JPS6284035A - Triphenol compound - Google Patents

Abstract

NEW MATERIAL:A triphenol compound of formula I (R1-R6 are H, halogen, 1-5C alkyl or 1-5C alkoxy). EXAMPLE:1-[alpha-Methyl-alpha-(4'-hydroxyphenyl)ethyl]-4-[alpha',alpha '-bis(4''-hydroxyphenyl) ethyl]benzene. USE:Useful as a branching agent of polycarbonate. A branched polycarbonate having excellent moldability and transparency can be produced by reacting a dihydric phenol such as bisphenol A with a carbonic acid derivative such as phosgene in the presence of the titled compound of formula I in the reaction system. PREPARATION:The compound of formula I can be produced according to the reaction formula by reacting isopropenylacetophenone with a phenolic compound in the presence of a catalyst such as hydrochloric acid at 40-80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to novel triphenolic compounds, and more particularly to 17 triphenolic compounds useful as branching agents for polycarbonates.

Technical background of the invention and its problems Polycarbonate is a synthetic resin widely used industrially, and is usually a synthetic resin made of 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as bisphenol A). It is produced by the reaction of dihydric phenols such as phenols with carbon B conductors such as phosgene.

By the way, polycarbonate made from bisphenol A has excellent properties such as excellent impact resistance, low moisture absorption, heat stability, and excellent weather resistance, but in the molten state it behaves as a Newtonian fluid. Therefore, the stress required to obtain a predetermined extrusion m is large, and the melt elasticity or melt strength, which is closely related to this, is low, making it difficult to produce large-sized hollow molded bodies. The problem was inevitable.

In order to solve these problems, polycarbonate l
Phloroglucin, 4,6-cymethyl-2.
4.6-tri(4°-hydroxyphenyl)-hebutene-2,4,6-dimethyl-2.4.6-tri(4-hydroxyphenyl)-hebutane or 2,6-bis(2
A trihydric phenol such as ゛-hydroxy-5゛-methylbenzyl)-4-methylphenol is allowed to coexist with a dihydric phenol such as bisphenol Δ in an amount of 0.01 mol% or more, and the resulting polycarbonate is branched. A method for doing this is described in Japanese Patent Publication No. 17.149 of 1972 and Japanese Patent Application No. 2 of 1973.
It has been proposed in No. 551 or Special Publication No. 16.277 of 1972.

The thermoplastic branched polycarbonate obtained by coexisting these trihydric phenols at the time of A production certainly exhibits non-Newtonian flow characteristics in the d melt state, and the melt has improved deformation strength to some extent, but usually Bisphenol A
Compared to polycarbonate synthesized from polycarbonate, there were several problems such as inferior hue and transparency of the molded product, and the deformation strength of the melt was not necessarily sufficiently improved.

As a result of intensive studies to solve the problems associated with the conventional technology as described above, the inventors of the present invention have developed a method for producing polycarbonate by reacting a dihydric phenol such as bisphenol A with a carbonic acid derivative such as phosgene. It has been found that the above problems can be solved at once by coexisting a novel triphenol compound having a specific structure.

Purpose of the Invention The present invention provides a method for producing polycarbonate by reacting a dihydric phenol such as bisphenol A with a carbon H conductor such as phosgene, and by coexisting in the reaction system, excellent moldability and transparency can be achieved. The object of the present invention is to provide a novel triphenol compound from which polycarbonate-1 can be obtained.

Summary of the Invention The novel triphenol compound according to the present invention is represented by the general formula N].

H3c -C-CH3 (in the formula, R1, R2, R3, R4, R5, and R6 may be the same or different or 1, and each represents hydrogen, halogen, a C1-C5 alkyl group, or C1
~C5 alkoxy toad. ) By coexisting the novel triphenol compound according to the present invention in the reaction system when producing polycarbonate by reacting a dihydric phenol such as bisphenol A with a carbonic acid derivative such as phosgene, moldability and transparency can be improved. A polycarbonate is obtained.

DETAILED DESCRIPTION OF THE INVENTION The novel triphenol compound according to the present invention is represented by the general formula [I].

(In the formula, R1, R2, R3, R4, R5 and R6 may be the same or different, and each represents hydrogen, halogen, C1-C5 alkyl group, or 01
~C5 alkoxy group. ) Specific examples of the triphenol compound represented by the above general formula [I] include the following compounds.

1-[α-Memethyα-(4-hydroxyphenyl)ethyl] -4-[α′,α′-bis(4”-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(4° -hydroxyphenyl)
ethyl]-3-[α′,α′-bis(4°′-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3°,5′-dimethyl-4°
-hydroxyphenyl)ethyl] -4-[α′, α′
- screw (3″, 5°.

-dimethyl-4"°-hydroxyphenyl)ethylcobenzene, 1-[α-methyl-α-(3°-methyl-4-hydroxyphenyl)ethyl] -4-[α', α'-bis(3
°゛-Methyl-4""-hydroxyphenyl)ethyl]
benzene.

The triphenol compound represented by the general formula [I] is produced by reacting isopropenylacetophenone and a phenol according to the following formula.

(In the formula, each R may be the same or different and is hydrogen, halogen, C1-C5 alkyl group, or C1-C5 alkoxy group.) The isopropenylacetophenone used in this reaction is , m-isopropenylacetophenone or p-
Examples include isopropenylacetonephenone or mixtures thereof.

Phenols used in this reaction include phenol, 0-cresol, m-cresol, P-cresol, 2,6-xylenol, 0-methoxyphenol, m-methoxyphenol, P-methoxyphenol, or mixtures thereof. can be mentioned. In addition, when a mixture of the above phenols is used as the phenol,
Among the triphenol compounds represented by the general formula [I], compounds in which all R's are different are also represented by 1q.

The above reaction between isopropenyl 7cetophenone and phenols can be carried out by, for example, mixing the phenol compound in excess of the chemical amount with a protonic acid such as hydrochloric acid as a catalyst, and dropping isopropenyl acetophenone into the resulting mixture. This can be done by doing. At this time, methyl mercaptan or mercaptoacetic acid may be added to the reaction system as a cocatalyst, if necessary.

This synthesis reaction is usually carried out at a humidity range of 40 to 80°C and under normal pressure or increased pressure.

In the above general formula, a triphenol compound in which R is a halogen can be produced using a phenol whose nucleus is substituted with a halogen as the base 11, and in some cases, a synthesized triphenol can also be produced using a phenol substituted with a halogen as base 11. V can also be produced by halogenating triphenols.

In order to separate and purify the triphenol compound, which is the target compound, from the reaction mixture left after the reaction, general methods such as extraction, concentration, and crystallization can be used.

The structure of the obtained 1-rifanol compound is determined by mass analysis, proton nuclear magnetic resonance, melting point, etc.

1-Usefulness of rifonicol-based compounds The triphenol-based compound according to the present invention can be used to produce polycarbonate by reacting a dihydric phenol such as bisphenol A with a carbonic acid derivative such as phosgene.
When added to the reaction system, the branched polycarbonate
This branched polycarbonate has an intrinsic viscosity ([η]) of 0.4 dN/g at 25°C in methylene chloride.
As above, it has excellent moldability and transparency.

The triphenol compound according to the present invention is added to the reaction system for polycarbonate production by the reaction of dihydric phenol and phosgene in an amount of 0.01 to 10 mol% based on dihydric phenol.
It is preferably used at a concentration of 0.01 to 3.0 mol %.

If the amount of triphenol-based compounds is less than 0.01 mole percent relative to dihydric phenol, the resulting polycarbonate resin will not exhibit the desired melt properties;
If it exceeds 1%, gelation occurs during resin production or resin molding processing, which is not preferable.

Dihydric phenols used in the production of polycarbonate include bisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 1,1-bis(4°-hydroxyphenyl)cyclohexane. , bis(4゛-hydroxyphenyl〉-diphenylmethane, 1.1-bis(4°-hydroxyphenyl)-1-phenylethane, 2.2-bis(3°, 5゛-dimethyl-4°-hydroxyphenyl)
Propane, bis(4-hydroxyphenyl)ether,
4,4°-dihydroxydiphenyl, 3,3°, 5.5
゛-Tetramethyl-4,4-dihydroxydiphenyl,
Bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)
-hydroxyphenyl) sulfoxide, hydroquinone, resorcinol or mixtures thereof. Among these, bisphenol 8 is particularly preferred.

Carbonyl halides such as phosgene, carbonic acid diaryl esters, and the like are used as carbonic acid derivatives to be reacted with dihydric phenols.

To produce a thermoplastic branched polycarbonate from a dihydric phenol such as bisphenol, a carbonic acid derivative such as phosgene, and the triphenol compound according to the present invention, 15% of carbon such as dihydric phenol, phosgene, etc.-conductor is used. A conventionally known method can be used, except that a triphenol-based compound is present in the reaction system. -Example (
Shown as a) to (C).

(a> A method in which dihydric phenol and the triphenol compound according to the present invention are dissolved in an organic base such as pyridine or triethylamine, and a carbonic acid derivative such as phosgene is blown into the solution to cause a reaction.

(b) j: In the presence of an inert solvent such as methylene chloride, chlorobenzene, or toluene and an acid acceptor such as pyridine, dihydric phenol and the triphenol compound according to the present invention, and a carbonic acid derivative such as phosgene. How to react.

(C) In the presence of an inert solvent such as methylene chloride, ethylene dichloride, or chlorobenzene, usually in the coexistence of a phase transfer catalyst such as a tertiary amine or a quaternary ammonium salt, the dihydric phenol and the present invention are combined. In an aqueous solution or slurry of an alkali metal salt of a triphenol compound,
A method in which a carbonic acid derivative such as phosgene is injected into the reaction.

In either method, the triphenol compound of the present invention can be added together with the dihydric phenol from the start of the polymerization reaction. In either method, 1 to 1% of dihydric phenol is used as a molecular weight regulator.
0 mol% monohydric phenol, e.g. phenol, P-
Tershaabdelphenol, P-cumylphenol, etc. may be added.

Another N-soaking method for polycarbonate includes a method in which a dihydric phenol and the triphenol compound according to the present invention are reacted with a carbonic acid diaryl ester in the presence of a transesterification catalyst such as a metal oxide. .

The branched polycarbonate produced using the triphenol compound according to the present invention is thermoplastic and can be easily processed from a melt into a molded product of a desired shape by ordinary molding methods such as extrusion molding and blow molding. can. It is also soluble in specific organic solvents, and can be processed into molded products such as films from this solution.

The branched polycarbonate produced using the triphenol compound according to the present invention can also be used in combination with other polycarbonates or thermoplastic polyesters. Furthermore, if necessary, it can be used in combination with a filler such as glass fiber, a stabilizer, a flame retardant, a foaming agent, or the like.

Effects of the Invention According to the present invention, a novel triphenol compound is obtained, and this triphenol compound is allowed to coexist in a reaction system for producing polycarbonate by reacting a dihydric phenol such as bisphenol A with a carbonic acid derivative such as phosgene. As a result, the iq polycarbonate becomes branched and has excellent moldability and transparency.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 1 from leaf isopropenylacetophenone and phenol
-[α-Methyl-α-(4-hydroxyphenyl)ethyl]-4-[α゛,α′-,α′-bishydroxyphenyl)ethyl]H′ of benzene? 5 (1) @ In a 500 ml round bottom flask equipped with a stirring bell, dropping funnel, thermometer, reflux condenser and gas blowing tube, add 194 g of phenol and 1
After charging 4 q of 5% methyl mercaptan soda aqueous solution and humidifying at 40'C, dry hydrogen chloride gas was blown into the system through a gas supply pipe while stirring until the system was saturated.

Then, a mixture of 32 g of p-impropenylacetophenone and 32 CJ of phenol was added dropwise from the dropping funnel over 2 hours. During this time, the reaction temperature was maintained at 40-43°C.
Blowing of dry hydrogen chloride gas also continued. After completion of the dropwise addition, stirring was continued for approximately 8 hours at a temperature of 40 to 43° C. while blowing dry hydrogen chloride gas little by little.

(2) After leaving the obtained reaction mixture at room temperature overnight,
1200C of toluene] and 600C1 of a 3% by weight aqueous sodium hydrogen carbonate solution were added, stirred at 80'C for 30 minutes, and the whole was cooled to room temperature. The precipitated crystals were separated using a centrifuge and washed with toluene and then with H2O. Roughly, the crystals were dissolved in a heated mixed solvent of methyl isobutyl ketone and toluene, washed with water, and then cooled to precipitate crystals again. When this crystal was separated, the melting point was 222.
70.80 white crystals at ~225°C were obtained. Based on the results of mass spectrometry and proton nuclear magnetic resonance, this crystal has the following structure: 1-[α-methyl-α-(4-hydroxyphenyl)ethyl]-4-[α′,α′-bis(4
It was confirmed that it was ゛-hydroxyphenyl)ethyl]benzene.

δ=6.6-7.2゜16H,m Example 2 1-[α-methyl-α-(4-hydroxyphenyl) from m-isopropenylacetophenone and phenol
Production of [ethyl]-3-[α゛, α′-, α′-bishydroxyphenyl)-ethyl]benzene (1) Example except that m-isopropenylacetonephenone was used instead of p-isopropenylacetophenone The reaction was carried out in the same manner as described in 1(1).

(2) The resulting reaction mixture was dissolved in 640 g of toluene, washed with a 3% by weight aqueous NaHC3 solution and then with a diluted aqueous solution, and then toluene and unreacted phenol were distilled off under reduced pressure. The resulting residue was recrystallized from toluene to obtain 69.3 g of white crystals. This crystal has a melting point of 18
7 to 189°C, and mass spectrometry and proton nuclear magnetic resonance results show that 1-(α-methyl-α-
(4-hydroxyphenyl)ethyl] -3-[α゛,
It was confirmed that it was α゛-,α゛-bisciphenyl)ethyl]benzene.

(Margin below) δ=6.6-7.2°16H,m Example 3 From p-impropenylacetophenone and 2,6-xylenol, 1-[α-methyl-α-(3',5°-dimethyl -4゛-Hydroxyphenyl)ethyl] -4-[
Production of α',α'-bis(3°Z511-dimethyl-4"-hydroxyphenyl)ethyl-1benzene (1) Into the reactor shown in Example 1 (1), 228 g of 2,6-xylenol, 15 5.89 wt% methyl mercaptan soda aqueous solution and 56 g of concentrated hydrochloric acid were charged.
Warmed to ℃. ``While stirring and blowing dry hydrogen chloride gas through the gas blowing tube, a mixture of 32 CJ of p-isopropenylacetophenone and 64 Cl of 2,6-xylenol was added dropwise from the dropping funnel over 2 hours. During this time, the reaction temperature was maintained at 46-48°C. After the dropwise addition was completed, the mixture was stirred at 46 to 48° C. for 70 hours while blowing dry hydrogen chloride gas to complete the reaction.

(2) Add toluene 400Q to the obtained reaction mixture,
After heating to 80'C and removing the separated aqueous layer, the oil layer was washed with a 3% aqueous Nal-1cO3 solution and then with a dilute aqueous phosphoric acid solution. After toluene and unreacted 2,6-xylenol were distilled off from the oil layer under reduced pressure, the residue was recrystallized twice from toluene to obtain white crystals 67.1Q. This crystal has a melting point of 191-194°C, and has the following structure according to the results of mass spectrometry and proton nuclear magnetic resonance.
-Methyl-α-(3°, 5-dimethyl-4-hydroxyphenyl)ethyl]-4-[α′, α′-bis(3″,
It was confirmed to be 5"-dimethyl-4'°-hydroxyphenyl)ethyl]benzene.

HFD-MS (U) 10H,m Example 4 1-[α-Methyl-α-(3゛-methyl-4°-hydroxyphenyl)ethyl]-4 from isopropenylacetophenone and O-cresol Production of α′,a′-bis(3°゛-methyl-4″-hydroxyphenyl)ethyl]benzene.

(1) The reaction was carried out in the same manner as described in Example 1 (1) except that O-cresol 227q was used instead of phenol.

(2) The obtained reaction mixture was dissolved in toluene (500C) and washed with a 3% by weight aqueous NaHCO3 solution and then with a dilute aqueous phosphoric acid solution, and then toluene and unreacted O-cresol were distilled off under reduced pressure.

The resulting residue was recrystallized from decane to give a pale yellow solid 69.
8g was obtained. This solid has a melting point of 87 to 91°C, and has the structure of 1-[α-methyl-α-(3°-methyl-4-
The product was confirmed to be hydroxyphenyl)ethyl]-4-[α', α゛-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene.

HFD-M3 C δ=6.5-7.3°13H, m Reference Example 1 Production of thermoplastic branched polycarbonate using the triphenol compound obtained in Example 1 (1) Bisphenol A228q (1 mol) , 4.9 g of turmeric butylphenol, 1-[α-methyl-α-(4′-hydroxyphenyl)ethyl]-4-[ obtained in Example 1
α゛,α゛-,α゛-bishydroxyphenyl)ethyl]benzene 4.24Q (0.01 mol), 9ul% caustic soda aqueous solution 1375q, 1, and methylene chloride 230
0 g of the mixture was bubbled with 121 g of Bosgun over a period of 2 hours while stirring at 20-25° C. under N2 atmosphere.

After the injection of Bosgun was completed, 0.49 g of triethylamine was added and stirring was continued for an additional hour. Thereafter, stirring was stopped, the separated aqueous layer was removed, and the organic layer containing polycarbonate was separated.

The organic layer was washed alternately three times with a 2% aqueous solution of caustic soda (B) and a 2% aqueous phosphoric acid solution, and washed 10 times with distilled water, then 500 g of chlorobenzene was added, and methylene chloride was distilled off. After cooling, the precipitated polycarbonate was separated and dried in vacuo at 120'C for 48 hours.

The obtained polycarbonate in methylene chloride at 25°C
Table 1 shows the intrinsic viscosity ([η]), and its properties are shown in Tables 2, 3, and 4.

Reference Example 2 In place of the compound obtained in Example 1 as the triphenol compound, 1-[α-methyl-(
4-hydroxyphenyl)ethyl]-3=[α′1α′
-Bis(4<<-hydroxyphenyl)ethyl]benzene A thermoplastic branched polycarbonate was produced in the same manner as described in Reference Example 1, except that 4.24 CI was used.

The obtained polycarbonate in methylene chloride at 25°C
Table 1 shows the intrinsic viscosity ゛([η]) at , and Table 2 shows its properties.
It is shown in Table 3a-3 and Table 4.

Reference Examples 3 to 4 1-[α-methyl-α- obtained in Example 3 instead of the compound obtained in Example 1 as the triphenol compound
(3°,5-dimethyl-4°-hydroxyphenyl)ethyl]-4-[α′,α゛-bis-(3”,5”-dimethyl-4”-hydroxyphenyl)ethyl]benzene 5°08 g ( Reference Example 3), and 1-[α-methyl-α-(3°-methyl-4′-hydroxyphenyl)ethyl]-4-[α゛, α″-bis(3
A polycarbonate was produced for one time in the same manner as described in Reference Example 1, except that 4.66 g of ゛-methyl-4゛-hydroxyphenyl)ethyl]benzene (Reference Example 4) was used. The obtained polycarbonate in methylene chloride,
The intrinsic viscosity ([η1) measured at 25°C is shown in Table 1, and the properties are shown in Tables 2, 3, and 4.

Comparative Examples 1 to 3 1.26 g of phloroglucin was used instead of the compound obtained in Example 1 as the triphenol compound (Comparative Example 1)
, 2.6-bis(2°-hydroxy-5′-methylbenzyl)-4-methylphenol, 3.480 (Comparative Example 2) and 4.6-dimethyl-2.4.6-to1(4
Polycarbonate was produced in the same manner as described in Reference Example 1, except that -hydroxyphenyl)hebutene-2,4,020 (Comparative Example 3) was used. The intrinsic viscosity of the obtained polycarbonate in methylene chloride at 25°C ([
η]) is shown in Table 1, and its properties are shown in Tables 2, 3 and 4.

The transparency of polycarbonate was determined as follows. That is, the polycarbonates obtained in Reference Examples 1 to 4 and Comparative Examples 1 to 3 were molded at 300'C, and the thickness Q was 3 m.
Blessy 1~ of m was created. Regarding this press sheet, the light transmittance of visible light at 420 nm was measured to determine the transparency of the polycarbonate.

The melt index ratio of polycarbonate indicates the non-Newtonian characteristics of the polycarbonate resin, and the melt index at 300° C. of the polycarbonates obtained in Reference Examples 1 to 4 and Comparative Examples 1 to 3 was determined by the following formula.

Melt index ratio = 1 when 21.6 kg of pressure is applied to the piston
The number of grams of polycarbonate extruded in 10 minutes when extruded in 0 minutes and the melt properties of polycarbonate are as follows: Reference Examples 1 to 4
And the polycarbonates obtained in Comparative Examples 1 to 3 were extruded from an extruder (heating zone 290°C, 290°C, 290'C, 1220°C, screw rotation speed 18 rpm), length 50
': m strings were created, and the time required for extrusion and the weight of the strings were shown.

Table 1 Intrinsic viscosity ((η)) of polycarbonate Table 2 Transparency (light transmittance) of polycarbonate Table 3 Melt index ratio Examples 5 to 7 Compounds shown in Table 5 instead of 2,6-xylenol as raw material phenol compound A triphenol-based compound was produced in the same manner as in Example 3, except for using Table 6.
A triphenol compound as shown in was obtained.

Table 5 Raw material phenolic compounds H Table 6 Triphenol compounds Polycarbonate was produced in the same manner as in Reference Example 1 except that 1 mol% was used. A thermoplastic branched carbonate containing the corresponding triphenol compound as a branching component was obtained.

Claims (5)

[Claims] (1) Triphenol compound represented by the general formula below: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3, R_4, R_5 and R_6 may be the same or different from each other. , respectively hydrogen, halogen, C_1-C_5 alkyl group or C_1-C_5 alkoxy group.) (2) The triphenol compound is 1-[α-methyl-α
-(4'-hydroxyphenyl)ethyl]-4-[α'
, α'-bis(4''-hydroxyphenyl)ethyl]benzene. (3) The triphenol compound is 1-[α-methyl-α
-(4'-hydroxyphenyl)ethyl]-3-[α'
, α'-bis(4″-hydroxyphenyl)ethyl]benzene. (4) The triphenol compound is 1-[α-methyl-α
-(3′-methyl-4′-hydroxyphenyl)ethyl]-4-[α′,α′-bis(3″-methyl-4″-hydroxyphenyl))ethyl]benzene Compounds described in Section. (5) The triphenol compound is 1-[α-methyl-α
-(3′5′,-dimethyl-4′-hydroxyphenyl)ethyl]-4-[α′,α′-his(3″,5″-dimethyl-4″-hydroxyphenyl))ethyl]benzene. A compound according to claim 1.