JPS63182336A - Production of heat-resistant polycarbonate - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate excellent in the degree of polymerization, refractive index, transparency and heat resistance within a short time in good yield, by performing the interfacial polycondensation of an aqueous alkaline solution of a specified compound with an organohalogen compound solution of a phosgene dimer. CONSTITUTION:The interfacial polycondensation of an aqueous alkaline solution of a 9,9-bis(4-hydroxyphenyl)fluorene (A) of the formula (wherein R is H, CH3 or C2H5), e.g., 9,9-bis(4-hydroxyphenyl)fluorene, and an organohalogen compound (e.g., 1,2-dichloroethane) solution of 0.5-3.0, preferably, about 1mol, per mole of component A, of a phosgene dimer (B), or trichloromethyl chloroformate, is performed at 0-90 deg.C, preferably, 20-30 deg.C form 20min-80h4 in the presence of a surfactant (C) (e.g., tetrabutyammonium chloride) to obtain the title polycarbonate of a glass transition temperature of about 260 deg.C, a decomposition temperature of bout 465 deg.C, transparency >=90% and a refractive index of about 1.7.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing heat-resistant polycarbonate, particularly 9
, 9-bis(4-hydroxyphenyl) fluorenes and phosgene dimer. The present invention relates to a method for producing a heat-resistant polycarbonate having a high degree of oxidation, a high refractive index, and a crushed transparency from ,9-bis(4-hydroxyphenyl)fluorenes and phosgene dimer.

Conventional technology Polycarbonate is often used in mechanical parts because of its excellent mechanical properties such as impact resistance and tensile strength, and for disassembling electrical parts etc. due to its excellent electrical properties such as insulation. ing.

There are two known methods for producing polycarbonate: phosgene υ and transesterification.

The phosgene method is described in U.S. Pat. No. 3,548,185 (1970).
Add dichloromethane as a solvent to an alkaline aqueous solution or suspension of sodium li! of bisphenol A or 9,9-bis(4-hydroxyphenyl)fluorene as shown in the following formula (υ) as described in This method involves blowing in phosgene while stirring.

The transesterification method is a method in which bisphenol A and diphenyl carbonate are mixed as shown in the following formula (2), heated and melted without using a solvent, and polycondensed by transesterification at high temperature and reduced pressure. The polycarbonate produced by this method has a characteristic that a product with a better molecular weight distribution can be obtained compared to the phosgene method, but it is difficult to produce a polycarbonate with a high molecular weight.

Formula (2) Problems to be Solved by the Invention The prior art phosgene method described above uses phosgene having th properties, and transesterified products are produced under harsh conditions of 1°/Y. 1. The present invention is a new heat-resistant polycarbonate that does not have these problems! I.J.
The purpose is to provide n'J)i.

The first step to solving the problem The present invention solves the problems mentioned in 111N.

9.9-Bis(4-hydroxyphenyl) fluoride is characterized by interfacial polycondensation of an aqueous alkaline solution of 9-bis(4-hydroxyphenyl) fluoride and an organic halogen compound solution of phosgene dimer while stirring. Further, a surfactant is present during the interfacial polycondensation of an alkaline aqueous solution of 9,9-bis(4-hydroxyphenyl)fluorenes and an organic halogen compound solution of phosgene dimer.

The present invention uses phosgene, which has the same structure as phosgene but has a different reactivity when producing polycarbonate using 9,9-bis(4-hydroxyphenyl)fluorenes as a raw material, and which is liquid and easy to handle. This method uses a dimer to obtain heat-resistant polycarbonate in high yield through a short reaction time at a relatively low temperature.

The contents of the present invention will be further explained in detail below.

The present invention is a method of interfacial polycondensation of 9,9-bis(4-hydroxyphenyl)fluorenes and phosgene dimer.

The 9,9-bis(4-hydroxyphenyl)fluorenes used in the present invention are those represented by the following formula (3). For example, 9,9-bis(4-hydroxyphenyl)
Fluorene, 9.9-bis(3-methyl-4-hydroxyphenyl)fluorene, 9.9-bis(3-ethyl-
(4-hydroxyphenyl)fluorene, and their alkali salts with sodium, potassium, etc. can also be used.

(However, in formula 1, R represents either H, CH3', or C2H1.) In addition, the phosgene dimer used in the present invention is trichloromethyl chloroformate, and the following formula % formula % Formula (4) Section 6 This invention In the above, the ratio of the 9,9-bis(4-hydroxyphenyl)fluorenes and the phosgene dimer is 0.5 to 3.0 times the mole of the latter phosgene dimer, preferably 0.5 to 3.0 times the mole of the former fluorene. is 0.7-2.
The amount is preferably set to 0 times the molar amount, most preferably around the same molar value, and within this range, the reaction proceeds well.

Further, the organic halogen compound used in the present invention may be one that dissolves phosgene dimer, and specific examples thereof include 1,2-dichloroethane, lyloloform, trichloroethane, dichloromethane, and the like.

To produce polycarbonate by the method of the present invention, 9,9-bis(4-hydroxyphenyl)fluorenes are first mixed with sodium hydroxide.

Dissolve in an aqueous solution containing potassium hydroxide, etc. to make an alkaline aqueous solution. At this time, it is preferable to add a small amount of an organic halogen compound, such as that used as a solvent for phosgene dimer, to the alkaline aqueous solution, as this facilitates the progress of the interfacial polycondensation reaction. Prepare a dimer organic halogen compound solution.

Then the above 9,9-bis(4-hydroxyphenyl)
An organic halogen compound solution of phosgene dimer is added to an alkaline aqueous solution of fluorenes. In this case, it is preferable to add the latter solution of phosgene dimer little by little to the former alkaline aqueous solution while stirring and react.
The reaction can also be carried out by mixing and stirring an alkaline aqueous solution of 9.9-bis(4-hydroxyphenyl)fluorenes and an organic halogen compound serving as a solvent for the phosgene dimer, and adding the phosgene dimer itself dropwise thereto. It is Noh.

When stirring is not performed during the reaction, 1; the layer is an aqueous alkaline solution of fluorenes, and the lower layer is a solution of an organic halogen compound of phosgene dimer. Contact occurs only at the interface between the upper layer and the lower layer, and the reaction progresses. is delayed.

Since the present invention is an interfacial polycondensation reaction in which the heptamer component is dissolved in two solvents that are immiscible and used at the interface,
If fl) is added to the reaction system to the extent that it does not emulsify the surfactant, the interface will expand due to Wl stirring and the reaction will proceed, so it is desirable to add the surfactant in a small amount in order to increase the reaction efficiency.

There are no particular restrictions on the surfactant, but it is preferable that it not be involved in one reaction, and it is generally preferable to use a cationic type. For example, it is preferable to use tetrabutylammonium chloride, tributylbenzylammonium chloride, etc. Addition of agent? Although it depends on the type, the F content in the aqueous solution is 5% or more, preferably 1% or less. The addition of surfactants has little effect on the degree of polymerization of the polycarbonate obtained.

The reaction temperature is θ to 30°C, preferably 20 to 30°C. 1. The reaction time is about 20 minutes to 80 hours, including the dropping time. The longer the reaction time, the lower the degree of polymerization of the resulting polycarbonate. Therefore, it is recommended that the reaction time not be too long.

By manufacturing as described above, polycarbonate can be obtained in high yield, and its physical properties include a glass transition temperature of 260°C.
It exhibits high heat resistance with a temperature of 465° C. for 1 minute, transparency of 90% or more, a refractive index of nearly 1.7, and a high degree of polymerization.

The present invention will be further explained in detail below with reference to Examples.

Examples Example 1 9.9-bis(4-hydroxyphenyl)fluorene 3
．． 5g (0.01 mol) of sodium hydroxide 2.28
g (0,057 mol), dissolved in wood 60- with 0.00175 g of tetrabutylammonium chloride as a surfactant, and 1,2-dichloroethane 60-
added.

[prepared] - Add 1 1,2-dichloroethane to the above-mentioned mixture.
A solution of 1.2 ml (0.01 mol) of hosten dimer (trichloromethyl chloroformate) dissolved in 5aQ was added dropwise over 7 minutes with stirring at a temperature of 21"0.
The reaction was carried out by stirring for an additional 15 minutes.9 After the reaction was completed, 1
．． The 2-dichloroethane layer was separated, concentrated, and then poured into hexane. The precipitate was filtered, dried, dissolved in chloroform, and reprecipitated into hexane.

The +1f precipitate was filtered and dried to obtain a polymer.

The reaction conditions and results are shown in Table 1.

The abbreviations in Table 1 indicate the following.

) IPF...9,9-bis(4-hydroxyphenyl)fluoreneTBG...tetrabutylammonium chloride (surfactant) DCE...l, 2-dichloro, luethane, ↑CMCF・
... Trichloromethyl chloroformate (phosgene dimer) Mn, 14w ... Number average molecular weight by gel permeability electron chromatography (GPC), weight average molecular weight yield ... Measure solid content Thermogravimetric analysis (TG) showed a thermogravimetric loss of 5%.

Examples 2 to 14 Reactions were carried out in the same manner as in Example 1 except that the reaction conditions were changed as shown in Table 1. The results are shown in Table 1.

In addition, in Example 12, HPF, H2O, and NaOH were mixed at 50%
It was heated to ℃ and then cooled before use.

As can be seen from Table 1, in Example 7, the dropping time was 35 minutes.

When the reaction time after dropping is 70 minutes, Mw/Mn is 4.19
In Example 8, when the dropping time was 80 minutes and the reaction time after dropping was 120 minutes, H9I/ii"nt*1, Htot4J, and nnb<r during the reaction.

When the temperature decreases, the degree of loading of the polycarbonate tends to decrease.

The decomposition temperature of the polymer obtained in Example 5 was 465°C,
Glass transition temperature 260℃, total light transmission -4t91.5%
, yellowness 1.7%, refractive index! , 67.

Example 15 The reaction was carried out in the same manner as in Example 5 except that no surfactant was used, and results similar to Example 5 and C were obtained.

Examples 1 to 7 shown in Table 1 examine the effects of the dropwise addition time of the phosgene dimer solution and the reaction time after the dropwise addition on the molecular weight and molecule-1 distribution.

Among these, Example 3 had the best molecule 4) distribution, and Example 5 had the best molecule 4) distribution, and was also good in film forming.

The Y# effect of the reaction time after dropping when the dropping time during the reaction is kept constant at 30 minutes can be judged from Example 5, 8.12゜13, but if one reaction time exceeds 60 minutes, It can be seen that there is not much merit in using a long time, and on the contrary, it tends to reduce the degree of dispersion. Also, use of phosgene dimer according to Example 8.9; 1: #stomach, Example 9. The #echo of alkali usage can be determined by lO.

Further, in Example 11, a large amount of surfactant was used, and the molecular weight distribution of the obtained polycarbonate was monodisperse. In Example 14, a large amount of dichloroethane was used, but no special influence π was observed in this case either.

Comparative Example A polycarbonate was produced by a homogeneous solution polymerization method instead of an interfacial polymerization method.

9.9-bis(4-hydroxyphenyl)fluorene and phosgene diamond are used as raw materials, and the solvents are tetrahydrofuran (THF) and dioxane.

Using pyridine, chloroform, benzene, and toluene,
As a result of conducting the reaction with and without using a base such as triethylamine or pyridine as a dehydrochlorination agent, there were many polymers having a number average molecular weight of about too much. Although some polymers with a molecular weight of about 30,000 were obtained, they could not be formed into films.

Moreover, the yields were all around 50%, which was not satisfactory.

(The following is a blank space) Effects of the Invention According to the present invention, the use of phosgene dimer improves the safety in one reaction, and since it is a liquid, it is easy to handle. Further, the reaction can be carried out under mild conditions, and a polycarbonate having a high degree of polymerization, excellent heat resistance and transparency, and a large refractive index can be produced in a yield of <111.

The product of the present invention has a high melting point and does not melt even when cut, so it is suitable for plastic lenses and various molded products. It can also withstand baking temperatures, so it can be used for exterior panels of 11.

This is an epoch-making product that can be used in fields where it was previously difficult to use.

Claims (2)

[Claims] (1) An alkaline aqueous solution of 9,9-bis(4-hydroxyphenyl)fluorenes represented by the general formula below, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R is H, CH_3
, C_2H_5. ) A method for producing a heat-resistant polycarbonate, which comprises interfacial polycondensation of phosgene dimer and an organic halogen compound solution under stirring. (2) Claim 1 in which a surfactant is present during the interfacial polycondensation of an alkaline aqueous solution of 9,9-bis(4-hydroxyphenyl)fluorenes and an organic halogen compound solution of phosgene dimer. Method for producing the heat-resistant polycarbonate described.