U.S. patent number RE29,316 [Application Number 05/311,138] was granted by the patent office on 1977-07-19 for cross-linked resins.
This patent grant is currently assigned to Rhone-Poulenc S.A.. Invention is credited to Michel Bargain, Andre Combet, Pierre Grosjean.
United States Patent |
RE29,316 |
Bargain , et al. |
July 19, 1977 |
Cross-linked resins
Abstract
Cross-linked resins of good thermal stability useful inter alia
for making multicellular materials, for bonding metals, and for
making laminates and moulded articles are made by reacting, e.g. by
heating together, an unsaturated bis-imide with a diprimary diamine
in a ratio of 1.2:1 to 50:1.
Inventors: |
Bargain; Michel (Lyon,
FR), Combet; Andre (Lyon, FR), Grosjean;
Pierre (Sainte-Foyte-les-Lyon, FR) |
Assignee: |
Rhone-Poulenc S.A. (Paris,
FR)
|
Family
ID: |
27244324 |
Appl.
No.: |
05/311,138 |
Filed: |
December 1, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
743025 |
Jul 8, 1968 |
03562223 |
Feb 9, 1971 |
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Foreign Application Priority Data
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Jul 13, 1967 [FR] |
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67.114381 |
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Current U.S.
Class: |
524/104; 428/435;
524/726; 528/170; 528/322; 524/233; 528/168; 528/321 |
Current CPC
Class: |
B32B
27/00 (20130101); C08G 73/122 (20130101); Y10T
428/31623 (20150401) |
Current International
Class: |
B32B
27/00 (20060101); C08G 73/12 (20060101); C08G
73/00 (20060101); C08G 073/12 () |
Field of
Search: |
;260/47CP,78UA,30.2,32.6N,47UA,47CZ |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lee; Lester L.
Attorney, Agent or Firm: Bacon & Thomas
Claims
We claim:
1. A cross-linked resin obtained by heating at 100.degree. C. to
350.degree. C. an unsaturated bis-imide selected from the group
consisting of maleic N,N'-ethylene-bis-imide, maleic
N,N'-hexamethylene-bis-imide, maleic N,N'-metaphenylene-bis-imide,
maleic N,N'-paraphenylene-bis-imide, maleic
N,N'-4,4'-diphenylmethane-bis-imide, maleic
N,N'-4,4'-diphenylether-bis-imide, maleic
N,N'-4,4'-diphenylsulphone-bis-imide, maleic
N,N'-4,4'-dicyclohexylmethane-bis-imide, maleic N,N'
-.alpha.,.alpha.'-4,4'-dimethylenecyclohexane-bis-imide, maleic
N,N'-metaxylylene-bis-imide and maleic
N,N'-4,4'-diphenylcyclohexane-bis-imide with a diamine selected
from the group consisting of 4,4'-diaminodicyclohexylmethane,
1,4-diaminocyclohexane, 2,6-diaminopyridine, metaphenylenediamine,
paraphenylenediamine, 4,4'-diaminadiphenylmethane,
2,2-bis-(4-aminophenyl)-propane, benzidine, 4,4'-diaminophenyl
oxide, 4,4'-diaminodiphenyl sulphide,
4,4'-diaminodiphenyl-sulphone, bis-(4-aminophenyl)diphenylsilane,
bis-(4-aminophenyl)methylphosphine oxide,
bis-(3-aminophenyl)methylphosphine oxide,
bis-(4-aminophenyl)phenylphosphine oxide,
bis-(4-aminophenyl)phenylamine, 1,5-diamino-naphthalene,
metaxylylenediamine, paraxylene diamine,
1,1-bis(paraaminophenyl)phthalene,
1,1-bis(4-aminophenyl)cyclohexane,
1,1-bis(4-amino-3-methylphenyl)cyclohexane and hexamethylenediamine
at a ratio of bis-imide to diamine of from 1.2:1 to 50:1.
2. The cross-linked resin of claim 1 wherein said unsaturated
bis-imide is maleic N,N'-4,4'-diphenylmethane-bis-imide and said
diamine is bis-(4-aminophenyl)methane.
3. The cross-linked resin of claim 1 wherein the ratio of bis-imide
to diamine is from 1.3:1 to 5:1.
4. The cross-linked resin of claim 2 wherein the ratio of bis-imide
to diamine is from 1.3:1 to 5:1.
5. The cross-linked resin of claim 2 wherein the ratio of bis-imide
to diamine is from about 2.3 to about 3.6. .Iadd. 6. A resinous
polymer soluble in inert polar organic solvent and containing amine
and imide groups formed by reacting a bis-maleimide with a
diprimary amine in a molar ratio of from 1.2:1 to 50:1 at a
temperature of from about 100.degree. C. to about 250.degree. C.
.Iaddend. .Iadd. 7. The resinous polymer of claim 6 wherein the
bis-malemide is maleic N,N'-4,4'-diphenylmethane-bis-imide and said
diprimary amine is bis-(4-aminophenyl)methane. .Iaddend..Iadd. 8.
The resinous polymer of claim 6 wherein the ratio of bis-imide to
diamine is from 1.3:1 to 5:1. .Iaddend..Iadd. 9. A lacquer
comprising the resinous polymer of claim 6 in solution in an inert
polar organic solvent. .Iaddend..Iadd. 10. The lacquer of claim 9
in which said solvent is selected from the group of dimethyl
formamide, dimethyl-acetamide and N-methyl pyrrolidone.
.Iaddend..Iadd. 11. A method for curing the resinous polymer of
claim 6 wherein the said polymer is heated up to a temperature of
about 350.degree. C. .Iaddend. .Iadd. 12. A resinous polymer
soluble in inert polar organic solvent and containing amine and
imide groups formed by reacting a bis-maleimide with a diprimary
amine in a molar ratio between 1.2 to 1 and 50:1, said reaction
being carried out in solution in an inert polar organic solvent at
a temperature of 100.degree. to 250.degree. C. .Iaddend..Iadd. 13.
A polymer as recited in claim 12 in which the ratio of said
bis-maleimide to said diprimary amine is from 1.3:1 to 5:1.
.Iaddend..Iadd. 14. A polymer as recited in claim 12 in which said
maleimide is based on maleic anhydride. .Iaddend..Iadd. 15. A
polymer as recited in claim 12 in which said diprimary amine is
aromatic. .Iaddend..Iadd. 16. A polymer as recited in claim 12 in
which the temperature of reaction is 150.degree. C. .Iaddend.
.Iadd. 17. A lacquer comprising the polymer of claim 12 in solution
in an inert polar organic solvent. .Iaddend. .Iadd. 18. A method of
forming a resinous polymer soluble in an inert polar organic
solvent and containing amine and imide groups comprising reacting a
bis-maleimide with a diprimary amine in a molar ratio of from 1.2:1
to 50:1 in an inert polar organic solvent medium at a temperature
of 100.degree. to 250.degree. C. .Iaddend..Iadd. 19. A lacquer
comprising a resinous polymer soluble in inert polar organic
solvent and containing amine and imide groups formed by reacting a
bis-maleimide with a diprimary amine in a molar ratio between 1.2:1
and 50:1, said reaction being carried out in solution in inert
polar organic solvent at a temperature of 100.degree. to
250.degree. C., said resinous polymer being in solution in an inert
polar organic solvent selected from the group of dimethyl
formamide, dimethylacetamide and N-methyl pyrrolidone. .Iaddend.
.Iadd. 20. A resinous moulded polymer soluble in polar organic
solvent and containing amine and imide groups formed by reacting a
bis-maleimide with a diprimary amine in a molar ratio of from 1.2:1
to 50:1 at a temperature of from about 100.degree. C. to about
250.degree. C. .Iaddend. .Iadd. 21. The product of the process as
defined by claim 11. .Iaddend.
Description
This invention relates to cross-linked resins of good thermal
stability and their production.
French Pat. No. 1,455,514 describes three-dimensional polyimides
prepared by heating N,N'-bis-imides of unsaturated carboxylic
acids, e.g. maleic N,N'-metaphenylene-bis-imide. These polyimides
are infusible and insoluble resins whose decomposition temperature
is high, but moulded objects made of them often undergo
deformations on the surface in the course of prolonged use at
temperatures in the neighbourhood of 200.degree. C. or above.
It has also been proposed (see U.S. Pat. No. 2,818,405) to prepare
linear elastomers by coupling liquid diprimary diamines having an
optionally halogenated aliphatic chain and a molecular weight from
750 to 12,000, with a bis-maleimide. These elastomers may be
converted into elastic films or filaments, but are obviously less
well adapted to the production of compact moulded articles, while
in addition they have low thermal stability.
It has now been found, and this forms the subject of the present
invention, that new cross-linked resins resistant to severe thermal
stresses are obtained when an N,N'-bis-imide of an unsaturated
dicarboxylic acid of the formula: ##STR1## in which D represents a
divalent radical containing a carbon-carbon double bond and A is a
divalent radical having at least 2 carbon atoms, is reacted with a
diamine of the formula:
in which B represents a divalent radical not having more than 30
carbon atoms, in a ratio of bis-imide to diamine of between 1.2:1
and 50:1.
The symbols A and B may be identical or different and may represent
linear or branched alkylene radicals having less than 13 carbon
atoms, cycloalkylene radicals having 5 or 6 carbon atoms in the
ring, heterocyclic radicals containing at least one of the atoms O,
N and S, or a phenylene or polycyclic aromatic radical. These
various radicals may carry substituents which do not give undesired
side-reactions under the operating conditions. The symbols A and B
may also represent a number of phenylene or alicyclic radicals
connected directly or by a divalent atom or group such as, for
example, oxygen or sulphur, an alkylene grouping of 1 to 3 carbon
atoms, or one of the groups --NR.sub.4 --, --P(O)R.sub.3 --,
--N.dbd.N--, ##STR2## in which R.sub.3, R.sub.4 and Y each
represent alkyl of 1 to 4 carbon atoms, or a cycloalkyl radical
having 5 or 6 carbon atoms in the ring, or a phenyl or polycyclic
aromatic radical, and X represents a straight or branched alkylene
radical having less than 13 carbon atoms, a cycloalkylene radical
having 5 or 6 carbon atoms in the ring, or a mono- or polycyclic
arylene radical.
The radical D is derived from an ethylenic anhydride of the
formula: ##STR3## which may be, for example, maleic anhydride,
citraconic anhydride, tetrahydrophthalic anhydride, itaconic
anhydride and the products of Diels-Alder reaction between a
cyclodiene and one of these anhydrides.
Preferred N,N'-bis-imides of Formula I which may be employed, are
maleic N,N'-ethylene-bis-imide, maleic
N,N'-hexamethylene-bis-imide, maleic N,N'-metaphenylene-bis-imide,
maleic N,N'-paraphenylene-bis-imide, maleic
N,N'-4,4'-diphenylmethane-bis-imide, maleic
N,N'-4,4'-diphenylether-bis-imide, maleic
N,N'-4,4'-diphenylsulphone-bis-imide, maleic
N,N'-4,4'-dicyclohexylmethane-bis-imide, maleic
N,N'-.alpha.,.alpha.'-4,4'-dimethylenecyclohexane-bis-imide, maleic
N,N'-metaxylylene-bis-imide, and maleic
N,N'-4,4'-diphenylcyclohexane-bis-imide.
Examples of diamines of Formula II which may be employed, are
4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane,
2,6-diaminopyridine, metaphenylenediamine, paraphenylenediamine,
4,4'-diaminodiphenylmethane, 2,2-bis-(4-aminophenyl)propane,
benzidine, 4,4'-diaminophenyl oxide, 4,4'-diaminodiphenyl sulphide,
4,4'-diaminodiphenylsulphone, bis-(4-aminophenyl)diphenylsilane,
bis-(4-aminophenyl)methylphosphine oxide,
bis-(3-aminophenyl)methylphosphine oxide,
bis-(4-aminophenyl)phenylphosphine oxide,
bis-(4-aminophenyl)phenylamine, 1,5-diaminonaphthalene,
metaxylylenediamine, paraxylylene diamine,
1,1-bis-(paraaminophenyl)phthalene, and hexamethylenediamine.
The quantities of N,N'-bis-imide and of diamine are chosen in such
manner that the ratio ##STR4## is between 1.2:1 and 50:1,
preferably between 1.3:1 and 5:1.
The preparation of the new resins of the invention may be carried
out in an inert polar diluent such as dimethylformamide,
N-methylpyrrolidone or dimethylacetamide. A solvent is
advantageously used when the application of the polymer formed
necessitates the use of a solution, because it makes it possible to
obtain directly solutions whose solids content may be very
high.
The preparation may also be carried out in bulk, by heating the
reactants which have previously been intimately mixed. Depending
upon the physical state of the reactants, conventional methods may
be employed for mixing finely divided solids, or a solution or a
dispersion of one of the reactants in the other, maintained in the
liquid state, may be prepared. For many uses, it is advantageous,
first to heat the mixture of the two reactants at a moderate
temperature of the order of 100.degree. to 250.degree. C. for a few
minutes to a few hours. The prepolymer thus obtained may then be
employed in solution in a solvent such as those referred to above
or in suspension in an inert diluent, or it may be shaped by simple
hot casting, or again it may be employed as powder. In a second
phase, the hardening of the prepolymer may be directly effected by
heating to temperatures of the order of 350.degree. C., optionally
under pressure.
The mixture may also be directly brought into the form of the
desired article and the hardening may be effected by heating,
optionally under pressure.
The new resins are infusible and insoluble. They have remarkable
resistance to thermal stresses, have good dielectric properties and
are endowed with excellent stability to chemical agents. They may
be converted into multicellular materials or employed for bonding
metals. They are also particularly useful for the preparation of
laminates based on mineral fibres or of moulded articles optionally
in association with fibrous or pulverulent fillers.
The following examples illustrate the invention. In these examples,
the tests are carried out in accordance with the following
standards:
Flexural test standard A.S.T.M. D790-63, the spans being specified
in each example.
Tensile strength test: Standard A.S.T.M. D882-61T.
Dielectric strength test: Standard A.S.T.M. D150-69T.
EXAMPLE 1
77.5 g. of maleic N,N'-4,4'-diphenylmethane-bis-imide are added to
33 g. of bis-(4-aminophenyl)methane previously heated to
125.degree. C. The mixture is stirred, maintained at 125.degree. C.
for 10 minutes and then run into a parallelepipedic mould (125 mm.
.times. 6 mm. .times. 75 mm.) heated at 200.degree. C. The whole is
maintained at 200.degree. C. for 3 hours. After mould release, the
plate is cut into test pieces (length 37.5 mm., width 9.57 mm.)
which have at 25.degree. C. a flexural strength of 15.3
kg./mm..sup.2 for a span of 25.4 mm.
After heating at 250.degree. C. for 910 hours, the strength is
still 10.6 kg./mm..sup.2.
EXAMPLE 2
A homogeneous mixture is prepared from identical quantities of the
same reactants as in Example 1. This mixture is spread on the plane
surface of an open metal receptacle to form a layer about 1 cm.
thick, and the whole is kept for 7 minutes in an oven heated at
200.degree. C. After cooling and mould release, the product
obtained is finely ground (mean diameter of the particles 80.mu.)
and 25 g. thereof are introduced into a cylindrical mould (diameter
75 mm.). The mould is introduced between the plates of a press
heated at 200.degree. C. and a pressure of 50 kg./cm..sup.2 is
applied. These conditions are maintained for 1 hour. After mould
release at elevated temperature, the object is further heated at
220.degree. C. for 24 hours and then at 240.degree. C. for 24
hours. After cooling, it has, at 25.degree. C., a flexural strength
of 12.1 kg./mm..sup.2.
After 1650 hours at 250.degree. C., this strength is still 11.9
kg./mm..sup.2 (for a span of 25.4 mm.).
EXAMPLE 3
The procedure of Example 1 is followed, starting with 33 g. of the
same diamine and 89.5 g. of the same bis-imide, the mixture being
heated at 120.degree. C. for 10 minutes.
(a) A portion of the hot liquid mixture is run into cylindrical
moulds (diameter 54 mm., height 6 mm.); the hardening is effected
by heating at 200.degree. C. for 2 hours and is followed by an
additional heat treatment for 15 hours at the same temperature. The
moulded bodies have the following characteristics at 25.degree.
C.:
______________________________________ After 113 hours at Initial
250.degree. C. ______________________________________ Dielectric
constant at 50 c./s 3.8 3.5 Tangent .delta. 2 .times.
10.sup.-.sup.3 <10.sup..sup.-3 Transverse resistivity, ohm-cm 2
.times. 10.sup.14 2 .times. 10.sup.15
______________________________________
(b) Another portion of the hot liquid mixture is run into the
parallelepipedic mould described in Example 1, preheated at
120.degree. C. The whole is heated to 200.degree. C. in 30 minutes
and maintained at this temperature for 1 hour 30 minutes. After
mould release, the plate is subjected to an additional heat
treatment for 15 hours at 200.degree. C. The test pieces obtained
have, at 25.degree. C., a flexural strength of 20 kg./mm..sup.2 for
a span of 25.4 mm. After heating at 250.degree. C. for 1465 hours,
the flexural strength has retained 67% of its initial value.
EXAMPLE 4
78.4 g. of maleic N,N'-4,4'-diphenylmethane-bis-imide are added to
21.7 g. of bis-(4-aminophenyl)methane previously heated to
130.degree. C. The mixture is stirred and is then maintained at
130.degree. C. for 30 minutes. After cooling and grinding, 93.1 g.
of the product obtained are dissolved in 106.1 g. of
N-methylpyrrolidone. 3600 cm..sup.2 of a glass fabric of the satin
type which has previously undergone thermal debatching and then a
treatment with .gamma.-aminopropyltriethoxysilane are coated with
79 g. of the solution. The fabric weighs 308 g./m..sup.2. The
coated fabric is dried at 90.degree. C. for 3 hours under reduced
pressure (10 mm. Hg), and then cut into 16 specimens (each 150 mm.
.times. 150 mm.), which are stacked to form a laminated assembly.
This assembly is compressed under 30 kg./cm..sup.2, and maintained
under this pressure for 1 hour, the temperature gradually being
raised to 200.degree. C. After mould release, the laminate is
gradually heated to 250.degree. C. in 70 hours. After cooling (to
25.degree. C.), it has the following properties:
Resin content--20.9%
Flexural strength (for a span of 50 mm.):
Initial--65 kg./mm..sup.2
After 232 hours at 250.degree. C.--74 kg./mm..sup.2
EXAMPLE 5
The procedure of Example 1 is followed with 90.2 g. of the same
bis-imide and 9.8 g. of the same diamine preheated at 150.degree.
C., the mixture being heated at 150.degree. C. for 5 minutes.
Moulding is then effected by casting in accordance with Example
3(b). An additional heat treatment is carried out at 230.degree. C.
for 50 hours. The test pieces have, at 25.degree. C., a flexural
strength of 13.3 kg./mm..sup.2 ; after 169 hours at 300.degree. C.,
it is still 9.5 kg./mm..sup.2.
EXAMPLE 6
45.15 g. of maleic N,N'-4,4'-diphenylphenylmethane-bis-imide are
intimately mixed with 9.90 g. of bis-(4-aminophenyl)methane. 10 g.
of this mixture are heated at 200.degree. C. for 5 minutes. After
cooling, the prepolymer is ground and place in a mould identical to
that employed in Example 1. The mould is heated to 195.degree. C.
under a pressure of 25 kg./cm..sup.2 and then maintained for 1 hour
at 195.degree.-205.degree. C. under a pressure of 100
kg./cm..sup.2. After mould release and cooling, the moulded bar
has, at 25.degree. C., a flexural strength of 8.6 kg./mm..sup.2
(for a span of 25.4 mm.).
EXAMPLE 7
The procedure of Example 6 is followed using 48.24 g. of maleic
N,N'-metaphenylene-bis-imide and 12 g. of
bis-(4-aminophenyl)-ether. The mould is heated to 195.degree. C. in
35 minutes under a low pressure (called the contact pressure) and
then maintained at 195.degree.-200.degree. C. for 1 hour under 100
kg./cm..sup.2. The flexural strength of the bar is 12.2
kg./mm..sup.2.
EXAMPLE 8
The procedure of Example 6 is followed using 64.3 g. of maleic
N,N'-metaphenylene-bis-imide and 15.8 g. of
bis-(4-aminophenyl)methane. The moulded article has a flexural
strength of 12 kg./mm..sup.2.
EXAMPLE 9
The experiment described in Example 6 is repeated, using 32.4 g. of
maleic N,N'-4,4'-diphenylether-bis-imide, and 6 g. of
bis(4-aminophenyl)ether. The mould is heated to 180.degree. C. in
20 minutes under 25 kg./cm..sup.2 and then from 180.degree. to
210.degree. C. in 1 hour under 100 kg./cm..sup.2. The bar has a
flexural strength of 10 kg./mm..sup.2.
EXAMPLE 10
41.3 g. of maleic N,N'-4,4'-diphenylmethane-bis-imide are added to
9.4 g. of 1,1-bis-(4-aminophenyl)cyclohexane previously heated to
130.degree. C. The mixture is stirred and then maintained at
130.degree. C. for 1 hour, 30 minutes. After cooling and grinding,
25 g. of the powder obtained are introduced into a cylindrical
mould having an internal diameter of 75 mm. The mould is heated to
110.degree. C. under a pressure of 100 kg./cm..sup.2 and then
heated to 220.degree. C. in 1 hour under the same pressure. After
mould release and cooling, the article formed is heated at
250.degree. C. for 272 hours. It then has at 25.degree. C., a
flexural strength of 12.4 kg./mm..sup.2 (for a span of 25.4
mm.).
EXAMPLE 11
A procedure similar to that described in Example 10 is followed
with 19.6 g. of maleic N,N'-4,4'-diphenylmethane-bis-imide and 5.36
g. of 1,1-bis-(4-amino-3-methylphenyl)cyclohexane. The moulding is
effected on the whole of the powder obtained, the mould being
heated to 130.degree. C. under 100 kg./cm..sup.2, and the
temperature is then raised to 230.degree. C. in 1 hour under this
pressure. After mould release, the article is heated at 250.degree.
C. for 96 hours. After cooling, it has a flexural strength of 14.2
kg./mm..sup.2 (for a span of 25.4 mm.).
EXAMPLE 12
Into 67 g. of N-methylpyrrolidone heated at 130.degree. C. are
introduced 21.68 g. of bis-(4-aminophenyl)methane and 78.32 g. of
maleic N,N'-4,4'-diphenylmethane-bis-imide. The mixture is stirred
and then maintained at 130.degree. C. for 15 minutes. After rapid
cooling, a portion of the solution obtained is employed to prepare
a laminate by the process described in Example 4. The compression
is effected under 15 kg./cm..sup.2 at 180.degree. C., and the mould
is subsequently heated to 250.degree. C. in 1 hour under this
pressure. After mould release, the laminate is heated at
200.degree. C. for 49 hours and then 250.degree. C. for 47 hours.
After cooling, it has, at 25.degree. C., the following
characteristics:
Resin content--20.9%
Flexural strength (for a span of 50 mm.):
Initial--59.5 kg./mm..sup.2
After 2000 hours at 250.degree. C.--35 kg./mm..sup.2
* * * * *