Catalytic process for preparing polycarbonates from carbonic acid

A process for preparing polycarbonates according to the invention by melt polycondensation of aromatic dihydroxy compounds and carbonic acid diesters, is characterized by using an aromatic dihydroxy compound and a carbonic acid diester, wherein the combined content of hydrolyzable chlorine in those monomers falls within the particular range. Another process for preparing polycarbonates according to the invention by melt polycondensation of aromatic dihydroxy compounds and carbonic acid diesters, is characterized by using a catalyst comprising (a) a nitrogen containing basic compound and (b) aromatic hihydroxy compound of an alkali metal or alkaline earth metal compound, or (a) and (b) and (c) boric acid or boric ester.

FIELD OF THE INVENTION 
This invention relates to processes for preparing polycarbonates and more 
particularly to processes for preparing polycarbonates which have high 
molecular eights, excellent heat resistance and water resistance and, 
moreover, which have been improved in color tone. 
BACKGROUND OF THE INVENTION 
Because of their excellent mechanical characteristics, such as impact 
resistance, and because of their excellent heat resistance and 
transparency, polycarbonates are widely used for various purposes. Known 
as the method for the preparation of polycarbonates as referred to above 
is a process (interface method) which involves a direct reaction of 
aromatic dihydroxy compounds such as bisphenol with phosgene, or a process 
in which aromatic dihydroxy compounds such as bisphenol and carbonic 
diesters such as diphenyl carbonate are allowed in molten state to undergo 
ester interchange reaction (polycondensation reaction). 
In a process for preparing polycarbonates by ester interchange reaction of 
aromatic dihydroxy compounds with carbonic diesters, usually the reactants 
are heated under reduced pressure at a temperature of 
250.degree.-330.degree. C. and allowed In molten state to undergo the 
ester interchange reaction in the presence of catalysts such as organic 
acid salts, inorganic acid salts, oxides, hydroxides or hydrides of metals 
or alcoholates. This process is advantageous over the above-mentioned 
interface method in that polycarbonates can be prepared at a relatively 
low cost. In this process, however, the aromatic dihydroxy compound and 
the carbonic acid diester are reacted in molten state, and the 
polycarbonate being formed is exposed to elevated temperatures for a 
prolonged period time, and in consequence, there has been posed such a 
serious problem that the product assumes a yellow color, and becomes poor 
in heat resistance or water resistance. For this reason, polycarbonates 
prepared by this process have hardly found application in field such as 
plastic glass and lenses where materials having a good color tone are 
required. 
Furthermore, Japanese Patent Laid-Open-to-Public Publn. No. 51719/1985 
proposes a process for preparing polycarbonates, which involves the use of 
catalysts comprising nitrogen containing basic compounds and boron 
compounds, and the desired polycarbonates assuming a relatively pale color 
are obtained by the proposed process when the catalysts as proposed are 
used therefor. However, the proposed catalysts involved such a problem 
that they are low in polymerization activity 
With the view of solving such problems as mentioned above, we conducted 
extensive research and eventually have accomplished the present invention 
on the basis of our finding that the purpose intended can be attained by 
carrying out the polycondensation of aromatic dihydroxy compounds with 
carbonic diesters either using starting monomers having a reduced content 
of a specific impurity or in the presence of a specific catalyst. 
OBJECT OF THE INVENTION 
The present invention is intended to solve such problems associated with 
the prior art as mentioned above and an object of the invention is to 
provide processes for preparing polycarbonates, said processes being 
capable of obtaining the polycarbonates which have high molecular weight 
and are excellent in heat resistance and water resistance and, moreover, 
which are improved in color tone. 
SUMMARY OF THE INVENTION 
A first process for preparing polycarbonates according to the invention by 
melt polycondensation of aromatic dihydroxy compounds and carbonic acid 
diesters used as monomers, is characterized by using an aromatic dihydroxy 
compound and a carbonic acid diester, the combined content of hydrolyzable 
chlorine in said monomers falling within the following range. 
Hydrolyzable chlorine content: not more than 3 ppm 
A second process for preparing polycarbonates according to the invention by 
melt polycondensation of aromatic dihydroxy compounds and carbonic acid 
diesters used as starting monomers, is characterized by using an aromatic 
dihydroxy compound and a carbonic acid diester, the combined content of 
hydrolyzable chlorine, the combined content of sodium ion and the combined 
content of iron ion in said monomers respectively falling within the 
following ranges. 
Hydrolyzable chlorine content: not more than 3 ppm 
Sodium ion content: not more than 1.0 ppm 
Iron ion content: not more than 1.0 ppm 
In the first process for preparing polycarbonates according to the 
invention there are used as starting monomers an aromatic dihydroxy 
compound and a carbonic acid diester having a combined content of 
hydrolyzable chlorine not more than a specific level. In the second 
process for preparing polycarbonates according to the invention there are 
used as starting monomers an aromatic dihydroxy compound and a carbonic 
acid diester having a combined of hydrolyzable chlorine, a combined 
content of odium ion and a combined content of iron ion respectively not 
more than specific levels. By these processes there can be prepared 
polycarbonates which do not assume undesirable colors such as yellow, and 
which are excellent in color tone, heat resistance, water resistance and 
boiling water resistance. 
A third process for preparing polycarbonates according to the invention by 
melt polycondensation of aromatic dihydroxy compounds and carbonic acid 
diesters, is characterized by using a catalyst comprising 
(a) a nitrogen containing basic compound, and 
(b) from 10.sup.-8 to 10.sup.-3 mole, based on 1 mole of the aromatic 
dihydroxy compound, of an alkali metal or alkaline earth metal compound. 
A fourth process for preparing polycarbonates according to the invention by 
melt polycondensation of aromatic dihydroxy compounds and carbonic 
diesters, is characterized by using a catalyst comprising 
(a) a nitrogen containing basic compound, 
(b) from 10.sup.-8 to 10.sup.-3 mole, based on 1 mole of aromatic dihydroxy 
compound, of an alkali metal or alkaline earth metal compound, and 
(c) boric acid or boric acid ester. 
The third and fourth processes according to the invention wherein an 
aromatic dihydroxy compound is melt polycondensed with a carbonic acid 
diester in the presence of specific catalysts, are productive of 
polycarbonates which have high molecular weight, excellent heat resistance 
and water resistance and, moreover which are improved in color tone.

DETAILED DESCRIPTION OF THE INVENTION 
The processes for preparing polycarbonates of the present invention will be 
illustrated below in detail. 
In the present invention, the polycarbonates are prepared from aromatic 
dihydroxy compounds and carbonic diesters as starting materials. 
The aromatic dihydroxy compounds used in the present invention are those 
which are represented by the following general formula [I] 
##STR1## 
wherein X is 
##STR2## 
--O--, --S--, SO-- or --SO.sub.2 --, R.sub.1 and R.sub.2 are each a 
hydrogen atom or a monovalent hydrocarbon group, R.sub.3 is a divalent 
hydrocarbon group, and the aromatic nuclei may by substituted by a 
monovalent hydrocarbon group or groups. 
Useful aromatic dihydroxy compounds as illustrated above include in the 
concrete bis(hydroxyaryl) alkanes such as bis(4-hydroxyphenyl)methane, 
1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 
2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 
bis(4-hydroxyphenyl)phenylmethane, 2,2 bis(4 hydroxy 1 
methylphenyl)propane, 1,1-bis(4-hydroxy-t-butylphenyl) propane, and 
2,2-bis(4-hydroxy-3-bromophenyl)propane; bis(hydroxyaryl)cycloalkanes such 
as 1,1-(4-hydroxyphenyl)cyclopentane and 
1,1-bis(4-hydroxyphenyl)cyclohexane; dihydroxyaryl ethers such as 
4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether; 
dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; dihydroxydiaryl sulfoxides 
such as 4,4'-dihydroxydiphenyl sulfoxide and 
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; and dihydroxydiaryl 
sulfones such as 4,4'-dihydroxydiphenyl sulfone and 
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. 
Of the compounds as exemplified above, particularly preferred is 2,2 bis(4 
hydroxyphenyl)propane. 
Useful carbonic diesters include in the concrete diphenyl carbonate, 
ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, 
dinaphthyl carbonate, bis(diphenyl) carbonate, diethyl carbonate, dimethyl 
carbonate, dibutyl carbonate and dicyclohexyl carbonate. 
Of the diesters as exemplified above, particularly preferred is diphenyl 
carbonate. 
The carbonic diester used herein may contain a minor amount, e.g., up to 50 
mole, preferably up to 30 mole, of a dicarboxylic acid or its ester. 
Examples of such dicarboxylic acids and esters thereof, include, for 
example, terephthalic acid, isophthalic acid, diphenyl terephthalate and 
diphenyl isophthalate. When such a dicarboxylic acid or its ester is 
conjointly used polyesterpolycarbonate is prepared. 
In preparing polycarbonates by carrying out the process of the present 
invention, it is desirable that the above-mentioned carbonic diester is 
used in an amount of 1.01 to 1.30 moles, preferably 1.02 to 1.20 moles 
based on 1 mole of the aforementioned aromatic dihydroxy compound. 
In the first and second processes according to the invention a combined 
content of hydrolyzable chlorine contained in the aromatic dihydroxy 
compound and the carbonic acid diester should be not more than 3 ppm, 
preferably not more than 2 ppm, and more preferably not more than 1 ppm. 
The term "hydrolyzable chlorine" means chlorine which is present in the 
form of salts such as sodium chloride and potassium chloride. A content of 
hydrolyzable chlorine contained in each starting material used herein can 
be determined by analysis, for example, ion chromatography of an extract 
of the material with water. 
If the combined content of hydrolyzable chlorine contained in the starting 
monomers exceeds 3 ppm, color tone of the product tends to become poor. 
It is also desirable in the present invention that a hydrolyzable chlorine 
content of the starting carbonic acid diester is not more than 2 ppm, 
preferabIy not more than 1 ppm, and more preferably not more than 0.5 ppm. 
Conventionally, the starting aromatic dihydroxy compound and carbonic acid 
diester (in particular carbonic acid diester prepared by the so-called 
phosgen process) are purified by distillation or recrystallization, and 
thereafter subjected to melt polycondensation. However, it is generally 
difficult to reduce the combined hydrolyzable chlorine content of the 
starting monomers by mere distillation below the desired level. This is 
especially true with carbonic acid diesters prepared by the phosgen 
process which may contain hydrolyzable chlorine in the form of phenyl 
chloroformate. 
It has been found that even with carbonic acid esters prepared by the 
phosgen process the content of hydrolyzable chlorine can be easily reduced 
below 2 ppm by washing with hot water having a pH of from 6 0 to 9.0, 
preferably from 7.0 to 8.5, and more preferably from 7.0 to 8.0, and kept 
at a temperature of from 78 to 105.degree. C., preferably from 80 to 
100.degree. C. and more preferably from 80 to 90.degree. C. 
Examples of the aqueous weak alkaline solution which can used herein 
include, for example, those of sodium hydroxide, potassium hydroxide, 
lithium hydroxide, sodium carbonate, potassium carbonate, ammonium 
hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate and 
tetramethylammonium hydroxide. Of these, aqueous solutions of sodium 
hydrogencarbonate, sodium carbonate, potassium hydrogencarbonate and 
potassium carbonate ar preferred. 
The carbonic acid diester so washed with a hot weakly alkaline aqueous 
solution is used in the melt polycondensation either directly or 
preferably after having been distilled. 
Incidentally, in the cases of carbonic acid diesters prepared by processes 
other than the phosgen process, such as carbonic acid diester prepared 
from dialkyl carbonates, it is sometimes possible to reduce the 
hydrolyzable chlorine content by mere distillation to 2 ppm or below. 
It is also advantageous to use the aromatic dihydroxy compound and carbonic 
acid diester having not only the combined content of hydrolyzable chlorine 
reduced to not more than 3 ppm. but also the combined content of sodium 
ion reduced to not more than 1.0 ppm, preferably not more than 0.8 ppm. 
and more preferably not more than 0.6 ppm. Further it is also advantageous 
to use the aromatic dihydroxy compound and carbonic acid diester having 
the combined content of iron ion reduced to not more than 1.0 ppm, 
preferably not more than 0.8 ppm, and more preferably not more than 0.6 
ppm. By doing so, polycarbonates of further improved color tone can be 
prepared. 
The sodium ion content and the iron ion content in the aromatic dihydroxy 
compound and the carbonic acid diester may be determined by 
atomic-absorption spectroscopy or induced coupling plasma emission 
spectroscopy. 
Suitable procedures to reduce the sodium ion content and the iron ion 
content in the aromatic dihydroxy compound and the carbonic acid diester 
include washing with a hot weakly alkaline aqueous solution, distillation 
and recrystallization. 
The melt polycondensation of the aromatic dihydroxy compound and the 
carbonic acid diester in the first and second processes according to he 
invention can be carried out either in the presence of any catalysts that 
have heretofore been known as being useful in the reaction concerned or in 
the presence of novel catalysts proposed herein. 
Examples of known catalysts, for example, those described in Japanese 
Patent Publications 36-694 and 36-13942, include acetates, carbonates, 
borates, oxides, hydroxides, hydrides and alcoholates of various metals 
including alkali metals such as lithium, sodium and potassium; alkaline 
earth metals such as magnesium, calcium and barium: and other metals such 
as zinc, cadmium, tin, antimony, lead, manganese, cobalt and nickel. 
Further, combinations of a nitrogen containing basic compound with boric 
acid or esters of boric acid or phosphorus compounds may be also used as 
catalysts in the first and second processes according to the invention. 
These catalysts may be used in an amount, based on 1 mole of the aromatic 
dihydroxy compound, of normally from 10.sup.-6 to 10.sup.-1 mole, 
preferably from 10.sup.-5 to 10.sup.-2 mole. 
The third and fourth processes according to the invention in which 
preferred catalysts are used will now be described. 
As mentioned previously, in the third process for preparing polycarbonates 
of the present invention preparation of the polycarbonates by melt 
polycondensation of the aromatic dihydroxy compounds and the carbonic 
diesters is carried out by using a catalyst comprising 
(a) a nitrogen containing basic compound, and 
(b) an alkali metal or alkaline earth metal compound. 
Useful nitrogen containing basic compound as component(a) of the catalyst 
includes in the concrete tetraalkyl-, aryl- or alkarylammonium hydroxides 
such as tetramethylammonium hydroxide (Me.sub.4 NOH), tetraethylammonium 
hydroxide (Et.sub.4 NOH), tetrabutylammonium hydroxide (Bu.sub.4 NOH) and 
trimethylbenzylammonium hydroxide 
##STR3## 
tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine 
and triphenylamine; secondary amines represented by R.sub.2 NH (in the 
formula, R is alkyl such as methyl or ethyl, or aryl such as phenyl or 
toluyl); primary amines represented by RNH.sub.2 (in the formula, R is as 
defined above); or basic salts such as ammonia, tetramethylammonium 
borohydride (Me.sub.4 NBH.sub.4), tetrabutylammonium borohydride(Bu.sub.4 
NBH.sub.4), tetrabutylammonium tetraphenyl borate(Bu.sub.4 NBPh.sub.4) and 
tetramethylammonium tetraphenyl borate (Me.sub.4 NBPh.sub.4). 
Of the basic compounds as exemplified above, particularly preferred are 
tetraalkylammonium hydroxides. 
Useful alkali metal compound as component (b) of the catalyst includes in 
the concrete sodium hydroxide, potassium hydroxide, lithium hydroxide, 
sodium hydrogencarbonate, potassium hydrogencarbonate, lithium 
hydrogencarbonate, sodium carbonate, potassium carbonate, lithium 
carbonate, sodium acetate, potassium acetate, lithium acetate, sodium 
stearate, potassium stearate, lithium stearate, sodium borohydride, 
lithium borohydride and sodiumborophenylate, sodium benzoate, potassium 
benzoate, lithium benzoate, disodium hydrogenphosphate, dipotassium 
hydrogenphosphate, dilithium hydrogenphosphate, disodium salt of BPA, 
dipotassium salt of BPA, dilithium salt of BPA, sodium phenylate, 
potassium phenylate, lithium phenylate. 
Furthermore, useful alkaline earth metal compound as component (b) of the 
catalyst includes in the concrete calcium hydroxide, barium hydroxide, 
magnesium hydroxide, strontium hydroxide, calcium hydrogencarbonate, 
barium hydrogencarbonate, magnesium hydrogencarbonate, strontium 
hydrogencarbonate, calcium carbonate, barium carbonate, magnesium 
carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium 
acetate, strontium acetate, calcium stearate, barium stearate, magnesium 
stearate and strontium stearate. 
The nitrogen containing basic compound (a) as exemplified above is used in 
an amount of 10.sup.-6 -10.sup.-1 mole, preferably 10.sup.-5 -10.sup.-2 
mole, based on 1 mole of the aforementioned aromatic dihydroxy compound, 
and the alkali metal or alkaline earth metal compound (b) as exemplified 
above is used in an amount of 10.sup.-8 -10.sup.-3 mole, preferably 
10.sup.-7 -10.sup.-4 mole, particularly preferably 10.sup.-7 -10.sup.-5 
mole, based on 1 mole of the aforementioned aromatic dihydroxy compound. 
The use of the nitrogen containing basic compound (a) in amount of 
10.sup.-6 -10.sup.-1 mole based on 1 mole of the aromatic dihydroxy 
compound is desirable, because the rates of the ester interchange and 
polymerization reactions increased and, the resulting polycarbonates are 
excellent in color tone, heat resistance and water resistance. 
Furthermore, the use of the alkali metal or alkaline earth metal compound 
in an amount of 10.sup.-8 -10.sup.-3 based on 1 mole of the aromatic 
dihydroxy compound is desirable, because the polymerization activity, 
particularly the rate of polymerization markedly increases and, the 
resulting polycarbonates are excellent in color tone, heat resistance and 
water resistance. 
The catalyst which comprises such a combination of the nitrogen containing 
basic compound (a) and the alkali metal or alkaline earth metal compound 
(b) in the manner as illustrated above has a high polymerizatIon activity 
and can form high molecular weight polycarbonates, when it is used in 
practicing the melt polycondensation of the aromatic dihydroxy compound 
and carbonic diester, according to the process for preparing 
polycarbonates of the present invention. In addition to that, the 
polycarbonate obtained thereby is excellent in heat resistance and water 
resistance, and what is more, it is improved in color tone and excellent 
in transparency. 
Furthermore, in the fourth process for preparing polycarbonates of the 
present invention, preparation of the polycarbonates by melt 
polycondensation of aromatic dihydroxy compounds and carbonic diesters is 
carried out by using a catalyst comprising 
(a) a nitrogen containing basic compound, 
(b) an alkali metal compound or an alkaline earth metal compound, and 
(c) boric acid or boric acid ester. 
Useful nitrogen containing basic compound as component (a) of the catalyst 
and useful alkali metal or alkaline earth metal compound as component (b) 
of the catalyst are those as exemplified previously with respect to the 
third process according to the invention. 
Useful boric acid or boric acid ester as component (c) of the catalyst 
includes boric acid and boric acid esters represented by the general 
formula B(OR).sub.n (OH).sub.3-n (in the formula, R is alkyl such as 
methyl and ethyl, or aryl such as phenyl, and n is 1,2 or 3). 
Concretely, such boric acid ester as illustrated above includes trimethyl 
borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl 
borate. triphenyl borate, tritolyl borate and trinapthyl borate. 
In the fourth process for preparing polycarbonates of the present 
invention, the nitrogen containing basic compound (a) is used in an amount 
of 10.sup.-6 -10.sup.-1 mole, preferably 10.sup.-5 -10.sup.-2 mole based 
on 1 mole of the aromatic dihydroxy compound, the alkali metal or alkaline 
earth metal compound (b) is used in an amount of 10.sup.-8 -10.sup.-3 
mole, preferably 10.sup.-7 -10.sup.-4 mole, and more preferably 10.sup.-7 
-10.sup.-5 mole based on 1 mole of the aromatic dihydroxy compound, and 
the boric acid or boric acid ester (c) is used in an amount of 10.sup.-8 
-10.sup.-1 mole, preferably 10.sup.-7 -10.sup.-2 mole, and more preferably 
10.sup.-6 -10.sup.-4 mole base on 1 mole of the aromatic dihydroxy 
compound. 
The use of the nitrogen containing basic compound (a) in an amount of 
10.sup.-6 -10.sup.-1 mole based on 1 mole of the aromatic dihydroxy 
compound is desirable, because the rates of ester interchange and 
polymerization increase and, the resulting polycarbonates are excellent in 
color tone, heat resistance, and water resistance. 
The use of the alkali metal or alkaline earth metal compound (b) in an 
amount of 10.sup.-8 -10.sup.-3 mole based on 1 mole of the aromatic 
dihydroxy compound is desirable, because the rate of polymerization 
increases and, the resulting polycarbonates are excellent in color tone, 
water resistance and heat resistance. 
Furthermore, the use of boric acid or boric acid ester (c) in an amount of 
10.sup.-8 -10.sup.-1 mole based on 1 mole of the aromatic dihydroxy 
compound is desirable, because the decrease of the molecular weight after 
heat aging was restrained and, the resulting polycarbonates are excellent 
in color tone, water resistance, and heat resistance. 
The catalyst used in the third process according to the invention 
comprising a combination of the nitrogen containing basic compound (a), 
and alkil metal compound (b), and the catalyst used in the fourth process 
according to the invention comprising a combination of the nitrogen 
containing basic compound (a), alkil metal or alkaline earth metal 
compound (b) and boric acid or its ester (c), are found much higher in 
polymerization activity than known catalysts for the same melt 
polycondensation. They can form high molecular weight polycarbonates which 
are excellent in heat resistance and water resistance and improved in 
color tone and transparency. 
In the third and fourth processes for preparing polycarbonates according to 
the invention, it is preferred that the starting aromatic dihydroxy 
compound and carbonic diester have combined contents of hydrolyzable 
chlorine, sodium ion and iron respectively falling within the range 
prescribed hereinabove, but such is not always necessary. 
In the first and second processes for preparing polycarbonates according to 
the invention, the melt polycondensation may be carried out in the 
presence of any suitable catalysts including not only those which have 
heretofore been used for the same reaction, those described hereinbefore 
with respect to the third and fourth processes according to the invention, 
but also catalysts comprising a combination of the above-mentioned 
nitrogen containing basic compound (a), and alkali metal or alkaline earth 
metal compound (b) or a combination of the above mentioned alkali metal or 
alkaline earth metal compound (b) and boric acid its ester (c). 
The polycondensation reaction of the aromatic dihydroxy compound with 
carbonic diester in the processes according to the invention may be 
carried out under the same conditions conventionally known as those 
commonly employed therefor. Concretely, a first stage reaction of the 
aromatic dihydroxy compound with carbonic diester is carried out under 
ordinary pressure at a temperature of 80.degree.-250.degree. C., 
preferable 100.degree.-230.degree. C., and more preferably 
120.degree.-190.degree. C., for 0-5 hours, preferably 0-4 hours, and more 
preferably 0.25-3 hours. Subsequently, the system is evacuated and the 
reaction temperature is elevated to carry out the reaction of the aromatic 
dihydroxy compound with carbonic diester, and finally the polycondensation 
reaction of the aromatic dihydroxy compound with carbonic diester is 
carried out under reduced pressure of less than 1 mmHg at a temperature of 
240.degree.-320.degree. C. 
The reaction of the aromatic dihydroxy compounds with carbonic diesters as 
illustrated above may be carried out by either continuous or batchwise 
process. Furthermore reaction apparatuses in which the above-mentioned 
reaction is carried out may be of a tank, tube or column type. 
EFFECT OF THE INVENTION 
By the first process for preparing polycarbonates according to the 
invention wherein an aromatic dihydroxy compound and a carbonic acid 
diester used as starting monomers have a combined content of hydrolyzable 
chlorine not more than a specific level, or have, in addition to such a 
combined level of hydrolyzable chlorine, a combined content of sodium ion 
and a combined content of iron ion respectively not more than specific 
levels, there can be prepared polycarbonates which do not assume 
undesirable colors such as yellow, and which are excellent in color tone, 
heat resistance, water resistance and boiling water resistance. 
The third and fourth processes according to the invention wherein an 
aromatic dihydroxy compound is melt polycondensed with a carbonic acid 
diester in the presence of specific catalysts, are productive of 
polycarbonates which have high molecular weight, excellent heat resistance 
and water resistance and, moreover which are improved in color tone. 
The present invention is illustrated below with reference to examples, but 
it should be constructed that the invention is in no way limited to those 
examples. 
TESTING METHOD 
Methods of measurement of physical properties employed are shown below. 
Intrinsic viscosity (IV): The test specimen was measured for intrinsic 
viscosity at 20.degree. C. in methylene chloride using a Ubbelohde's 
viscometer. 
Hue (b value): The test specimen of a press sheet of a 2mm thickness was 
measured for Lab values by the transmission method using Color and Color 
Difference Meter ND-1001 Dp manufactured and sold by Nippon Denshoku Kogyo 
K.K., and the measured b value was taken as an index of yellowness. 
Heat aging test: pellets of the test specimen were dried at 120.degree. C. 
under 400 mmHg for 12 hours, and 4.5 g of the pellets thus dried was kept 
for 16 hours at 250.degree. C. in a gear oven (GHPS-212 manufactured and 
sold by Tabai Seisakusho K.K., air replacement ratio 71.6 times/hr.), and 
then cooled to room temperature. The test specimen thus treated was formed 
into a press sheet of 2 mm thick, and measured for hue(b value) and IV. 
Boiling water test: A dumbbell of 5 mm width x 5 cm length was punched out 
from a press sheet of 0.5 mm thickness, immersed in boiling water, and 
withdrawn therefrom after the lapse of 1 day, 3 days and 7 days, 
respectively. Within 1 hour after the removal, the dumbbell thus treated 
was subjected to tensile test with Instron 1132 under the conditions a 
distance of 30 mm between zippers, a rate of pulling of 50 mm/min, and a 
range of measurement of 50 kg, thereby measuring a value of elongation 
(%). 
CONDITIONS OF PREATION OF PRESS SHEET: Pellets of the test specimen were 
dried for 12 hours at 120.degree. C. under 400 mmHg, maintained for 10 
minutes under nitrogen atmosphere. Thereafter, the pellets were pressed 
for 5 minutes at 280.degree. C. and 100 kg/cm.sup.2, and then pressed for 
5 minutes at room temperature for cooling. 
Hydrolyzable chlorine content: Five g of a material was dissolved in 10 ml 
of toluene. After addition of 10 ml of an eluent (2.8 mM of NaHCO.sub.3 
2.25 mM of Na.sub.2 CO.sub.3), the solution was extracted with water. The 
chlorine content of the extract was determined by ion chromatography(using 
Ion chrophatograph 2000i supplied by DIONEX K.K.). 
Sodium ion content: Sodium content of a material was determined on 20 g of 
the material by atomic-absorption spectroscopy (using HITACHI 180-80). 
Iron content: Iron content of a material was determined on 20 g of the 
material by induced coupling plasma emission spectroscopy (using NJA ICPA 
575supplied by Nippon Jarrelasch K.K.). 
EXAMPLE 1 
Diphenyl carbonate supplied by BAYER A G. having a hydrolyzable chlorine 
content of 5.9 ppm was washed with hot water at a temperature of 
80.degree. C. and a pH of 7.0, and distilled under reduced pressure at a 
yield of 90% to provide diphenyl carbonate having a hydrolyzable chlorine 
content of 0.3 ppm. 
In a glass reactor 51.36 g(0.24 mole) of the so treated diphenyl carbonate, 
45.6 g (0.2 mole) of Bisphenol A having a hydrolyzable chlorine content of 
0.2 ppm supplied by GE corporation and 3.1 mg(2.5.times.10.sup.-4 
mole/mole of BAP) of boric acid H.sub.3 BO.sub.3 (guaranteed reagent 
supplied by WAKO K.K. was stirred using a stirrer made of Ni, under a 
nitrogen atmosphere at a temperature of 180.degree. C. and under a 
pressure of 760 mmHg for a period of 30 minutes. At the end of the period 
there were added to the reactor 30.4 mg of 15% tetramethylammonium 
hydroxide Me.sub.4 NOH aqueous solution supplied by TOYO GOSEI K.K. 
(2.5.times.10.sup.-4 mole of Me.sub.4 NOH/mole of BPA) and 0.42 mg 
(0.25.times.10.sup.-4 mole/mole of BAP) of sodium hydrogencarbonate 
NaHCO.sub.3 guaranteed reagent supplied by WAKO K.K., and the mixture was 
stirred for further 30 minutes at a temperature of 180.degree. C. under 
nitrogen atmosphere to effect the ester interchange reaction. 
The reaction mixture was then heated to a temperature of 210.degree. C. and 
the pressure was slowly reduced to 200 mmHg. The mixture was maintained 
under these conditions for 1 hour, and further maintained for 20 minutes 
at 240.degree. C. and 200 mmHg. The pressure was then slowly reduced to 
150 mmHg, and the mixture was maintained at 240.degree. C. for 20 minutes 
under this pressure and for further 20 minutes under 100 mmHg, for 0.5 
hour under 15mmHg. Finally, the temperature was then raised to 270.degree. 
C. and the pressure was reduced to 0.5 mmHg, and the reaction was 
continued under these conditions for 2.5 hours. Polycarbonate having an 
intrinsic viscosity of 0.55 was obtained. The b value of the product was 
1.3. 
The results are shown in Table 1. 
EXAMPLES 2 AND 3 
Diphenyl carbonates (DPC) having hydrolyzable chlorine sodium ion and iron 
ion contents indicated in Table 1 were prepared in the same manner as in 
Example except that the recovery yield of DPC at the stage of distillation 
under reduced pressure was varied. Using the so prepared DPC 
polycarbonates were prepared following the procedures of Example 1. 
The results are shown in Table 1. 
EXAMPLE 4 
Example 1 was repeated except that the purified BAYER DPC was replaced with 
DPC obtained by distillation of DPC supplied Eni company which had been 
prepared from dimethyl carbonate. 
The results are shown in Table 1. 
COMATIVE EXAMPLE 1 
Example 1 was repeated except that the unpurified DPC as such was used in 
the melt polycondensation. 
The results are shown in Table 1. 
COMATIVE EXAMPLE 2 
Example 1 was repeated except that instead of the purified BAYER DPC 
undistilled by DPC supplied by Eni company was used in the melt 
polycondensation. 
The results are shown in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Comp. 
Comp. 
Starting material Ex. 1 
Ex. 2 
Ex. 3 
Ex. 4 
Ex. 1 
Ex. 2 
__________________________________________________________________________ 
Starting 
DPC Hydrolyzable Cl (ppm) 
0.30 
0.20 
0.10 
0.09 
5.90 
4.12 
material 
Na ion (ppm) &lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
0.10 
1.10 
Fe ion (ppm) 0.15 
0.10 
0.05 
0.07 
0.40 
1.18 
Bisphenol A 
Hydrolyzable Cl (ppm) 
0.20 
0.20 
0.20 
0.20 
0.20 
0.20 
Na ion (ppm) 0.06 
0.06 
0.06 
0.06 
0.06 
0.06 
Fe ion (ppm) 0.21 
0.21 
0.21 
0.21 
0.21 
0.21 
Physical 
IV (dl/g) 0.55 
0.54 
0.54 
0.53 
0.50 
0.53 
properties 
b value 1.3 1.2 1.0 0.9 2.0 2.1 
of the 
Heat resistance 250.degree. C. .times. 16 hr IV (dl/g) 
0.50 
0.49 
0.49 
0.48 
0.39 
0.40 
product 
color tone b value 21.3 
21.2 
20.8 
20.9 
34.5 
34.8 
Boiling water resistance 
Elongation (%) after in boiling water 
for 
0 day 97.0 
98.1 
103.5 
102.1 
87.3 
93.2 
1 day 57.4 
61.5 
62.7 
61.3 
43.5 
35.4 
3 day 24.7 
29.3 
31.5 
32.5 
12.3 
11.6 
7 day 21.4 
23.2 
25.3 
26.4 
7.6 5.3 
__________________________________________________________________________ 
EXAMPLE 8 
Into a 100 ml glass reactor was charged a mixture comprising 47.9 g (0.22 
mole) of diphenyl carbonate used in Example 12, 4.56 g (0.20 mole) of 
Bisphenol A used in Example 12 and 3.7 mg (3.times.10.sup.-4 mole/BPA 1 
mole) of boric acid (guaranteed reagent, a product of Wako Shiyaku). The 
mixture was then heated in N.sub.2 atmosphere at 180.degree. C., followed 
by stirring with a nickel stirring rod for 30 minutes. Thereafter, the 
reactor was charged with a mixture comprising 36.5 mg Me.sub.4 NOH 
3.times.10.sup.-4 mole/BPA 1 mole) of a 15% aqueous solution of 
tetramethylammonium hydroxide Me.sub.4 NOH (a product of Toyo Gosei) and 
0.50 mg (0.3.times.10.sup.-4 mol/BPA 1 mole) of sodium hydrogencarbonate 
NaHCO.sub.3 (guaranteed reagent, a product of Wako Shinyaku), and the 
contents of he reactor was stirred in N.sub.2 atmosphere at 180.degree. C. 
for 30 minutes to effect ester interchange reaction. 
Subsequently, the reaction was continued continuously for 1 hour at 
210.degree. C. and a pressure gradually reduced to 200 mmHg, for 20 
minutes at a temperature raised up to 240.degree. C. , for 20 minutes at a 
pressure gradually reduced to 150mmHg, for 20 minutes at a pressure 
reduced to 100 mmHg, and for 0.5 hours at a pressure reduced to 15 mmHg. 
The reaction was finally carried out for 2.5 hours at a temperature raised 
to 270.degree. C. and a pressure reduced to 0.5 mm Hg, whereby a 
polycarbonate having IV of 0.58 was obtained. 
The results obtained are shown in Table 2. 
EXAMPLES 6-11 AND COMATIVE EXAMPLES 3-7 
The same procedure as described in Example 5 was repeated except that in 
place of the sodium hydrogencarbonate, tetramethylammonium hydroxide and 
boric acid used in Example 5 in amounts as shown in Table 2, there were 
used nitrogen containing basic compounds, alkali metal compounds(alkaline 
earth metal compounds) and boric acid or boric acid esters in amounts as 
shown in Tables 2 and 3, respectively. 
The results obtained are shown in Tables 2 and 3, respectively. 
TABLE 2 
__________________________________________________________________________ 
Ex. 5 
Ex. 6 Ex. 7 Ex. 8 
Ex. 9 
Ex. 10 
Ex. 11 
__________________________________________________________________________ 
Catalyst 
(a)Component amount(10.sup.-4 mole/BPA) 
Me.sub.4 NOH 3 
Me.sub.4 NOH 3 
Me.sub.4 NOH 3 
Me.sub.4 NOH 3 
Bu.sub.4 NOH 4 
Bu.sub.4 NBph.sub.4 2 
##STR4## 
(b)Component NaHCO.sub.3 
C.sub.17 H.sub.35 COOLi 
C.sub.17 H.sub.35 COONa 
NaOH NaHCO.sub.3 
NaHCO.sub.3 
NaHCO.sub.3 
amount(10.sup.-4 mole/BPA) 
0.3 0.3 0.3 0.3 0.2 0.2 0.2 
(c)Component H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
B(OPh).sub.3 
H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
amount(10.sup.-4 mole/BPA) 
3 2 1 1 3 0 1 
Physical properties 
of the product 
IV(dl/g) 0.58 0.56 0.57 0.57 0.53 0.50 0.57 
Hue(b value) 1.0 1.1 1.0 1.2 1.0 1.1 1.0 
Heat resistance 
(250.degree. C., 16 hr. after) 
IV(dl/g) 0.50 0.49 0.48 0.48 0.48 0.40 0.55 
Hue(b value) 21.3 21.2 22.0 23.5 21.0 24.0 22.0 
Boiling water resistance 
Tensile elongation (%) after 
boiling water immersion 
0 day after 97.0 95.0 96.2 103.1 
90.2 95.0 106.2 
1 day after 57.4 45.8 48.4 86.7 67.2 65.0 75.0 
3 days after 24.7 29.3 30.6 30.2 35.7 43.6 37.0 
7 days after 22.3 23.3 13.8 18.0 24.2 26.0 25.4 
__________________________________________________________________________ 
TABLE 3 
__________________________________________________________________________ 
Comp. Comp Comp. 
Comp. 
Comp. 
Ex. 3 Ex. 4 
Ex. 5 
Ex. 6 
Ex. 7 
__________________________________________________________________________ 
Catalyst 
(a) 
Component Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
-- 
amount (10.sup.-4 mole/BPA) 
3 100 30 100 -- 
(b) 
Component -- -- NaHCO.sub.3 
NaHCO.sub.3 
NaHCO.sub.3 
amount (10.sup.-4 mole/BPA) 
-- -- 30 100 100 
(c) 
Component H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
-- 
amount (10.sup.-4 mole/BPA) 
3 100 1 0 0 
Physical properties of the product 
IV (dl/g) 0.36 0.50 0.68 0.69 0.67 
Hue (b value) 1.1 1.1 2.6 2.7 2.8 
Heat resistance (250.degree. C., 16 hr .multidot. after) 
IV (dl/g) 0.29 0.33 0.54 0.45 0.43 
Hue (b value) No molding 
30.0 39.0 37.0 38.1 
Boiling water resistance 
can be formed 
Tensile elongation (%) after 
boiling water immersion 
0 day after 48.5 56.1 98.0 99.0 98.1 
1 day after 5.3 5.8 5.2 9.5 8.3 
3 days after 2.8 3.5 2.5 8.2 7.6 
7 days after 2.3 2.5 2.7 7.3 5.1 
__________________________________________________________________________ 
EXAMPLE 12 
Diphenyl carbonate supplied by BAYER A.G. having a hydrolyzable chlorine 
content of 5.9 ppm was washed twice with hot water at a temperature of 
80.degree. C. and a pH of 7.0, and distilled under reduced pressure at a 
yield of 90% to provide diphenyl carbonate having a hydrolyzable chlorine 
content of less than 0.1 ppm. 
In a 500 ml glass reactor 143.8 g(0.672 mole) of the so treated diphenyl 
carbonate, 136.8 g (0.600 mole) of Bisphenol A supplied by GE plastics 
Japan Ltd. having a hydrolyzable chlorine content of less than 0.1 ppm and 
3.0 mg(H.sub.3 BO.sub.3 0.025.times.10.sup.-4 mole/mole of BPA) of 3% 
boric acid H.sub.3 BO.sub.3 aqueous solution stirred using a stirrer made 
of Ni was heated to a temperature of 180.degree. C. under a nitrogen 
atmosphere, followed by stirring for 30 minutes. At the end of the period 
there were added to the reactor 91.2 mg of 15% tetramethylammonium 
hydroxide Me.sub.4 NOH aqueous solution (2.5.times.10.sup.-4 mole of 
Me.sub.4 NOH/mole of BPA) and 24.0 mg (NaOH 0.010.times.10.sup.-4 
mole/mole of BPA) of 0.1% sodium hydroxide NaOH aqueous solution, and the 
mixture was stirred for further 30 minutes at a temperature of 180.degree. 
C. under nitrogen atmosphere to effect the ester interchange reaction. 
The reaction mixture was then heated to a temperature of 210 .degree. C. 
and the pressure was slowly reduced to 200 mmHg. The mixture was 
maintained under these conditions for 1 hour, and further maintained for 
20 minutes at 240.degree. C. and 200 mmHg. The pressure was then slowly 
reduced to 150 mmHg, and then the mixture was maintained at 240.degree. C. 
for 20 minutes under this pressure and for 0.5 hour under 15 mmHg. 
Finally, the temperature was then raised to 270.degree. C. and the 
pressure as reduced to 0.5 mmHg, and the reaction was continued under 
these conditions for 2.5 hours. Polycarbonate having an intrinsic 
viscosity of 0.55 (dl/g) was obtained substantially quantitatively. The b 
value of the product was 0.7. 
The results are shown in Table 4 and Table 6. 
EXAMPLES 13 AND 14 
Diphenyl carbonates (DPC) having hydrolyzable chlorine, sodium ion and iron 
ion contents indicated in Table 4 were prepared in the same manner as in 
Example 12 except that the recovery yield of DPC at the stage of 
distillation under reduced pressure was varied. Using the so prepared DPC 
polycarbonates were prepared folloWing the procedures of Example 12. 
The results are shown in Table 4. 
EXAMPLE 15 
Example 12 was repeated except that the purified DPC was replaced with DPC 
obtained by distillation of DPC supplied Eni company which had been 
prepared from dimethyl carbonate. 
The results are shown in Table 4. 
EXAMPLE 16 
Example 12 was repeated except that the 0.1% sodium hydroxide NaOH aqueous 
solution was replaced with 50.4 mg (NaOH 0.02.times.10.sup.-4 mole/BPA 1 
mole) of 0.2% sodium hydrogencarbonate NaHCO.sub.3 aqueous solution. 
The results are shown in Table 4. 
EXAMPLE 17 
Example 12 was repeated except that the 0.1% sodium hydroxide NaOH aqueous 
solution was replaced with 34.8 mg (NaOH 0.02.times.10.sup.-4 mole/BPA 1 
mole) of 1% Lithium Stearate C.sub.17 H.sub.35 COOLi aqueous solution. 
The results are shown in Table 4. 
EXAMPLE 18 
Example 12 was repeated except that the 0.1% sodium hydroxide NaOH aqueous 
solution was replaced with 43.2 mg 
##STR5## 
of 0.2% sodium benzoate aqueous solution. 
The results are shown in Table 5. 
EXAMPLE 19 
Example 12 was repeated except that the 0.1% sodium hydroxide NaOH aqueous 
solution was replaced with 42.6 mg (Na.sub.2 HPO.sub.4 
0.005.times.10.sup.-4 mole/BPA 1 mole) of 0.1% disodium hydrogenphosphate 
aqueous solution. 
The results are shown in Table 5. 
EXAMPLE 20 
Example 12 was repeated except that the 0.1% sodium hydroxide NaOH aqueous 
solution was replaced with 39.9 mg 
##STR6## 
of 0.2% disodium salt of BPA in tetrahydrofuran solution. 
The results are shown in Table 5. 
COMATIVE EXAMPLE 8 
Example 12 was repeated except that the unpurified DPC as such was used in 
the melt polycondensation. 
The results are shown in Table 5. 
COMATIVE EXAMPLE 9 
Example 12 was repeated except that instead of the purified DPC undistilled 
DPC supplied by Eni company was used in the melt polycondensation. 
The results are shown in Table 5. 
TABLE 4 
__________________________________________________________________________ 
Starting material Ex. 12 
Ex. 13 
Ex. 14 
Ex. 15 
Ex. 16 
Ex. 17 
__________________________________________________________________________ 
Starting 
DPC Hydrolyzable Cl (ppm) 
&lt;0.10 
0.13 
0.25 
&lt;0.10 
&lt;0.10 
&lt;0.10 
material 
Na ion (ppm) &lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
Fe ion (ppm) &lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
Bisphenol A 
Hydrolyzable Cl (ppm) 
&lt;0.10 
&lt;0.10 
&lt;0.10 
&lt;0.10 
&lt;0.10 
&lt;0.10 
Na ion (ppm) &lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
Fe ion (ppm) &lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
Physical 
IV (dl/g) 0.55 
0.54 
0.54 
0.55 
0.56 
0.56 
properties 
b value 0.7 0.8 0.9 0.7 0.8 0.7 
of the 
Heat resistance 250.degree. C. .times. 16 hr IV (dl/g) 
0.51 
0.49 
0.50 
0.50 
0.52 
0.52 
product 
color tone b value 17.3 
19.2 
20.3 
17.5 
18.3 
19.2 
Boiling water resistance 
Elongation (%) after in boiling water 
for 
0 day 99.3 
98.2 
105.2 
102.1 
103.0 
107.3 
1 day 95.2 
90.3 
83.4 
96.3 
90.4 
93.5 
3 day 88.4 
82.6 
78.6 
89.1 
82.7 
80.8 
7 day 75.3 
72.4 
69.5 
76.7 
71.3 
70.9 
__________________________________________________________________________ 
TABLE 5 
__________________________________________________________________________ 
Comp. 
Comp. 
Starting material Ex. 18 
Ex. 19 
Ex. 20 
Ex. 8 
Ex. 9 
__________________________________________________________________________ 
Starting 
DPC Hydrolyzable Cl (ppm) 
&lt;0.10 
&lt;0.10 
&lt;0.10 
5.90 
4.12 
material 
Na ion (ppm) &lt;0.05 
&lt;0.05 
&lt;0.05 
0.10 
0.92 
Fe ion (ppm) &lt;0.05 
&lt;0.05 
&lt;0.05 
0.40 
1.05 
Bisphenol A 
Hydrolyzable Cl (ppm) 
&lt;0.10 
&lt;0.10 
&lt;0.10 
&lt;0.10 
&lt;0.10 
Na ion (ppm) &lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
Fe ion (ppm) &lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
&lt;0.05 
Physical 
IV (dl/g) 0.54 
0.53 
0.55 
0.56 
0.56 
properties 
b value 0.7 0.6 0.7 1.5 1.6 
of the 
Heat resistance 250.degree. C. .times. 16 hr IV (dl/g) 
0.51 
0.51 
0.51 
0.46 
0.47 
product 
color tone b value 17.0 
16.9 
17.4 
30.5 
31.2 
Boiling water resistance 
Elongation (%) after in boiling water 
for 
0 day 102.4 
99.5 
103.2 
93.2 
95.4 
1 day 96.4 
93.2 
95.4 
53.2 
51.3 
3 day 89.7 
89.1 
88.3 
22.9 
25.3 
7 day 76.4 
72.4 
74.5 
13.4 
14.7 
__________________________________________________________________________ 
EXAMPLES 21-36 AND COMATIVE EXAMPLES 10-14 
The same procedure as described in Example 12 as repeated except that in 
place of the sodium hydroxide, tetramethylammonium hydroxide and boric 
acid used in Example 12 in amounts as shown in Table 4, there were used 
nitrogen containing basic compounds, alkali metal compounds(alkaline earth 
metal compounds) and boric acid or boric acid esters in amounts as shown 
in Tables 6-9 and 10, respectively. 
The results obtained are shown in Tables 6-9 and 10, respectively. 
TABLE 6 
__________________________________________________________________________ 
Ex. 12 
Ex. 21 Ex. 22 Ex. 23 
Ex. 24 
Ex. 
Ex. 
__________________________________________________________________________ 
26 
Catalyst 
(a) 
Component Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
amount (10.sup.-4 mole/BPA) 
2.5 2.5 2.5 2.5 2.5 2.5 2.5 
(b) 
Component NaOH C.sub.17 H.sub.35 COONa 
C.sub.17 H.sub.35 COOLi 
NaHCO.sub.3 
NaOH NaOH KOH 
amount (10.sup.-4 mole/BPA) 
0.010 
0.010 0.010 0.010 
0.010 
0.025 0.050 
(c) 
Component H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
B(OPh).sub.3 
H.sub.3 BO.sub.3 
H.sub.3 
BO.sub.3 
amount (10.sup.-4 mole/BPA) 
0.025 
0.025 0.025 0.025 
0.025 
0.025 0.025 
Physical properties of the product 
IV (dl/g) 0.55 0.52 0.51 0.53 0.56 0.58 0.60 
Hue (b value) 0.7 0.7 0.7 0.8 0.7 0.8 1.0 
Heat resistance (250.degree. C., 16 hr .multidot. after) 
IV (dl/g) 0.51 0.49 0.48 0.50 0.52 0.54 0.55 
Hue (b value) 17.3 17.8 17.2 17.9 17.4 18.3 19.4 
Boiling water resistance 
Tensile elongation (%) after 
boiling water immersion 
0 day after 99.3 103.1 95.7 96.7 102.3 
107.5 107.9 
1 day after 95.2 93.4 91.3 90.3 95.4 88.4 81.9 
3 days after 88.4 82.7 81.7 81.2 86.7 79.3 71.3 
7 days after 75.3 73.9 71.8 73.4 76.9 67.4 59.2 
__________________________________________________________________________ 
TABLE 7 
__________________________________________________________________________ 
Comp. Comp Comp. 
Comp. 
Comp. 
Ex. 10 Ex. 11 
Ex. 12 
Ex. 13 
Ex. 14 
__________________________________________________________________________ 
Catalyst 
(a) 
Component Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
-- 
amount (10.sup.-4 mole/BPA) 
2.5 100 30 100 -- 
(b) 
Component -- -- NaOH NaOH NaOH 
amount (10.sup.-4 mole/BPA) 
-- -- 15 30 30 
(c) 
Component H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
-- -- 
amount (10.sup.-4 mole/BPA) 
0.025 100 1 -- -- 
Physical properties of the product 
IV (dl/g) 0.36 0.43 0.68 0.69 0.67 
Hue (b value) 0.8 0.9 2.4 2.6 2.7 
Heat resistance (250.degree. C., 16 hr .multidot. after) 
IV (dl/g) 0.30 0.34 0.55 0.45 0.43 
Hue (b value) No molding 
23.3 35.2 29.3 28.4 
Boiling water resistance 
can be formed 
Tensile elongation (%) after 
boiling water immersion 
0 day after 65.3 73.2 98.0 104.5 
101.5 
1 day after 5.3 17.6 3.1 1.5 1.2 
3 days after 3.5 10.5 2.6 1.8 1.3 
7 days after 2.3 5.9 1.7 1.3 0.9 
__________________________________________________________________________ 
TABLE 8 
__________________________________________________________________________ 
Ex. 27 
Ex. 28 
Ex. 20 
__________________________________________________________________________ 
Catalyst 
(a)Component amount(10.sup.-4 mole/BPA) 
Bu.sub.4 NOH 2.5 
Bu.sub.4 NBPh.sub.4 2.5 
##STR7## 
(b)Component LiOH NaOH NaOH 
amount(10.sup.-4 mole/BPA) 
0.010 
0.010 0.010 
(c)Component H.sub.3 BO.sub.3 
-- H.sub.3 BO.sub.3 
amount(10.sup.-4 mole/BPA) 
0.025 
-- 0.025 
Physical properties of the product 
IV(dl/g) 0.56 0.57 0.55 
Hue(b value) 0.7 0.7 0.8 
Heat resistance (250.degree. C., 16 hr. after) 
IV(dl/g) 0.51 0.52 0.51 
Hue(b value) 17.2 17.7 17.4 
Boiling water resistance 
Tensile elongation (%) after 
boiling water immersion 
0 day after 103.4 
99.5 101.5 
1 day after 94.7 95.3 93.3 
3 days after 84.9 83.3 84.1 
7 days after 74.6 76.7 72.6 
__________________________________________________________________________ 
TABLE 9 
__________________________________________________________________________ 
Ex. 30 
Ex. 31 
Ex. 32 
Ex. 33 
Ex. 34 
__________________________________________________________________________ 
Catalyst 
(a) 
Component Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
amount (10.sup.-4 mole/BPA) 
2.5 2.5 2.5 2.5 2.5 
(b) 
Component NaHCO.sub.3 
NaOH NaOH KOH LiOH 
amount (10.sup.-4 mole/BPA) 
0.250 
0.250 
0.010 
0.010 
0.010 
(c) 
Component H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
-- -- -- 
amount (10.sup.-4 mole/BPA) 
1.000 
1.000 
-- -- -- 
Physical properties of the product 
IV (dl/g) 0.61 0.63 0.55 0.56 0.55 
Hue (b value) 1.1 1.1 0.7 0.8 0.7 
Heat resistance (250.degree. C., 16 hr .multidot. after) 
IV (dl/g) 0.55 0.56 0.49 0.50 0.49 
Hue (b value) 21.3 22.4 15.2 15.7 15.1 
Boiling water resistance 
Tensile elongation (%) after 
boiling water immersion 
0 day after 103.1 
101.2 
104.7 
102.5 
98.7 
1 day after 86.7 87.3 90.2 93.4 83.4 
3 days after 57.4 45.4 81.4 85.3 79.2 
7 days after 24.2 23.3 64.2 69.5 61.8 
__________________________________________________________________________ 
TABLE 10 
__________________________________________________________________________ 
Ex. 35 Ex. 36 Ex. 18 Ex. 19 
Ex. 20 
__________________________________________________________________________ 
Catalyst 
(a)Component Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
Me.sub.4 NOH 
amount(10.sup.-4 mole/BPA) 
2.5 2.5 2.5 2.5 2.5 
(b)Component amount(10.sup.-4 mole/BPA) 
C.sub.17 H.sub.35 COONa 0.010 
C.sub.17 H.sub.35 COOLi 0.010 
##STR8## 
Na.sub.2 HPO.sub.4 0.005 
##STR9## 
amount(10.sup.-4 mole/BPA) 
(c)Component -- -- H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
H.sub.3 BO.sub.3 
amount(10.sup.-4 mole/BPA) 
-- -- 0.025 0.025 0.025 
Physical properties of the product 
IV(dl/g) 0.53 0.52 0.54 0.53 0.55 
Hue(b value) 0.7 0.7 0.7 0.6 0.7 
Heat resistance (250.degree. C., 16 hr. after) 
IV(dl/g) 0.48 0.47 0.51 0.51 0.51 
Hue(b value) 15.4 15.3 17.0 16.9 17.4 
Boiling water resistance 
Tensile elongation (%) after 
boiling water immersion 
0 day after 99.8 97.1 102.4 99.5 103.2 
1 day after 92.5 85.4 96.4 93.2 95.4 
3 days after 83.4 80.0 89.7 89.1 88.3 
7 days after 67.3 63.2 76.4 72.4 74.5 
__________________________________________________________________________