U.S. patent number [Application Number ] was granted by the patent office on 1975-12-09 for united states patent: re28646 ( 1.
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United States Patent |
RE28,646 |
|
Issue Date: |
December 9,
1975 |
Current U.S.
Class: |
523/213; 523/212;
524/606 |
Current CPC
Class: |
C08K
9/06 (20130101); C08K 9/06 (20130101); C08L
77/00 (20130101) |
Current International
Class: |
C08K
9/06 (20060101); C08K 9/00 (20060101); C08L
077/02 () |
Field of
Search: |
;260/37N,448.2B |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Anonymous: Plastics Technology, Feb. 1965, pp. 42-44. .
T. P. Murphy: A.C.S., Div. of Org. Coating and Plastics Chem.,
papers presented at Atlantic City Meeting, Sept. 1965, 25(2), pp.
76, 77, 79, 83, 85, 89, 90. .
J. S. Marsden and S. Sterman: A.C.S. Div. or Org. Coating and
Plastics Chem., papers presented at Atlantic City meeting, Sept.
1965, 25 (2); pp. 91, 97-100..
|
Primary Examiner: Jacobs; Lewis T.
Parent Case Text
.Iadd.
This is a continuation of application Ser. No. 154,451, filed June
18, 1971, and now abandoned.
The present application is an application for a reissue of U.S.
3,419,517 issued on Dec. 31, 1968. U.S. 3,419,517 issued from U.S.
Patent Application Ser. No. 560,247 filed on June 24, 1966 as a
continuation-in-part of then copending U.S. Patent Application Ser.
No. 284,375 filed May 31, 1963 and now abandoned..Iaddend.
Claims
What is claimed is:
1. A reinforced polymeric composition comprising a polyamide and at
least about 25% by volume of an inorganic filler material having a
length to diameter ratio of up to about 25 to 1, said material
having been treated with an organosilane coupling agent of the
formula ##EQU11## where X is a hydrolyzable group capable of
reaction with a hydroxyl group, Y is hydrogen or a monovalent
hydrocarbon group, R is an alkylene group having from 1 to about 20
carbon atoms, Z is a group capable of reaction with a polyamide, n
is an integer from 0 to 1, a is an integer from 1 to 3, b is an
integer from 0 to 2, c is an integer from 1 to 3 and the sum of a+
b+ c equals 4.
2. A reinforced polymeric composition according to claim 1 wherein
said polyamide is a polylactam.
3. A reinforced polymeric composition according to claim 1 wherein
said polyamide is a polylactam whose monomeric units contained at
least six carbon atoms.
4. A reinforced polymeric composition according to claim 1 wherein
said polyamide is polycaprolactam.
5. A reinforced polymeric composition according to claim 1 wherein
siad polyamide is a condensation product of a polyamine and
polycarboxylic acid.
6. A reinforced polymeric composition according to claim 1 wherein
said polyamide is polyhexamethylene adipamide.
7. A reinforced polymeric composition according to claim 1 wherein
said filler comprises from about 25 to about 90% by volume of the
total composition.
8. A reinforced polymeric composition according to claim 1 wherein
said filler comprises from about 33 to about 67% by volume of the
total composition.
9. A reinforced polymeric composition according to claim 1 wherein
said filler is an inorganic siliceous material which has a
3-dimensional crystal structure, a somewhat refractory nature with
a melting point above about 800.degree.C, a Mohs' hardness of at
least 4, and a water solubility of less than 0.1 gram per
liter.
10. A reinforced polymeric composition according to claim 1 wherein
said filler is a plate-like filler with a length to diameter ratio
of less than 1 to 1.
11. A reinforced polymeric composition according to claim 1 wherein
said filler has a length to diameter ratio from about 1 to 1 up to
about 20 to 1.
12. A reinforced polymeric composition according to claim 1 wherein
said coupling agent has the formula
X.sub.3 --Si--R.sub.n Z
where X is halogen or alkoxy, R is an alkylene group having from
about 2 to about 18 carbon atoms, Z is amino, secondary amido,
isocyanato, halogen, alkoxycarbonyl, epoxy, vinyl, acryloxy, or
methacryloxy, and n is 0 or 1, provided that n can be zero only
when Z is a vinyl group.
13. A reinforced polymeric composition according to claim 1 wherein
said coupling agent is 3-trialkoxysilylpropyl amine.
14. A reinforced polymeric composition according to claim 1 wherein
said coupling agent is 11-(trialkoxysilyl)-undecyl bromide.
15. A reinforced polymeric composition according to claim 1 wherein
said coupling agent is tri(.beta.-methoxyethoxy)vinyl silane.
16. A reinforced polymeric composition according to claim 1 wherein
said coupling agent is 3-(trialkoxysilyl)propyl chloride.
17. A reinforced polymeric composition according to claim 1 wherein
said composition is characterized by a Strength Index at least
triple that of an equivalently filled but uncoupled composition and
a flexural modulus at least double that of the base resin.
18. A reinforced polymeric composition according to claim 1 wherein
said polyamide is polycaprolactam or polyhexamethylene adipamide
and wherein said composition is characterized by a Strength Index
of at least 40 .times. 10.sup.6 and a flexural modulus of at least
250,000 p.s.i.
19. A reinforced polymeric composition comprising a polyamide and
from about 33 to about 67% by volume of an inorganic siliceous
filler material which has a 3-dimensional crystal structure, a
somewhat refractory nature with a melting point above about
800.degree.C, a Mohs' hardness of at least 4, a water solubility of
less than 0.1 gram per liter and a length to diameter ratio from
about 1 to 1 up to about 20 to 1, said filler material having been
treated with an organosilane coupling agent of the formula
X.sub.3 --Si--R.sub.n Z
where X is halogen or alkoxy, R is an alkylene group having from
about 2 to about 18 carbon atoms, Z is amino, secondary amido,
isocyanato, halogen, alkoxycarbonyl, cyclohexylepoxy, epoxy, vinyl
acryloxy, or methacryloxy, and n is 0 to 1, provided that n can be
zero only when Z is a vinyl group, said reinforced polymeric
composition being characterized by a Strength Index at least triple
that of an equivalently filled but uncoupled composition and a
flexural modulus at least double that of the base resin.
20. A reinforced polymeric composition according to claim 19
wherein said polyamide is polycaprolactam or polyhexamethylene
adipamide and wherein said composition is characterized by a
Strength Index of at least 40 .times. 10.sup.6 and a flexural
modulus of at least 250,000.
21. A process for preparing a filler-reinforced polyamide
composition having at least 25% by volume filler comprising
(a) treating an inorganic filler material having a length to
diameter ratio of at least 1 to 1 up to about 25 to 1 with an
organosilane coupling agent of the formula ##EQU12## where X is a
hydrolyzable group capable of reaction with a hydroxyl group, Y is
hydrogen or a monovalent hydrocarbon group, R is an alkylene group
having from 1 to about 20 carbon atoms, Z is a group capable of
reaction with a polyamide but incapable of a reaction with a
monomeric lactam which leaves the resultant silane-lactam adduct
incapable of entering into a polymerization, n is an integer from 0
to 1, a is an integer from 1 to 3, b is an integer from 0 to 2, c
is an integer from 1 to 3, and the sum of a+ b+ c equals 4 and
(b) conducting a base-catalyzed, substantially anhydrous, anionic
polymerization of a lactam in the presence of said filler and said
coupler.
22. A process according to claim 21 wherein said filler is treated
with said coupler prior to its addition to the monomer.
23. A process according to claim 21 wherein the monomer which is
polymerized is .epsilon.-caprolactam.
24. A process according to claim 21 wherein the Z group of said
organosilane coupling agent is an amino group having at least one
hydrogen atom, which amino group functions as a polymerization
regulator.
25. A process according to claim 21 wherein said organosilane
coupling agent has the formula
(R.sub.1 O).sub.3 Si--R--NH.sub.2
where R.sub.1 is an alkyl group and R is an alkylene group having
from about 2 to 18 carbon atoms.
26. A process according to claim 21 wherein said organosilane
coupling agent is 3-(triethoxysilyl)propyl amine.
27. A process according to claim 21 wherein the Z group of said
organosilane coupling agent contains a nitrogen atom capable of
functioning as a polymerization promoter.
28. A process according to claim 21 wherein said organosilane
coupling agent is N-phenyl, N'-3-(triethoxysilyl)propyl urea.
29. A process according to claim 21 wherein the promoter is a
polyfunctional isocyanate.
30. A process according to claim 21 wherein the catalyst is an
alkylmagnesium halide.
31. A process according to claim 21 wherein the catalyst is sodium
caprolactam.
32. A process according to claim 21 wherein said filler is an
inorganic siliceous material having a length to diameter ratio of
from about 1 to 1 up to about 25 to 1, a three-dimensional crystal
structure, a somewhat refractory nature with a melting point above
about 800.degree.C, a Mohs' hardness of at least 4, and a water
solubility of less than 0.1 gram per liter.
33. A process for preparing a filler-reinforced polyamide
composition having at least 25% by volume filler comprising
(a) adding to a monomeric lactam, an inorganic siliceous filler
having a length to diameter ratio of at least up to about 25 to 1,
a somewhat refractory nature with a melting point above about
800.degree.C, a Mohs' hardness of at least 4, and a water
solubility of less than 0.1 gram per liter, an organosilane
coupling agent of the formula
(R.sub.1 O).sub.3 --Si--R--NH.sub.2
where R.sub.1 is an alkyl group and R is an alkylene group having
from about 2 to 18 carbon atoms, and a lactam polymerization
promoter,
(b) removing volatile reaction products if any,
(c) holding the umpolymerized mixture for an indefinite period of
time.
(d) adding a lactam polymerization catalyst,
(e) casing the resultant mixture into a mold, and
(f) maintaining the mixture at a temperture and for a time
sufficient to achieve polymerization.
34. A reinforced polyamide article comprising a polyamide and at
least 25% by volume of an inorganic filler material having a length
to diameter ratio of up to about 25 to 1 and a water solubility of
less than 0.15 grams per liter, said material having been treated
with an organosilane coupling agent of the formula ##EQU13## where
X is a hydrolyzable group capable of reaction with a hydroxyl
group, Y is hydrogen or a monovalent hydrocarbon group, R is an
alkylene group having up to about 20 carbon atoms, Z is a group
capable of reaction with a polyamide, n is an integer from 0 to 1,
a is an integer from 1 to 3, b is an integer from 0 to 2, c is an
integer from 1 to 3 and the sum of a+ b+ c equals 4.
35. A reinforced polyamide article according to claim 34, said
article characterized by a Strength Index at least triple that of
an equivalently filled but uncoupled article and a flexural modulus
at least double that of an unfilled article made from the base
polyamide resin.
36. A reinforced polymeric composition according to claim 17
wherein said polyamide is a polylactam.
37. A reinforced polymeric composition according to claim 17
wherein said polyamide is a condensation product of a polyamine and
a polycarboxylic acid.
38. A reinforced polymeric composition according to claim 1 wherein
said filler is a crystalline silica having a maximum particle size
of about 5 microns and an average particle size of about 2
microns.
39. A reinforced polymeric composition according to claim 1 wherein
said coupling agent has the formula
X.sub.3 --Si--R--Z
where X is halogen or alkoxy, R is an alkylene group having from
about 2 to 18 carbon atoms, and Z is amino, secondary amido,
isocyanato, alkoxycarbonyl or epoxy.
40. A reinforced polymeric composition comprising a polyamide and
from about 33 to 67% by volume of an inorganic siliceous filler
material which is characterized by a 3-dimensional crystal
structure, a somewhat refractory nature with a melting point above
about 800.degree.C, a Mohs' hardness of at least 4, a water
solubility of less than about 0.1 gram per liter and a length to
diameter ratio from about 1:1 up to about 20:1, said filler
material having been treated with an organosilane coupling agent of
the formula
X.sub.3 --Si--R--Z
where X is halogen or alkoxy, R is an alkylene group having from
about 2 to 18 carbon atoms, and Z is amino, secondary amido,
isocyanato, alkoxycarbonyl or epoxy, said reinforced polymeric
composition being characterized by a Strength Index at least triple
that of an equivalently filled but uncoupled composition and a
flexural modulus at least double that of the base resin. .Iadd.
41. A reinforced polymeric composition according to claim 1 wherein
said filler has a Mohs' hardness of at least 4..Iaddend..Iadd. 42.
A reinforced polymeric composition according to claim 41 wherein
said filler has been treated with an organosilane coupling agent
having the formula
X.sub.3 --Si--R--Z
where X is alkoxy having up to 8 carbon atoms, R is an alkylene
group having from about 2 to about 18 carbon atoms and Z is
amino..Iaddend..Iadd. 43. A reinforced polymeric composition
according to claim 42 wherein said coupling agent is
3-triethoxysilylpropyl amine..Iaddend..Iadd. 44. A reinforced
polymeric composition according to claim 43 wherein the polyamide
is polycaprolactam..Iaddend..Iadd. 45. A reinforced polymeric
composition according to claim 43 wherein the polyamide is
polyhexamethylene adipamide..Iaddend.
Description
This invention relates to polyamide compositions reinforced by the
inclusion therein of modified particulate materials. One feature of
the invention pertains to reinforced polyamides having mechanical
properties significantly improved by comparison to the properties
of polyamides described in the prior art. This invention also
relates to processes for preparing the polyamides referred to
above. Another feature of the invention pertains to a
base-catalyzed, substantially anhydrous anionic polymerization of a
lactam monomer in the presence of a modified particulate material.
Yet another feature of the invention is directed to a condensation
polymerization of a diamine and a dicarboxylic acid in the presence
of a modified particulate material.
It is well known in the prior art that polymeric compositions can
be "filled" with non-polymeric substances to form a uniform
finished product. Initially, various fillers were used in a
polymeric material to color the polymer, change its coefficient of
expansion, improve abrasion resistance, modulus, and strength, and
to dilute the polymer thereby lowering its costs. It was, and is
now, common practice to admix a filler and polymer in several ways
to produce a dispersion of the filler in the polymer. One method
has been to mix thoroughly a monomer and filler and subsequently
polymerize the monomer, thereby producing a composition wherein the
filler is intimately dispersed throughout the finished product.
Another method has been to subject uncured polymer and filler to a
shearing force thereby dispersing the filler in the polymeric
matrix. Various other methods of filling polymers are also well
known in the art.
However, the upper limit of filler that can be used in such
mixtures without adversely affecting the mechanical properties of
the product is low. The tensile and flexural strengths particularly
fall off sharply at relatively low concentrations of filler. An
exception to this generalization has been the use of fibrous
material, particularly fibrous glass particles, in polymeric
compositions. The incorporation of fibrous glass into a polymer
increases mechanical properties significantly. As yet, such
improvement has not been achieved by the use of particulate
material. The reason for the decrease in strength exhibited by
particulately filled polymers is that a particulate filler in a
polymer is not a component comparable to a fiber in load
distribution characteristics. Normally a filler acts to concentrate
stresses rather than distribute them. As a result, the
polymer-filler interface is the weak link in the composite. With a
fibrous filler, the plurality of weak links along the fiber
structure result in a reasonably strong bond when stress is applied
in a direction parallel to the orientation of the fibers. When a
transverse stress is applied to longitudinally oriented fibrous
filler or when any stress is applied to particulate filled
materials, the stress is not well distributed and the composition
is weak. Therefore a filled polymeric product which contains less
polymer per unit volume of the product than an unfilled polymer,
oridinarily possesses mechanical properties inferior to the
unfilled polymer, particularly at granular filler concentrations of
about 50% or more by weight or 25% or more by volume.
The reinforcement of polyamide compositions by means of particulate
as distinguished from fibrous particles is a desirable feature
since a particulate inorganic-monomer mixture is more fluid, hence
more easily cast or molded, than a mixture containing an equivalent
amount of a fibrous material. Further, fabrication techniques are
far simpler for a mixture of particulate inorganic and polymer than
for a mixture of fibers and polymer.
Those skilled in the art will recognize, however, that certain of
the mechanical properties of polyamides as well as other polymers
have in the past been improved by the inculsion of inorganic
particulate materials within the polymeric matrix. Young's modulus
of elasticity for instance can be increased by filling a polyamide
with a high level of particulate inorganic. The flexural and
tensile strengths are compromised, however, as is the resistance to
impact. For many uses, what is required is not an improvement in
one mechanical property but rather an improvement in a combination
of properties. Which combination of properties should be emphasized
for improvement depends upon the uses envisioned for the final
product. For uses such as furniture, furniture components,
automobile components, equipment housings, building panels and
other applications where the tensile and flexural strengths and
moduli and impact strength are important factors, one value helpful
in screening suitable materials from unsuitable materials is the
Strength Index. The Strength Index is a property of a material
which is based upon the relationship of the flexural strength to
the impact strength of a material. Generally, the higher the
Strength Index of a composition, the more valuable it is for
several of the uses mentioned above.
It a particulately filled polyamide could be fabricated with a
Strength Index high enough to permit its use in several
applications heretofore unsuitable for polyamides, the development
would certainly represent a valuable and unobvious advance in the
art. Providing such a particulately filled, highly reinforced
polyamide constitutes a principal object of this invention. Another
object is the provision of a method for preparing polyamides with
an unusually high Strength Index and rigidity. Additional objects,
benefits and advantages will become apparent in view of the
following detailed description.
The polymeric compositions of this invention comprise a polyamide,
and at least 25% by volume of an inorganinc filler material having
a length to diameter ratio of up to 25 to 1, said material having
been treated with an organo-silane coupling agent of the formula
##EQU2## where X is a hydrolyzable group capable of reaction with a
hydroxyl group, Y is hydrogen or a monovalent hydrocarbon group, R
is an alkylene group having from about 1 to about 20 carbon atoms,
Z is a group capable of reaction with a polyamide, n is an integer
from 0 to 1, a is an integer from 1 to 3, b is an integer from 0 to
2, c is an integer from 1 to 3 and the sum of a + b + c and equals
4.
POLYMER
Polyamides useful in the compositions of this invention include two
broad categories. One category includes the polylactams produced by
the polymerization of lactam monomers of the formula ##EQU3## where
R.sub.1 is an alkylene group having from 3 to 12 or more carbon
atoms, preferably from 5 to 12 carbon atoms. A preferred monomer is
.EPSILON.-caprolactam. Lactam monomers in addition to
.EPSILON.-caprolactam include .alpha.-pyrrolidone, piperidone,
valerolactam, caprolactams other than the .EPSILON.-isomer, methyl
cyclohexanone isoximers, capryllactam, cyclodecanone isoxime,
lauryllactam, etc. A specific polyamide to which this invention is
applicable is polycaprolactam, commonly known as nylon 6. Also
included are copolymers of two or more of the above or similar
lactam monomers as well as copolymers containing more than 50%
lactam and a smaller quantity of other monomers polymerizable by an
anionic, base-catalyzed mechanism. Examples include copolymers of
caprolactam with capryllactam, copolymers of caprolactam with
lauryllactam and copolymers of pyrrolidone with piperidone or
caprolactam as well as copolymers of a lactam with a bislactam
having a formula such as the following: ##EQU4## The second
category of polyamides comprises those polymers formed by the
condensation polymerization of dicarboxylic acids with diamines,
one of the most significant polymers being polyhexamethylene
adipamide (nylon 6,6). Other related polyamides include those
formed from polyamines such as propanediamine, hexamethylenediamine
and octamethylenediamine and polycarboxylic acids such as adipic
acid, pimelic acid, suberic acid, sebacic acid and dodecanedioic
acid. Also included are copolymers or polyblends of polyamides of
the two above categories. The copolymers or polyblends can consist
of mixture of the two forms of polyamides with each other or with
other compatible resin systems. The copolymers or polyblends of
this invention are limited to those containing at least 50% by
weight polyamide. Most of the preferred compositions will contain
at least 90% by weight polyamide in the resin phase. Examples of
resins which can be mixed with polyamides to form a blend or
copolymer include polypropylene, polyethylene, polystyrene,
polyacrylonitrile, polybutadiene, acrylonitrile-containing rubbers,
styrene-acrylonitrile copolymer and polyphenylene oxide.
The polyamides may be linear or crosslinked. A crosslinked
polyamide provides some improvement in mechanical properties,
particularly impact strength, but linear polyamides are also
definitely included within the scope of the invention. The maximum
amount of tolerable crosslinking in the polymer depends upon the
proposed use of the finished composition. Moderate crosslinking
produces compositions with high impact resistance and somewhat
diminished flexural strength and modulus. Consequently, control of
crosslinking provides a variable which enables one to "tailor" the
polyamide in many respects to produce a composition of the desired
properties. Suitable crosslinking agents are well known in the art
and can be used here in the conventional manner. Two compounds
which we have used include polyethyleneimine and
tetra-(3-aminopropoxymethyl)methane. In addition, crosslinking can
be achieved through the coupler by hydrolysis of silanol groups to
form siloxane linkages, i.e. ##EQU5## by the use of polyfunctional
promoters in a lactam polymerization, such as di- and
triisocyanates or by the inclusion of polymers such as
polyisopropyl acrylamide or polymethyl methacrylate.
REINFORCING AGENTS
The term filler as used herein refers to those nonpolymerizable,
discrete particles which are capable of existing and remaining in a
discontinuous phase when placed in the presence of a polymer or
polymerizing monomer and subjected to processing conditions
necessary to shape the composite into a solid finished article.
Inorganic filler materials useful herein can be selected from a
wide variety of minerals, metal oxides, metal salts such as metal
aluminates and metal silicates, other siliceous materials and
mixtures thereof. The term reinforcing agent is used to designate
filler materials which have been treated with a coupling agent to
provide a capability for adherent bonding of filler to polyamide.
To function as effective reinforcing agents under conditions of
high moisture, it is imperative that the filler materials be at
most sparingly soluble in water, not exceeding a solubility of
about 0.15 gram per liter. If, however, the finished composition is
to be used in an application where moisture sensitivity is not a
problem, more soluble filler materials can be used. Generally,
those hard, high modulus materials which have or can acquire an
alkaline surface upon treatment with a base are well suited for our
reinforced polymeric compositions. By high modulus is meant a
Young's modulus of elasticity at least twice as great as that of
the base polyamide. More preferably, suitable inorganic fillers
will have a Young's modulus of 10.sup.7 p.s.i. or greater. Many
inorganics fulfill both preferred characteristics of high modulus
and alkaline surface and therefore constitute one class of
preferred filler materials. Since metal silicates and siliceous
materials usually have or can readily acquire the desired alkaline
surface, and since they are characterized by modulus values well
above the preferred minimum, a preferred mixture is one which
contains a major amount, i.e. more than 50% by weight of metal
silicates or siliceous materials.
Materials with such characteristics are preferred because of the
ease with which they are coupled to the polymer. However, other
substances such as alumina, Al.sub.2 O.sub.3, which are not easily
coupled to a polyamide by means of coupling agents employed herein,
can nevertheless be used as a reinforcing component either singly
or preferably combined with other minerals which are more
susceptible to coupling, and more preferably combined in minor
amounts, i.e. percentages of less than 50% of the total reinforcing
material. An example of such a material useful in the production of
a reinforcing agent, with which alumina can be mixed, is feldspar.
Feldspar can be converted into one of the preferred reinforcing
agents of this invention and a feldspar-alumina mixture is also
useful. Other materials particularly preferred for conversion into
reinforcing agents include wollastonite, which is a calcium
metasilicate; mullite, an aluminum silicate; calcium magnesium
silicates; and an acicular aluminum silicate, Al.sub.2 SiO.sub.5.
Other useful inorganics which can be converted into reinforcing
agents include quartz and other forms of silica such as silica gel,
carbon black, graphite, cristobalite, calcium carbonate, etc;
metals such as aluminum, tin, lead, magnesium, calcium, strontium,
barium, titanium, zirconium, vanadium, chromium, manganese, iron,
cobalt, nickel, copper and zinc; metal oxides in general such as
oxides of aluminum, tin, lead, magnesium, calcium, strontium,
barium, titanium, zirconium, vanadium, chromium, manganese, iron,
cobalt, nickel, copper, and zinc; heavy metal phosphates, sulfides,
and sulfates, and basic mineral and mineral salts such as
spodumene, mica, montmorillonite, kaolinite, bentonite, hectorite.
beidellite, attapulgite, chrysolite, garnet, saponite and
hercynite.
The term inorganic filler material or simply inorganic used in this
disclosure refers to materials such as exemplified above. It should
be noted that carbon black and graphite have been listed as
suitable inorganic fillers. The term inorganic, in addition to
conventional inorganic materials, also includes those
carbon-containing materials characterized by the substantial
absence of carbon-hydrogen bonds, i.e. less than 1.5% by weight
hydrogen. Particularly preferred are those inorganic siliceous
materials which have a 3-dimensional crystal structure as opposed
to a 2-dimensional or planar crystal configuration. These siliceous
materials are also characterized by a somewhat refractory nature
with a melting point above about 800.degree.C, a Mohs' hardness of
at least 4, and a water solubility of less than 0.1 gram per liter.
Examples of preferred siliceous materials include minerals such as
feldspar, quartz, wollastonite, mullite, kyanite, chrysolite,
cristobalite, crocidolite, acicular aluminum silicate having the
formula Al.sub.2 SiO.sub.5, spodumene and garnet. These minerals
are especially desirable for use in reinforced polyamide
compositions for a number of reasons. For instance, they provide a
composition with better abrasion resistance, flexural strength and
modulus, tensile strength and modulus, impact resistance,
resistance to heat distortion and resistance to thermal expansion
than do conventional clay fillers and inorganic pigments such as
whiting. Further, the minerals described above provide higher
loading levels than can be achieved with glass fibers, an important
economic consideration. In addition, highly loaded lactam monomer
slurries can be directly cast into a final polymerized form,
thereby eliminating several processing steps necessary with glass
fiber-reinforced compositions.
Metals have been suggested above as suitable reinforcing agents. In
addition to providing high strength, reinforced polymeric
compositions, the use of certain metals such as copper, silver,
iron and others can provide certain important auxiliary advantages.
Moderate to high concentrations of metals can make the polymeric
composite electrically conductive, thereby rendering the composite
suitable for an electroplating operation wherein the composite can
be electroplated with a thin coat of a metal such as chromium,
silver, gold, etc. Or the use of iron or steel as a reinforcing
agent can give the polymeric composite magnetic properties if the
particles are oriented within the composition.
Inorganic filler materials useful herein are referred to as
particulate. The term particulate as used in this disclosure refers
to granular, plate-like and acicular particles having a length to
diameter ratio (1/d) up to about 25 to 1. Preferably, the
inorganics useful herein have an 1/d ratio up to about 20 to 1, and
more preferably from about 1 to 1 up to about 15 to 1. In contrast,
the term fibrous refers to particles whose 1/d ratios are greater
than 25 to 1, and usually are greater than 50 to 1.
It is pointed out that plate-like particles, which can be
considered as rods compressed in a direction parallel to their
longitudinal axes, are considered herein to have 1/d ratios of less
than 1 to 1. The plate-like fillers such as bentonite, kaolinite,
talc and mica perform quite satisfactorily when treated with a
silane coupler and mixed with a preformed polyamide as described
subsequently herein. Plate-like reinforcing agents also perform
satisfactorily when placed in the presence of diamine-dicarboxylic
acid salts which are subsequently polymerized to form a polyamide.
The use of plate-like reinforcing agents in polylactams provides
only slight improvement, however, when the treated filler is placed
in the presence of the lactam during polymerization. Perhaps this
is due to the difficulty encountered in thoroughly drying such
hydrated, high surface area minerals. Regardless of the
explanation, the plate-like fillers represent under those
circumstances an important exception to the general reinforcing
attributes of fillers of this invention.
Several characteristics of fillers have an effect on the maximum
attainable loading of the composition. When the reinforced
composition is produced by casting a monomer-reinforcing agent mix
directly into a mold where the monomer is polymerized, the maximum
content of reinforcing agent is limited primarily by the viscosity
of the umpolymerized mixture, i.e. too high a concentration of
reinforcing agent produces mixtures too viscous to cast or mold.
The limitation imposed by viscosity is in turn dependent to some
extent upon the shape of the particulate filler. That is, spherical
particles do not increase the viscosity of the monomer mix as much
as highly acicular particles. By choosing particulate fillers of
suitable shape, it is possible to modify the viscosity of the
monomer mix and prepare castable monomer mixtures which can be used
to produce polymeric compositions containing a very large amount of
reinforcing agent.
Another factor which has an effect upon the upper limit of
reinforcing agent concentration is the particle size distribution
of the filler. A wide distribution of particle sizes provides a
composition with a small amount of voids or spaces between the
particles, thereby requiring less polymer to fill these spaces and
bind the particles together. Regarding granular particle size,
generally particles which pass through a 60 mesh screen (250
microns) are small enough to be used in the compositions of this
invention although particles as large as 1000 microns (18 mesh) or
more can be used with equal or nearly equal success; with regard to
a lower limit on particle size, particles as small as 0.5.mu. have
been successfully employed and smaller particles in the range of
100 to 200m.mu. can also be used. More descriptive of suitable
filler particles than limits on particle size is a specification of
particle size distribution. A suitable wide particle size
distribution is as follows:
Percent 250.mu. or less (60 mesh) 100 149.mu. or less (100 mesh) 90
44.mu. or less (325 mesh) 50 5.mu. or less 10
A narrower distribution also suitable for use in this invention
is:
Percent 62.mu. or less (230 mesh) 100 44.mu. or less (325 mesh) 90
11.mu. or less 50 8.mu. or less 10
A relatively coarse mixture useful in this invention has the
following particle size distribution:
Percent 250.mu. or less (60 mesh) 100 149.mu. or less (100 mesh) 90
105.mu. or less (140 mesh) 50 44.mu. or less (325 mesh) 10
A finely-divided mixture has the following particle size
distribution:
Percent 44.mu. or less (325 mesh) 100 10.mu. or less 90 2.mu. or
less 50 0.5.mu. or less 10
Other typical particle size distributions of reinforcing minerals
used in this invention include:
Wollastonite: Percent 74.mu. or less (200 mesh) 100 44.mu. or less
(325 mesh) 99.7 11.mu. or less 50 1.mu. or less 8 Feldspar: Percent
50.mu. or less 100 40.mu. or less 90 14.mu. or less 50 10.mu. or
less 38 3.mu. or less 10
These figures regarding particle size distribution should not be
construed as limiting since both wider and narrower ranges of
distribution will also be useful as well as both coarser and finer
compositions. Rather these figures are intended as representative
illustrations of filler compositions suitable for use in the
reinforced polymeric compositions of this invention.
Proper combination of the two variables of particle shape and
particle size distribution, together with a satisfactory processing
technique, permits the preparation of molded polymeric compositions
containing as much as 90% by volume or more reinforcing agent. The
lower limit of reinforcing agent concentration is restricted
insofar as it is necessary to have sufficient agent present to
provide the extraordinary improvement in mechanical properties
achieved by the compositions of this invention. The minimum level
of reinforcing agent required to provide compositions with
properties significantly superior to prior art compositions is
about 25% by volume. The accompanying figure illustrates the
theoretical values of modulus predicted by the Einstein and by the
Kerner equations. Inspection of the figure indicates that at 20
volume percent filler or slightly higher, the two theoretical
equations predict significantly different modulus values. The
reason for this departure is that the Einstein equation is only
reasonably accurate at low volume fractions of filler. Since
considerations such as the relative mechanical properties of the
two phases and the concentrations and size of the particulate
filler, which become important as the quantity of filler is
increased, are not considered in the Einstein equation, it is of
little value in predicting modulus values of composites having more
than about 20 to 25 volume percent rigid dispersed filler. When the
above factors present in composites having high filler loadings are
considered as in the Kerner equation, the theoretical moduli of
composites increases at a significantly different rate. Comparison
of the two equations shows the above factors exert such an
important influence on composite containing more than 20 to 25%
filler that composites containing high filler loadings actually
differ in kind from composites containing lesser amounts. Also
provided as points on the graph are actual experimental results
obtained on some of the reinforced compositions of this invention
which show a rough adherence to the trend indicated by the Kerner
equation.
Suitable values, therefore, for reinforcing agent concentration in
the finished compositions range from about 25 to about 90% by
volume of the total compositions. The above range corresponds
approximately to about 45 to about 95% by weight using a filler
density of 2.7 and a polymer density of 1.1. Filler concentrations
are expressed herein in terms of volume percent since mechanical
properties are more directly related to the volume fraction of
filler present as opposed to weight fractions. A preferred range of
filler concentration is from about 33 to about 67% by volume or
about 55 to about 84% by weight.
In addition, a small amount of fibrous material may be incorporated
into a polymer system if the amount of granular or acicular
material is reduced by some proportionately larger amount. For
example, 2 or 3% by volume, based on the total reinforced
composition, of glass fibers about 0.5 inch in length can be
incorporated into a monomer slurry containing about 30 to 33% by
volume granular feldspar. Similar quantities of chopped asbestos
fibers or other fibrous materials can also be used. The resultant
slurry can be cast about as readily as a monomer slurry containing
40% by volume granular feldspar. Alternatively, if pourability is
not required, larger amounts of fibrous material can be included in
the composition, thereby reinforcing the final product to an even
greater extent.
COUPLING AGENTS
An essential material in the preparation of our reinforced
polymeric compositions is the coupling agent which binds the
inorganic filler to the polymer. Coupling agents useful herein are
those substituted silanes of the formula ##EQU6## where X is a
hydrolyzable group capable of reaction with a hydroxyl group, Y is
a hydrogen or a monovalent hydrocarbon group, R is an alkylene
group having from 1 to about 20 carbon atoms, Z is a group capable
of reaction with the polyamide, n is an integer from 0 to 1, a is
an integer from 1 to 3, b is an integer from 0 to 2, c is an
integer from 1 to 3, and the sum of a+ b+ c equals 4.
Examples of suitable X groups include halogen, hydroxy, alkoxy,
cycloalkoxy, aryloxy, alkoxy-substituted alkoxy such as
.beta.-methoxy ethoxy, alkoxycarbonyl, aryloxycarbonyl, alkyl
carboxylate and aryl carboxylate groups, preferably having eight or
less carbon atoms. Examples of Y groups in the above formula are
hydrogen, methyl, ethyl, vinyl isobutyl and other hydrocarbyl
groups, preferably having ten or less carbon atoms. The function of
the Y grouup can be to modify the extent of the polymer-filler
bond, to regulate viscosity of the monomer slurry or polymer mix or
to modify the thermal stability of the coupler. The R group can be
any alkylene group having up to about 20 carbon atoms and
preferably from about 2 to about 18 carbon atoms; examples include
ethylene, propylene, decylene, undecylene, and octadecylene.
Further, the R group need not necessarily be present at all as
indicated by the value of zero for the letter n. For instance,
vinyl-substituted silanes are effective couplers. In such an
instance, the vinyl group which is a Z group, is attached directly
to the silicon atom. Usually, however, the Z group is separated
from the silicon atom by an R group having at least two carbon
atoms in the linking chain. As the number of carbon atoms in the R
group increases, the coupler can perform as a vicosity reducer.
Further, the activity of the Z group on the alkylene chain is often
modified somewhat, thereby making the coupler perform more suitably
under some processing conditions. The Z group can be any functional
group capable of reacting with a polyamide. Examples include,
amino, primary or secondary amido, epoxy, isocyanato, hydroxy
alkoxycarbonyl, aryloxycarbonyl, vinyl, allyl and halogen such as
chloro and bromo groups.
It can be considered, as a working hypothesis, that chemical bonds
are formed between polymer and coupler and between coupler and
filler, but this has not been conclusively established. But those
couplers which have functional groups capable of such reactions
provide compositions with excellent properties whereas couplers not
containing such functional groups generally provide compositions
with inferior properties. Adhesion of polymer to filler involves
dual considerations if the working hypothesis upon which this
invention is based is accurate. The first consideration is the
polymer-coupler interface. Adhesion of polymer and coupler can be
achieved under any conditions which permit thorough contact of the
two components. One means has been to mix the coupler and filler
with the polyamide-forming monomers and conduct a polymerization.
Another means has been to mix thoroughly a coupler, filler and
preformed polymer. Other techniques which provide the requisite
contact of polymer and coupler can also be used. Reaction can occur
by several mechanisms such as aminolysis, alcoholysis, ester
interchange and alkylation. Aminolysis can occur by reaction of
amino groups or by amide interchange with primary or secondary
amido groups with the amide groups of the polymer. Ester
interchange can occur by the reaction of esters with the amide
groups of the polymer. Alkylation can occur by a reaction where an
ethylenically unsaturated group reacts with the amide group of the
polymer. Alcoholysis can take place by the reaction of hydroxyl
groups with an amide group. Additional reactions of amide groups
with other functional groups are also known and can be used herein
to provide the degree of adhesion of polymer to filler which forms
the basis of the present invention. It should be noted in
connection with the above comments on polyamide-functional group
reaction that neither complete nor instantaneous reaction may be
necessary. That is, if covalent bonding of polymer and coupler is
responsible for the extraordinary improvement achieved by the
practice of this invention, it is further theorized that only a
fraction of the possible polymer-coupler bonds may provide as good
or nearly as good properties in the finished compositions as would
a complete reaction. The above hypothesis could explain why
analytical characterization of the polymer-filler interface in
terms of convalent or other types of bonds is as yet beyond the
skill of the art.
The second consideration regarding the adhesion of polymer and
filler is the coupler-filler interface. Filler and coupler can be
joined by combining them in the absence or presence of a solvent
for the coupler, such as water, alcohol, dioxane, benzene, etc.
Presumably, the hydrolyzable group of the coupler reacts with
appended hydroxyl groups attached to the alkaline surface of
inorganic materials. Theoretically, hydroxyl groups are present on
the surface of, or can be developed on the surface of, most
metallic and siliceous substances, thereby providing a site
available for reaction with a hydrolyzable group of a coupler. This
theory of availability of hydroxyl groups on an inorganic surface
may explain why many silicon-containing minerals are preferred
reinforcing agents and why silicon-based coupling agents are
particularly preferred for use with the siliceous minerals, i.e.
the silane groups of the coupler --S--(or).sub.3, react with the
silanol groups of the inorganic, ##EQU7## to produce the very
stable siloxane linkage, ##EQU8## If the above theory is accurate,
chemical bonding of coupler to the inorganic is achieved in the
compositions of the present invention. Other theories can be
advanced which deny the existence of true covalent bonds between
inorganic and coupler. Regardless of any theoretical explanation
advanced herein, to which we do not intend to be limited, the
coupler is attached to the inorganic by contacting the two
substances. The mixture is preferably but not necessarily
subsequently dried. A bond between the inorganic and coupler is
thus obtained. The reaction of filler and coupler can be carried
out separately, and the filler-coupler adduct subsequently added to
the monomer, or preformed polymer, or the reaction may be carried
out in the presence of the monomer or polymer and the whole mixture
dried to remove volatile reaction products and solvents, if used.
Preferably, heat in the range of 50 to 200.degree.C or more is
applied to a coupler-filler adduct to increase the extent of
bonding.
Examples of suggested silane coupler include
Several of the compositions of this invention are characterized by
mechanical properties superior to related prior art compositions.
As previously mentioned, one value helpful in screening suitable
materials from unsuitable materials is the Strength Index.
Generally, the higher the Strength Index of a composition, the more
valuable it is for several of the uses mentioned above. Strength
Index is the product of the notched Izod impact strength and the
square of the flexural strength and is referred to herein by the
abbreviated notation S.sup.2 I (strength.sup.2 impact).
Compositions particularly preferred for several heavy-duty uses are
those having a Strength Index at least triple that of an
equivalently filled but uncoupled polyamide and a flexural modulus
at least double that of the corresponding unfilled polyamide.
Equivalent filling is obtained by using the same filler, same
particle size, same concentration and same manner of mixing with
the same polymer matrix. For many preferred compositions, the
Strength Index of the reinforced compositions will be six or eight
times as great as the Strength Index of the equivalently filled
compositions and the flexural modulus will be at least triple that
of the base resin. Numerical values will vary depending upon the
particular polyamide under consideration. The reinforced nylons
such as polycaprolactam and polyhexamethylene adipamide are
characterized by Strength Index values of at leasat 40 .times.
10.sup.6 ft. lbs..sup.3 in..sup..sup.-5 together with flexural
moduli of at least 250,000 p.s.i. Preferable minimum levels for
Strength Index and flexural modulus of reinforced nylon 6 and 6,6
are 50 .times. 10.sup.6 and 300,000, respectively. Flexural
strength and modulus are measured as described in ASTM D-790. Izod
notched impact strength is measured as described in ASTM D-256,
procedure A. The above measurements of properties are made on
moisture-equilibrated samples which have been boiled in water 72
hours, cooled to room temperature and tested while wet.
PROCESS
The compositions of this invention can be prepared by polymerizing
polyamide-forming monomers in the presence of coupler-treated
fillers.
One technique used with considerable success in the practice of
this invention has been to conduct a base-catalyzed, substantially
anhydrous polymerization of a lactam having a coupler-treated
filler dispersed therein. The filler can be treated with the
coupler prior to its addition to the lactam monomer or the
treatment can be achieved by mixing together filler, coupler,
monomer and other optional additives. Base-catalyzed substantially
anhydrous lactam polymerizations are carried out by methods known
to those skilled in the art using appropriate catalysts, promoters,
regulators, stabilizers, curing agents, etc. necessary to achieve
the polymerization of a selected lactam monomer. To prepare the
compositions of this invention, it is necessary to add to a lactam
monomer, in addition to the above components, the coupler-treated
filler. The polymerization is advantageously carried out in a
manner described in U.S. Pat. Nos. 3,017,391, 3,017,392, 3,018,273
or 3,028,369 utilizing promoters, catalysts and regulators
specified therein. One procedure suitable for preparing reinforced
polyamides comprises first mixing the lactam monomer, coupler,
filler, water and if desired, a cross-linking agent, internal mold
release agent, stabilizer or other additives. Mixing is most
effectively carried out if the lactam is in a molten condition.
When high concentrations of reinforcing agent are used, e.g. 35 or
40% by volume or more, it may be advisable to add the components in
the order just given in order to effectively disperse the
ingredients. If water is used, it is advisable to use a small
quantity, less than 10% of the total weight of the mixture, so that
its complete removal from the mixture is facilitated. About 1 to 5%
water based on the weight of the mixture is usually sufficient.
After thorough mixing, the mixture is heated to about 110 -
120.degree.C, but less than 160.degree.C, to remove any water and
the hydrolyzed R groups of the coupler. A vacuum can be applied to
aid in removing the volatile materials. The temperature of the
mixture is then adjusted to some temperature above the melting
point of the lactam, about 100.degree.C for .epsilon.-caprolactam,
and the polymerization catalyst is added. Any of the catalysts
known to be acceptable for base-catalyzed lactam polymerizations
are adequate; a preferred catalyst is an alkylmagnesium halide such
as ethylmagnesium bromide. Another preferred catalyst is sodium
caprolactam. If a Grignard reagent is used, the temperature of the
mixture is held around 100.degree.C to permit the volatilization of
the alkane formed by reaction of the Grignard with the lactam
monomer. Following addition of the catalyst and removal of alkane
if necessary, the promoter or initiator is added. Any of the
promoters useful in base-catalyzed lactam polymerizations can be
used. Examples include carbon monoxide; acyl caprolactams such as
acetyl caprolactam; N,N'-substituted carbodiimides such as
diisopropylcarbodiimide and dicyclohexylcarbodiimide; and
N,N-substituted cyanamides such as N,N-diphenyl cyanamide. Other
suitable promoters include lactams having attached to the imido
group a heterocyclic substituent containing from one to three
heterocyclic atoms wherein at least one of the heterocyclic atoms
is a nitrogen atom and wherein the imido group of the lactam is
attached to a carbon atom in the heterocyclic ring so situtated
that the nitrogen atom of the imido group and the nitrogen atom of
the heterocyclic ring are connected by an odd number of conjugated
carbon atoms. Examples of this class of promoters include:
N-(2-pyridyl)-.epsilon.-caprolactam;
N-(4-pyridyl)-.epsilon.-caprolactam;
tris-N-(2,4,6-triazino)-.epsilon. -caprolactam; and
N-(2-pyrazinyl)-.epsilon.-caprolactam. These promoters can be
formed by the in situ reaction of a lactam with such compounds as
2-chloropyridine, 4-bromopyridine, 2-bromopyrazine,
2-methoxypyridine, 2-methoxypyrazine, 2,4,6-trichloro-s-triazine,
2-bromo-4,6-dichloro-s-triazine, and
2,4-dimethoxy-6-chloro-s-triazine. A preferred class of promoters,
namely organic isocyanates, is described in detail in U.S.
3,028,369. Specific promoters preferred in our present
polymerization include phenyl isocyanate, 2,4- and 2,6-tolylene
diisocyanate, di-(p-isocyanatophenyl) methane and a polyfunctional
isocyanate such as Mondur MR manufactured by Mobay Chemical
Company. Alternately, the promoter may be added before the
catalyst. Whichever procedure is followered, once the mixture
contains the monomer, promotor, and catalyst, for most systems it
is necessary to keep the temperature below 140.degree.C, preferably
below 120.degree.C, to prevent too rapid polymerization until the
mixture is cast. Some catalyst-promoter systems, such as the alkyl
magnesium chloride-acetyl caprolactam system, will require even a
further reduction in heat to less than 80.degree.C. to prevent
polymerization. It is also advisable when employing a reactive
catalyst-promoter system to reduce the time intervening between the
addition of the catalyst-promoter and the casting or molding of the
mixture. After the mixture has been thoroughly stirred and allowed
to come to equilibrium, the mixture is cast into a mold, which is
preferably preheated, and polymerized at a temperature from about
the melting point of the lactam up to about 250.degree.C,
preferably from about 140.degree. to about 200.degree.C. Time for
polymerization can vary from as little as one minute or less up to
an hour or more and usually requires from two or three minutes up
to about ten minutes with most preferred catalyst-promoter systems.
Other lengths of time and temperatures for polymerization are of
course satisfactory and can be used with equal or nearly equal
success.
Selection of specific coupling agents can provide important
benefits in the preparation of reinforced polyamides by a
base-catalyzed lactam polymerization process. For instance, U.S.
Pat. No. 3,017,392 describes the use of polymerization regulators
in a base-catalyzed lactam polymerization. By choosing an
aminosilane coupler such as 3-triethoxysilylpropyl amine, the
coupler can function as a polymer adherent, filler adherent and
polymerization regulator simultaneously. In an alternate process, a
compound such as N-phenyl, N-3-(triethoxysilyl) propyl urea can be
used as a promoter as well as a coupler to achieve good adhesion of
polymer to filler as well as initiation of the lactam
polymerization.
Not all coupling agents described herein as useful in preparing
reinforced polyamides can be used successfully when the polyamide
is prepared by a base-catalyzed anhydrous lactam polymerization in
the presence of coupler and filler. Again, theoretical conclusions
are uncertain but experimental data indicate that for a compound to
be an effective coupler in a base-catalyzed lactam polymerization,
it must not only be capable of reaction with a polyamide but must
further be incapable of a reaction with a monomeric lactam which
will leave the silane reaction product incapable of entering into
the polymerization. For instance, ethylenically unsaturated silanes
perform as satisfactory couplers in a reinforced polyamide when the
preformed polymer is mixed with the coupler and filler, and the
composition fabricated into a finished article. Similarly, the
above couplers can be used advantageously in a condensation
polymerization of a polyamine and polycarboxylic acid. But the
ethylenically unsaturated silane couplers are only marginally
effective in a base-catalyzed lactam polymerization. Silane
couplers where the Z group is a halogen atom are also only
marginally effective. It is postulated that a reaction of monomeric
lactam and coupler such as the following occurs before
polymerization; ##EQU10## The substituted monomeric lactam product,
absent its active hydrogen atom, cannot enter into the
polymerization and the coupler cannot become bound to the polymer.
Hence, preferred silane couplers useful in a lactam polymerization
have Z groups which are capable of reaction with a polyamide but
incapable of a reaction with a monomeric lactam which leaves the
silane reaction product unable to enter the polymerization. Vinyl,
allyl and halogens are examples of Z groups included by the broad
definition of suitable couplers but excluded by the above narrower
class.
Regarding the preparation of castable compositions by the preferred
method previously mentioned, it may be advisable, particularly in
the case of high loadings, of reinforcing agents where a slight
increase in viscosity caused by partial polymerization cannot be
tolerated, to provide means for injection of the promoter (or
alternately the catalyst) into the monomer mixture as it is being
poured or forced into the mold. Such a technique completely
prevents an increase in viscosity of the monomer mixture due to
polymerization until the mixture is cast. Another technique useful
with high loadings of reinforcing agents which aids in overcoming
the difficulties presented by high viscosity is a pressurized
injection of the monomer mixture into the mold. A technique which
we have found useful in decreasing the viscosity of monomer
filler-coupler slurries comprises adding a small amount of a
surface-active agent to the slurry. Such a decrease in viscosity is
advantageous for two reasons. It permits the formation of a finer,
smoother finish on the final product. Occasionally a finished
composition with a high reinforcing agent content, e.g. 60% by
volume or about 79% by weight filler, may have a granular or coarse
texture and may even contain voids or open spaces due to the
inability of the viscous mixture to flow together completely prior
to polymerization. The addition of a surface-active agent
eliminates this problem and produces a smooth, attractive finish on
highly reinforced compositions. Alternatively, if a smooth finish
is not a necessary feature for certain applications, then a
decrease in viscosity permits incorporation of larger amounts of
reinforcing mineral into the monomer mixture. This surface active
agent may be either anionic, cationic, nonionic or mixtures
thereof. Examples include zinc stearate, dioctadecyl dimethyl
ammonium chloride, and ethylene oxide adducts of stearic acid.
Preferred compounds are the metal and quaternary ammonium salts of
long-chain carboxylic acids. A concentration of surfactant in the
range of 0.05-0.5% by weight of the total compositions has been
found useful. However, lower concentrations may also be used. At
higher concentrations of surface-active agent, it may be necessary
to use additional catalyst and promoter.
In addition to the base-catalyzed, substantially anhydrous anionic
lactam polymerization referred to above, reinforced polyamides can
also be prepared by the conventional hydrolytic polymerization of
lactams in the presence of coupler and filler as well as by
polymerization of aminocaproic acids.
Another process useful herein is the condensation polymerization of
a polyamine and polycarboxylic acid in the presence of coupler and
filler. Preferably the amine and carboxylic acid are both
difunctional. Examples of amines include tetramethylene diamine,
pentamethylene diamine, hexamethylene diamine, octamethylene
diamine, dodecamethylene diamine and bis(paraamino cyclohexyl)
methane. Suitable dicarboxylic acids include adipic, pimelic,
suberic, azelaic, sebacic, dodecanedioic and terephthalic acids.
Amine salts of the acids are formed by reacting equivalent amounts
of the amine and acid in a suitable solvent for the salt such as
water or alcohol and recovering the salt. By way of example, the
salt is dissolved in water to form a 50 to 75% aqueous solution. A
filler pretreated with a silane coupler is added to the solution.
The reactor is then sealed and heated to about 200 to 240.degree. C
to develop a pressure of 250 p.s.i. After an hour or two, the
temperature is raised to 270 to 300.degree.C as steam is bled off
to maintain the pressure at 250 p.s.i. The pressure is then
gradually reduced to atmospheric pressure and additional water
removed. The polymer-coupler-filler mixture can be extruded,
chopped and molded to form compositions having excellent mechanical
properties. Other methods of preparing reinforced polyamides by
condensation polymerization can also be employed using an inert
solvent for the salt such as phenol, cresol or xylenol and a
non-solvent such as the hydrocarbons or chlorinated hydrocarbons
optionally included.
Still another method of preparing reinforced polyamides comprises
mixing together a polyamide, coupler and filler under conditions
which provide thorough contact of the filler-coupler adduct with
the polyamide. One method has been to place the three components in
some container and agitate them to achieve some sort of crude
dispersion. The dispersion is then processed through an extruder,
chopped into granules and injection molded. The filler can either
be pre-treated with the coupler or treated with the coupler in the
presence of the polymer. Another processing technique comprises
milling the components followed by compression molding. Oxidative
degradation of the polymer becomes a problem, however, unless care
is taken to exclude air during the milling operation. Other
processing techniques are also applicable to this invention.
Polyamides prepared by any of the above processes can be reformed
into granules, pellets or powders and subsequently reworked if the
degree of crosslinking in the polymer is minimized. One technique
for reworking comprises extrusion followed by injection
molding.
Such techniques, either singly or in combination with other
techinques known in the art, are useful in obtaining the highly
reinforced compositions of this invention.
The invention will be more clearly understood from the detailed
description of the following specific examples which set forth some
of the preferred compositions, the methods of preparing them, and
the superior mechanical properties attained by the practice of this
invention. Quantities of reinforcing agents are expressed in weight
percent.
EXAMPLE 1
A quantity of 300 grams (2.65 moles) of .epsilon.-caprolactam was
melted in a flask under an atmosphere of dry nitrogen. To this melt
was added with stirring 750 grams of milled spodumene, a lithium
aluminum silicate. Following this, 3.5 ml. water and 6.4 grams (6.8
ml.) of 3-aminopropyl triethoxysilane were also added. The mixture
was heated to 150.degree.C under a slight vacuum to remove water
and ethanol. The distillation was continued until 50 grams of
caprolactam had also been removed. The vacuum was released and the
mixture allowed to cool to around 115.degree.C, at which time 3.7
grams (3ml.) of an 80/20 mixture of 2,4- and
2,6-diisocyanatotoluene (TD-80) was added and mixed for several
minutes. To this mixture, 8.3 ml. of a 3 molar solution of
ethylmagnesium bromide in diethyl ether was added slowly with
stirring. Again a vacuum was applied until all the ether and ethane
were removed, as evidenced by the complete dispersal of the
catalyst in the mixture. After release of the vacuum, the slurry
was poured into a mold, preheated to 200.degree.C and polymerized
for one hour. The finished product contained 51% by volume (75 wt.
percent) spodumene.
Subsequent preparations patterned on this example use identical
quantities of all materials specified above unless otherwise
noted.
EXAMPLE 2
The procedure described in Example 1 was followed except that 750
grams of quartz with a wide particle size distribution was
substituted in place of the spodumene. The finished product
contained 55% by volume (75 wt. percent) quartz.
EXAMPLE 3
The procedure described in Example 1 was followed except that 750
grams of crystalline silica having a maximum particle size of 5.mu.
and an average particle of 2.mu. was used instead of the spodumene.
The finished product contained 55% by volume silica.
EXAMPLE 4
The procedure described in Example 1 was followed except that 450
grams of .epsilon.-caprolactam, 456 grams of wollastonite, a
calcium metasilicate, 5.7 grams (4.7 ml.) of the difunctional
isocyanate and 13.3 ml. of a 3 molar solution of ethylmagnesium
bromide in diethyl ether were used in place of the corresponding
materials or quantities stated in Example 1. The finished product
contained 32% by volume (53 wt. percent) wollastonite.
EXAMPLE 5
The procedure described in Example 1 was followed except that 350
grams of .epsilon.-caprolactam, 700 grams of feldspar which is an
aluminum-alkali metal-alkaline earth metal silicate, 4.3 grams (3.5
ml.) of the difunctional isocyanate, and 10 ml. of a 3 molar
solution of ethylmagnesium bromide in diethyl ether were used in
place of the corresponding materials or quantities stated in
Example 1. The finished product contained 49% by volume (70 wt.
percent) feldspar.
EXAMPLE 6
The procedure described in Example 1 was followed except that 400
grams of .epsilon.-caprolactam, 650 grams of wollastonite, 4.9
grams (4.0 ml) of the difunctional isocyanate, and 10 ml. of a 3
molar solution of ethylmagnesium bromide dissolved in diethyl ether
were used in place of the corresponding materials or quantities
stated in Example 1. The finished product contained 43% by volume
(65 wt. percent) wollastonite.
EXAMPLE 7
The procedure described in Example 1 was followed except that 400
grams of .epsilon.-caprolactam, 700 grams of mullite which is an
aluminum silicate, 6.8 grams (7.3 ml.) of 3-aminopropyl
triethoxysilane, 3.7 ml water, 4.3 grams (3.5 ml.) of the
difunctional isocyanate and 10 ml. of a 3 molar solution of
ethylmagnesium bromide in diethyl ether were used in place of the
corresponding materials or quuantities stated in Example 1. In
addition, 100 grams of .epsilon.-caprolactam was withdrawn by
distillation instead of 50 grams. The finished product contained
48% by volume (70 wt. percent) mullite.
EXAMPLE 8
The procedure described in Example 1 was followed except that 750
grams of mullite was used instead of spodumene. The finished
product contained 54% by volume (75 wt. percent) mullite.
EXAMPLE 9
the procedure described in Example 6 was followed. In addition,
1.25 grams of polyethylene imine was added as a crosslinking
agent.
EXAMPLE 10
The procedure described in Example 6 was followed except that
3-(N-ethylamino)-aminopropyl trimethoxysilane was substituted in
place of the 3-aminopropyl triethoxysilane.
EXAMPLE 11
The procedure described in Example 6 was followed except that 7 ml.
water was used. In addition, 6.4 grams (6.8 ml.) of tetraethyl
silicate was added.
EXAMPLE 12
The procedure described in Example 6 was followed. In addition, 6.4
grams of diphenylsilanediol was added.
EXAMPLE 13
The procedure described in Example 1 was followed except that 342
grams of .epsilon.-caprolactam, 650 grams of wollastonite, 58 grams
of a chlorinated terphenyl (62% Cl), 4.1 grams (3.4 ml.) of a
difunctional isocyanate, and 8.8 ml. of a 3 molar solution of
ethylmagnesium bromide in diethyl ether were added in place of the
corresponding materials or quantities stated in Example 1. The
finished product contained 43% by volume (65 wt. percent)
wollastonite, 29.2% by weight polycaprolactam, and 5.8% by weight
of the chlorinated terphenyl.
EXAMPLE 14
The procedure described in Example 1 was followed except that 750
grams of alumina was used in place of the spodumene. The finished
product contained 49% by volume (75 wt. percent) alumina.
EXAMPLE 15
The procedure described in Example 6 was followed except that 7.2
grams (6.0 ml.) of Mondur MR (a polyfunctional isocyanate) was used
as the promoter instead of the difunctional isocyanate of Example
1.
EXAMPLE 16
The procedure described in Example 6 was followed except that 450
grams of .epsilon.-caprolactam and 600 grams of wollastonite were
used in place of the corresponding quantities stated in Example 6.
In addition, 7.2 grams (6.0 ml) of Mondur MR was used as the
promoter instead of the difunctional isocyanate. Further, 1.25
grams of polyethylene imine was added as a crosslinking agent. The
finished product contained 38% by volume (60 wt. percent)
wollastonite.
EXAMPLE 17
The procedure described in Example 1 was followed except that 750
grams of enstatite which is a magnesium metasilicate was used in
place of the spodumene. The finished product contained 51% by
volume (75 wt. percent) enstatite.
EXAMPLE 18
A quantity of 350 grams (3.1 moles) of .epsilon.-caprolactam was
melted in a flask under an atmosphere of dry nitrogen. To this melt
was added with stirring 6.4 grams (6.8 ml.) of 3-aminopropyl
triethoxysilane, 650 grams of wollastonite, and 3.5 ml. water. The
mixture was heated to 150.degree.C under a slight vacuum to remove
water and ethanol by-product. The distillation was continued until
50 grams of caprolactam had also been removed. The vacuum was
released and the mixture allowed to cool to around 115.degree.C, at
which time 11.7 ml. of a 3 molar solution of ethylmagnesium bromide
in diethyl ether was added with stirring. A vacuum was applied
until the catalyst was dispersed. Then a mixture of 50 grams of
caprolactam and 14.4 grams (12 ml.) of Mondur MR was added. This
mixture was prepared by mixing the two components, heating them to
around 120.degree.C to cause their reaction, and distilling
volatile reaction products under a high vacuum. After addition of
the reacted Mondur MR promoter, the mixture was stirred for 5 or 10
minutes under a vacuum, then cast into a mold preheated to
200.degree.C and allowed to polymerize for one hour. The finished
product contained 43% by volume (65 wt. percent) wollastonite.
EXAMPLE 19
The procedure described in Example 18 was followed except that 28.8
grams (24 ml.) of Mondur MR was used instead of the 14.4 grams (12
ml.) stated in Example 18. In addition, 11 grams of
tetra-(3-oxymethylene-1-propylamine)methane was added to the
caprolactam before melting. This compound was added as a
crosslinking agent.
EXAMPLE 20
The procedure described in Example 18 was followed except that 12.0
grams (10 ml.) of the difunctional isocyanate was used in place of
the Mondur MR. In addition, 1.0 gram of zinc stearate was added
with the catalyst and 2.6 grams of polyethyleneamine was added with
the promoter. The surface of the finished composition had a smooth
attractive appearance.
EXAMPLE 21
A quantity of 300 grams (2.65 moles) of .epsilon.-caprolactam was
melted in a flask under an atmosphere of dry nitrogen. To this melt
was added with stirring 12.8 grams (13.6 ml.) of 3-aminopropyl
triethoxysilane, 1500 grams of mullite, and 7.0 ml. of water in the
order given. The mixture was heated to 150.degree.C under a slight
vacuum to remove water and hydrolyzed ethanol. This distillation
was continued until 50 grams of caprolactam were removed. The
mixture was allowed to cool to around 115.degree. C, whereupon 2.0
grams of zinc stearate and 8.5 ml. of a 3 molar solution of
ethylmagnesium bromide in diethyl ether was added with stirring. A
vacuum was applied to remove the ether and then 7.2 grams (6.0 ml)
of Mondur MR was added and stirred for about 30 to 60 seconds. The
slurry was cast into the preheated mold, using a pressurized
injection to insure complete filling of the mold, and polymerized
at 200.degree.C for one hour. The surface of the finished
composition had a grain-like, somewhat coarse texture but was
entirely free from voids or open spaces large enough to adversely
affect the physical properties. The finished product contained 68%
by volume (86 wt. percent) mullite.
EXAMPLE 22
A polymeric composition was prepared according to Example 6 except
that a finely-divided wollastonite was used with a particle size
distribution comparable to that previously designated as suitable
for a finely-divided mixture. Additionally, a phenyl isocyanate
promoter was used in place of the difuctional isocyanate. In
addition, 1.8 grams of zinc stearate was added to the monomer
slurry. The product was chopped into small pieces, placed in a melt
index device, heated to about 250.degree.C, and extruded through a
1/16 inch orifice. The filament so produced was then drawn by hand
to approximately 0.020 inch in diameter. The filament surface was
smooth and possessed excellent physical properties.
The Table I below gives flexural strengths, flexural moduli, and
impact resistance values for polymeric compositions of this
invention. The flexural strength and modulus values were determined
in accordance with ASTM test D 790-61. Impact resistance was
determined by the notched Izod impact test described in ASTM D
256-56. The numerical designations of polymeric compositions
indicate compositions prepared as described in the corresponding
examples. Composition A is a unfilled, unreinforced polycaprolactam
prepared according to Example 6 of this disclosure except that no
reinforcing agent or coupling agent was used. Composition B is a
filled polycaprolactam containing 43% by volume wollastonite
prepared according to Example 6 of this disclosure except that no
coupling agent was used.
TABLE I ______________________________________ Flexural Flexural
Polymeric Strength, Modulus, Izod Notched Impact Composition psi
psi Resistance, ft. lbs./in. ______________________________________
A 12,000 0.30.times.10.sup.6 0.80 B 19,740 1.55 0.71 1 23,500 2.34
0.86 2 19,600 2.16 0.64 3 25,200 2.6 0.58 4 20,200 1.36 0.91 5
24,700 1.82 0.87 6 27,900 1.81 0.78 7 25,400 1.89 0.80 8 25,200
2.53 0.80 9 28,800 1.99 0.80 10 23,500 1.73 0.72 11 25,700 1.61
0.58 12 25,800 1.75 0.82 13 22,000 1.57 0.74 14 24,900 2.53 0.66 15
30,200 2.09 0.80 16 22,700 1.34 1.00 17 24,800 2.15 0.77 18 25,820
1.69 0.74 19 15,475 1.03 0.84 20 28,120 1.79 0.76
______________________________________
The above Table I demonstrates the great improvement in mechanical
properties achieved by the reinforced polymeric compositions of
this invention as compared to an unfilled, unreinforced polyamide
and a filled but unreinforced polyamide. The flexural strength of
unfilled, unreinforced polyamides has been more than doubled in
some cases by reinforcement and has been increased by from 5% to
more than 30% when compared to merely filled polyamides. The
modulus has been increased approximately by a factor of 6 to 8 when
compared to the unfilled, unreinforced polyamide prepared in a
comparable manner and by as much as 70% when compared to the filled
polyamide prepared in a comparable manner. Additionally, impact
resistance of 1 foot pound per inch has been achieved with certain
reinforcing media. The most accurate comparison for assessing the
improvement achieved by the adherent bonding of the present
invention vs. conventional filling is obtained by comparing Sample
B with Sample 6, the only difference in preparation being the
inclusion of a coupling agent in Sample 6. It should be noted here
that normal filling of a polyamide, although occasionally resulting
in increased flexural strength and modulus, also results in poorer
impact resistance. However, this invention provides not only
increased strength and modulus but also increased impact
resistance.
Sample 19 is an example of a highly crosslinked polyamide which can
be prepared to satisfy certain particular requirements. Although
the flexural strength and modulus of this composition is somewhat
lower than similarly prepared uncrosslinked polyamides and the
notched impact resistance is only average, the composition does not
break during flexural strength testing, but rather bends into a
U-shape without fracturing. Further the impact resistance increases
markedly when the sample is wet. The following is a comparison of
Samples 15 and 19 which are similar in all respects except as to
the degree of crosslinking:
Flexural Deflec- Flexural Modulus Izod Notched Polymeric Strength,
tion, psi impact Composition psi inches dry wet dry wet
__________________________________________________________________________
15 30,200 .29 2.09 .80 .80 .89 19 15,475 no break 1.03 .25 .84 2.04
__________________________________________________________________________
Of course, compositions with properties intermediate between these
two samples can easily be prepared to take advantages of the high
wet impact strength and resistance to fracture of the crosslinked
polyamide composition. Further improvements due to crosslinking of
the polymer may be seen by comparison of Samples 6 and 9, Sample 9
containing polymer crosslinked with polyethylene imine. Comparison
of Samples 6 and 15 shows the improvement achieved by the use of
the polyfunctional isocyanate promoter as compared to the
difunctional isocyanate.
EXAMPLES 23 to 38
The following runs were carried out to demonstrate the effects of
different coupling agents upon reinforced polyamides prepared by
the base-catalyzed, substantially anhydrous anionic polymerization
of a lactam in the presence of a coupler-treated filler.
The inorganic mineral was contacted with 0.3% by weight of the
silane coupling agent and stirred for 30 minutes at 130.degree.C
and for an additional 20 minutes as the mixture was cooled to
90.degree. C. The treated mineral was added to molten
.epsilon.-caprolactam. To the monomer-mineral slurry was added 10
mmoles of toluene diisocyanate per mole of caprolactam. A vacuum
was then applied for 5 minutes to remove volatile reaction
products. To the resultant slurry either 7 millimoles of the
magnesium catalyst or 11 millimoles of the sodium polymerization
catalyst per mole of caprolactam was added and the mixture cast
into a sheet mold 1/4 inch thick. The mold was preheated to
200.degree.C and maintained at this temperature for 10 minutes
after casting, after which time the mold was cooled and the
polymerized article removed. Properly data are reported in Table II
below. Also reported in the table are the type of filler, volume
fraction of filler, type of silane coupler and catalyst system. One
of two types of catalyst were used -- ethylmagnesium bromide or
sodium caprolactam .Iadd., which are designated in the table as Mg
and Na, respectively.Iaddend. .
TABLE II
__________________________________________________________________________
DRY Com- position Volume Flex. Str. Flex. Mod. Impact No. Filler
Fraction Coupler psi .times. 10.sup.-.sup.3 psi .times.
10.sup.-.sup.6 ft.lb./in.
__________________________________________________________________________
23 wollastonite .42 (C.sub.2 H.sub.5 O).sub.3 SiC.sub.3 H.sub.6
NH.sub.2 25.4 1.70 0.5 24 wollastonite .42 (C.sub.2 H.sub.5
O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2 24.3 1.42 0.7 25 wollastonite
.42 (C.sub.2 H.sub.5 O).sub.3 SiC.sub.2 H.sub.4 CN 11.5 0.95 0.2 26
wollastonite .42 (CH.sub.3 O).sub.3 SiC.sub.11 H.sub.22 Br 14.7
1.15 0.3 27 wollastonite .42 (C.sub.2 H.sub.5 O).sub.3 SiC.sub.3
H.sub.6 Cl 15.8 1.01 0.5 28 quartz .52 (C.sub.2 H.sub.5 O).sub.3
SiC.sub.3 H.sub.6 Cl 9.3 0.75 0.1 29 quartz .52 (CH.sub.3 O).sub.3
SiC.sub.2 H.sub.4 10.6 0.70 0.4 30 quartz .52 (C.sub.2 H.sub.5
O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2 12.4 0.71 0.5 31 wollastonite
.42 (CH.sub.3 OC.sub. 2 H.sub.4 O).sub.3 SiCH=CH.sub.2 14.7 1.15
0.3 32 wollastonite .42 (CH.sub.3 O).sub.3 Si(CH.sub.2).sub.11
NH.sub.2 -- -- -- 33 wollastonite .42 Cl.sub.3 SiCH=CHCOOC.sub.4
H.sub.9 -- -- -- 34 wollastonite .42 Cl.sub.2
Si(CH.sub.3)CH=CHCOOC.sub.4 H.sub.9 -- -- -- 35 wollastonite .42 --
-- -- 36 wollastonite .42 Cl.sub.2 --Si(CH.sub.3)CH.sub.2
CH(CH.sub.3)COOCH.sub.3 -- -- -- 37 wollastonite .42 Cl.sub.3
SiCH=CHCOOC.sub.2 H.sub.5 -- -- -- 38 wollastonite .42 H.sub.2
N(CH.sub.2).sub.5 --CO--NH(CH.sub.2).sub.3 Si(OMe).sub.3 -- -- --
__________________________________________________________________________
WET Com- position Volume Flex. Str. Flex. Mod. Impact No. Filler
Fraction Coupler psi .times. 10.sup.-.sup.3 psi .times.
10.sup.-.sup.6 ft.lb./in. S.sup.2 I
__________________________________________________________________________
23 wollastonite .42 (C.sub.2 H.sub.5 O).sub.3 SiC.sub.3 H.sub.6
NH.sub. 9.3 0.48 1.0 87 24 wollastonite .42 (C.sub.2 H.sub.5
O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2 6.8 0.35 2.3 106 25
wollastonite .42 (C.sub.2 H.sub.5 O).sub.3 SiC.sub.2 H.sub.4 CN 5.0
0.36 0.8 20 26 wollastonite .42 (CH.sub.3 O).sub.3 SiC.sub.11
H.sub.22 Br 4.9 0.27 0.9 22 27 wollastonite .42 (C.sub.2 H.sub.5
O).sub.3 SiC.sub.3 H.sub.6 Cl 5.3 0.34 0.7 20 28 quartz .52
(C.sub.2 H.sub.5 O).sub.3 SiC.sub.3 H.sub.6 Cl 3.5 0.35 1.4 17 29
quartz .52 (CH.sub.3 O).sub.3 SiC.sub.2 H.sub.4 5.2 0.34 0.6 16 30
quartz .52 (C.sub.2 H.sub.5 O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2 6.4
0.36 1.9 78 31 wollastonite .42 (CH.sub.3 OC.sub.2 H.sub.4 O).sub.3
SiCH=CH.sub.2 4.9 0.27 0.9 22 32 wollastonite .42 (CH.sub.3
O).sub.3 Si(CH.sub.2).sub.11 NH.sub.2 10.6 -- 0.71 80 33
wollastonite .42 Cl.sub.3 SiCH=CHCOOC.sub.4 H.sub.9 10.9 -- 0.44 52
34 wollastonite .42 Cl.sub.2 Si(CH.sub.3)CH=CHCOOC.sub.4 H.sub.9
10.9 -- 1.0 119 35 wollastonite .42 10.2 -- 0.40 42 36 wollastonite
.42 Cl.sub.2 --Si(CH.sub.3)CH.sub.2 CH(CH.sub.3)COOCH.sub.3 10.0 --
0.71 71 37 wollastonite .42 Cl.sub.3 SiCH=CHCOOC.sub.2 H.sub.5 13.7
-- -- -- 38 wollastonite .42 H.sub.2 N(CH.sub.2).sub.5
--CO--NH(CH.sub.2).sub.3 Si(OMe).sub.3 13.3 -- -- --
__________________________________________________________________________
Inspection of the above data shows that silanes having as their Z
groups a vinyl group or halogen atom are inferior to silane
couplers whose Z groups are capable of reacting in the manner
described. Specifically, Compositions 23, 24, 30, 32, 33, 34, 35,
36, 37 and 38 have mechanical properties significantly superior to
Compositions 25, 26, 27, 28, 29 and 31.
EXAMPLES 39 to 51
The following runs demonstrate the applicability of the present
invention to reinforced polyamides prepared by dispersing the
coupler-treated filler in the preformed polyamide.
Nylon 6,6 (Zytel 101) molding powder was placed in a polyethylene
bag to which was added sufficient wollastonite to provide a
finished composition having 0.42 volume fraction filler (65% by
wt.) and alkoxysilane coupler equal to 1% by weight of the filler.
The contents of the bag were agitated for about 30 to 60 seconds
and then placed in an extruder having a 1 inch screw and 18 inch
barrel length. The contents were run through the extruder twice at
270.degree. C. The extrudate was chopped into a molding powder and
injection molded at 260.degree.C and 600 p.s.i. Mechanical
properties are reported to Table III below.
TABLE III
__________________________________________________________________________
DRY Com- position Flex. Str. Flex. Mod. Ten. Str. Impact No.
Coupler psi .times. 10.sup.-.sup.3 psi .times. 10.sup.-.sup.6 psi
.times. 10.sup.-.sup.3 ft.lb./in.
__________________________________________________________________________
39 no coupler 17.6 1.33 9.1 0.4 40 (C.sub.2 H.sub.5 O).sub.3
SiC.sub.2 H.sub.4 CN 17.6 1.67 10.5 0.2 41 (C.sub.2 H.sub.5
O).sub.3 SiOC.sub.10 H.sub.21 16.9 1.51 9.4 0.2 42 Cl.sub.3
SiCH.sub.3 13.0 1.47 7.6 0.1 43 (C.sub.2 H.sub.5 O).sub.3 SiC.sub.5
H.sub.11 12.0 1.48 7.2 0.2 44 (C.sub.2 H.sub.5 O).sub.3 Si-- 13.7
1.64 7.8 0.2 45 (C.sub.2 H.sub.5 O).sub.3 SiC.sub.3 H.sub.6 Cl 20.5
1.51 11.2 0.3 46 (CH.sub.3 O).sub.3 SiCH=CH.sub.2 19.7 1.39 11.6
0.5 47 (C.sub.2 H.sub.5 O).sub.3 SiCH=CH.sub.2 21.7 1.49 12.0 0.4
48 (CH.sub.3 O).sub.3 SiC.sub.2 H.sub.4 22.3 1.66 12.5 0.5 49
(C.sub. 2 H.sub.5 O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2 24.9 1.57
13.1 0.5 50 (CH.sub.3 OC.sub.2 H.sub.4 O).sub.3 SiCH=CH.sub.2 21.4
1.43 12.1 0.5 51 (CH.sub.3 O).sub.3 SiC.sub.11 H.sub.22 Br 22.0
1.62 12.3 0.4
__________________________________________________________________________
WET Com- position Flex. Str. Flex. Mod. Ten. Str. Impact No.
Coupler psi .times. 10.sup.-.sup.3 psi .times. 10.sup.-.sup.6 psi
.times. 10.sup.-.sup.3 ft.lb./in. S.sup.2 I
__________________________________________________________________________
39 no coupler 2.8 0.12 2.4 0.7 5 40 (C.sub.2 H.sub.5 O).sub.3
SiC.sub.2 H.sub.4 CN 5.7 0.41 3.1 0.4 13 41 (C.sub.2 H.sub.5
O).sub.3 SiOC.sub.10 H.sub.21 4.4 0.27 3.3 1.2 23 42 Cl.sub.3
SiCH.sub.3 4.0 0.27 2.2 (1.5)* 24 43 (C.sub.2 H.sub.5 O).sub.3
SiC.sub.5 H.sub.11 4.4 0.3 2.3 (1.3)* 25 44 (C.sub.2 H.sub.5
O).sub.3 Si-- 4.8 0.33 2.4 (1.2)* 28 45 (C.sub.2 H.sub.5 O).sub.3
SiC.sub.3 H.sub.6 Cl 8.3 0.39 4.6 0.7 48 46 (CH.sub.3 O).sub.3
SiCH=CH.sub.2 8.0 0.39 4.9 0.8 51 47 (C.sub.2 H.sub.5 O).sub.3
SiCH=CH.sub. 2 8.7 0.38 5.2 0.8 61 48 (CH.sub.3 O).sub.3 SiC.sub.2
H.sub.4 9.6 0.45 5.5 0.7 65 49 (C.sub.2 H.sub.5 O).sub.3 SiC.sub.3
H.sub.6 NH.sub.2 9.4 0.39 5.3 0.8 71 50 (CH.sub.3 OC.sub.2 H.sub.4
O).sub.3 SiCH=CH.sub.2 9.5 0.36 5.2 0.8 72 51 (CH.sub.3 O).sub.3
SiC.sub.11 H.sub.22 Br 10.0 0.41 5.8 0.8 80
__________________________________________________________________________
*Samples did not break; calculated from scale reading.
Inspection of the above data of Table III indicates the importance
of a silane coupler containing a functional group capable of
reacting with a polyamide. Compositions improperly coupled because
of unreactive Z groups on the coupler, Nos. 40 to 44 in the above
table, are somewhat improved over a merely filled nylon but the
choice of proper silane coupler, as in Nos. 48 to 51, provides at
least as much additional improvement of the properly coupled
compositions over the improperly coupled compositions in the
important Strength Index category as is shown by the improperly
coupled materials over the filled material of Example 39.
EXAMPLES 52 to 55
The following runs were carried out as described in the procedure
for Examples 39 to 51 except that the type of filler was varied as
indicated in Table IV below.
TABLE IV
__________________________________________________________________________
DRY Com- position Flex.Str. Flex.Mod. Ten.Str. Impact No. Mineral
Coupler psi .times. 10.sup.-.sup.3 psi .times. 10.sup.-.sup.6 psi
.times. 10.sup.-.sup.3 ft.lb./in.
__________________________________________________________________________
52 feldspar (CH.sub.3 O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2 21.4 1.25
11.2 0.4 53 quartz (CH.sub.3 O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2
20.9 1.12 10.8 0.4 49 wollastonite (CH.sub.3 O).sub.3 SiC.sub.3
H.sub.6 NH.sub.2 24.9 1.57 13.1 0.5 54 feldspar (C.sub.2 H.sub.5
O).sub.3 SiC.sub.3 H.sub.6 Cl 21.7 1.28 11.7 0.4 55 quartz (C.sub.2
H.sub.5 O).sub.3 SiC.sub.3 H.sub.6 Cl 21.6 1.35 11.8 0.4 45
wollastonite (C.sub.2 H.sub.5 O).sub.3 SiC.sub.3 H.sub.6 Cl 20.5
1.51 11.2 0.3
__________________________________________________________________________
WET Com- position Flex.Str. Flex.Mod. Ten.Str. Impact No. Mineral
Coupler psi .times. 10.sup.-.sup.3 psi .times. 10.sup.-.sup.6 psi
.times. 10.sup.-.sup.3 ft.lb./in. S.sup.2 I
__________________________________________________________________________
52 feldpsar (CH.sub.3 O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2 10.5 0.41
6.5 0.9 99 53 quartz (CH.sub.3 O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2
8.6 0.32 5.6 0.8 59 49 wollastonite (CH.sub.3 O).sub.3 SiC.sub.3
H.sub.6 NH.sub.2 9.4 0.39 5.3 0.8 71 54 feldspar (C.sub.2 H.sub.5
O).sub.3 SiC.sub.3 H.sub.6 Cl 10.0 0.40 5.7 0.8 80 55 quartz
(C.sub.2 H.sub.5 O).sub.3 SiC.sub.3 H.sub.6 Cl 9.8 0.40 5.8 0.8 78
45 wollastonite (C.sub.2 H.sub.5 O).sub.3 SiC.sub.3 H.sub.6 Cl 8.3
0.39 4.6 0.7 48
__________________________________________________________________________
The above data of Table IV indicate the specificity of different
coupler-filler adducts with polyamides and the variation in
properties obtained using different couplers with different fillers
in the resin. Compare for instance Compositions 52 and 53 with 49
and Compositions 54 and 55 with 45.
EXAMPLES 56 to 64
The following data reported in Table V below demonstrate that
various resins perform in different manners when subjected to the
action of a reinforcing filler.
The polyester compositions were prepared by mixing Paraplex P-43 (a
70/30 mix of an unsaturated polyester in styrene) with
wollastonite, 0.5% by weight based on the mineral of
3-trimethoxysilylpropyl methacrylate and benzoyl peroxide catalyst
in a Banbury mixer for 10 minutes. The dough-like mix was molded
and polymerized for 5 minutes at 110.degree.C and 300 p.s.i. The
product was then cured for 20 hours at 110.degree.C. The finished
product contained 55% by volume (75 wt. percent) wollastonite.
The epoxy compositions were prepared by mixing 140 parts of
wollastonite with 4 parts of 3-trimethoxysilylpropylamine and 50
parts of an epoxy prepolymer (Oxiron 200). To the mix was added 20
parts of a 7/1 blend of maleic anhydride/propylene glycol. The
mixture was cured in a press for two hours at 85.degree.C and
subsequently post cured in an oven for 20 hours at
135.degree.C.
The polycaprolactams were prepared according to the procedure
followed for Example 1.
TABLE V
__________________________________________________________________________
DRY Vol. Frac. Flex.Str. Flex.Mod. Impact Composition No. Resin
Filler Coupler psi .times. 10.sup.-.sup.3 psi .times.
10.sup.-.sup.6 ft.lb./in.
__________________________________________________________________________
56 polyester none none 14.1 .55 0.2 57 polyester .57 none 9.6 2.7
>0.1 58 polyster .57 CH.sub.2 =C(CH.sub.3)C(O)O 18.8 4.0 >0.1
.vertline. (CH.sub.3 O).sub.3 SiH.sub.6 C.sub.3 59 epoxy none none
7.9 .30 -- 60 epoxy .47 none 8.9 1.8 -- 61 epoxy .47 (C.sub.2
H.sub.5 O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2 10.2 1.8 -- 62
polycapro- none none 12.0 0.3 0.80 lactam 63 polycapro- .49 none
16.0 1.9 0.50 lactam 64 polycapro- .49 (C.sub.2 H.sub.5 O).sub.3
27.1 2.2 0.50 lactam
__________________________________________________________________________
Inspection of the above data shows that the impact strength of
filled and of reinforced polyesters is adversely affected. As a
matter of fact, the impact strength is reduced virtually to zero.
The flexural strength of a reinforced polyester is improved about
26% by comparison to the base resin. Granular reinforcement of an
epoxy resin has little effect on the flexural properties; no impact
data is available for comparison. Polyamides, on the other hand,
show remarkable improvement in flexural strength, 113% over the
base resin, as well as good retention of impact strength. Hence,
the specific nature of polymer systems has considerable effect upon
its capability ot respond to granular reinforcement.
EXAMPLES 65 and 66
The procedure described for Examples 39 to 51 was used. Instead of
wollastonite, a plate-like filler, mica, was used at a loading of
28% by volume (52 wt. percent). The composition of Example 65 did
not contain a coupler. In Example 66, 1% by weight based on the
filler of 3-trimethoxysilylpropyl amine was used. Results are
reported in Table VI.
TABLE VI
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DRY Compo- Flex. Str. Flex. Mod. Tens. Str. Impact sition Coupler
psi .times. 10.sup.-.sup.3 psi .times. 10.sup.-.sup.6 psi .times.
10.sup.-.sup.3 Strength
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65 no 19.2 1.5 10.1 0.3 66 yes 21.5 1.5 12.1 0.4 WET Compo- Flex.
Str. Flex. Mod. Tens. Str. Impact sition psi .times. 10.sup.-.sup.3
psi .times. 10.sup.-.sup.6 psi .times. 10.sup.-.sup.3 Strength
S.sup.2 I
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65 5.6 0.4 3.3 0.7 22 66 9.2 0.5 5.6 0.8 68
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EXAMPLE 67
A quantity of 500 parts of feldspar (average particle size 25.mu.)
was mixed with 5 parts of 11-trimethoxysilylundecyl bromide and 50
parts of a nylon 6,6 molding powder (Zytel 101). The mixture was
extruded and injection molded as described above in Examples 39 to
51. The finished product was molded into a cylindrical shape 1.25
inches in diameter. The cylinder was smooth, hard, strong and of
excellent uniform appearance. The article contained 80% by volume
(91 wt. percent) feldspar.
EXAMPLES 68 to 76
The accompanying figure shows the modulus values at different
filler loadings for some of the compositions of this invention.
The quartz-loaded nylon 6,6 compositions were prepared as described
in Examples 39 to 51 using 1% 3-triethoxysilylpropyl amine on the
quartz.
The wollastonite-loaded and quartz-loaded polycaprolactams were
prepared as described in Examples 23 to 38 using the sodium
caprolactam catalyst. Table VII below sets forth the properties of
the reinforced compositions.
TABLE VII
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Compo- Vol. Flex.Str. Flex.Mod. Impact sition Polymer Frac. Filler
psi .times. 10.sup.-.sup.3 psi .times. 10.sup.-.sup.6 ft.lb./in.
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68 nylon 6,6 .15 quartz 24.2 0.53 0.5 69 nylon 6,6 .20 quartz
>16.7 0.41 0.4 70 nylon 6,6 .30 quartz >20.1 0.78 0.5 71
nylon 6 .42 quartz 23.8 1.50 0.6 72 nylon 6 .50 quartz 24.2 1.78
0.5 73 nylon 6 .52 quartz 25.2 1.92 0.5 74 nylon 6 .62 quartz --
2.66 0.4 75 nylon 6 .15 wollastonite >16.0 0.53 0.5 76 nylon 6
.45 wollastonite 25.4 1.70 0.5
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The improved properties of the reinforced polyamides permit their
use in many applications in which the unreinforced polyamides are
unsuitable, such as the fabrication of tables, chairs, drawers, and
other furniture and furniture components, heavy duty equipment
housings, automobile components and building construction
components. The reinforced filaments are useful in the manufacture
of tire bodies. They can also be used as an oriented reinforcing
material in other compositions to improve impact resistance and
strength. Further, the compositions of this invention are generally
useful in those applications in which unreinforced polyamides have
been useful but where increased strength, rigidity, and impact
resistance are desirable features.
Although the invention has been described in terms of specified
embodiments which are set forth in considerable detail, it should
be understood that this was done for illustrative purposes only,
and that the invention is not necessarily limited thereto since
alternative embodiments and operating techniques will become
apparent to those skilled in the art in view of this disclosure.
For instance, it is possible to "fill" these compositions with a
filler, i.e. with additional inorganic particulate material which
is not coupler-treated as is the reinforcing agent. As an example,
a mold may be loosely filled with a mixture of large (approximately
1 cm. in diameter) irregular mineral particles and sand, and a
monomer-coupler-filler slurry as described in the preceding
examples may be poured into the mold, thereby "wetting" the large
particles in the mold and filling the spaces between the particles
before polymerization occurs. In such a case, the reinforced
polymer binds the sand and larger aggregates together in much the
same way as cement binds sand gravel together to form a finished
concrete. As an alternate method, the inorganic aggregate in the
mold may be treated with a suitable coupling agent prior to the
introduction of the monomer-coupler-filler slurry so that upon
casting, the entire mixture is adherently bound to the polymer,
thereby producing a reinforced composition wherein the reinforcing
medium may exceed 90% by volume of the total composition.
Similarly, glass fibers in the form of mats or woven cloth can be
impregnated with the particulately reinforced compositions of this
invention to produce articles having a very high inorganic
content.
Accordingly, these and other modifications are contemplated which
can be made without departing from the spirit of the described
invention.
* * * * *