CA1161190A - Copolymers of etherimides and amideimides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Copolymers of etherimides and amideimides have been found to be useful in the coating and molding arts.

Description

L91.~1 RD- 12, 3 0 7 COPOLYMERS OF ETHERIMIDES AND ~IDEIMIDES
This invention is concerned wi~h copolymers cbntaining amideimide (AI) uni~s and etherimide (EIJ l~nits useful in the coating and molding arts. More particularly the invention is concerned with a copolymer comprising (a) from 5 to 95 mol percent of AI chemically combined units of the formula o H ~?. Rl ~

and (2) from 95 to 5 mol percent of EI chemically combined units of the formula O O
.. ..

O '' , O

wh~re R is a member selected from the class consisting of (a) the followinq divalent organic radicals:
f ~ fH3 C1~3, IC~13 ~,~

~ r ~ 9 ~ RD-12,307 . _ Br ~CH3 Br Br H3 ~ ~CH3) $

and (b) divalent organic radicals of the general formula:
' ~(X~ , where X is -CyH2y~, y is a whole number equal to from 1 to 5 inclusive, and Rl is a divalent organic radical selected fxom the class consisting of ~a~ aromatic hydrocarbon radicals having from 6-20 caxbon atoms and halogenated derivatives thereof, (b) alkylene radicals and cycloalkylene radicals having from

2-20 carbon atoms, (c) C(2 8) aIkylene terminated polydiorgano-siloxanes, and (d) divalent radicals included by the formula, ~Q~ ' where Q is a member selected from the class consistin~ of O O
-0 , -C-, -S-, -S-, and - CXH2 - , and x is a whole number equal to from 1 to 5, inclusive.

RD-lZ,307 The co~ined random ff~s-~E-b~e~ copolymers can be considered as having the general formula .
III

i~ _~ \~ / ~o_l~_o~ ~N-=

where R and Rl have the meanin~s above, m and n are whole numbers independently equal to at least 1, e.g., 5 to 5000 or more, and p is a whole number greater than 1, e.g., from 5 to 10,000 or more and advantageously from 10 to 1000.
Prior to imidization, the copolymers are in the amide state as exemplified by the following general formula;

0 ~y_~ Rl~-"-~c-I~ ~ C - N - o H J

and specifical.~.L.y of the general formula where R, ~, m' n, and p have the meanings above.
Polyamideimides are known to have good chemical resis-tance and moderate heat resistance. Although such polyamide-imides can be dissolved in suitable solvents for coating ~ 9t~ RD-12,307 applications such polyamideimides are quite difficult ko mold and require excessive temperatures and pressures in the mold-ing cycle. Polyetherimides are known to have good high tem-perature characteristics and are more amenable to viable mold-ing cycles; however, it would be advantageous to upgrade thechemical resistance of these polyetherimides and reduce their cost for molding and coating applications.
We have unexpectedly discovered that copolymers containing chemically com~ined units of formulas I and II over a wide range of molar concentrationj can be made in which the properties of the copolymer show modified properties over the propertiès of homopolymers of these units. In some instances, the improvement in properties are unexpected cons:Ldering the proportion of either the AI unit or the EI unit pxesent in the copolymer. By making the above-described copolymers, the utility of the latter can be considera~ly expanded. In addi-tion, by combining these two units in the copolymer, products can be obtained which are lower in cost than is usually associated with the manufacture of polyetherimides alone, without signi-ficant sacrifice (if any) in physical properties.
A preferred class of copolymers which are included byformula III are copolymers consisting essentially of from about 2 to 5000 or more units and preferably from 5 to 100 units of EI units of the formula O o IV. - N ~ R 0- ~ ~ JRl-O O
where Rl i~ p~eviously derined, and R2 is ~ D-1~,307 Included in the etherimide units of formula IV as part of the copolymer molecules are the following chemically combined units, 'O O
.. ..
V. --N ~ ~ ~ ~ R
-R -O O

O O

V~. - N~ ~ ~ NRl and O O -VII. - N~ _~N - Rl -O--R2 "

and mixtures thereof, where Rl and R2 are defined above.
The copolymèrs of formula III can be made by effecting reaction between an aromatic bis(etheranhydride) of the gèneral formula, VIII. ~ RO -O O

RD- 12, 3 0 7 a trimellitic acid chloride (TMAC) of the formula O

b , IX. Cl~-~C

n and an organic diamine of the general formula, X ~12NR NH2 where R and Rl are as previously defined.
There can be employed from 0.95 to 1.05 total mols of the anhydrides of formulas VIII and IX per mol of organic diamine of formula X. It is preferred to employ substantially, equal molar amounts of (a) the anhydride6 of fo~nulas VIII and IX and ~b) the organic diamine. The copolymers employed in the present invention can be those where there are f~om 10 to 5000 or more units of either formuIas I and II and p in for-mula III is 5 or more, e.g., from 10 to 1000.
The acyl halide derivative of formula IX derived from lS trimellitic anhydride (1,3,4-benzene tricarboxylic acid anhydride) can have at least one acyl halide and that in the 4-ring position, and includes derivatives, such as the 4-acid chloride 1,4- and 2,4-diacid chloride. The bromide and other reactive halide derivatives are also suitable.
Chain stoppers such as aniline or mono-organic acid deri-vatives or monoanhydrides may be used in making khe copolymers, Generally the copolymers of the present invention can he obtained by effecting reaction between the chosen organic diamine and the, particul~ didnhydride and monoanhydride, of formulas VIII and IX, respectively, in the presence of a dipolar ~. ~

~ 12,307 aprotic organic solvent under ambient conditions to produce a copolymeric amide acid. Upon further heating, the amide acid converts to the imidized state with the copolymer com-prising the units of formulas I and II in a random distri-bution. Depending upon the solids content of the polyamideacid solution, reaction can be completed in from 0.5 to 2 hours or more. Upon completion of the reaction, the solution can be cast on a substrate so that eyaporation of the organic solvent occurs. By heating at tempe.ratures of from 150-200C or higher one converts the copolymeric polyamide acid to the polyimide state, so that the copolymer at this point has good heat resistance, chemical resistance such as solvent resistance, and moldability. Such compositions are particularly useful as wire coating enamels and impart solvent resistance and heat resis-~ance properties to various substrates.
The aromatic bis(etheranhydride~ of formula VII can beprepared from the hydrolysis followed by dehydration of fhe reaction product of the nitrosubstituted phenyl dinitri,le and then reaction with a dialkali metal salt of a dihydric aryl compound in the presence of a dipolar aprGtic solvent, where the alkali metal salt has the general formula Alk - 0 - Rl - 0 - Alk where Rl has the meanings given above and preferably is the same as R and Alk is an alkali metal ion. Various well known procedures can be used to convert the resulting tetranitriles to the corresponding tetracids and dianhydrides.
Included among the alkali metal salts of the abo~e described dihydric phenols are sodium and potassium salts of the follow-in dihydric phenols:

~ RD-12,307 2,2-bis(hydroxyphenyl)propane;
2,4'-dihydroxydiphenylm~thane bis-(2-hydroxyphenyl~-methane;
2,2-bis-~4-hydroxyphenyl)-propane hereinafter iden-as "bisphenol-A" or "BPA;"
1,1-bis-(4-hydroxyphenyl)-ethane;
1,1-bis-(4-hydroxyphenyl)-propane

3,3-bis-(4-hydroxyphenyl)-pentane;

4,4'-dihydroxybiphenyl;
4,4'-dihydroxy-3,3',-5,5'-tetramethylbiphenyl;
2,4-dihydroxybenzophenone;
4,4'-dihydroxydiphenyl sulfone;
2,4'-dihydroxydiphenyl sulfone;
4,4'-dihydroxydiphenyl sul~oxide;
4,4'-dihydroxydippenyl sulfide; etc.
Included by the organic diamines of formula X
are, for example,.
m-phenylenediamine;
p-phenylenediamine;
4,4'-diaminodiphenylpropane;
4,4'-cliaminodiphenylmethane;
ben~idine;
4~4'-diaminodiphenyl sulfide;
4,4'-diaminodiphenyl sulfone;
4,4'-diaminodiphenyl ether;
1,5-diaminoaphthalene;
3,3'-dimethylbenzidine;
3,3'-dimethoxybenzidine;
2,4-diaminotoluene; 2,6-diaminotoluene;

~ g ~ RD-12,307 2,4-his (~-amino-t-butyl)toluene;
bis(p-~-methyl-o-aminopentyl)benzene;
1,3-diamino-4-isopropylbenzene;
1,2-b~s(3-aminopropoxy)ethane;
m-xylylenediami.ne;
p-xylylenediamine;
bis(4-aminocyclohexyl)methane;
3-methylheptamethylenediamine;
4,4-~imethylheptamethylenediamine;
2,11-dodecanediamine;
2,2-dimethylpropylenediamine;
octamethylenediamine;
3-methoxyhexamethylenediamine;
2,5-dimethylhexamethylenediamine;
3-methylheptamethylenediamine;

5-methylnonamethylenediamine;
1,4-cyclohexanediamine;
1.12-octadecanediamine;
bis(3-aminopropyl)sulfide;
N-methyl-bis(3-aminopropyl)amine;
hexamethylenediamine;
nonamethylenediamine; 2,6-diaminotoluene;
bis-(3-aminopropyl~tetramethyldisiloxane, etc.
The copolymeric composition can be reinforced with ~Jarious particulated fillers such as glass ~ibers, silica, fillèrs, carbon whiskers, up to 50% or more, by weight, of the copolymer.

~ RD-12,307 In order that those skilled in the art may better under-stand how the present invention may be practiced, the following examples are given by way of illustration and not by way of limitation. All parts are by weight unless otherwise indicated.

A copolymer containing AI units and EI was prepared by effecting reaction of 2 grams 4,4'-methylenedianiline, 1.56 grams of 4,4'-BPA-dianhydride and 1.47 grams of 4-chloroformyl phthalic anhydride in 15 cc of N-methylpyrrolidone. The mixture was stirred at xoom temperature until it became clear with the mixture exotherming to 40C. Upon cooling, the copolymer composition was cast as a film on glass at a temperature of about 150-280C to imidize the amic acid groups.
This polymer which had a molar ratio of 30 mol percent of EI
units and 70 mol percent of AI units softened at about 300C.

This example illustrates the preparation of a homopoly-etherimide which will be compared further on with a copolymeric composition containing the same diamino organic compound. Means for making such homo polyetherimides are described in U.S.
patent 3,847,867 issued November 12, 1974, and assigned to the same assignee as the present invention. 5.2 grams (0.01 mol) 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl] propane dianhydride (hereinafter referred to as "BPA dianhydride") and 1.08 grams (0.01 mol) m-phenylenediamine were dissolved in 30 cc N-methyl~
pyrrolidone. Upon stirring the mixture exothermed at 42C to give a clear homopolymeric amic acid solution. A film was cast from this solution at 280-300C yielding an imidized polymeric film.

&~ ~ 9 ~ ~D-12,307 This example illustra~es the preparation of a homopolymeric amideimide. More particularly, 2.1 grams (0.01 mol) tri-mellitic acid chloride (T~C formula IX) and 1.08 grams (0.01 mol) m-phenylenediamine were dissolved in 30 cc N-methyl-pyrrolidone. The mixture was stirred during which time the solution exothermed to about 43C to give a clear polymeric amic acid amide. A portion of this solution was cast at 280-300C on a flat surface to yield an imidized homopolymeric AI Cilm.

A copolymer was prepared by mixing together 1.89 grams (0.009 mol) TM~C, 0.52 grams (0.001 mol) BPA dianhydride and 1.08 grams (0.01 mol) of m-phenylenediamine dissolved in 30 cc N-methylpyrrolidone. After stirring at room tem-perature the mixture exothermed to about 47C, at which point a clear polymeric amide acid amide solution was obtained.
A film was cast from this solution a~ a temperature of 280-300C yielding an imidized copolymeric film.

Employing the conditions and reactants of Example 4, TMAC, bisphenol A dianhydride, and m-phenylenediamine were interacted in the same manner to form copolymeric compositions which when cast as films at elevated temperatures of 280-300C
yielded imidized copolymer films having good resistance to abrasion. The following Table I shows the proportions of the various ingredients and the temperature, at which the solutions of the three reactants exothermed after stlrring, In each instance, 30 cc N-methylpyrrolidone was used in making the - `

RD-12,307 initial solution of the three reactants.
TABLE I
TMAC BP~ Dianhydri~e m~phenylene ~xotherm diamine Temp.
Wt. W~. Wt.
gms.Mols gms. Mols ~. Mols Ex. 4 1.89 0.009 0.52 0.001 1~08 0.01 47C
5A 1.68 0~008 1.04 0.002 1.08 0.01 48C
5B 1.26 0.006 2,08 0.004 1.08 0.01 46C
5C 0.84 0.004 3.12 0.006 1.08 0,01 44C
5D 0.42 0.002 4.16 0.008 1.08 0.01 43C
SE 0.21 0.001 4.68 OOOO9 1.08 0.01 44C
*5F 1.05 0.005 2.6 0.005 1.08 0.01 41C
* Used 15 cc N-methyl pyrrolidone The Tg's (which measur~ the degree of sofl:ening of the polymers) of all of the copolymers of Examples 4 and 5A to 5F were determined with the results shown in Table II.
TABLE II
Test No. Tg C

. 5B 223 . Example 2 193 Example 3 241 Example 4 222 The copolymers obtained in Examples 4, and 5A to 5F can be represented by the formula 12~307 XI~ C~ ,1 ~ c(CH3)2~3{~

where the units are in random arrangement, m and n are whole numbers greater than 1 and conform essentially to the molar concentrations of the reactants originally used, and p is a whole number greater than 1.
EXAMæLE 6 Employing the same conditions as used in Example 4, 2.1 grams (0.01 mol) TMAC and 2.48 grams (0.01 mol) 4,4'-di-phenyldiaminosulfone having the formula o `- XII. NE~2~ S ~NH2 O
-`~ 20 were dissolved with stirring in 15 cc N-methylpyrrolidone;
tile mixture exothermed at 37C. The clear polymeric amic acid . amide solution which was obtained was cast at 280-300C to ~ield an imidized homopolymeric film.

~ .

~ .

.

12,3~7 Employing the conditions recited in Example 4, 5.2 grams (0.01 mol) BPA dianhydride and 2.48 grams (0.01 mol) of the sulfone of formula XII used in Example l were dissolved in 15 cc N-methylpyrrolidone, which after stirring exothermed to 38C, yielding a clear homopolym~ric amic acid solution. A film cast from this solution at 280-300C yielded an imidized homo-polymeric film.

In this example copolymers were made from TMAC, BPA
dianhydride and the sulfone of formula XII by dissolving the reactants in 15 cc N-methylpyrrolidone and effecting stirring.
of the mixture until a clear polymeric amic acid amide was obtained. In each instance, films were cast at 280-300C to yield imidized copolymeric films having.good resistance to abrasion. The following Table III shows the weight and molar concentrations of the ingredients, the exotherm temperatures, and the glass transition temperature (Tg's) for each of the compositions described,in Examples 6-8.

~0 TABLE III

Test TMAC BPA Dianhydride *Sulfone Exotherm No. Wt. gms. Mols Wt. gms. Mols ~ . Mols Temp. C Tg C

Ex. 6 ~ 37 220 Ex. 7 - - ~ 37 220 8A 1.05 0.005 2.6 0.005 2.48 0.01 41 8B 0.42 0.0024.16 0.008 2.48 0.01 39 181 8C 1.6& 0.0~81.04 O.C02 2.48 0.01 37 208 *4,4'-diaminodiphenyl sulone ~ 9~ RD-12,307 The imidized copolymers in Example 8 can be illustrated by the following formula Yl~r~;~0~o 1 ~~;!

where m, nl and p have the meanings above.
The following examples illustrate the prepaxation of homopolymers from either a dianhydride with 4,4'-oxydianiline of the formula XIV. NH2 ~ ~ NH2 of from TMAC and the same oxydianiline, as well as copolymers made from the mixture of the oxydianiline, the BPA dianhydride, and the TMAC

5.2 grams (0.01 mol) BPA dianhydride and 2 grams tO.Ol mol) 4,4l-oxydianiline were dissolved in 15 cc N-methylpyrrolidone and stirred to yield after the mixture exothermed to 51C, a clear polymeric amic acid solution. A film was ~ast from this solution at 280-300C to yield an imidized homopolymeric film.

2.1 grams (0.01 mol) TMAC and 2.0 grams (0.01 mol) 4,4'-oxydianiline were dissolved 15 cc N-methylpyrrolidone and the mixture stirred vigorously after which it exothermed to 53C. Tne cle~r homopolymeric amic aciQ amide solution which was obtained was cast at 280-300C to yield an imidized ~G~9~ RD-12,307 homopolymeric film.

In this example TMAC, BPA dianhydride and 4,4'-oxydianiline were copolymerized similarly as is done in Example 4 by dissolving the reactantsin 15 cc of N-methylpyrrolidone and thereafter casting th~ polymeric amic acid amide solution -into a film at 280-300C to yield an imidized copolymeric film~
The ~ollowing Table IV shows the weight and molar concentrations of the reactants and the exotherm temperature of each mixtuxe as the result of stirrin~ the reactants.

Table IV

Test TMAC BPA Dianh dride 4,4'-Oxydianiline Temp.
No. Wt. gms. Mols Wt gms. Mols Wt. gms. Mols Exotherm llA 1.05 0.005 2.6 0,005 1.98 0.01 41C
llB 1.68 0.008 1.04 0.002 2.0 0.01 50C
The Tg's of the homopolymers and copolymers prepared in Examples 9, 10, 11A, and llB were determined with the res~lts shown in Table V.

Table V

Test No. Tg Ex. 9 213C
Ex. 10 230C

llA 205C
llB 206C

The copolymers obtained in test llA and llB can be considered as having random units associated in the manner described in the following formula ~.3L~ RD-12 ,307 ~- O - r~,, . ;'l where m and n are values corresponding to the molar concén~ ~-tration of the reactants used, and p is a whole number greater than one.
The following examples illustrate the preparation and properties of homopolymers and copolymers made using 4,4~~
methylenedianiIine having the formula XVI. NH2 ~ C~2 ~ 2 as the orqanic diamine.

2.1 qramS (0.01 mO1) TL~AC and 1.98 grams (G.01 mol) 4,4'-methYlenedianiline were dissolved in 15 cc N-methyl-~vrrolidone and stirred until the mixture exothermed at 54C.
The clear homo~olymeric acid amide solution obtained was cast at 15 2~0-300C to yield an imidized homopolymeric film, 5.2 grams (0~01 mol) BPA dianhydride and 1.98 grams ~0.01 mol) 4,4'-methylenedianiline were dissolved with stirring in 15 cc of N-methylpyrrolidone thereby causing the tem-perature of the mixture to exotherm to 49C. The clear homo-polymeric amic acid solution which resulted was cast as a film at 280-300C to form a homopolymeric lmidized film RD-12, 3 07 In this example, employing the same conditions as in Example 4, T~C, BPA dianhydride, and 4,4'-methylenedianiline were mixed together and dissolved in 15 cc N-methylpyrrolidone to yield a copolymeric amic acid amide solution which when cast at 280-300C yielded an imidized copolymeric film. The follow-ing Table V shows the weights and molar concentrations of the reactants as well as the exotherm temperatures.
Table V

Methylene TMAC BPA Dianhydride Dianiline Test Exotherm ~.~o. Wt. gms. Mols Wt. gms. Mols Wt. yms. Mols Temp.
14A 1.05 0.005 2.6 0.005 1.98 0.01 41C
-14B 1.68 0.008 1.04 0.002 1.98 0.01 49C
Each of the polymers of Examples 12, 13, 14A and 14B were analy~ed for Tg!swith Table VI giving the results of these analyses. These copolymers can be represented by the formula ~nl l~ ~ ~ 32 1 I~ ~ ~ (33~ Q3 where m, n, and p have the meanings above.

~fi~g~ RD-12,307 Table VI
Test No. Tg Ex. 12 21SC
Ex. 13 187C

It will of course be apparent to those skilled in the art that in addition to the diamino compounds used in making the above copolymers, other diamino compounds, many examples of which have been recited previously, can be used instead. In the same manner, in addition to the bisphenol-A dianhydride employed in the examples in this application, other dian-hydrides, many examples of which have been given above, can be employed to make other types of copolymers. Finally, the molar proportions of the reactants can be varied widely to give units of varying molar range previously described without departing from the scope of the invention.
Other polymers and resins can be added to the claimed co-polymers in amounts ranging from 1 to 50% or more~ by weight, based on the total weight of the copolymer. Among such polymers may be added for instance, polyolefins, polystyrene, poly-phenylene oxides, such as shown in U.S. patent 3,306,875, epoxy resins, polycarbonate resins, such as shown in U.S. patent 3,028,365, silicone resins, polyarylene polyethers such as shown in U.S. patent 3,329,909, etc. many of which are well known in the art~
The compositions of the present invention have applica-tlon ln a wide variety ~f physi~al shapes and forms, in-cluding their use as films, molding compounds, ekc. When used RD-12,307 as fllms or when made in~o molded products, these copolymers, including the laminated products prepared thereorm, not only possess good physical properties at room temperature but they retain their strength and excellent response to workloading S at elevated temperatures for long periods of time.
Films formed from the copolymers of this invention may be used in applications where films have been used previously.
They serve effectively in an extensive variety of wrapping and packaging applications. Thus, the compositions of the present invention can be used in automobile and aviation applications for decorative and protective purposes, and as high temperature electrical insulation for motor slot liners, in transformers, and as dielectric capacitors.
Alternatively, solutions of the curable compositions herein describedcan be coated on electrical conductors such as copper, aluminum, etc. and thereafter the coated conductor can be heated at elevated temperatures to remove the solvent and to effect curing (imidization) of the resinous composition thereon. If desired, an additional overcoat may be applied to such in-sulated conductors includin~ the use of ~olvmeric coatin~s. such as Polvamides ~olvesters. silicones PolYvinvlformal resins,ePoxY resins, polyimides, Polytetrafluoroethylene, etc.
Applications which recommend these resins include their use as binders for asbestos fibers, carbon fibers, and other fibrous materials in making brakelinings. In addition, grind-ing wheels and other abrasive articles can be made from suchresins by incorporating abrasive grains such as alundum, silicon carbide,silicon nitride, carborundum, diamond dust, cubic 12,307 boron nitride, etc., and shaping or molding the mixture under heàt and pressure to obtain the desired configuration and shape for grinding and abrasive purposes.

Claims (7)

The embodiments of the invention in which an exclu sive property or privilege is claimed are defined as follows:
1. A random copolymeric composition selected from the class of general formulas consisting of (a) and (b) where R is a member selected from the class consisting of (a) the following divalent organic radicals:

RD 12,307
1. Claim 1 continued:
   
   and and (b) divalent organic radicals of the general formula where X is -CyH2y-, y is a whole number equal to from 1 to 5 inclusive, and R1 is a divalent organic radical selected from the class consisting of (a) aromatic hydrocarbon radicals having from 6-20 carbon atoms and halogenated derivatives thereof, (b) alkylene radicals and cycloalkylene radicals having from 2-20 carbon atoms, (c) C(2 8) alkylene terminated polydiorgano-siloxanes, and (d) divalent radical included by the formula where Q is a member selected from the class consisting of and x is a whole number equal to from 1 to 5 inclusive, m and n are whole numbers independently equal to at least 1, and p is a whole number greater than 1, with the proviso that the reactants used to prepare the random copolymeric composition are interacted simultaneously.
   
   2. A random copolymer comprising (a) from 5 to 95 mol percent of chemically combined units of the formula and (b) from 95 to 5 mol percent of chemically combined units of the formula where R is a member selected from the class consisting of (a) the following divalent organic radicals:
   
   and RD 12,307
2. Claim 2 continued:
   
   and (b) divalent organic radicals of the general formula where X is -CyH2y-, y is a whole number equal to from 1 to 5 inclusive, and R1 is a divalent organic radical selected from the class consisting of (a) aromatic hydrocarbon radicals having from 6-20 carbon atoms and halogenated derivatives thereof, (b) alkylene radicals and cycloalkylene radicals having from 2-20 carbon atoms, (c) C(2 8) alkylene terminated polydiorganosiloxanes, and (d) divalent radicals included by the formula where Q is a member selected from the class consisting of and x is a whole number equal to from 1 to 5 inclusive, with the proviso that the reactants used to prepare the random copolymer are interacted simultaneously.
3. 3. A random copolymer having the formula RD 12, 307 where m and n are whole numbers independently equal to at least l, and p is a whole number greater than 1, with the proviso that the reactants used to prepare the random copolymer are interacted simultaneously.
4. 4. A random copolymer having the formula where m and n are whole numbers independently equal to at least 1, and p is a whole number greater than 1, with the proviso that the reactants used to prepare the random copolymer are interacted simultaneously.
5. 5. A random copolymer having the formula where m and n are whole numbers independently equal to at least 1, and p is a whole number greater than 1, with the proviso that the reactants used to prepare the random copolymer are interacted simultaneously.
   
   RD 12, 307
6. 6. A random copolymer having the formula where m and n are whole numbers independently equal to at least 1, and p is a whole number greater than 1, with the proviso that the reactants used to prepare the random copolymer are interacted simultaneously.
7. 7. A random copolymer having the formula where m and n are whole numbers independently equal to at least 1, and p is a whole number greater than 1, with the proviso that the reactants used to prepare the random copolymer are interacted simultaneously.