CA1136329A - Organic materials having meta, para-isopropylidene diphenoxy units, and method - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Meta,para-isopropylidene bisphenol is homopolymerized and copolymerized to produce a variety of high performance thermoplastics having improved processing characteristics. In addition to polycarbonates, there are provided polyesters, poly-estercarbonates, polyepoxides, polysulfones, polyetherimides, polyformals, epoxy resins and polycarbonate-polydiorganosiloxane block polymers.

Description

1~3~i3;~3 RD~10975 .

ORGANIC MATERIALS HAVING META, PA~A ISOPROPYLIDENE
DIPHENOXY UNITS AND ME'rHOD _ Backgrolmd _f the Inventlon Polycarbonates have been used in a wide variety of applications requiring high performance thermoplastic materials Although polycarbonates consistin~s essentially of chemlcally combined units of the formula, (1) _o{~C{~ OC~

has been satisfactorily molded at temperatures exceeding 250C, or injection molded to plastic foams at temperatures exceeding 300C using particular blowing agents, the use of such poly-carbonates, or the employment of additional blowing agents has been somewhat restricted due to the high temperature poly-carbonate shaping requirements. It is also known, for example, that polycarbonate consisting essentially of chemically com-bined units of formula (1) has a glass transition temperature of 150C while the corresponding polycarbonate derived from ortho,para-bisphenol-A has a glass transition temperature of 142C. Continued efforts have been made by the organic thermo-plastics industry to improve the flow characteristics of poly-carbonates and other organic thermoplastics having chemically combined isopropylidene bisphenol units.
Statement of the Invention _ _ In Can. Appl. S..~N- 3 4 Sj~ 3 ~ , iled Fæl~
t~,iq ~ and assigned to the same assignee as the pre-sent invention, there îs sho~m meta,para-isopropylidene bis-phenol of the formula .

, . " .. ...

11363~:9 ~D-10975 (~a

(2) HO ~ C- ~
(X)b H
where R is selected from the class consisting of C(l 8) alkyl radicals, C(l 6) alkoxy radicals, X is selected rom halogen, a is a whole number equal to 0 to 4 inclusive, b is a whole number equal to 0 to 3 inclusive and the sum of a and b is equal to 0 to 4 inclusive.
I have found that meta,para-isopropylidene bisphenol included within the scope of formula (2) can be polymerized to a polycarbonate having an ~ of 72,175, an Mn of 13,380 and a io glass transition tem~erature of 112C~
.

Description of the Invention There is provided by the present invention, a method for making polycarbonates having a~ least three mole percent of chemically comblned bisphenol units of the formula, ~C~

:~ based on the total moles of chemically combined bisphenol units !
which comprises, .-(A) phosgenating a mixture comprlsing from 3 to :;~ 100 mole percent of a bisphenol o formula (2) and from 0 to 97 mole percent of a bisphenol of th~ formula, ::

(4) HO ~ C ~ OH

, ~L3f~
Rn-los7s to produce a polycarbonate, and (B) effecting the separation of the polycarbonate from the mixture of (A), where R, X a and b are as previously defined.
Bisphenols included by formula (3) are, for example, HO ~ C

OH

CH ~

Br CH ~

OH

~H

~ C}~

In a further aspect of tha present invention, there are provided aromatic polyformals con9isting essentially of .. ,, , .. , ,, . , . ,, .. , .. . . . . .... ... ~ .. ......... . . . . . . ..

~3~

(~)a (5) -O ~ C ~
(X)b OCH2 chemically combined with O mole percent to 97 mole percent of ~nits of the form~tla, (6) -O ~ ~ CH2~- ' In addition, there are provided aromatic polysulfones consisting essentially of chemically combined units of the formula, (R)a (7~ -O ~ C ~

(~)b ~ S ~ ~

where R, X, a and b are as previously defined.
Another aspect of the present invention is directed to aromatic polyesters consisting essentially of chemicaLly combined units of the formula, (~ 0_(~ 0~,0, (X)b C- , where R, ~, a and b are as previously defined.
~15 An:additional aspect of:the present invention is directed to bisimides of the formula, .

~ -4-~:
:::

~3b;3~
RD-:L097S
o RlN~ ~()~C~
(9) O (X)b 3 - ~ ~ R

o where R, X, a and b are as previously defined and Rl is selected from C(l_8) alkyl radicals and C(6 12) aryl radicals.
The bisimides of formula (9) can be made by ~he procedure of Heath et al U.S. Patent 3,879,428, assigned to the same asslgnee as the present invention. A nitro phthal-imide O

N2~ /NRl ' . . .

can reacted with a bisphenoxide of the ~ormula, : (R)a M ~ C ~

to produce a bisimide within formula (8~, where R, X, Rl, a and b are as previously defined and M is an alkali me~al ion ::~ such as sodium.
The bisimide of formula (9) can thereafter be hydroljzed to produce the dianhydride of the formula, ~ -~ 5-, ,,, , .. , , ., , , , , , , .. . .. .. . . .. , . , , .. .,.. ., . , . , . , . ---- - - - , -: . I ,.~. ;. . ~ . .. . . .
. ~ , ,;, "

~IL3~

(10~
/ C ~ CH3 0 O ~O~C~O~ C
\ C ~ ~ CH3 ~ ~ ~0 /

where R, X, a and b are as previously defined. Polyetherimides also can be made from the dianhydride by a melt polymerization procedure, or an organic solvent solution polymerization with an organic diamine of the formula, NH2R NH2 ~
in accordance with Takekoshi et al U.S. Patents 3,803,085 and

3,9~1,004, where R2 is a divalent organo radical selected.
from the class consisting of (a) aromatic hydrocarbon radicals havin~ from 6-20 carbon atoms and halogenated derivatives thereof, (b) alkylene radicals, C( 2 8) alkylene terminated polydiorganosiloxane cycloalkylene radicals having from 2-20 carbon atoms, and (c) divalent radicals included by the : formula, ~ (Q)m ~
where Q is a member selected from the class consisting of O O
.. .---O--, --C-- , --S--, --S--, O
-CXH2x- and x is a whole number from 1 to 5 inclusive, and m is O o~
The polyetherimides of the present invention con-sist essentially of chemically combined units of the formula, 1~3!~;3~
RD-lO975 (10) 0 -N / ~ 0 ~ CH ~ C0~ 2_ O C/
O .
where R, X, a~ b and R2 are as previously defined.
In addi~ion to para,para-bisphenol of ormula (4), the meta,para-bisphenol of formula (2) al~o can be copolymer-ized with l,l-dichloro-2,2-bi3(4-hydroxyphenyl)ethylene. The meta,para-bisphenol of formula (2) or mixtures thereof with p,p-bisphenol-A also can be used to make polycarbonate-organo-polysiloxane block polymers by effecting reaction in the pre-sence of an acid acceptor between one or more moles of the m,p-bisphenol ~f formula (2) and a chlorine chain-stopped polydiorganosiloxane of the formula, ~ R3 \ R3 Cl~ -SiO~ - Si~l R3 n R3 where R3 is a monovalent organic radical selected from methyl, : ethyl, propyl, vinyl, phenyl, chlorophenyl, perfluoropropyl, cyanoethyl and mixtures thereof and n has an average value of 5-200 inclusive. A typical procedure is shown by Vaughn patent ~ 3,189,602, assigned to the same assignee as the present inventio~.
The above aromatic organic poIymeric materials can -have an intrinslc viscosity in methylene cllloride at 25~ of at least ~.l and preferably at least 0.3 and are selected from poiycàrbonates consisting essentially of formula (3) units, copolymers cons:isting eseentially of formula (l) and (33 2~ units, polyesters, polyestercarbonates, polyformals, poly-etherimides, polysulfones and polycarbonate-polydiorgano-"

'' ` ' ' ; ~ I ' ' ~ , ~3t;3~3 siloxane block polymers, etc. The organic polymeric materials can have at least 3 mole percent to 100 mole percent of chem-ically combined units of formula (3) and preferably from 10 to 100 mole percent of swch unit~. These organic polymeric materials can be injection molded to a variety of shapes, transformed into high performance shaped foams, used in form-ing plastic sheets, laminates, etc. The organic polymers hav-ing chemically combined formula (3) units have improved pro cessing characteristics and can be reinforced with various particulated fillers such as glass fibers, silica fillers, carbon whiskers, up to 50 percent by weight of the resulting total blend. Reinforcement of polymer can be accomplished prior to polymer formation by effecting polymerization in the presence of filler. Melt blending and solution blending also can be employed.
In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limitation.
All parts are by weight.
Example 1.
A mixture of 5 parts o phenol, 1 part of meta-iso-propenyl phenol and about 21 parts of toluene was added drop- -wise to about 5 parts of a 75% aqueous solution of sulfuric acid. When the addition was completed, the reaction mixture was stirred an additional 5 minutes, diluted with about 35 parts of diethylether resulting in the separation of 2 layers.
The organic layer was washed with about 25 parts of a saturated aqueous sodium bicarbonate solution, dried over magnesium sul-fate and concentrated under reduced pressure. There was obtained a brown oil which was crystallized from chloroform ~13~i3Z9 RD-l0975 resulting in an 81% yield of a white powder having a melting point of 97-98C. Based on methocl of preparation and its IR
spectrum, the product was meta,para isopropylidene bisphenol of the formula, HO ~ C- ~
-~ OH
Phosgene was introduced into a mixture over a 20 minute period of 2 parts of the above meta,para-bisphenol, 22 parts of methylene chloride, about 7 parts of water, about 0.04 part of triethylamine and 0.016 part of phenol. There was added a total of 0.9 part of phosgene while the mixture was agitated along with a sufficient amount of an aqueous sodium hydroxide solution to maintain the reaction mixture at a pH of 10-12.
After the phosgene addition, the mixture was flushed with nitrogen and washed once with about 25 parts of a 10% hydro-chloric acid solution. The mixture was then blended with about 100 parts of methanol resulting in the precipitation of product.
The product was recovered by vacuum filtration and dried under vacuum at 65C for 18 hours. Based on method of preparatlon the product was a polycarbonate consisting essentially of chemically combined units of the formula, ~}
C~3 C-and chain terminated with phenoxy units. The product was found to be a valuable inj ction moldable thermoplastic matPrial having a glass transition temperature of about 112C. Those skilled in the art know that the polycarbonate has improved processing characteristics as compared to para,para-isopropyl-idene bisphenol polycarbonate having a glass transition temper-ature of about 150C.

:: .
::

.,, ~. ...

~3L3~32~

Example 2.
A mixture of 3.5 parts of the meta,para-bisphenol-A
of Example 1, 3.5 parts of para,para-bisphenol~A, 16 parts of wa~erJ about 26 parts of methylene chloride, a~out 0.03 part of trie~hylamine, and o.n72 part of phenol was phosgenated over a 20 minute period. During phosgenation 3.4 parts of phosgene was introduced and sufficient 20% aqueous sodium hydroxide solution to maintain the reaction mixture at a pH in the range of 10-11.5. After phosgenation, the organic layer was separated from the mixture and added dropwise to about 240 parts of methanol in a blender. There was obtained a precipitated polymer which was recovered by vacuum filtration and redissolved in methylene chloride and reprecipitated from methanol. Based on method of preparation, the product was a copolymer consist-ing essentially of meta,para-isopropylidene bisphenoxy units chemically combined with para,para-isopropylidene bisphenoxy units which were present in about equal molar amounts. The polymer had an Mw of 29,204l an ~ of 10,78S and a Tg of 130C.
Those skilled in the art would know that the processing char-acteristics of the aforementioned copolymer with respect to its ability to be molded to various parts would be superior to a polycarbonate consisting essentially~of chemically combined para,para-isopropylidene bisphenoxy units having a glass trans-ition temperature of 150C.
Example 3.
There was added with stirring 1.7 part of sodium hydroxide to a mixture of 4.54 parts of meta,para-bisphenol-A, 0.0459 part of 4-t-butyl phenol, about 8.2 parts o~ methylene chloride and about 10.2 parts of N-methylpyrrolidone. The . : - . ............. . ~ ,, , .. .. .

~31~i3;~

reaction mixture was refluxed for S hours at 90C. The reaction mixture was then cooled slightly and poured into about 120 parts of methanol in a blender. The product which precipitated was collected by vacuum filtration, dissolved in about 20 parts of methylene chloride and reprecipitated with about 120 parts of methanol followed by drying at 70C under vacuum for 16 hours. There was obtained a polyformal having an ~ of 49,700, an Mn of about 15,560 and a glass transi-tion temperature of 55C. The polyformal was found to be a valuable thermoplastic injection moldable material reinforce-able wi~h a variety of inert materials and useful in a variety of applications, such as for organic solvent resistant wire coating formulations.
Example 4.
A mixture of 7 parts of meta,para-bisphenol-A, 16.6 parts of dimethylsulfoxide and 45 parts of chlorobenzene was stirred and heated to 70C to ~roduce a clear solution. Nitrogen was then bubbled into the mixture and about 3.2 parts of a 50% aqueous sodium hydroxide solution was added during a 5 minute period resulting in a ratio of about 2 moles of sodium hydroxide per mole of the meta,para-bisphenol-A. The mixture was then brought to reflux and the solvent was distilled from the mixture until the pot temperature reached a 160C. There was then added a 50% solution of 8.81 parts of 4,4'-dichloro-diphenylsulfone and chlorobenzene at such a rate to maintain the temperature of the mixture at least 150C. The resulting mixture had an equal molar amount of sulfone and bisphenol and the stirring of the mixture continued for 2 hours at 150-160C.
The polymerization was terminated by passing methyl chloride gas into the mixture until it faded to a light amber color.

~3~3~

The mixture was then cooled to room temperature and diluted with 133 parts of methylene chloride and precipitated twice from methanol. Based on method of preparation there was obtained a polysulfone having an ~ or 49,153, an Mn of 23,293 and a glass transition temperature of 142C. It was found that the corresponding polysulfone having chemically combined para,para-isopropylidene bisphenol units has a glass transition tempera-ture of 190C~ Those skilled in the art would know that the polysulfone made in accordance with the practice of the present invention has improved processing characteristics and convert-ible to a variety of high performance shapes and parts by standard injection molding techniques.
Example 5 Phosgene is introduced into a mixture at a rate of 3.5 parts of phosgene per hour consis~ing of 77.75 parts of meta,para-bisphenol-A, 136.9 parts of a bisphenol-A terminated polydimethylsiloxane having an average of 15 dimethylsiloxy units, 330 parts of chloroformj 0.6 part of phenol, 0.9 part s of sodium gluconate, 2.14 parts of triethylamine and 1400 parts of water. During the phosgenation, aqueous sodium hydroxide is added to the mixture to maintain a pH of about 11.
After the mixture is stirred for 27 minutes, the phosgene flow rate is reduced to about 1 part per minute and continued until the entire amount of base is consumed, which includes 144 parts of sodium hydroxide added as an aqueous mixture. The total reaction time is 111 minutes. Nitrogen is then bubbled into the two phase mixture to remove any residual phosgene. The reaction mixture is then diluted with an equal volume of chloroform~and the aqueous layer is separ-,. . ;,~

i~L3~%~

ated and discarded. The organic layer is washed with deionized water having a pH of 6.7 and aqueou~ HCL having a pH of 2 0 and thereafter our tim~s with deionized water The organic layer ls washed with additional water untll i~
i~ chloride ree, based on a sil.ver nitrate test. The organic layer i9 ~hen dried over magnesi.um sulfate and filtered. The resul~ing clear solution i9 ~hen added over a 30 minute period to a well stirred mi~ture of acetone and methanol to effect the precipitation of product. There i~ obtained a fibrous polymer which i~ filtered and pre9sed dry and then washed wi~h additional acetone-methanol ~olution and reiltered.
Based on method of preparation, there i9 obtained a block polymer containing about 30% by weight o~ timethylpolysiloxane and about 70~/O by weight of polycarbonate. The block polymer i8 useul a3 ~or making semi permeable membranes.
~.
A mixture of 20.52 p8rt~ of me~a,para-bisphenol-A, 38.97 parts of 4-nitro,N-m~thylphthalimide, 7.92 parts of sodium hydroxide, 101 psrts of dimethylformamide and 58.; part~ of toluene is heated at reflux under a nltrogen atmosphere. The pot temperature durlng ~hi~ period is 125C. The mixture l~
heated for 6 hours and then refluxed for an addition~l two hour~ and allowed to cool to 100C. Toluene i8 then removed under reduced pre~sure and the mixture i~ allowed ~o cool to room temperature. There i8 obtained a precipitate The mixture is then dilu~ed with about 300 parts of ethanol and ~iltered. There is obtained a white solid ater the precipi-tate i~ washed with water and dried. The yield o produc~
is about 90~/O. Based on method of the prep~ration the product is a bi~imide of the form~la, 1~3~3~2~
RD- 1.09 7 5 ~ ~ C ~ O

A mixture of 93 parts o:E the above bisimide and 52.25 parts of sodium hydroxide, and 260 parts of water i8 heeted to reflux. Methylamine is distilled along with water at a rate S of about 80 parts per hour and fresh water is added to the mix-ture. A mixture is heated for a total of 20 hours and the mix-ture is allowed to cool slowly. There is obtained a solid which is isolated by filtration in a centrifuge. Based on method of preparation there is formed tetra-acid having the formula, HOC ~ ~ C ~
O O ~ COH
o A mixture of 45 parts of the above tetra-acid, 30 parts o~ acetic anhydride and 217 parts of toluene is heated to reflux and held at reflux for 1 hour. The filtrate is allowed to cool slowly. There is obtained a crystalline dianhydride lS having the following formula, O

/ ~ ~C~ C~

O ' ~:

'.

~3~3'~
RD~10975 Example 7.
A mîxture of 5.0205 parts of meta,para-bisphenol-A
dianhydride of Example 6, 1.47 part of metaphenylenediamine and 0.089 part of phthalic anhydride is stirred and heated under a nitrogen atmosphere. The result:ing viscous melt is further heated at 280C for 1 hour. There is obtained upon cooling a tough clear amber colored material. Based on method of pre-paration the product is a polye~herimide consisting essentially of chemically combined units of the formula, o -N ~ ~ C ~ ,~

The above polyetherimide is injection molded to a finished shape resulting in a tough solvent resistant structure.
Exam~e 8.
A mixture is phosgenated consisting of 3.5 parts of lS m,p-bisphenol-A, 4.31 parts of 1,1-dichloro-2,2-bis(4-hydroxy phenyl)ethylene, 16 parts of water, 39 parts of methylene chlor-ide, 0.040 part of trie~hylamine and 0.027 part of phenol. There is added 3.4 parts of phosgene and sufficient 20% aqueous ~odium hydroxide solution during the 20 minute phosgenation period to maintain the pH of the mixture in the range of 10-11.5. The reac-tion mixture is then allowed to separate into 2 layers and the organic layer is added dropwise to about 250 parts of methanol while it is rapidly agitating. There i9 obtained a precipitated product which is collected by vacuum filtration. Based on method of preparation the product is a polycarbonate copolymer ~15-':

,~

1~3~i32~
RD~10975 consisting ess~ntial]y of ~ilen~ically com~ined units "r ~:he formula, o CH3 -C-0 ~ CH ~

3 C-0 ~ C
Cl~ ~C'l A solution of the above copolymer in methylene chloride is cast onto a glass plate. The resulting film is found to be a tough thermoplastic exhibiting flame retardant properties.
_a~ç~
There was added a solution of 3 parts of sodium laurylsulfate in 12 parts of water to a solutivn while it was stirred of 4.56 parts of meta,para-bisphenol-A and 1.6 part of sodium hydroxide in 120 parts of water. There was then added to the resulting mixture a solution of 4.06 parts of terephthaloyl chloride in about 90 parts of chloroform.
An emulsion was formed from the resulting mixture which was stirred an additional 5 minutes. The reaction mixture was then poured into 500 parts of acetone to effect the precipi-~ation of product which was collected and washed well with water. The product was then reprecipitated. There was obtained a polyester having a glass transition temperature of 150C, an Mw of 54,834 and an Mn of 36,999. Based on method of pre-paration the product consists essentially of chemically com-bined units of the formula, CH ~ ,, C~O

ti32~

The above polyes~er is found to be injection mold-able and convertible to a high strength material.
Although the above examples are directed to only a few of the very many thermoplastic organic materials whlch can be made in accordance with the practice of the present inven-tion, it should be understood that the present invention is directed to a much broader varilety of thermoplastic materials based on the use of bisphenols of formula (2) alane or in com-bination with various other materials which are described in the specification preceding these examples. Included are, for example, epoxy resins consisting essentially of units derived from the diglycidyl ether of meta,para-isopropylidene bisphenol.

Claims (13)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. Thermoplastic organic polymers having chemically combined units of the formula, which are selected from the class consisting of polycarbonates, polyestercarbonate copolymers, polyesters, polyformals, poly-sulfones, polyetherimides and organopolysiloxane-polycarbonate block polymers.

2. A thermoplastic organic polycarbonate in accord-ance with claim 1, consisting essentially of chemically combined meta,para-isopropylidene bisphenoxy units and para,para-iso-propylidene bisphenoxy units.

3. An organic polycarbonate in accordance with claim 2 having at least 3 mole percent of chemically combined meta,para-isopropylidene bisphenoxy units.

4. A thermoplastic organic polycarbonate in accord-ance with claim 2, having substantially equal molar amounts of meta,para-isopropylidene bisphenoxy units and para,para-isopro-pylidene bisphenoxy units.

5. A thermoplastic organic polymer in accordance with claim 1 consisting essentially of meta,para-isopropyli-dene bisphenoxy units and normal units.

6. A thermoplastic organic polymer in accordance with claim 1, consisting essentially of meta,para-isopropyli-dene bisphenoxy units and diphenylsulfone units.

7. A thermoplastic organic polymer in accordance with claim 1, consisting essentially of meta,para-isopro-pylidene bisphenoxy units and organosiloxy units.

8. A thermoplastic polyetherimide in accordance with claim 1, consisting essentially of chemically combined units of the formula, , where R2 is a divalent organo radical selected from the class consisting of (a) aromatic hydrocarbon radicals having from 6-20 carbon atoms and halogenated derivatives thereof, (b) alkylene radicals, C(2-8) alkylene terminated polydiorgano-siloxane cycloalkylene radicals having from 2-20 carbon atoms, and (c) divalent radicals included by the formula, , where Q is a member selected from the class consisting of , -CxH2x , x is a whole number from 1 to 5 inclusive, and m is 0 or 1.

9. A thermoplastic organic polymer in accordance with claim 1, consisting essentially of meta,para-isopro-pylidene bisphenoxy units and dimethylsiloxy units.

10. A thermoplastic organic polymer in accordance with claim 1, consisting essentially of meta,para-isopropyli-dene bisphenoly units chemically combined with units of the formula, .

11. A thermoplastic organic polymer in accordance with claim 1, consisting essentially of meta,para-isopropyli-dene bisphenoxy units chemically combined with units of the formula, where n has an average value of 5 to 200.

12. A thermoplastic organic polymer in accordance with claim 1, consisting essentially of meta,para-isopropylidene bisphenoxy units chemically combined with dicarboxyphenylene units.

13. An organic polymer consisting essentially of chemically combined diglycidyl ether units of meta,para-isopro-pylidene bisphenol.