JPS63199225A - Polycarbonate - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate, consisting of respective specific two kinds of repeating units, having terminal pentahalogenophenoxy groups, specific viscosity-average molecular weight, excellent flame retardance, impact resistance, high fluidity as well as transparency and suitable as household appliances, etc. CONSTITUTION:A polycarbonate, obtained by blowing phosgene into, e.g. a bisphenol sulfone expressed by formula I, bisphenol A expressed by formula II and pentahalogenophenol expressed by formula III in a solvent, such as methylene chloride, etc., and an aqueous solution of an alkali incompatible therewith to carry out interfacial polymerization, etc., consisting of repeating units expressed by formula IV and repeating units expressed by formula V {preferably the mol. fraction (m) of the repeating units expressed by formula IV and the mol. fraction (n) of the repeating units expressed by formula V satisfy [m/(m+n)]=0.01-0.1}, pentahalogenophenoxy groups at the terminal, preferably both terminals and >=5,000, preferably 10,000-30,000 viscosity-average molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new polycarbonate, and more particularly to a highly transparent polycarbonate resin that has flame retardancy, impact resistance, and high fluidity.

[Prior art and problems to be solved by the invention] Conventionally, flame-retardant polycarbonates have, for example, a halogen-substituted phenoxy group (pentabromophenoxy group, tetrachlorophenoxy group, tribromophenoxy group, etc.) at the end. polycarbonate with
40715).

Copolymer of tetrahalogenobisphenol sulfone and bisphenol A (BPA) (JP-A-51-1232
No. 94) Polycarbonate having an aromatic monosulfonyl group at the end of the 9-molecule (Japanese Patent Application Laid-Open No. 54-21497), a copolymer of tetrabromobisphenol A and BPA (Japanese Patent Application Laid-open No. 155233-1989), or a molecule Polycarbonate with sulfonate at the end (Special Publication 1986)
0-501212) and the like are known.

However, although these conventional polycarbonates have excellent flame retardancy, they do not have sufficient impact resistance, fluidity, or transparency. A polycarbonate that is excellent in all respects has not yet been obtained.

[Means for solving problems]

The flame retardance of the present invention is UL-941/16 inch (thickness) -0 or V-1, and the impact resistance is Izot impact value (notched, ductile fracture at room temperature) of 50.
kg-crtr/cm or more, and has a flow value of 6X10-''lll1/sec that allows thin wall molding.
The purpose of this invention is to provide a transparent polycarbonate having the above structure, which has a repeating unit (I) represented by 8 and a repeating unit (n) represented by , and a pentahalogen at the terminal position. This is a polycarbonate characterized by bonding phenoxy groups and having a viscosity average molecular weight of 5,000 or more.

The polycarbonate of the present invention has a repeating unit (1) represented by the above-mentioned formula (A) and a repeating unit (n) represented by the formula (B).

The molar fraction of repeating units (1) and (II) is not particularly limited and may be selected as appropriate depending on the purpose of use, etc., but usually the molar fraction of repeating unit (1) is m ,
When the mole fraction of the repeating unit (n) is n, a+/(
m+n) ~0.005~0.2, preferably 0.01
~0.1.

Further, in the polycarbonate of the present invention, a pentahalogenophenoxy group, that is, a functional group represented by the general formula % is bonded to the terminal position of the molecule, particularly at both ends.

Furthermore, regarding the degree of polymerization of the polycarbonate of the present invention, the viscosity average molecular weight is s, ooo or more, preferably 10.
A range of 000 to 30.000 is suitable. If the viscosity average molecular weight is less than s, o o o, mechanical strength such as impact resistance is insufficient.

The polycarbonate of the present invention has the above repeating unit (I)
, (n), 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 (I) and (II) are mixed into the molecular chain of this polycarbonate.

The polycarbonate of the present invention can be produced by various methods, but the following two methods are preferable.

According to the first method, formula Bisphenol sulfone, (BPS), represented by

Bisphenol A (BPA) represented by the formula, pentahalogenophenol (pentabromophenol, pentachlorophenol, pentafluorophenol, etc.) represented by the general formula), and methylene chloride.

Solvents such as chlorobenzene, pyridine, chloroform, and carbon tetrachloride, as well as alkaline aqueous solutions that are incompatible with these (sodium hydroxide aqueous solution, potassium hydroxide aqueous solution,
Aqueous sodium carbonate solution, etc.) are mixed and stirred at a predetermined ratio, and phosgene is blown into this to advance interfacial polymerization. Since the reaction system generates heat at this time, it should be cooled with water or ice. Also, as the reaction progresses, the reaction system shifts to the acidic side, so add alkali while measuring with a PL meter.
It is preferable to maintain pl at 10 or more.

In the above polymerization reaction, the bisphenol sulfone of formula (A) is used as a repeating unit (I) in the resulting polycarbonate.
), and since bisphenol A of formula (B') constitutes the repeating unit (II), the above charge ratio of bisphenol sulfone and bisphenol A is the same as the repeating unit (1) of the polycarbonate to be produced, The room temperature is determined as appropriate depending on the molar fraction of (■). On the other hand, the amount of pentahalogenophenol and phosgene introduced determines the degree of polymerization of each of the repeating units (1) and (n), and further determines the degree of polymerization of the entire polycarbonate, and thus the molecular weight. Therefore, the amount of phosgene to be introduced can be adjusted according to the purpose. Also, when blowing phosgene, adjust the amount of phosgene blown per hour as appropriate so that the total amount blown in at the end of the reaction is the same as that required for the reaction. Manage to maintain the supply amount.

When the reaction product thus obtained is poured into a large amount of a precipitating agent such as methanol, the polycarbonate of the present invention is precipitated.

In the above reaction, various carbonate-forming derivatives such as bromophosgene, diphenyl carbonate, g-p-1 lyl carbonate, etc. can be used instead of phosgene.
Phenyl-p-)lyl carbonate, di-p-chlorophenyl carbonate.

It is also possible to use dinaphthyl carbonate and the like.

Next, according to the second method, a polycarbonate oligomer is synthesized in advance using bisphenol A and phosgene, and this oligomer, bisphenol sulfone and pentahalogenophenol, a solvent such as methylene chloride that can dissolve this oligomer, and an aqueous alkaline solution are prepared. (aqueous sodium hydroxide solution, etc.) and a catalyst such as triethylamine or trimethylbenzylammonium chloride are mixed and stirred in a predetermined ratio, and the resulting reaction product is poured into a large amount of a precipitant (methanol, etc.). As a result, the polycarbonate of the present invention is precipitated.

In the case of the above method, the chloroformate groups present at both ends of the oligomer react with the hydroxyl groups at the ends of the bisphenol sulfone to promote polymer growth, so there is no need to blow phosgene into this process. In addition, the polycarbonate obtained by this method has repeating units interposed therebetween with the degree of polymerization of the oligomer intact, and pentahalogenophenoxy groups are bonded to the ends.

The polycarbonate of the present invention can be efficiently produced by the method described above, but other methods include
A method in which a polycarbonate oligomer is synthesized in advance using bisphenol sulfone and phosgene, and this oligomer is reacted with bisphenol A and pentahalogenophenol in the presence of an appropriate solvent, aqueous alkaline solution, catalyst, etc., ■Bisphenol A (or bisphenol sulfone) and Bisphenol sulfone (or bisphenol A) and pentahalogenophenol are added to the carbonate oligomer synthesized from phosgene in an appropriate solvent.
A method of reacting in the presence of an alkaline aqueous solution, a catalyst, etc., and blowing phosgene in the process;
A method in which oligomers are synthesized from bisphenol sulfone and phosgene, and these two types of oligomers are reacted with each other in the presence of pentahalogenophenol, an appropriate solvent, an aqueous alkaline solution, a catalyst, etc. In the method described above, it is also effective to employ a multistage polymerization method in which polymerization is divided into two or more stages.

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 oligomer of bisphenol A) 91 g of bisphenol A, 330 o+1 methylene chloride, and 560 mβ of a 1.7N aqueous sodium hydroxide solution were placed in a flask with an internal volume of 21 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 had an oligomer concentration of 300 g/l, a number average molecular weight of 1550, and a chloroformate group concentration of 1.0 mol/β.

Example 1 Internal volume 50! In a container equipped with a stirrer, a sodium hydroxide aqueous solution of polycarbonate oligomer 81° bisphenol sulfone synthesized in the above synthesis example [bisphenol sulfone 123 g (0.49 mol), sodium hydroxide 6
9 g (520 ml) of water, 640 rall of water, and 4.4 g (0,043 mol) of triethylamine were added, and the mixture was stirred at 500 revolutions.

After 10 minutes, sodium hydroxide L of pentabromophenol
Water R liquid C pentabromophenol 215g (0.44 mol), sodium hydroxide 3.5.1g.

2.8 J of water was added and stirred. After 50 minutes, a sodium hydroxide aqueous solution of bisphenol A [bisphenol A51
0 g (2.24 mol), 260 g of sodium hydroxide,
Wed 4.41) 4.1! and methylene chloride 61 were added and stirred.

After stirring for 60 minutes, the resulting reaction 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 (0.1N 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 drying at 120° C. day and night, the mixture was melted in an extruder and made into pellets. The glass transition temperature (Tg) of this pellet was measured and found to be 153.8°C. The viscosity average molecular weight was 17,600, and when the molecular weight distribution was measured by gel permini-silane chromatography, it showed a distribution with a single peak at the above value.

Furthermore, the molar ratio of the repeating unit (I) in this copolymer was determined to be 0.02.

Next, this pellet was molded using an injection molding machine at a temperature of 280°C.
A test piece was obtained by injection molding at an injection pressure of 55 kg/am. The Izod impact strength and flame retardance of this test piece were measured. Transparency was also visually measured. Measured using a flow tester.

The bromine content of the obtained pellet was measured and found to be 5.8.
It was wt%. (The sample was subjected to alkaline decomposition and analyzed using the Polhardt method.) These results are shown in the table.

Examples 2 to 6 By changing the amounts of bisphenol sulfone, polycarbonate oligomer, pentabromophenol, etc. used in Example 1, copolymers having different repeating units (I) and bromine contents were produced. The properties of these copolymers are summarized in the table.

Incidentally, the infrared absorption (IR) spectrum according to the Criminal Law of the copolymer KBr tablet obtained in Example 3 is shown in FIG. 1, and the nuclear magnetic resonance (NMR) spectrum (solvent: deuterated chloroform) is shown in FIG.

Comparative Example 1 Example 1 was carried out in the same manner as in Example 1, except that bisphenol sulfone was not used, and a polymer containing only repeating unit (II) was used, both ends of which were terminated with pentabromophenol. Polycarbonate was obtained. The results are shown in the table.

Comparative Example 2 In Example 1, instead of using an alkaline aqueous solution of pentabromophenol, an alkaline aqueous solution of p-tert-butylphenol (44.5 g of p-tert-butylphenol, 351 g of bisphenol sulfone) was used.
1.40 mol), 211 g of sodium hydroxide, 4.
A copolymer was produced in the same manner as in Example 1 except that 675N was used.

The results are shown in the table.

Comparative Example 3 In Example 1, instead of using the sodium hydroxide aqueous solution of bisphenolsulfone, a sodium hydroxide aqueous solution of tetrabromobisphenolsulfone [tetrabromobisphenolsulfone 377 g (0.67 mol), sodium hydroxide 120 g, water 520 mjri89
7 val and instead of using aqueous sodium hydroxide solution of pentabromophenol, p-te
alkaline aqueous solution of rt-butylphenol (1)-t,
52.8 g of ert-butylphenol, 35.1 g of sodium hydroxide.

A copolymer of tetrabromobisphenol sulfone and bisphenol A was produced in the same manner as in Example 1, except that water 2.111) was used. 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 (1) and repeating unit (If). In this measurement, the sample was burned, the decomposed gas was absorbed into water, and HasO in the water was 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 flow value was measured in accordance with JIS-7210 (load: 160 kg/cm").

*5...Measurement of Izot impact value is based on JIS-7
110.

*6...Flame retardancy test UL-941/16E941) (Vertical combustion test conducted in accordance with Underwriters Laboratory Subject 94.) [Effects of the invention] As seen on the surface, the polycarbonate of the present invention It has excellent flame retardancy, good fluidity, sufficiently high impact resistance, and excellent transparency.

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]

FIG. 1 is an infrared absorption (IR) spectrum measured by the KBrBr method of the copolymer obtained in Example 3, and FIG. 2 is a nuclear magnetic resonance (NMR) spectrum (solvent double chloroform) of this copolymer.

Claims (2)

[Claims] (1) It has a repeating unit (I) represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and a repeating unit (II) represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. A polycarbonate having a halogenophenoxy group bonded to it and having a viscosity average molecular weight of 5,000 or more. (2) Mole fraction m of repeating unit (I) and repeating unit (
II) molar fraction n is m/(m+n)=0.005 to 0
．． 5. The polycarbonate according to claim 1, which is