U.S. patent number RE30,699 [Application Number 06/026,381] was granted by the patent office on 1981-08-04 for polyurethanes containing amino organosilane modified clay.
This patent grant is currently assigned to J. M. Huber Corporation. Invention is credited to Joseph Iannicelli.
United States Patent |
RE30,699 |
Iannicelli |
August 4, 1981 |
Polyurethanes containing amino organosilane modified clay
Abstract
The instant disclosure is directed to the polyurethane polymer
compositions which are filled with a kaolin clay which has been
modified with from 1% to 3% of an amino organosilane. The modulus
and tear resistance of the polymers is improved without degradation
of the remaining properties.
Inventors: |
Iannicelli; Joseph (Macon,
GA) |
Assignee: |
J. M. Huber Corporation
(Locust, NJ)
|
Family
ID: |
21831506 |
Appl.
No.: |
06/026,381 |
Filed: |
April 2, 1979 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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269695 |
Apr 1, 1963 |
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Reissue of: |
480090 |
Aug 16, 1965 |
03390120 |
Jun 25, 1968 |
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Current U.S.
Class: |
524/262;
524/445 |
Current CPC
Class: |
C08K
9/06 (20130101); C08K 9/06 (20130101); C08L
75/04 (20130101) |
Current International
Class: |
C08K
9/06 (20060101); C08K 9/00 (20060101); C08L
075/04 () |
Field of
Search: |
;260/37N,4TN
;106/38N |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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689318 |
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Jun 1964 |
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CA |
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948163 |
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Jan 1964 |
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GB |
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Other References
Jellinek et al., Silane Finishes for Fibrous Glass, 1957,
Presentation before the Society of Plastic Industries, Union
Carbide Corp..
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Primary Examiner: Jacobs; Lewis T.
Attorney, Agent or Firm: Price; Robert L. Price; Harold
H.
Claims
I claim:
1. A polyurethane polymer composition containing as a filler,
modified kaolin clay, said kaolin clay .Iadd.having been
.Iaddend.modified .Iadd.by treatment .Iaddend.with from 1% to 3% by
weight with an aminoorganosilane of the formula ##STR2## wherein
R.sub.1 is selected from the group consisting of hydrogen, alkyl,
aryl, cycloalkyl, and alkaryl, R.sub.2 is selected from the group
consisting of hydrogen, alkyl, aryl, cycloalkyl, and alkylaryl,
R.sub.3 is selected from the group consisting of hydrogen, lower
alkyl, aryl, lower alkylaryl, and lower arylalkyl, R.sub.4 is
selected from the group consisting of hydrogen, lower alkyl, aryl,
lower alkylaryl, and lower arylalkyl, R.sub.5 is selected from the
group consisting of hydrogen, lower alkyl, aryl, lower alkylaryl,
and lower arylalkyl, and X is selected from the group consisting of
alkylene, arylene, alkylarylene, arylalkylene, cycloalkylene,
cycloalkylene containing secondary amino nitrogen and cycloalkylene
containing tertiary amino nitrogen.Iadd., the modification of said
kaolin clay being carried out by spray drying kaolin slurries
having one or more of said amonoorganosilanes dispersed therein,
said spray drying effecting a uniform distribution of said
aminoorganosilane on the kaolin. .Iaddend.
2. The composition of claim 1 wherein the filler is kaolin clay
modified with from 1% to 3% by weight of a diamino functional
silane.
3. The composition of claim 1 wherein the filler is kaolin clay
modified with 1% to 3% by weight of
gamma-aminopropyltriethoxysilane. .Iadd. 4. A polyurethane polymer
composition containing as a filler, modified kaolin clay, said
kaolin clay having been modified by treatment with from 1% to 3% by
weight of an aminoorganosilane of the formula:
wherein R is selected from the group consisting of phenylene, lower
alkyl substituted phenylene, lower alkoxy substituted phenylene,
and lower alkylene, R' is a monovalent hydrocarbon group free of
aliphatic unsaturation selected from the group consisting of lower
alkyl, aryl, lower alkaryl and lower aralkyl, and wherein R' can
represent the same or different groups. .Iaddend.
Description
This invention relates to polyurethane polymer compositions
containing finely divided amino organosilane modified kaolin clay
fillers.
The present application is a continuation-in-part of applicant's
copending application Ser. No. 269,695, filed Apr. 1, 1963, now
Patent No. 3,290,165, entitled, "Surface Modified Pigments," which
in turn is a continuation-in-part of applicant's application Ser.
No. 189,321, filed Apr. 23, 1962, entitled, "Surface Modified
Pigments," now abandoned.
Polyurethane polymer compositions can be formed from a variety of
polymers, l.e., thermosetting gums, thermoplastic polymers and
liquid or casting polymers. The preparations for various classes
and grades of polyurethanes are well known in the art and need not
be detailed here; however, the general reaction by which they are
formed is by a chain extension process rather than the usual
polymerization reaction. In this process a relatively short chain
polymer, either a polyester or a polyether, is reacted with an
organic diisocyanate to form long chain urethane polymer. The
process variations and polymerization variations caused thereby
result in a multitude of compositions all broadly falling in one of
the three classes mentioned.
The polyurethanes have several outstanding properties which make
them desirable products, chief among them is abrasion resistance,
good low temperature characteristics, good resistance to heat
deterioration, ozone cracking, weathering, and oil or solvent
swelling.
Thermosetting gum vulcanizates have a variety of uses in conveyor
belts, roll covers, sandblast-hose tubes and other applications
where good abrasion resistance is needed.
Thermoplastic resins can be processed on standard extrusion,
injection molding, and transfer molding equipment. These resins are
useful in small parts such as mallet heads, sprocket gears,
adhesive coatings and unsupported sheetings such as fuel tanks,
tarpaulins and chute liners.
Liquid polyurethane valcanizates exhibit good abrasion resistance,
non-marking and a wide range of hardnesses. These products have use
in large rolls for the steel industry, fork lift truck wheels,
ladies toplifts, ball-joint seals, automotive seals, potting
compounds, conveyor belts, V-belts, and tank linings.
Despite the fact that the polyurethanes have outstanding properties
and are suitable for a large variety of uses, industry is
constantly attempting to improve them by various means. Properties
which are desirable to improve are modulus, tear resistance,
hardness and abrasion resistance. In many cases reinforcing fillers
have been tried but on the whole, while some improvements resulted,
the degradation of other properties resulted and a completely
satisfactory filler has not been found.
It is an object of this invention to provide solid polyprethane
vulcanizates and thermoplastic resin compositions containing
reinforcing fillers of modified kaolin clays.
Other objects and advantages will be apparent from the following
specification.
I have discovered that kaolin clay modified with saturated amino
organosilanes are reinforcing fillers for polyurethane polymers and
impart improved properties to them. Particularly, modulus and tear
resistance are improved with little, if any, degradation of other
important properties.
The kaoline clays which are suitable as substrates for the modifier
are refined clays of the rubber and paper grades.
The modified kaolin clays can be prepared by dissolving the desired
amount of amino organosilane in a suitable solvent, adding the
pigment and heating until the reaction is complete. The amount of
modifier added depends upon the specific modifier used and the
intended polymer to be reinforced. Generally from 1% to 3% by
weight of the modifier is sufficient for most purposes.
A particularly useful process for modifying the kaolin clay
involves spray drying kaolin slurries having one or more of the
amino organosilanes dispersed therein. The spray drying process
effects a uniform distribution of the modifier on the kaolin.
Another satisfactory method of modifying the kaolin involves
dissolving the desired amount of amino organosilane in a suitable
solvent, adding the kaolin and heating until the reaction is
complete.
The compounds used to modify the kaolin clays can be depicted by
the formula: ##STR1## wherein R.sub.1 is hydrogen, alkyl, aryl,
cycloalkyl, or alkylaryl; R.sub.2 is hydrogen, alkyl, aryl,
cycloalkyl, or alkylaryl; R.sub.3 is hydrogen, lower alkyl, aryl,
lower alkylaryl, or lower arylalkyl; R.sub.4 is hydrogen, lower
alkyl, aryl, lower alkylaryl, or lower arylalkyl; R.sub.5 is
hydrogen, lower alkyl, aryl, lower alkylaryl, or lower arylalkyl;
and X is alkylene, alkylene containing secondary amino nitrogen,
alkylene containing tertiary amino nitrogen, arylene, arylene
containing secondary amino nitrogen, arylene containing tertiary
amino nitrogen, alkylarylene, alkylarylene containing secondary
amino nitrogen, alkylarylene containing tertiary amino nitrogen,
arylalkylene, arylalkylene containing secondary amino nitrogen,
arylalkylene containing tertiary amino nitrogen, cycloalkylene,
cycloalkylene containing secondary amino nitrogen and cycloalkylene
containing tertiary amino nitrogen. Some of these amino
organosilanes are disclosed along with methods for their
preparation in U.S. Patents Nos. 2,832,754, 2,930,809, 3,007,957,
and 3,020,302. Commercially available amino organo silanes useful
in the practice of this invention include "A-1100," a
gamma-aminopropyltriethoxy silane (GAPTS), and "Y-2967," an amino
organosilane which is a modified gamma-aminopropyltriethoxy silane,
sold by Union Carbide Corporation, New York, N.Y., "Z-6020," a
diamino functional silane, sold by Dow Corning Corporation,
Midland, Michigan.
Representative commercially available polyurethane polymers
suitable for use in this invention are "Vibrathane 5003," a
thermosetting gum which is cross-linked, produced by Naugatuck
Chemical Division of U.S. Rubber Company; "Elastothane 455," a
thermosetting gum which is cross-linked, produced by Thiokol;
"Genthane S," a cross-linked thermosetting gum produced by General
Chemical; "Estane," a thermoplastic resin produced by B. F.
Goodrich Chemical; "Texin," a thermoplastic resin produced by
Mobay; "Multrathane," a liquid polymer produced by Mobay;
"Cyanoprene 4590," a liquid polymer produced by American Cyanamid;
"Adiprene L," produced by Du Pont; "Vibrathane 6000," produced by
Naugatuck; and "Neothane," produced by Goodyear.
In the following formulations the gums were mill-mixed or
Banbury-mixed and the thermoplastic resins were mill-mixed and
injection molded.
The following formulations illustrate this invention.
Example I
______________________________________ Parts
______________________________________ Vibrathane 5003 100 Stearic
acid 0.25 Dicup 40C (polymerizing agent) 5 Filler (modified clay)
60 ______________________________________
The compounds were mixed on a 6 inch by 12 inch laboratory mill and
cured for 30 minutes at 307.degree. F., except for the NBS abrasion
test where the cure was for 60 minutes at 307.degree. F.
The data tabulated in Table I indicates the results when 1%, 2% and
3% by weight of GAPTS modified kaolin clay and 1% by weight
Silicone Z-6020 modified kaolin clay is the filler.
TABLE I
__________________________________________________________________________
1% 2% 3% 1% GAPTS GAPTS GAPTS Z-6020 Control Kaolin on Kaolin on
Kaolin on Kaolin on Kaolin
__________________________________________________________________________
Parts Filler/100 parts Polymer None 60 60 60 60 60 Tensile, p.s.i.
3,500 (.sup.1) 3,920 3,600 3,840 3,270 Stress 300%, p.s.i. 1,040
(.sup.1) 2,600 3,390 -- 2,520 Elongation, percent 440 (.sup.1) 470
350 265 365 Shore A Hardness 58 -- 74 74 74 73 NBS Abrasion,
percent of Standard 100 -- 89 134 157 193 Minutes Cured at
305.degree. F. 30 30 30 30 30 60
__________________________________________________________________________
.sup.1 No cure.
Example II
______________________________________ Parts
______________________________________ Texin 480A 100 Modified clay
20 ______________________________________
The resin was molded at 390.degree.-410.degree. F. and post cured
at 110.degree. C. for 24 hrs. The results are tabulated in Table
II.
TABLE II ______________________________________ 1% Con- Kao- GAPTS
trol lin on Kaolin ______________________________________ Parts
Filler/100 parts Polymer None 20 20 Stress 300%, p.s.i. 1,720 2,170
2,430 Tensile, p.s.i. 5,700 2,540 2,620 Elongation, percent 640 510
400 Shore A Hardness 75 78 78 NBS Abrasion, percent of Standard 100
77 92.5 ______________________________________
Example III
______________________________________ Parts
______________________________________ Texin 480A 100 Modified clay
20 ______________________________________
The resin was molded at 390.degree.-410.degree. F. and was not post
cured. The results are shown in Table III.
TABLE III ______________________________________ 0.25% 0.5% 1%
GAPTS GAPTS GAPTS Con- Kao- on on on trol lin Kaolin Kaolin Kaolin
______________________________________ Parts Filler/100 0 20 20 20
20 parts Polymer Stress 300%, p.s.i. 1,090 1,680 1,725 1,735 1,720
Tensile, p.s.i. 4,380 4,470 3,340 4,250 4,400 Elongation, 610 640
560 655 595 percent Shore A Hardness 85 88 88 88 88
______________________________________
Example IV
______________________________________ Parts
______________________________________ Estane 5701 100 Barium
stearate 3 Modified clay 25 or 50
______________________________________
The resin was molded 5' at 350.degree. F. held in the mold under
pressure until the temperature dropped below 200.degree. F. The
results are tabulated in Table IV.
TABLE IV ______________________________________ Con- Kaolin plus
trol Kaolin 1% Z 6020 ______________________________________ Parts
Filler/100 parts Polymer 0 25 50 25 50 300% Modulus, p.s.i. 1,220
1,580 1,640 2,840 3,300 ASTM Test "Die" C, lbs./in 410 500 300 560
580 NBS Abrasion Index, percent 492 521 720 1,285 16.72 NBS
Abrasion Shore A 82 90 92 90 92
______________________________________
Example V
______________________________________ Parts
______________________________________ Estane 5701 100 Barium
stearate 3 Filler 25, 50 or 100
______________________________________
The polymer batch was treated as in Example IV. The results are
shown in Table V.
TABLE V
__________________________________________________________________________
Kaolin Kaolin Kaolin Kaolin Kaolin Kaolin Kaolin Kaolin Con- Kao-
plus 2% plus 2% plus 3% plus 1% Kao- plus 2% plus 1% Kao- plus plus
1% trol lin GAPTS GAPTS GAPTS Z 6020 lin GAPTS Z 6020 lin GAPTS Z
__________________________________________________________________________
6020 Parts Filler/100 parts 0 25 25 25 25 25 50 50 50 100 100 100
Polymer 200% Modulus, p.s.i. 860 -- -- -- -- -- 1,700 3,500 3,740
-- -- -- 300% Modulus, p.s.i. 1,440 1,780 2,940 3,260 3,040 3,000
-- -- -- -- -- -- Shore A Hardness 88 93 91 92 91 91 94 94 95 97 97
97 NBS Abrasion, Index 460 641 827 703 641 746 624 936 568 334 553
575
__________________________________________________________________________
Example VI
______________________________________ Parts
______________________________________ Estane 5701 100 Barium
Stearate 3 Pigment 25 or 50
______________________________________
The recipe was treated the same as in Example IV. The results are
shown in Table VI.
TABLE VI ______________________________________ Kaolin Kaolin plus
plus Con- Kao- 2% 1% trol lin GAPTS Z-6020
______________________________________ Parts Filler/100 None 25 50
25 50 25 50 parts Polymer 300% Modulus, 1,220 1,580 1,640 2,880
3,600 2,840 3,300 p.s.i. ASTM Tear "Die 410 500 500 550 480 560 580
C," lbs./in NBS Abrasion, 492 521 720 1,015 1,411 1,285 1,672 Index
percent NBS Abrasion, 82 90 92 90 91 90 92 Shore A Hardness
______________________________________
Example VII
______________________________________ Parts
______________________________________ Estane 5701 100 Barium
Stearate 3 Filler 10, 20, 60 or 100
______________________________________
The recipe was treated as in Example IV. The results are shown in
Table VII.
TABLE VII
__________________________________________________________________________
Con- Kaolin Plus Kao- Kaolin Plus Kao- -trol 1% Z-6020 lin 1%
Z-6020 lin
__________________________________________________________________________
Parts Filler/100 parts Polymer 0 10 20 20 60 100 100 300% Modulus,
p.s.i. 1,280 2,040 2,740 1,640 3,420 -- 2,040 ASTM Tear "Die C,"
lbs./in 420 500 600 530 540 406 510 NBS Abrasion, Index percent 570
867 1,095 957 1,722 1,465 717 NBS Abrasion, Shore A 84 85 89 89 94
95 95
__________________________________________________________________________
Example VIII
______________________________________ Parts
______________________________________ Adiprene L-100 100
Methylene-bis-orthochloraniline 11 Pigment 20
______________________________________
The mixture was cured for 180 minutes at 212.degree. F. The results
are shown in Table VIII.
TABLE VIII ______________________________________ Kaolin Plus 1%
Control Kaolin Z-6020 ______________________________________ Parts
Filler/100 parts Polymer 0 20 20 300% Modulus, p.s.i. 1,530 --
1,940 Tensile, p.s.i. 2,570 1,310 2,710 -Elongation, Percent 495
285 480 5 Shore A Hardness 87 88 90 ASTM Tear "Die C," lbs./in 450
408 505 NBS Abrasion, Index Percent 224 126 194
______________________________________
The examples and data indicate that when the modified kaolin clays
useful in this invention are used as fillers in thermosetting gum
polyurethanes increases in modulus, hardness and abrasion
resistance occur. The remaining properties of the polymer remain
within acceptable levels. When these fillers are used to reinforce
thermoplastic resins, increases in modulus, tear resistance, and
abrasion resistance occur while the remaining polymer properties
remain within acceptable levels. When these modified kaolin clay
fillers are used to reinforce liquid polymers, increases in
modulus, tensile strength, hardness, and tear resistance occur
while the remaining properties of the polyurethane remain within
acceptable levels. In all the polymers tested the general level of
performance of the modified kaolins was superior to the unmodified
kaolins.
The foregoing is illustrative only and additional modifications may
be made without departing from the substance of the invention as
defined in the appended claims.
* * * * *