JPH0198623A - Polycarbonate and its production - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate excellent in flame retardancy, impact resistance, flow and transparency, having a structure composed of two specified kinds of repeating units and terminated with pentahalogenophenoxy groups. CONSTITUTION:This polycarbonate is composed of repeating units [I] of formula I and repeating units [II] of formula II (wherein R<1>-R<4> are each a hydrogen atom. or a 1-4C alkyl group, and m and n are each an integer of 1-4), is terminated with pentahalogenophenoxy groups of formula III (wherein X<1>-X<5> are each a halogen) and has a viscosity-average MW >=5,000. The molar fraction (a) of the repeating units [I] and the molar fraction (b) of the repeating units [II] are usually controlled so that the ratio a/(a+b) may be about 0.005-0.2.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polycarbonate and a method for producing the same, and more specifically, a novel polycarbonate with excellent transparency that has flame retardancy, impact resistance, and high fluidity, and its production method. Concerning efficient manufacturing methods.

[Prior Art and Problems to be Solved by the Invention] Conventionally, copolycarbonates having thiodiphenoxy groups have been developed in order to improve the impact resistance of transparent flame-retardant polycarbonates. For example, thiodiphenol (
TDP), terpolymerized polycarbonate made from halogenated bisphenol and bisphenol A (BPA) (Japanese Unexamined Patent Publication No. 140597/1983), TDP and B
A mixture of a copolymerized polycarbonate made from PA and a halogen-containing copolycarbonate or a halogen-containing compound (JP-A-54-50065).

Copolymerized polycarbonates having tetrabromothiodiphenoxy groups (Japanese Patent Application Laid-open No. 56-99226) are known.

However, although these polycarbonates have excellent flame retardancy and impact resistance, they have problems such as poor fluidity and difficulty in molding.

[Means for solving problems]

The present invention has flame retardancy and impact resistance.2. The object of the present invention is to provide a polycarbonate with excellent fluidity and transparency, and an efficient method for producing the same. That is, the present invention provides a repeating unit (1) represented by
and general formula [wherein R'-R' each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m and n each represent an integer of 1 to 4. ] It has a repeating unit (If) represented by the following, and at the terminal position, the general formula [wherein X1~] (s each represents a halogen atom).

) is bonded with a pentahalogenophenoxy group,
The present invention also provides a polycarbonate characterized by having a viscosity average molecular weight of 5,000 or more. The present invention also provides a method for producing a thiodiphenol represented by the following in the presence of a molecular weight regulator in a liquid medium and [wherein R14R4 and m and n are the same as above. ]
In producing polycarbonate from an organic dihydroxy compound represented by and a carbonate-forming derivative,
As a molecular weight regulator [wherein X1 to X5 are the same as above]. A method for producing the polycarbonate described above by using a pentahalogenophenol represented by the following is also provided.

The polycarbonate of the present invention has the repeating unit (1) represented by the above-mentioned formula (A) and the repeating unit (If) represented by the -pattern hole (B). Here, −
R'-R' in the hole (B) is each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
butyl group, S-butyl group, t-butyl group). Note that these R1 to R4 may be the same or different. Further, m and n each represent an integer of 1 to 4.

The mole fraction of repeating units (1) and (n) is not particularly limited and may be selected as appropriate depending on the purpose of use, etc., but usually the mole fraction of repeating unit (1) is a , when the molar fraction of the repeating unit (U) is b, a/ (a+
b)=O, OO5-0.4, preferably 0.02-0.
The range is 2. The value of this a/(a+b) is 0.005
If it is less than 0.4, the effect of improving fluidity will not be sufficient. On the other hand, if it exceeds 0.4, the resulting polymer will be difficult to dissolve in the solvent, making it difficult to perform operations such as stirring.

Further, in the polycarbonate of the present invention, a pentahalogenophenoxy group represented by the above-mentioned crest (C) is bonded to the terminal position of the molecule, particularly to both ends.

X1 to XS in this pattern hole (C) each represent a halogen atom (chlorine, bromine, fluorine, etc.), and these may be the same or different. Specific examples of the pentahalogenophenoxy group include a pentabromophenoxy group, a pentachlorophenoxy group, a pentafluorophenoxy group, and the like.

Furthermore, regarding the degree of polymerization of the polycarbonate of the present invention, the viscosity average molecular weight is 5.000 or more, preferably 10,
A range of 000 to 30,000 is suitable. If the viscosity average molecular weight is less than 5.000, mechanical strength such as impact resistance is insufficient.

The polycarbonate of the present invention has the above repeating unit (I)
, (If), and a pentahalogenophenoxy group of general formula (C) is bonded to the terminal position, and various copolymers of these, such as random copolymers, block copolymers, and alternating copolymers, are available. be.

Note that there is no problem even if a small amount of repeating units other than repeating units (1) and (n) are mixed into the molecular chain of this polycarbonate.

The polycarbonate of the present invention can be produced by various methods, but according to the above-described production method of the present invention, a polycarbonate of high quality can be obtained efficiently.

In the method of the present invention, a thiodiphenol represented by the formula (Ao), an organic dihydroxy compound represented by the general formula (Bo), and a carbonate-forming derivative are used as raw materials.

Here, there are various organic dihydroxy compounds of Monana (Bo), but specifically 2,2-bis(4
-hydroxyphenyl)propane [commonly known as bisphenol A]; bis(4-hydroxyphenyl)methane; 1,
1-bis(4-hydroxyphenyl)ethane; 1.1
-bis(4-hydroxyphenyl)propane; 2゜2-
Bis(4-hydroxyphenyl)butane; 2゜2-bis(4-hydroxyphenyl)pentane; 2.2-bis(
4-hydroxyphenyl)isopentane; 2,2-bis(4-hydroxyphenyl)hexane; 2,2-bis(
4-hydroxyphenyl)isohexane; 4,4-dihydroxytriphenylmethane; 4,4-dihydroxytetraphenylmethane; 1. l-Bis(4-hydroxyphenyl)cyclohexane; 2,2-bis(4,4-hydroxy-3-methylphenyl)propane; 2゜2-bis(4,4-hydroxy-3,5-dimethylphenyl)propane Bisphenols such as

Further, as the carbonate ester-forming derivative, phosgene is usually used, but in addition to this phosgene, various compounds such as bromophosgene, diphenyl carbonate, and di-p-tolyl carbonate can be used.

It is also possible to use phenyl-p-)lyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate, and the like.

Furthermore, in the method of the present invention, when producing polycarbonate from the thiodiphenol of the formula (Ao), the organic dihydroxy compound of the general formula (B'), and the carbonate-forming derivative, the general formula It is necessary to have a pentahalogenophenol represented by (Co) present.

There are various types of pentahalogenophenol, and specific examples include pentabromophenol, pentachlorophenol, and pentafluorophenol.

According to the method of the present invention, a repeating unit represented by formula (A) is formed from a thiodiphenol of formula (Ao) and a carbonic acid ester-forming derivative, and an organic dihydroxy compound of formula (Bo) is formed. A repeating unit (It) represented by the general formula (B) is formed from the carbonic acid ester-forming derivative and the pentahalogenophenol of the general formula (C) bonded to the terminal position from the pentahalogenophenol of the pentahalogeno(Co). A phenoxy group is formed. From this, the above formula (A
The charging ratio of the thiodiphenol o) and the organic dihydroxy compound of the general formula (B'') may be determined as appropriate depending on the molar fraction of the repeating units CI) and (II) in the polycarbonate to be produced. On the other hand, the amount of pentahalogenophenol and the carbonate-forming derivative introduced determines the degree of polymerization of each of the repeating units (1) and (II), and also the degree of polymerization of the entire polycarbonate, and thus the molecular weight. Therefore, The amount of pentahalogenophenol to be introduced may be determined according to the purpose.The specific amount of pentahalogenophenol to be introduced is an amount sufficient to bind to the terminal positions (particularly both terminal positions) of the polycarbonate to be produced, or a slightly smaller amount of pentahalogenophenol. The amount of rising tide can be used as a guideline.

In the method of the present invention, polycarbonate is produced by allowing the reaction to proceed in a liquid medium, and specifically, the reaction is allowed to proceed in accordance with known interfacial polymerization methods, pyridine methods, and the like.

Example: Thiodiamide of formula (A") dissolved in an aqueous alkaline solution (aqueous sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) in an inert organic solvent such as Eva, methylene chloride, chloroform, chlorobenzene, or carbon tetrachloride. Phenol and the organic dihydroxy compound of general formula (B'') are added, and a carbonate-forming derivative such as phosgene is blown into the mixture to proceed with interfacial polycondensation. In this reaction, pentahalogenophenol of the general formula (Co) as a molecular weight regulator is added to the reaction system in advance or at a stage where the reaction has progressed to a certain extent. It is also effective to add a tertiary amine such as triethylamine to the reaction system as a catalyst (dehydrohalogenating agent). moreover,
At this time, the reaction system generates heat, so it is preferable to cool it with water or ice.Also, as the reaction progresses, the reaction system shifts to the acidic side, so add alkali while measuring with a pH meter to adjust the pH to 10. It is preferable to maintain the temperature at or above.

Note that a polycarbonate oligomer is synthesized in advance using an organic dihydroxy compound of general formula (Bo) and a carbonate-forming derivative, and this oligomer is combined with thiodiphenol of formula (Ao) and pentahalogenophenol of general formula (C'). It is also effective to proceed with interfacial polycondensation by mixing and stirring the above-mentioned inert organic solvent, alkaline aqueous solution, and catalyst in a predetermined quantitative ratio.

On the other hand, according to the pyridine method, the raw material general formula (Ao)
Thiodiphenol, an organic dihydroxy compound of general formula (Bo), and pentahalogenophenol as a molecular weight regulator are dissolved in pyridine or a mixed solvent of pyridine and an inert solvent, and a carbonate-forming derivative such as phosgene is added to this solution. By blowing, the desired polycarbonate is produced.

The method of the present invention may proceed as described above, but more specifically, the following three embodiments are preferred. ■ Polycarbonate oligomers are synthesized in advance using thiodiphenol and carbonate-forming derivatives such as phosgene,
A method in which this oligomer is reacted with an organic dihydroxy compound such as bisphenol A and pentahalogenophenol in the presence of an appropriate solvent, aqueous alkaline solution, catalyst, etc.
■ Carbonate oligomers synthesized from organic dihydroxy compounds such as bisphenol A (or thiodiphenol) and carbonate-forming derivatives such as phosgene,
Thiodiphenol (or organic dihydroxy compounds such as bisphenol A).

A method of reacting pentahalogenophenol in the presence of a suitable solvent, aqueous alkaline solution, catalyst, etc., and injecting a carbonate-forming derivative such as phosgene in the process, and
Oligomers are synthesized from organic dihydroxy compounds such as bisphenol A and carbonate ester-forming derivatives such as phosgene, and oligomers are synthesized from thiodiphenol and carbonate ester-forming derivatives such as phosgene, and these two types of oligomers are combined with each other. It is also effective to employ a method in which the reaction is carried out in the presence of pentahalogenophenol, a suitable solvent, an aqueous alkali solution, a catalyst, etc., or a multistage polymerization method in which the polymerization is divided into two or more stages in the method described above.

The polycarbonate of the present invention can be obtained by any of these methods.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Synthesis Example (Synthesis of Polycarbonate I Oligomer of Bisphenol A) 91 g of bisphenol A, 330 mf of methylene chloride, and 560 ml of a 2.0 N aqueous sodium hydroxide solution were placed in a flask with an internal volume of 21 mm and equipped with a stirrer, and stirred.
While cooling in a water bath, phosgene was blown therein for 70 minutes. When the resulting reaction solution was allowed to stand at room temperature, a methylene chloride solution of the oligomer was separated and produced in the lower layer. This oligomer solution has an oligomer concentration of 320g/j! It had a number average molecular weight of 550 and a chloroformate group concentration of 0.7 mol/l.

Example 1 Polycarbonate oligomer 102° thiodiphenol (TDP) and pentabromophenol (PB) synthesized in the above synthesis example were placed in a container with an internal volume of 50 ffi and equipped with a stirrer.
P) aqueous solution (TDP149g (0.68 mol), PB
291 g (0.60 mol) of P.

26% NaOH aqueous solution 300d, water 1710d) 245
0m and 2.25 g (0,022 mol) of triethylamine were added and stirred at 500 rps+. After 60 minutes, an aqueous solution of bisphenol A (BPA) (458 g of BPA) was added.
(2.0 mol), 26% NaOH aqueous solution 890111
! , water 3020d) 4350d and methylene chloride5.
71 was added and stirred.

After 60 minutes, the resulting product was separated into an aqueous phase and a methylene chloride phase containing the formed copolymer.

This methylene chloride phase was mixed with water and acid (0, IN hydrochloric acid).

Washed with water. Methylene chloride was removed from this methylene chloride phase at 40° C. under reduced pressure to obtain a white powder. After further drying at 120°C for a day and night, it was melted in an extruder and made into pellets. The viscosity average molecular weight of this pellet is 18.0
It was 00. In addition, the repeating unit (1
) was found to be 0.05.

Next, the pellets were molded into an injection molding machine at a temperature of 280°C.
Injection molding was performed at an injection pressure of 56 kg/cd to obtain a test piece. Izot impact strength of this test piece.

Heat distortion temperature and flame retardancy were measured. In addition, the flow value of the pellets was measured using a descending flow tester. Furthermore, when the bromine content of the obtained pellets was measured, it was found that 6
．． It was 9wt%. These results are shown in the table.

Example 2 BPA aqueous solution (BPA 60 kg dissolved in 5% sodium hydroxide aqueous solution 4001), TDP and P were passed through an orifice plate into a front-type reactor with a low inner diameter and a pipe length of 10 m.
Aqueous solution of BP (TDP33.7kg.

32.7 kg of PBP was added to 5% aqueous sodium hydroxide solution 4
0ON), methylene chloride and triethylamine aqueous solution (concentration 33 g/jJ at 1381 ml each)
/hr, 271/hr, 801t/hr.

100j! /hr, and phosgene was added to this at a flow rate of 1
The reaction was carried out by cocurrent blowing at a flow rate of 1 kg/hr.

The tubular reactor used here is a double tube, and cooling water is passed through the jacket part to maintain the reaction liquid discharge temperature at 25°C.
I tried to keep it at . After the reaction in the tubular reactor, the reaction was continued for 3 hours in a 1 oz seed reactor, and the polymer solution after the reaction was treated in the same manner as in Example 1 to obtain a white powder, which was analyzed in the same way. went. The results are shown in the table, and FIG. 1 shows the infrared absorption (IR) spectrum of the copolymer by the KBr tablet method, and FIG. 2 shows the nuclear magnetic resonance (NMR) spectrum (solvent: deuterated chloroform).

Example 3 (1) Synthesis of oligomer Into the tubular reactor used in Example 2, a BPA aqueous solution (same as in Example 2) and an aqueous solution of TDP and PBP (Example 2) were added.
), methylene chloride and triethylamine aqueous solution (same as in Example 2) at 1381/hr, respectively.
, 27 f/hr, 801/hr, 100
j! /hr, and phosgene was introduced at a flow rate of 11
The reaction was carried out by blowing in cocurrent flow at a flow rate of kg/hr.

When the resulting reaction solution was allowed to stand at room temperature, a methylene chloride solution of the oligomer was separated and produced in the lower layer.

The number average molecular weight of this oligomer was 820, and the concentration of chloroformate groups was 0.6 mol/l.

(2) The oligomer 50 obtained in (1) above was placed in the reactor of polycarbonate synthesis 21.
0d, BPA aqueous solution (BPA 30.8g.

NaOH1B, 0g3260d,) ethylamine 0.
061 g and methylene chloride 30. Add Od, 500
The reaction was carried out by stirring at rpm for 1 hour.

After the reaction, the polymer solution was treated as in Example 1,
A white powder was obtained and subjected to the same analysis.

The results are shown in the table.

Example 4 In Example 1, TDP in an aqueous solution of TDP and PBP
The same procedure as in Example 1 was carried out except that the amount was changed to 57.6 g (0.26 mol). The results are shown in the table.

Example 5 Internal volume 50! 10Il of the polycarbonate oligomer synthesized in the synthesis example was placed in a container equipped with a stirrer.

Aqueous solution of TDP and PBP (645 g (296 mol) of TDP, 322 g (0.66 mol) of PBP, 26% NaOH
1500 mL of aqueous solution, 6.31 N of water, 3.74 g (0,037 mol) of triethylamine, and 61 methylene chloride were added and stirred for 60 minutes.

After the reaction was completed, the polymer solution was treated and analyzed in the same manner as in Example 1. The results are shown in the table.

Comparative Example 1 Polycarbonate oligomer 10 synthesized in the synthesis example was placed in a container with an internal volume of 501 and equipped with a stirrer. , tetrabromobisphenol A (TBA) aqueous solution (TBA 272 g (
0.50 mol), NaOH 55.3 g (1.38 mol)
, 500ytj water 770ml, p-tert-
Butylphenol (PTBP) 90.1 g (0,
60 mol) and 2.25 g (0,022 mol) of ethylamine
mol) and stirred at 500 rpm.

After 60 minutes, a BPA aqueous solution (400 g (1.75 mol) of BPA, 233 g (5.83 mol) of NaOH, 2980 mol of water)
at) 3400d and methylene chloride 5.72,
After 60 minutes of stirring, the polymer solution was processed and analyzed as in Example 1. The results are shown in the table.

*1... Shown as the number of moles of repeating unit (I) relative to the total number of moles of repeating unit (I) and repeating unit (II). In this measurement, the sample was burned, the decomposed gas was absorbed into water, and H and SO in the water were analyzed using barium ions.

*2...The bromine content in the polymer was determined by alkali decomposition of the sample and analysis using the Holhardt method.

*3...The viscosity average molecular weight (Mv) is calculated from the viscosity of a methylene chloride solution at 20°C using an Ubbelohde viscosity tube.

*4...The measurement of the flow value was based on JIS-7210 (load: 160 kg/c+a'').

*5...Izod impact value was measured in accordance with JIS-7110 using a 1/8 inch thick test piece.

*6...Flame retardancy test UL-941/16 E941) (vertical combustion test conducted in accordance with Underwriters Laboratories Subject 94) Polycarbonate has excellent flame retardancy, good fluidity, sufficiently high impact resistance, and excellent transparency. especially,
UL-941/16 inch (thickness) is v- for flame retardancy.
0, the impact resistance is Izot impact value (notched, ductile fracture at room temperature) is 50 ICg-O1/c11 or more, and the fluidity is 5X, which allows thin wall molding.
It is a transparent polycarbonate having a speed of 1O-" ld/sec or more. Furthermore, according to the production method of the present invention, a polycarbonate having the above-mentioned characteristics can be efficiently produced.

Therefore, the polycarbonate of the present invention can be widely (and effectively) used in various industrial materials, such as home appliances, OA equipment, and building materials.

[Brief explanation of the drawing]

Figure 1 is an infrared absorption (IR) spectrum of the copolymer obtained in Example 2 by the KBr tablet method, and Figure 2 is a nuclear magnetic resonance (NMR) spectrum of this copolymer (solvent: dichloroform , 7MS standard). Procedural amendment (voluntary) November 11, 1986

Claims (3)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The repeating unit (I) represented by the general formula ▲ Mathematical formula,
Chemical formulas, tables, etc. are available▼ [In the formula, R^1 to R^4 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m and n each represent an integer of 1 to 4. ] It has a repeating unit (II) represented by , and has a general formula ▲ numerical formula, chemical formula, table, etc. at the terminal position ▼ [In the formula, X^1 to X^5 each represent a halogen atom. ] A polycarbonate having a pentahalogenophenoxy group bonded thereto and having a viscosity average molecular weight of 5,000 or more. (2) Molar fraction a of repeating unit (I) and repeating unit (
The molar fraction b of II) is a/(a+b)=0.005 to 0
．． 2. The polycarbonate according to claim 1, which is (3) In the presence of a molecular weight regulator in a liquid medium, thiodiphenol represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R ^1 to R^4 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m and n each represent an integer of 1 to 4. ] In producing polycarbonate from an organic dihydroxy compound represented by and a carbonate ester-forming derivative,
As a molecular weight regulator, there are general formulas▲mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X^1 to X^5 each represent a halogen atom. There are formulas ▲mathematical formulas, chemical formulas, tables, etc. that are characterized by the use of pentahalogenophenol represented by
There are chemical formulas, tables, etc. ▼ [In the formula, R^1 to R^4, m, and n are the same as above. ] It has a repeating unit (II) represented by the general formula ▲numeric formula, chemical formula, table, etc. at the terminal position▼ [In the formula, X^1 to X^5 are the same as above. ] A method for producing a polycarbonate having a pentahalogenophenoxy group bonded thereto and having a viscosity average molecular weight of 5,000 or more.