JPH05222182A - Branched polycarbonate resin and its production - Google Patents

Abstract

PURPOSE:To obtain the title resin improved in transparency, impact resistance and melt flow characteristics by reacting a specified bisphenol compound modified with a carboxylic acid, a specified bisphenol compound, and phosgene (oligomer). CONSTITUTION:A mixture of 0.01-5mol% bisphenol compound modified with a carboxylic acid of formula I (wherein R1 to R4 are each H, lower alkyl or halogen) and a bisphenol compound of formula II (wherein R5 to R8 are each R1; and X is a direct bond, alkylene, alkylidene, -O-, -S-, -SO2 or -CO-) is reacted with phosgene (oligomer) or a carbonic diester at a molar ratio of 1:(1.1 to 1.5) to give a branched polycarbonate resin having repeating units of formula III [wherein Ar is a divalent aromatic group of formula IV; and a, b, c and d are molar ratios satisfying the relations: a+c=:(0.01 to 5) and b+d=(99.99 to 95) when a+b+c+d=100].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel branched polycarbonate resin and a method for producing the same.

[0002]

Polycarbonate resin, which is known as an engineering plastic having excellent transparency and impact resistance, is a linear polymer generally produced by a condensation reaction of bisphenols and phosgene or carbonic acid diesters, and when melted, Shows Newtonian fluid behaviour.
Such a resin has a small shear rate dependence of the melt viscosity in the shear flow process, and exhibits an extremely low viscosity in the extension flow process. Therefore, when performing extrusion molding or blow molding, resin dripping due to its own weight (draw Down) is likely to occur, and it is difficult to mold a large product.

In order to improve such a point, a partially branched polycarbonate resin has been proposed so that it exhibits non-Newtonian fluidity when melted. For example, Japanese Patent Publication Sho 47-
No. 23,918 discloses a method of using a trivalent phenol compound as a branching agent, and US Pat. No. 4,621,132 discloses a trivalent carboxylic acid such as trimellitic acid. Is disclosed as a branching agent. However, in these methods, since the reactivity of the three functional groups is equal, coexistence of these branching agents in the initial stage of the polymerization causes the degree of branching to be too large to make them insoluble in a solvent, or a monovalent end-capping agent. And a low molecular weight by-product is produced by the reaction with the phenol compound. Therefore, a report example in which the problem is solved by devising the order of addition of the divalent phenol compound as the main component, the trivalent phenol compound as the branching agent, and the monovalent phenol compound as the terminal terminator There is. For example, Japanese Examined Patent Publication No. 53-28,193 discloses a method in which a divalent and monovalent phenol compound is phosgenated to form a low molecular weight polycarbonate, and then a catalyst and a trivalent or higher polyphenol are added. .. In addition, JP-A-59-
Japanese Patent No. 191,719 discloses a method of phosgenating a divalent and trivalent phenol compound and then adding a catalyst and a terminal stopper. Further, JP-A-59-45,318 discloses a method in which a divalent phenol compound is phosgenated, then a monovalent and a polyvalent phenol compound is added, and a catalyst is further added to carry out polymerization. However, it cannot be denied that any of these methods makes the manufacturing process complicated.

[0004]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a branched polycarbonate resin having melt flow characteristics suitable for large-scale extrusion molding and blow molding without impairing the transparency and impact resistance of the polycarbonate resin. To aim.

[0005]

That is, the present invention provides the following general formula (1)

[Chemical 7] [Wherein Ar is the following general formula (2)

[Chemical 8] Represents a divalent aromatic group, R _{1 to} R ₈ represent a hydrogen atom, a lower alkyl group or halogen, X represents a direct bond, an alkylene group, an alkylidene group, —O—, —S—,
-SO ₂ - or -CO- indicates, also, a, b, c and d represent the molar ratio, an (a + c) = 0.01~5 when the a + b + c + d = 100 (b + d) = 99.
It is a branched polycarbonate resin having a repeating unit represented by 99 to 95].

The present invention also provides the following general formula (3):

[Chemical 9] (Wherein R _{1 to} R ₄ represent a hydrogen atom, a lower alkyl group or halogen) and a carboxylic acid-modified bisphenol compound represented by the following general formula (4)

[Chemical 10] (However, in the formula, R _{5 to} R ₈ represent a hydrogen atom, a lower alkyl group or halogen, and X represents a direct bond, an alkylene group, an alkylidene group, —O—, —S—, —SO ₂ — or —CO—.
Of a bisphenol compound represented by the formula (1) is reacted with phosgene, a phosgene oligomer or carbonic acid diesters to produce a branched polycarbonate resin having a repeating unit represented by the general formula (1).

The branched polycarbonate resin of the present invention is represented by the above general formula (1), and Ar is a divalent aromatic group represented by the general formula (2). In the general formulas (1) and (2), R _{1 to} R ₈ are a hydrogen atom, a lower alkyl group or a halogen, and they may be the same or different, but from the viewpoint of reactivity during polymerization. , All of which are hydrogen atoms are preferred. Moreover, as the lower alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable for the same reason. X is easy to obtain as a raw material,
Direct bond, alkylene group, alkylidene group, -O-,-
S -, - SO ₂ - and a divalent group selected from -CO-, isopropylidene groups are particularly preferred in view of reactivity and cost. Further, a, b, c and d represent the abundance ratio of each structural unit in a molar ratio, and (a + c) / (b
The value of + d) can be controlled by the molar ratio of the raw materials used in the reaction.

The value of (a + c) is a + b + c + d = 10
When set to 0, it must be in the range of 0.01 to 5.
When it is less than 0.01, the effect of branching is not sufficient, and when it is more than 5, it becomes difficult to avoid side reactions such as gelation. Also, c / (a
The value of + c) is preferably as small as possible in consideration of branching efficiency, and is preferably controlled to be substantially 0.01 or less. Further, the value of d / (b + d) can obtain a polymer having a higher degree of branching as the value approaches 0.5, and it is preferably in the range of 0.1 to 0.5.

In order to produce the branched polycarbonate resin of the present invention, the carboxylic acid-modified bisphenol compound represented by the general formula (3) is required as a branching agent. In the general formula (3), R _{1 to} R ₄ are a hydrogen atom, a lower alkyl group or halogen, as in the above formula. Such a compound can be produced by any method, for example, the method described below. First, 9-fluorenone-4-carboxylic acid is synthesized by heating and reacting diphenic acid in concentrated sulfuric acid. Next, the obtained 9-fluorenone-4-carboxylic acid was mixed with β in a phenol compound.
The target carboxylic acid-modified bisphenol compound can be synthesized by reacting with mercaptopropionic acid as a catalyst while introducing hydrogen chloride gas.
Examples of the phenol compound used here include phenol, 2,6-dimethylphenol, 2,6-diethylphenol, and 2,6-dibromophenol. Phenol is not preferable in terms of reactivity and product purity. preferable.

When the obtained carboxylic acid-modified bisphenol compound is reacted with, for example, phosgene, first, two phenolic OH groups react to form a linear polycarbonate, and then the carboxyl group also forms a chloroformate. It becomes an acid chloride via and forms a branch by reacting with another bisphenol molecule. Since this branch is formed later than the formation of the main chain, when the carboxylic acid-modified bisphenol compound of the present invention is used as a branching agent, even if it is mixed with another bisphenol component from the beginning and polymerization is performed, No insoluble matter or low molecular weight by-products are produced. Moreover, when a polyfunctional phenol compound is used as the branching agent, the reactivity is generally inferior to that of the bisphenol compound, so that there is a drawback that the branching does not proceed sufficiently, but the carboxylic acid-modified bisphenol compound of the present invention has high polymerization. Since it has activity, a sufficient branched structure can be formed. The reaction reagent is not limited to phosgene. For example, the same branch can be formed by selecting a carbonic acid diester such as carbonic acid diphenyl as a reaction partner and performing an ester exchange reaction in a molten state.

Due to the above-mentioned characteristics, the bisphenol compound represented by the general formula (4) is used together with the carboxylic acid-modified bisphenol compound represented by the general formula (3), and phosgene, phosgene oligomer or carbonic acid diester is used. A branched polycarbonate resin can be obtained by reacting with.

In the general formula (4), X is the same as the above 2
The valence group is shown. Specifically, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-
Dibromo-4-hydroxyphenyl) propane, 2,2
-Bis (3,5-dimethyl-4-hydroxyphenyl)
Propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl,
4,4'-dihydroxydiphenyl ether, 4,4 '
-Dihydroxydiphenylmethane, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl)
Examples thereof include sulfide and bis (4-hydroxyphenyl) sulfone, and these can be used alone or in combination as necessary. Among these compounds, 2,2-bis (4-hydroxyphenyl) propane is preferable in terms of reactivity and cost.

The production of branched polycarbonate by the phosgene method will be specifically described below. When the carboxylic acid-modified bisphenol compound of the present invention is used as a branching agent, the amount used is required to be an amount that can sufficiently form branching, and an amount that does not form an insoluble matter due to excessive crosslinking. is there. Specifically, it is in the range of 0.01 to 5 mol%, preferably 0.1 to 2 mol%, based on the total amount of the bisphenol compound used.

The carboxylic acid-modified bisphenol compound and the bisphenol compound are dissolved in an alkaline aqueous solution and dispersed in an organic solvent before use. In this case, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferably used, and the concentration thereof is 5 to 15
Weight percent is suitable. Also, the amount of alkali used is
It is preferably about 2 to 4 times the number of moles of the bisphenol compound used. The organic solvent used with this aqueous alkaline solution must be insoluble in water and inert to the reaction and should dissolve the resulting polycarbonate. Examples of such organic solvents include chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, 1,2-dichloroethane, and chlorinated aromas such as chlorobenzene, dichlorobenzene, and chlorotoluene. Examples thereof include group hydrocarbons, acetophenone, cyclohexane, anisole and the like, but methylene chloride is most preferable.

The end terminator used in the present invention may be any one as long as it is one used in the production of publicly known polycarbonate, but a monovalent phenol compound typified by p-tert-butylphenol is usually used. The amount used is selected in the range of 0.5 to 10 mol%, preferably 1 to 5 mol%, based on the bisphenol compound.

The polymerization catalyst used in the present invention may also be any one as long as it is used in the production of known polycarbonates, usually tertiary amines typified by triethylamine and trimethylamine, or triethylbenzylammonium chloride, tetramethylammonium. Examples thereof include quaternary ammonium salts represented by chloride. The addition amount is usually 0.01 to 1 mol% with respect to the bisphenol compound, preferably 0.05.
~ 0.5 mol%.

An example of the reaction for producing the branched polycarbonate resin of the present invention is as follows. While maintaining the reaction system as described above at 25 ° C or below,
A desired branched polycarbonate can be produced by blowing for 1 minute and continuing the reaction for 1 to 2 hours while continuing the reaction. At that time, the preferable molar ratio of the bisphenol compound and phosgene is 1: 1.1 to 1: 1.5. After completion of the reaction, the mixture is diluted with an organic solvent and separated from the aqueous phase. After thoroughly washing the organic phase with diluted hydrochloric acid, water, etc.,
A solid branched polycarbonate can be obtained by removing the organic solvent. The resin of the present invention preferably has a logarithmic viscosity of 0.4 or more, which is suitably used in extrusion molding and blow molding.

[0018]

EXAMPLES The present invention will be specifically described below based on examples. The physical properties shown in the examples are defined as follows. Logarithmic viscosity η _inh (dl / g) = (ln η _rel ) /
In the formula c, η _rel is a polymer solution having a concentration c (g / dl),
The specific viscosity when measured at 30 ° C. using a capillary viscometer is shown. In the present invention, the measurement was performed at c = 0.5 g / dl (methylene chloride solution). Non-Newtonian index N = (logγ ₁ −logγ ₂ ) / (logτ ₁ −lo
g τ ₂ ) In the equation, τ ₁ is the shear stress (dyne / cm ² ) when the shear rate is γ ₁ (sec ⁻¹ ), and γ ₂ is the shear rate γ ₂
Shear stress (dyne / cm ² ) at (sec ^-1 ). Izod impact value JIS standard K7110 [with notch, sample thickness 3.2 m
m (1/8 inch)].

Example In a 1 liter glass reactor equipped with a phosgene blowing tube, a thermometer and a stirrer, 72 g of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A)
(0.315 mol) and carboxylic acid-modified bisphenol compound (R _{1 to} R ₄ = H) 50 represented by the general formula (1) 50
0 mg (0.4 mol% relative to bisphenol A),
1.5 g of p-tert-butylphenol (0.3 mol% with respect to bisphenol A), 378 g (0.945 mol) of 10% NaOH aqueous solution, 0.1 g (0.001 mol) of triethylamine, and 400 g of methylene chloride.
Then, while stirring, 46 g (0.465 mol) of phosgene gas was blown thereinto at a temperature of 25 ° C. over about 30 minutes. After the completion of blowing the phosgene gas, stirring was continued for another hour to complete the reaction. The methylene chloride phase was separated from the aqueous phase, washed thoroughly with water until the inorganic ions disappeared, and then methylene chloride was distilled off to obtain a solid branched polycarbonate. The physical properties of the obtained branched polycarbonate are such that the logarithmic viscosity η _inh is 0.58 (dl / g) and the non-Newton index N is
Was 1.56 and the Izod impact value (with notch) was 780 J / m.

[0020]

The branched polycarbonate resin of the present invention is
Since it exhibits a large non-Newtonian fluidity when melted, a large molded product can be obtained without causing resin dripping during extrusion molding or blow molding.

Claims (2)

[Claims] 1. The following general formula (1): [Wherein Ar is the following general formula (2): Represents a divalent aromatic group, R _{1 to} R ₈ represent a hydrogen atom, a lower alkyl group or halogen, X represents a direct bond, an alkylene group, an alkylidene group, —O—, —S—,
-SO ₂ - or -CO- indicates, also, a, b, c and d represent the molar ratio, an (a + c) = 0.01~5 when the a + b + c + d = 100 (b + d) = 99.
A branched polycarbonate resin having a repeating unit represented by 99 to 95]. 2. The following general formula (3): (Wherein, R _{1 to} R ₄ represent a hydrogen atom, a lower alkyl group or halogen) and a carboxylic acid-modified bisphenol compound represented by the following general formula (4): (However, in the formula, R _{5 to} R ₈ represent a hydrogen atom, a lower alkyl group or halogen, and X represents a direct bond, an alkylene group, an alkylidene group, —O—, —S—, —SO ₂ — or —CO—.
And a bisphenol compound represented by the formula (1) is reacted with phosgene, a phosgene oligomer, or carbonic acid diesters. [Wherein Ar represents the following general formula (2): Represents a divalent aromatic group, R _{1 to} R ₈ represent a hydrogen atom, a lower alkyl group or halogen, X represents a direct bond, an alkylene group, an alkylidene group, —O—, —S—,
-SO ₂ - or -CO- indicates, also, a, b, c and d represent the molar ratio, an (a + c) = 0.01~5 when the a + b + c + d = 100 (b + d) = 99.
It is a 99-95], and the manufacturing method of the branched polycarbonate resin which has a repeating unit represented by these.