FR2474515A1 - COPOLYMERS OF AMIDES AND ETHERIMIDES - Google Patents

Abstract

EASY TO MOLD COPOLYMERS AND INCREASED CHEMICAL RESISTANCE. THEY INCLUDE: A. FROM 5 TO 95 MOLES PERCENT OF CHEMICALLY COMBINED PATTERNS OF FORMULA: (CF DRAWING IN BOPI) AND B. FROM 95 TO 5 MOLES PERCENT OF EI CHEMICALLY COMBINED PATTERNS OF FORMULA: (CF DRAWING IN BOPI) OR R AND R ARE DIVALENT ORGANIC RADICALS. APPLICATION TO THE MANUFACTURE OF FILMS, MOLDED PRODUCTS, ETC.

Description

The present invention relates to copolymers containing both

  amide (A) and etherimide (EI) units useful in

  coating and molding techniques. More specifically

  The invention relates to a copolymer containing (a) from 5 to 95 mole percent of chemically cimbinated units A of the formula: (I) M

u- Q C-N-R1-

-N-C

H

  and (b) 95 to 5 mole percent of EI chemically compatible

formula of the formula: (II) O 0

IO O

c C

-N Q O-R-O Q N-R -

CI I

He he

0 0

  where the -C- units of formula (I) are in meta or para to each other, R is selected from the group consisting of: (a) the following divalent organic radicals:

H3 H3 3

CH3 H3

QQQ

CH3 CH3

/ __

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  ## STR1 ## and divalent organic radicals of the general formula:

- 4- (X) 4} -, X)

  where X is --CyH2 -, y is an integer from 1 to 5 inclusive, and k is a divalent organic radical selected from the group consisting of (a) aromatic hydrocarbon radicals having 6 to 20 carbon atoms and derivatives thereof halogenated, (b) alkylene and cycloalkylene radicals having 2 to carbon atoms, (c) C2-C8 alkylene terminated polydiorganosiloxane radicals, and (d) divalent radicals covered by the formula: o Q is a member selected from - the group comprising:

O O

  It II -O-, -C-, -S-, -S-, and -CxH2x-, and I1 O

  x is an integer from 1 to 5 inclusive.

  The randomly combined block or sequence copolymers can be considered to have the general formula: ## STR1 ## and R 1 are as defined above, m and n are integer numbers independently equal to at least 1, for example 5000 or more, and p is an integer greater than 1, for

  for example, from 5 to 10,000 or more and advantageously from 10 to 1000.

  Before imidization, the copolymers are in the amide state as shown by the following general formula:

O O

0 lIl

HO-C C - OH

  ## STR2 ## ## STR1 ##

H --N-C C-NR

L lm 1 II III

HO O

  and in particular the following general formula: ## STR2 ##

  o R, R 1, m, n and p have the above meanings.

  The polyamides of the general formula: ## STR5 ## have the above meanings, are known to have good chemical resistance to heat. Although these polyamides can be dissolved in solvents suitable for coating applications, these polyamides are often very difficult to mold and require high temperatures.

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  excessive temperatures and pressures of the molding cycle.

  Polyetherimides are known to have good

  at higher temperatures and better match

  acceptable molding cycles; however, it would be

  They are also known to increase the chemical resistance of these polyetherimides and to reduce their cost for molding and coating applications. It has been discovered that copolymers containing chemically combined units of formulas (I) and (II) can be made over a wide range of molar concentrations and

  Properties are modified in relation to the properties of homo-

  polymers of these patterns. In some cases, improvements

  properties are unexpected if we consider the proportion

  of either A or E motifs in the copo-

  lymère. By making the above copolymers, it is possible to

  unfairly extend the field of utility. Moreover, by combining these two units in the copolymer, it is possible to obtain products

  cost less than that usually associated with

  polyetherimides alone, without significant sacrifice (otherwise

none) physical properties.

  A recommended class of copolymers covered by

  formula (III) comprises copolymers consisting essentially of

  from about 2 to 5,000 or more units and preferably from 100 units of the formula: OO (IV)

C C

N ORO \

c He He

- O O

  o R is defined as above, and R is CH -o C: CH3

? 474,515

  Among the etherimide units of formula (IV) constituting part of the molecules of the copolymer, mention may be made of the following chemically combined units: (V)

O O

II I1

(N 2 NR1

ÈoÈ-R2-o A C c n

O O0 0

(VI) '

-

Onpu arqe egoe efrue (III) in

0 I-R- 0 '

  0. 230 lfaring a laromatic bis (theranhydride) of formula C

Q N-R-

general:

O O

l - O-

C

2 O

O C --R -O

-1 2

  and mixtures thereof, or R and R are defined as above.

  The copolymers of formula (III) can be made by reacting an aromatic bis (ether-anhydride) of the general formula

O O

(VIII) C c 0 -ORO o

C C

  with an isophthaloyl or terephthaloyl chloride (hereinafter referred to as "phthaloyl chloride") of the general formula: (IX) ## STR1 ## where the groups -C 1 -C are in meta or para relative to the other and an organic diamine of the general formula: (X)

H2NR1NH2

  o R and R are defined as before.

  It is possible to use from 0.95 to 1.05 moles in total of the compounds

  combinations of formulas (VIII) and (IX) per mole of diamine

  that of formula (X). It is recommended to use small quantities

  equal to (a) the compounds of formulas (VIII) and (IX) and (b) the organic diamine. The copolymers used in the present invention may be those wherein there are from 10 to 5,000 or more units of either of the formulas (I) and (II) and p in the formula (III) represents 5 or more , for example, 10

to 1,000.

  The acyl halide of formula (IX) derived from terephthalic acids

  talic or isophthalic acid can also be bromide and other

  Reacted halogenide reagents in addition to chlorides.

  It is possible to use copolymers

  string-limiters such as aniline or mono- derivatives

  organic acids or monoanhydrides.

  Generally, the copolymers of the present invention can be obtained by reacting the chosen organic diamine and the particular dianhydride and phthaloyl chloride with the following formulas:

  (VIII) and (IX), respectively, in the presence of an organic solvent

  Dipic acid at ambient conditions to produce a copolymeric acid amide. On subsequent heating, the amideacide converts to the imidized state with the copolymer comprising the units of formulas (I) and (II) in a random (statistical) distribution. Depending on the solids content of the polyamide acid solution, the reaction can be carried out in 0.5 to 2 hours or more. Once the reaction is complete, the solution can be run on a substrate so that evaporation of the organic solvent takes place. By heating

  at temperatures of 150-200 C or more, the polya-

  copolymer acid in the form of polyimide, so that the copolymer at this point has good heat resistance, good chemical resistance such as solvent resistance,

  and good moldability. These compositions are particularly

  are useful as enamels for wire coating and confer

  properties of solvent resistance and heat resistance

than to various substrates.

  The aromatic bis (ether-anhydride) of

  formula (VIII) by hydrolysis followed by dehydration of the

  reaction product of the nitrosubstituted phenyldinitrile then reaction of a double alkali metal salt of a dihydroxyaryl compound in the presence of a dipolar aprotic solvent, wherein the alkali metal salt has the general formula: Alk-OR 1-O-Alk o R1 to the previous meaning and preferably is the same

  that R2 and Alk is an alkali metal ion. We can use

  to well-known processes for converting tetranitriles

  resulting in corresponding tetraacids and dianhydrides.

  Among the alkali metal salts of the above-mentioned diphenols, mention may be made of the potassium and sodium salts of the following diphenols: bis (hydroxyphenyl) -2,2-propane; 2,4-dihydroxy-diphenylmethane; bis (2-hydroxyphenyl) methane; 2- (4-hydroxyphenyl) propane, hereinafter referred to as "bisphenol-A" or "BPA", bis (4-hydroxyphenyl) -1, ethane, bis (4-hydroxyphenyl), bis (4-hydroxyphenyl) propane; 1-propane, bis (4-hydroxyphenyl) -3,3-pentane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3'-tetramethyl-5'-biphenyl; 2,4-dihydroxybenzophenone, 4,4'-dihydroxy diphenyl sulfone, 2,4-dihydroxy diphenyl sulfone, 4,4'-dihydroxy diphenyl sulfoxide, 4,4'-dihydroxy diphenyl sulfide, etc. the organic diamines of formula (X) may be mentioned,

for example,

  m-phenylenediamine; p-phenylenediamine; diamino-4,4'-diphenylpropane; diamino-4,4'-diphenylmethane; benzidine; 4,4'-diamino diphenyl sulfide; diamino-4,41 diphenyl sulfone; 4,4'-diamino diphenyl ether; 1,5-diamino naphthalene; 3,3-dimethylbenzidine; 3,3-dimethoxybenzidine; 2,4-diamino toluene; 2,6-diamino toluene; bis (e-amino-t-butyl) -2,4 toluene; bis (p-emethyl-o-aminopentyl) benzene; 1,3-diamino-4-isopropylbenzene; bis (3-amino-propoxy) -1,2 ethane; m-xylylenediamine; pxylylenediamine; bis (4-aminocyclohexyl) methane; 3-methylheptamethylenediamine; 4,4-dimethylheptamethylenediamine; diamino2,11dodecane; 2,2-dimethylpropylenediamine; octamethylenediamine; 3-methoxyhexamethylenediamine; 2,5-dimethyl-hexamethylenediamine; 3-methylheptamethylenediamine; 5-methyl-nonamethylenediamine; 1,4-diamino cyclohexane; diamino-1,12 octadecane; bis (3-aminopropyl) sulfide; N-methyl-bis (3-aminopropyl) amine; hexamethylenediamine; nonamethylenediamine; 2,6-diamino toluene; bis (3-aminopropyl) tetramethyldisiloxane, etc. The copolymer composition can be reinforced with various particular fillers such as glass fibers, silica, carbon whiskers, up to 50% or more,

by weight, copolymer.

  In the following examples, unless otherwise indicated,

  all parts are by weight.

EXAMPLE 1

  This example illustrates the preparation of a homopolyether

  mide formed from isophthaloyl chloride and oxy-4,4'-dianiline which will be compared later with a copolymer composition containing the same organic diamino compound. 2.03 g (0.01 mol) of isophthaloyl chloride and 2.0 g (0.01 mol) of 4,4'-oxy were dissolved in 15 cm3 of N-methylpyrrolidone.

  dianiline. During stirring, the mixture warmed up

  at 64 C to give a solution of a homopolymeric amide.

  This solution was poured at 280-300 ° C. and an imidized film was obtained.

polymer.

EXAMPLE 2

  A copolymer containing A and EI units was prepared by reacting 2.0 g (0.01 mole) of oxy-4,4'-dianiline, 4.16 g (0.008 mole) of bis [(3,4-dicarboxy) phenoxy) -4-phenyl] -2.2 propane (bisphenol A dianhydride) and 0.41 g (0.002 mole) of

  isophthaloyl chloride (CI) in 15 cm3 of N-methylpyrrolidone.

  The mixture was stirred at room temperature until

  became clear, the mixture warmed to 52 C.

  cooling, the copolymer composition was cast as a film on glass at 280-300 ° C. to imitate the

  amino acid groups. The polymer that had a modest relationship

  80 mole percent of EI units and 20 mole percent of A units had the formula: (XI) "e '" 0- - o o

N-C N 0 \ C (CH3) * X

1C 1 i 1 jN L P

  o the patterns are arranged randomly, m and n are independently

  integers greater than 1, and p is a number

integer greater than 1.

EXAMPLE 3

  Using the conditions of Example 2, isophthaloyl chloride, bisphenol-A dianhydride and oxy-4,4'-dianiline were interacted in varying proportions using in each case 15 cm 3 of N methylpyrrolidone as solvent. The following Table 1 shows the proportions and molar concentrations of the ingredients, the temperature of each exothermic reaction, and the glass transition temperature Tg, which measures the degree of softening of the polymers.

  of the homopolymer of Example 1 and the copolymers of the examples

  Ples 2 and 3. The copolymers of Example 3 can be represented by the same general formula as in Example 2 where m and n have the above meanings and are essentially the same.

  same as the molar concentrations of the reagents used.

TABLE I

  CI Dianhydride Oxy-4,4 'Temperature Tg of BPA dianiline reaction Test Weight Moles Weight Moles Weight Moles n (g) (g) (g)

  30 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

Ex.1 200 C Ex.2 221 C

  3A 1.02 0.005 2.6 0.005 2.0 0.01 55 C 213 C

  3B 1.62 0.008 1.04 0.002 2.0 0.01 59 C 234 C

EXAMPLE 4

  Using the same conditions as in Example 1, 15 cm3 of N-methylpyrrolidone, 2.07 g (0.01 mole) of isophthaloyl chloride and 1.98 g (0.01 g) were thoroughly mixed. mole) of 4,4'-methylene dianiline of formula: (XII)

NH2 2 Q NH2

  the mixture was heated to 55 ° C. to give a lim-

  pide of polymeric amide resin. We sank the solution

  obtained at 280-300 C to obtain a homogeneous film.

EXAMPLE 5

  Using the conditions of Examples 2 and 4, isophthaloyl chloride, dianhydride of

  BPA and methylene-4,4'-dianiline in 15 cm3 of N-methyl-

  pyrrolidone to obtain a clear solution of a polymeric amide acid amide which, cast at 280-300 C, provides imidized copolymeric films. Table II below gives the weights and molar concentrations of the various ingredients,

  temperatures of ex-thermal reactions, and the temperature of transi-

  (Tg) for the homopolymer and the copolymers

with methylene dianiline.

  TABLE 2 4,4'-Methylene Temperature IC Test BPAdianiline Dianhydride Reaction Tg N Weight Moles Weight Moles Weight Molec C C (g) (g) (g)

4,234 C

  A 0.41 0.002 4.16 0.008 1.98 0.01 52 C 211 C

  5B 1.02 0.005 2.6 0.005 1.98 0.01 48 C 229 C

  C 1.62 0.008 1.04 0.002 1.98 0.01 47 C 239 C

  The copolymers using 4,4'-methylene dianiline can be illustrated by the following formula:

(XIII)

0 0 IIil c

N H

H C (H3H

m c

L J ML 0 '

o -

  o m, n have the above meanings and reflect the molar concentration of reagents and p is a whole number

greater than 1.

EXAMPLE 6

  Using the same conditions as in Example 1,

  it was dissolved and thoroughly mixed in 15 cm3 of N-methyl-

  pyrrolidone, 2.03 g (0.01 mol) of isophthaloyl chloride and 2.48 g (0.01 mol) of 4,4'-diaminodiphenylsulfone of formula: (XIV) N Si N2 o -NH The mixture was heated to 59 ° C. The resulting polymeric amide resin solution was cast at 280 ° C to 300 ° C to give

homogeneous flexible film.

EXAMPLE 7

  Using the conditions of Examples 2 and 4, isophthaloyl chloride, BPA dianhydride and the sulfone of formula (XIV) were reacted in 15 cm3 of N-methylpyrrolidone until a solution of clear polymeric amic acid which, when poured at 280-300 ° C., provided imidized polymeric films. Table III below gives the weights and molar concentrations of the various ingredients used to make the copolymers, the exothermic reaction temperatures, and the glass transition temperature (Tg).

  for homopolymer and copolymers made with diamino-

diphenyl sulfone.

  Temperature TABLE III Temperature

of échauffe-

  BMP Dianhydride Assay: Sulfone Tg N Weight Moles Weight Moles Weight Moles C C (g) (g) (g)

6,186 C

  7A 0.41 0.002 4.16 0.008 2.48 0.01 410C 156 C

  7B 1.02 0.005 2.6 0.005 2.48 0.01 48 C 168 C

4,4'-diaminodiphenyl sulfone.

  The copolymers of Example 7 can be illustrated by the following formula: (XV)

0 ''

II 0 -

  ## STR1 ## ## STR2 ##

L 0

m lU

  o m, n and p have the above meanings.

EXAMPLE 8

  Using the conditions of Example 1, the mixture was stirred vigorously to the point where the mixture warmed to 63 ° C, 2.03 g (0.01 mole) of CI and 1.08 g (0.01 mole). ) of m-phenylene diamine dissolved in 15 cm3 of N-methylpyrrolidone. The clear homopolymeric amide solution obtained at 280.degree.

  on a surface to form a homogeneous film.

EXAMPLE 9

  Using the conditions of Examples 2, 4 and 7, 15 cm 3 of N-methylpyrrolidone was reacted with

  isophthaloyl, BPA dianhydride and m-phenylenediamine.

  mine to obtain a solution of polymeric amic acid amide

  that, cast on a surface heated to 280-300 C,

  know an imidized polymeric film, having good resistance to abrasion. Table IV below shows the quantities of reagents used for the manufacture of the copolymers, the exothermic reaction temperature for each of the copolymers.

  and the glass transition temperature, Tg, for the homopolymer

  mother of Example 8 and the copolymers of Examples 9A, 9B and 9C.

TABLE IV

  M-phenylene BPA dianhydride test Temperature Tg reaction diamine n Ppids Moles Weight Moles Weight Moles C C

Lg L (. ------------------ _-----

8,245 C

  9A 0.41 0.002 4.16 0.008 1.08 0.01 54 C 191 C

  9B 1.02 0.005 2.6 0.005 1.08 0.01 48 C 242 C

  9C 1.62 0.008 1.04 0.002 1.08 0.01 46 C 244 C

  The copolymers of Example 9 can be represented by the following formula: ## STR2 ##

  o m and n are integers and correspond to the con-

  molar centering of the reagents used, and p is a number

-greater than 1.

EXAMPLE 10

  When terephthaloyl chloride is used in place of isophthaloyl chloride in the preceding examples

  to make copolymers using the various compounds

  diamino compounds used for this purpose, copolymers represented by formula (II) are obtained which are useful for

  coating, insulation and molding.

  It is obvious to those skilled in the art that in addition to the diamino compounds used to make the above copolymers, other diamino compounds may be used, many of which have been previously cited. In the same manner, in addition to the bisphenol-A dianhydride used in the examples, other dianhydrides, many of which have been mentioned above, can be used to make other types of dianhydrides.

  copolymers. Finally, the proportions can be varied widely

  molar concentrations of the reagents to obtain proportional patterns

  variable molar composition without departing from the scope of the present invention.

  Other polymers and resins can be added to the copo-

  polymers of the invention, in amounts ranging from 1 to 50% or more, by weight, based on the total weight of copolymers. Among these polymers that can be added include, for example, polyolefins, polystyrene, poly (oxyphenylenes), k474515 such as those described in US Pat. No. 3,306,875, epoxy resins. polycarbonate resins such as those described in U.S. Patent No. 3,329,909, etc., many of which are well known in the art. The compositions of the present invention have applications in many fields and in various physical forms such as films, molding compounds, and the like. When used in the form of films or in the form of

  molded products, these copolymers, including

  prepared from them, not only possess

  good physical properties at room temperature but

  their mechanical strength and excellent response to high temperature workloads over long periods of time.

periods of time.

  Films formed with these copolymers can be used

* in applications where movies were used previously.

  They can indeed be used in a wide variety of applications.

  wrapping and wrapping cations. Thus, the compositions of the present invention can be used in the field of automobiles and aviation for decorative and protective purposes, and as electrical insulation for gutters.

  engine notches, in transformers and as dielectrics

three capacitors.

  Alternatively, electrical conductors such as copper, aluminum, etc., can be coated with solutions of the curable compositions of the invention and heated at high temperatures to remove the solvent and effect curing (imidization) of the composition. resinous. If necessary, an additional layer can be applied to these isolated conductors, including polymeric coatings such as polyamides, polyesters, silicones, polyvinyl formal resins, epoxy resins, polyamides, polytetrafluoroethylene, and the like. Applications for which these resins are recommended include their use as binders for potassium titanate fibers, glass fibers

L474515

  carbon fibers and other fibrous materials for the manufacture of composites. In addition, grinding wheels and other abrasive articles can be made from these resins by incorporating abrasive grains such as alumina, silicon carbon, silicon nitride, carborundum, diamond dust, nitride. cubic boron, and by shaping or molding the mixture under pressure and hot to obtain the desired configuration for grinding and abrasion.

: 474515

Claims (6)

  1. A copolymeric composition characterized in that it is chosen from the class corresponding to the general formulas (a) O it and (b) I. C-N-R I O I o groups -C-   one with respect to consisting of: (a) the radicals CH3 o CH3 mi -O HO-C t OR-O -NC O il O of the unit m are either in meta or para the other, and o R is chosen from the following divalent organic group: CH3 CH3   ## STR2 ## Q and -C (Cl 3) - CH 3 Br Br CH 3 Br Br (b) divalent organic radicals of general formula: -X .. (X) X> -   where X is -C H-, y is an integer ranging from 1 to 5 inclusive ylzy, and R is a divalent organic radical selected from the group consisting of (a) aromatic hydrocarbon radicals having 6 to 20 carbon atoms and their derivatives halogenated, (b) alkyl radicals and cycloalkylenes having from 2 to 20 atoms   (c) polydiorganosiloxane radicals at the terminal   C2 to C8 alkylenes, and (d) the divalent radicals covered by the formula: - oQ / -   o Q is an element selected from the group consisting of: O O   It 1i -O-, -C-, -S-, -S-, and -Cx2x-, II x 2x on and x is an integer from 1 to 5 inclusive, m and n are integers independently at least equal at 1, and p is an integer greater than 1.   2. Copolymer characterized in that it comprises (a) from 5 to 95 mole percent of units IASB-N-R1 -N-C - II   And (b) from 95 to 5 mole percent of chemically combined units of formula: O O He I c c -N O-R-O N-R - / C / C He He O O 0   Wherein the groups -C in the units of (a) are in meta or para to each other, and wherein R is selected from the group consisting of: (a) the following divalent organic radicals: CH3 CH3 3 H '3 CH3 H 3 3   CH 3 Br Br CH 3 Br Br X O- and C - (CH 3); and b) divalent organic radicals of the general formula: X is -CH -, y is an integer from 1 to 5 inclusive Y12Y, and R is a divalent organic radical selected from group comprising (a) aromatic hydrocarbon radicals having 6 to 20 carbon atoms and their halogenated derivatives, (b) alkylene and cycloalkylene radicals having 2 to 20 atoms   (c) polydiorganosiloxane radicals with a final   C2 to C8 alkylenes, and (d) the divalent radicals covered by the formula: O .. * Q, .0.   o Q is a member selected from the group consisting of O O   II-O-, -C-, -S-, -S-, and -C H-, where x is x and x is an integer from 1 to 5 inclusive, - 474515   3. A composition of matter characterized in that it corresponds to the formula: ## EQU1 ## and n are integers independently at least   equal to 1 and p is an integer greater than 1.   4. A composition of matter characterized in that it corresponds to the formula: ## STR2 ## and n are integers independently at least equal to one another -) o! I 0- 0   o m and n are integers independently at least equal i   a 1 and p is an integer greater than 1.   5. A composition of matter characterized in that it corresponds to the formula: H N 0..lCC, - -N   Where n and n, are independently whole numbers, at least   equal to 1, and p an integer greater than 1.   6. Composition characterized in that it has the formula: -N-C Y aC - 'X C112 - @> _ _ H H - s.-   M, 0 - c (CH 3) 2 <I] C X I i o o o o m and n, are independently integers at least   equal to 1, and p an integer greater than 1. o0 t p