 atmosphere.
2,2'-bis(4-hydroxyphenyl) in the flask
Gropan (bisphenol A) 221.90g 1 bis(
8,5-dimethyl-4-hydroxyphenyl)methane (
TM BisF) 124.57F, sodium thiosulfate2.
4f, 4N strength soda aqueous solution 96 (1+/ and water 16
60+++/! After adding 'Th' and stirring to dissolve the bisphenol, the mixture was cooled to 5°C.

On the other hand, dichlora terephthalate (F218.15y,
Isophthalic acid dichloride 91.81M'(tere/ia='l/8) and P-methoxyphenol 9.07F
I (5.5 mol of total bisphenol) and methylene chloride 2500 tnlk5 (l) were added to a flask, dissolved and cooled, and then the catalyst solution. While vigorously stirring, the bisphenol and acid were mixed together in a bottle 1. The dichloride was charged over a period of approximately 13 minutes so that equimolar amounts of dichloride were dripped out.

After 1 hour, a small amount of benzoyl chloride 8.87fk 14
f-Himethylene was bath-dissolved and added to the above polymerization reaction system. 2
After 0 minutes, stirring was stopped and the polymer solution and aqueous layer quickly separated. After decanting the aqueous layer, the polymer solution was neutralized with a dilute hydrochloric acid water bath. After washing with water 5 times, polyvinyl alcohol (ken system width 88.0, 4 width aqueous solution viscosity 43 cp)
The polymer solution was dispersed in water 31 containing f(250 PPm).The jacket was then heated to 42-43 °C.
When the temperature was raised to 28 t and methylene chloride was distilled off, the
00g? After distillation, the polymer was dispersed in water as mutually insoluble pearl-like particles with a particle size of about 1 mm. The polymer was isolated by coarse filtration, washed twice with water, and then dried.

η, p/c fd (concentration o, a 2
Q/dll) There was 0.6Of in chloroform at 82°C.

The yield was 94%. The result of molecular weight measurement by gel permeation chromatography is Mw 7Mn=2.
It was 0.

Implementation VAJ 2-4 Instead of p-methoxyphenol in Example 1, p-
T-butylphenol, 2.6-xylenol, and 0-phenylphenol/I/fc were used. The results are shown in Table 1.

Table 1 Recycling Comparative Example 1 The same procedure as in Example 1411 was carried out except that 7 monophenols and 21 monophenols were dissolved in an alkaline aqueous solution of phenol. The reduced viscosity η /C of the obtained polymer is 0
．． 64i2"C chlorophor I rem, 0.32 P y/al), kettv hermutation chroma I
“As a result of rough molecular it rMIJ determination, Mw/Mn
= 8.0 and the yield was 94%. Only products with a wide distribution of molecules could be obtained.

Comparison 1 Example 2 In Comparison 1 row 1, after all of the aqueous alkaline solutions of 21 and 7 phenols were put into the reaction vessel, the acid dichloride salt r himethylene? The same operation was carried out except for the addition of

The obtained polymer has a η /C of 1.0P (0.82 f/dl in 82'C chloroform)
, Mw/Mn=8.8 Comparative Example 3 In Comparative Example 1, prephthalic acid dichloride 804
, fM only kl14, and a pond using 4.6 mol qb of methoxyphenol (versus dihydric phenol) was operated in the same manner. The resulting polymer had a η/C of 0.63 IP (0.8297 c1g in chloroform at 32°C),
The one-run rate was 94 wins.

REFERENCE EXAMPLE The polymers of Example 1 and Comparative Example 3 were extruded at 330° C. in 11 hours, and then injection molded at 860° C.

Table 2 shows the measurement results of the obtained test piece.

Table 2 (a) Izotsu and Nottsuchi use samples (b)
J I 8 i% Tambell sample used (e) Heat distortion temperature under load 18.67 cu/ci (d) 8
20'0. 100 &/ci (lφ×lO) load As shown above, the polymer of the present invention has significantly improved impact value and melt flowability compared to the comparative example. However, the decrease in heat distortion temperature is small.

Next, the films made of each polymer were immersed in a 10-alcoholic soda water bath solution (70°C) for 60 hours, and the results are shown in Table 3.As a comparison, 211111 phenol was mixed with bispheno-7, and only A was mixed with Misaki Ebisu. A commercially available product (U-1
00 (manufactured by Unitika)] are also shown. As described above, the alkali resistance is superior to commercially available products and is not significantly different from Comparative Example 3.

Table 8

Claims (6)

[Claims] (1) Terephthalic acid and isophthalic acid (terephthalic acid/isophthalic acid = 9/l to 2/8 molar ratio) and a dihydric phenol represented by the following general formula (1) and 0D (however, (I)/ (II) = 5/95-9515 mo〃ratio)
and an aromatic polyester containing monophenols represented by the following general formula ID (0-X+H(I) (wherein, 15 cycloalkylene group or cycloalkylidene group, -O,-,, -S, -1-co-1-so2-1
R1, it2; alkyl having 1 to 20 carbon atoms, allyl,
Monovalent group selected from aralkyl, alkoxyl, alkoxyl and allyl alkoxynyl groups and their substituents, halogens and mixtures thereof, p, q; p+q = an integer of 1 to 8, m, n; 0 or 1, provided that m = l indicates n~0) (几; alkyl group having 1 to 7 carbon atoms, alkenyl group, alkoxyl group and hiscyano group, phenyl group, nitro group, halogen i, r; integer from o to 5) (2) The aromatic polyester according to claim 1, wherein the dihydric phenol is represented by the following general formula (in the formula, R, ~R6; Itl, same as R2, X, m
is the same as above) (3) The aromatic polyester according to claim 1 or 2, wherein the molar ratio of the terephthalic acid component and the isophthalic acid component is from 9/1 to 7/8. (4) Reduced viscosity (82'C in chloroform, concentration o, a
2g/dn) is 0.8 to 2.0d1. /9 The aromatic polyester according to any one of claims 1 to 3. (5) Water containing the catalyst being stirred and/or an organic bath agent in which the catalyst is substantially incompatible with water [general formula (1) and (
21111I phenol represented by a mountain (however, (I)
/ (U) -95/5 to 5/95 molar ratio) alkali aqueous solution, terephthalic acid dichloride and isophthalic acid dichloride (however, terephthalic acid/isophthalic acid = 9/l to 2/8) and the following. Monophenol represented by the general formula Tsukuda)? A method for producing an aromatic polyester comprising interfacial polycondensation with a solution dissolved in an organic solvent substantially incompatible with water. no-○YX-○ton (I) (in the formula, X, R
1, R2 are the same as above) (in the formula, 托 and r are the same as above) (6) Monophenols account for 0.0% of all dihydric phenols.
Special irF used in molar amounts of 5 to 10
Manufacturing method described in section.