U.S. patent application number 10/600883 was filed with the patent office on 2004-05-27 for colloidally stabilized emulsions.
Invention is credited to Krishnan, Venkataram.
Application Number | 20040101700 10/600883 |
Document ID | / |
Family ID | 27616213 |
Filed Date | 2004-05-27 |
United States Patent
Application |
20040101700 |
Kind Code |
A1 |
Krishnan, Venkataram |
May 27, 2004 |
Colloidally stabilized emulsions
Abstract
A filter substrate impregnated with an emulsion polymer, the
emulsion polymer being substantially devoid of phenolics and
stabilized using a protective colloid.
Inventors: |
Krishnan, Venkataram; (Cary,
NC) |
Correspondence
Address: |
MYERS BIGEL SIBLEY & SAJOVEC
PO BOX 37428
RALEIGH
NC
27627
US
|
Family ID: |
27616213 |
Appl. No.: |
10/600883 |
Filed: |
June 20, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10600883 |
Jun 20, 2003 |
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09657707 |
Sep 8, 2000 |
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6599638 |
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60153441 |
Sep 10, 1999 |
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Current U.S.
Class: |
428/474.4 |
Current CPC
Class: |
Y10T 428/31783 20150401;
Y10T 428/31779 20150401; B01D 39/1623 20130101; B01D 39/18
20130101; Y10T 428/31725 20150401; C08F 2/22 20130101; B01D
2239/0464 20130101 |
Class at
Publication: |
428/474.4 |
International
Class: |
B32B 027/08 |
Claims
That which is claimed is:
1. In a system using phenolics alone or in combination with one or
more other polymers, the improvement comprising using an emulsion
polymer, which includes crosslinkable functionality and which
includes the addition of a protective colloid, to replace or
substantially eliminate or substantially reduce the amount of
phenolics.
2. The system according to claim 1, wherein the protective colloid
is a polyvinyl alcohol.
3. The system according to claim 2, wherein the polyvinyl alcohol
is fully hydrolyzed.
4. The system according to claim 2, wherein the polyvinyl alcohol
is partially hydrolyzed.
5. The system according to claim 1, wherein the crosslinkable
functionality is provided by a self-crosslinking monomer selected
from the group consisting of N-methylol acrylamide, N-methylol
methacrylamide and C.sub.1 to C.sub.4 ethers thereof.
6. A filter comprising a filter substrate impregnated with an
emulsion polymer, the emulsion polymer being substantially devoid
of phenolics and stabilized using a protective colloid.
7. The filter according to claim 6, wherein the protective colloid
is a polyvinyl alcohol.
8. The filter according to claim 7, wherein the polyvinyl alcohol
is fully hydrolyzed.
9. The filter according to claim 7, wherein the polyvinyl alcohol
is partially hydrolyzed.
10. The filter according to claim 6, wherein the emulsion polymer
has crosslinkable functionality provided by a self-crosslinking
monomer selected from the group consisting of N-methylol
acrylamide, N-methylol methacrylamide and C.sub.1 to C.sub.4 ethers
thereof.
11. A filter comprising a filter substrate impregnated with an
emulsion polymer, the emulsion polymer being substantially devoid
of phenolics and stabilized using a polyvinyl alcohol.
12. The filter according to claim 11, wherein the protective
colloid is a polyvinyl alcohol.
13. The filter according to claim 12, wherein polyvinyl alcohol is
fully hydrolyzed.
14. The filter according to claim 12, wherein the polyvinyl alcohol
is partially hydrolyzed.
15. The filter according to claim 11, wherein the emulsion polymer
has crosslinkable functionality provided by a self-crosslinking
monomer selected from the group consisting of N-methylol
acrylamide, N-methylol methacrylamide and C.sub.1 to C.sub.4 ethers
thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The instant application claims priority to U.S. Provisional
Application Serial No. 60/153,441 filed Sep. 10, 1999, the
disclosure of which is incorporated herein by reference in its
entirety.
FIELD AND BACKGROUND OF THE INVENTION
[0002] The present invention relates to colloidally stabilized
emulsions, and particularly colloidally stabilized emulsions having
reduced or no phenolics.
[0003] Phenolics (e.g., phenol-formaldehyde resins), have been used
as adhesives, laminates, molding materials, paints and the. like.
Of particular interest is the use of phenolics as adhesives or
binders in non-woven substrates and papers. More specifically,
phenolics are used in bonding of refractory shapes; fiber bonding
such as in filters; felt bonding; binding of friction products such
as brake pads; in papermaking; in insulation; in roofing products;
and in the binding of foundry sands such as abrasives. Of
particular interest is the use of phenolics in filters. Typically,
the filter is provided by impregnating a continuous roll of paper
with a phenolic resole in the form of an alcohol solution of a
condensate of phenol with formaldehyde. The impregnated and
saturated paper is heated to remove the solvent (alcohol) and
corrugated to increase surface area. The resin is then cured in an
oven and the paper is rolled again. The rolls of the impregnated
paper are provided to the filter manufacturer for completion of the
process which includes pleating and final curing. Such filters are
used in the both air and oil filtering systems in stationary and
mobile internal combustion engines.
[0004] Phenolics, however, have disadvantages such as high phenol
and formaldehyde levels, brittleness when fully cured, slow curing
characteristics, instability and poor shelf life. Moreover,
phenolics, particularly water-based phenolics, are difficult to use
to impregnate fiber substrates. In such impregnation, co-solvents
such as alcohols, must be used and then removed.
[0005] To this end, it would be desirable to substantially
eliminate, or in the alternative, substantially reduce the amount
of phenolics used in products and with substrates wherein phenolics
have traditionally been used as binders or adhesives.
SUMMARY OF THE INVENTION
[0006] The present invention provides compositions wherein
phenolics are substantially eliminated, substantially reduced or
replaced by the use of a colloidally stabilized emulsion polymer.
By using the colloidally stabilized polymer of the invention and
eliminating or replacing the use of phenolics, a wide variety of
polymers having crosslinkable functionality such as provided by
crosslinkers such as epoxies, polyisocyanates, polyurethanes,
N-methylol acrylamide, melaminelformaldehyde and the like, can be
used or blended together while providing properties comparable to
those of polymers having phenolics or of phenolics alone.
[0007] Alternatively, the colloidally stabilized emulsion polymers,
when blended with phenolics, are more stable and compatible with
phenolics as compared to surfactant stabilized emulsions. By
compatibility, it is meant that the emulsion polymers, when blended
with phenolics, remain stable without coagulating or gelling or
becoming a paste over longer periods of time. Thus, the blended
product can be used over extended periods of time without concern
for instability or degradation of performance. Moreover, the need
to use undesirable solvents is eliminated.
DETAILED DESCRIPTION OF THE INVENTION
[0008] The present invention will now be described more fully
hereinafter, in which preferred embodiments of the invention are
shown. This invention may, however, be embodied in different forms
and should not be construed as limited to the embodiments set forth
herein. Rather, these embodiments are provided so that this
disclosure will be thorough and complete, and will fully convey the
scope of the invention to those skilled in the art.
[0009] It is believed that a wide variety of polymers in emulsion
form can be colloidally stabilized, particularly with polyvinyl
alcohol, and optionally blended with phenolics. Specific polymers
in emulsion form include polyvinylacetate,
vinylacetate-ethylene(VAE), vinyl acrylics, epoxies, urethanes,
acrylics, styrene acrylics, butadiene copolymers, and hybrid
emulsions of combinations of the foregoing. The present invention
can be used in systems to replace phenolics wherein phenolics are
used alone, or can be used in systems wherein phenolics are used
with other polymers. In the latter, the phenolics can be
substantially eliminated or can be substantially reduced.
[0010] Of particular interest are emulsion polymers that have high
levels (i.e., greater than about 15 percent by weight) of
nitrogen-containing monomers such as acrylonitrile. By being able
to increase the level of acrylonitrile, properties such as oil and
grease resistance can be improved without adversely affecting the
physical properties contributed to by the phenolics.
[0011] As stated above, it is desirable to substantially eliminate
the use of phenolics; however, phenolics may still be used at a
reduced level. The phenols employed in the formation of the
phenolic resins generally include any phenol which as heretofore
been employed in the formation of phenolic resins and which are not
substituted at either the two ortho positions or at the one ortho
and the para position. Such unsubstituted positions are necessary
for the polymerization reaction to occur. Substituted phenols
employed in the formation of the phenolic resins include: alkyl
substituted phenols, aryl-substituted phenols,
cycloalkyl-substituted phenols, alkenyl-substituted phenols, alkoxy
substituted phenols, aryloxy substituted phenols, and
halogen-substituted phenols. Specific examples of suitable phenols
include: phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol,
3-4-xylenol, 3,4,5-trimethylphenol, 3-ethyl phenol, 3,5-diethyl
phenol, p-butyl phenol, 3,5-dibutyl phenol, p-amyl phenol,
p-cyclohexyl phenol, p-octyl phenol, 3,5-dicyclohexyl phenol,
p-phenyl phenol, p-crotyl phenol, 3,5-dimethoxy phenol,
3,4,5-trimethoxy phenol, p-ethoxy phenol, p-butoxy phenol,
3-methyl4-methyoxy phenol, and p-phenoxy phenol.
[0012] The aldehydes reacted with the phenol component can include
any of the aldehydes heretofore employed in the formation of
phenolic resins and include, for example, formaldehyde, and
benzaldehyde. In general, the aldehydes employed have the formula
R'CHO wherein R' is a hydrogen or hydrocarbon radical of 1-8 carbon
atoms. A particularly preferred phenolic is Resafen 8121 available
from Resana, Sao Paulo, Brazil.
[0013] With respect to the polymers, of particular interest are the
ones with aliphatic conjugated dienes. Suitable aliphatic
conjugated dienes are C.sub.4 to C.sub.9 dienes and include, for
example, butadiene monomers such as 1,3-butadiene,
2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, and the like, such
as described in U.S. Pat. No. 5,900,451 to Krishnan et al., the
disclosure of which is incorporated herein by reference in its
entirety. Blends or copolymers of the diene monomers can also be
used. The aliphatic conjugated diene is used in an amount, based on
total weight of the starting monomers, from about to 1 to about 99
percent by weight, preferably from about 5 to about 30 percent by
weight, and most preferably from about 5 to about 15 percent by
weight. A particularly preferred aliphatic conjugated diene is
1,3-butadiene.
[0014] Suitable non-aromatic unsaturated monocarboxylic ester
monomers include acrylates and methacrylates. The acrylates and
methacrylates may include functional groups such as amino groups,
hydroxy groups, epoxy groups and the like. Exemplary acrylates and
methacrylates include methyl acrylate, methyl methacrylate, ethyl
acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate,
2-ethylhexyl acrylate, glycidyl acrylate, glycidyl methacrylate,
hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl
acrylate, hydroxypropyl methacrylate, isobutyl methacrylate,
hydroxybutyl acrylate, hydroxybutyl methacrylate,
3-chloro-2-hydroxybutyl methacrylate, n-propyl methacrylate and the
like. Exemplary amino-functional methacrylates include t-butylamino
ethyl methacrylate and dimethylamino ethyl methacrylate. Suitable
non-aromatic dicarboxylic ester monomers are dialkyl fumarates,
itaconates and maleates, with the alkyl group having two to eight
carbons, with or without functional groups. Specific monomers
include diethyl and dimethyl fumarates, itaconates and maleates.
Other suitable non-aromatic dicarboxylic ester monomers include
di(ethylene glycol) maleate, di(ethylene glycol) itaconate,
bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate, and
the like.
[0015] The non-aromatic unsaturated mono- or dicarboxylic ester
monomer is used in an amount, based on total weight of the starting
monomers, preferably from about 5 to about 95 percent by weight,
and most preferably from about 20 to about 80 percent by weight. A
particularly preferred non-aromatic unsaturated monocarboxylic
ester monomer is methyl methacrylate.
[0016] Various aromatic unsaturated monomers may be used and
include, but are not limited to, styrene and styrene derivatives
such as alphamethylstyrene, p-methyl styrene, vinyltoluene,
ethylstyrene, tert-butyl styrene, monochlorostyrene,
dichlorostyrene, vinyl benzyl chloride, fluorostyrene,
alkoxystyrenes (e.g., paramethoxystyrene) and the like. Mixtures of
the above may be used. Preferably, styrene is employed. The
aromatic unsaturated monomer is preferably used from about 5 to
about 95 percent based on the total monomer weight, and more
preferably from about 20 to about 80 percent by weight.
[0017] Exemplary nitrogen-containing monomers which may be used
include, for example, acrylonitrile, methacrylonitrile, acrylamide,
and methacrylamide. Acrylonitrile is preferred. Mixtures of the
above may be used. The nitrogen-containing monomer is preferably
used, for example, in an amount ranging from about 5 to about 95
percent based on the total weight of the monomers, and more
preferably from about 15 to about 80 percent by weight.
[0018] Known and conventional protective colloids may be employed
in the emulsion polymer such as partially and fully hydrolyzed
polyvinyl alcohols; cellulose, ethers, e.g., hydroxymethyl
cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, starch
ad start derivatives, carboxymethyl cellulose (CMC); the natural
and synthetic gums, e.g., gum tragacanth and gum Arabic,
polyacrylic acid; acrylates; poly(vinyl alcohol)co(vinyl amine)
copolymers and the like. Partially and fully hydrolyzed polyvinyl
alcohols such as those available from Air Products, sold under the
trademark Airvol.TM. are preferred and are preferably employed from
about 0.1 to about 10 percent based on the weight of the total
monomer, more preferably from about 0.5 to 5 percent, and most
preferably from about 1 to about 4 percent.
[0019] In accordance with the invention, a polymerizable surfactant
which contains ethylenic unsaturation is used and is copolymerized
with the other monomers during emulsion polymerization. As a
result, the surfactant is incorporated in to the backbone of the
polymer and serves to stabilize the latex. Examples of suitable
surfactants containing ethylenic unsaturation are provided in U.S.
Pat. No. 5,296,627 to Tang et al., the disclosure of which is
incorporated by reference herein in its entirety.
[0020] Various polymerizable surfactants are also described in U.S.
Pat. No. 5,900,451 to Krishnan et al. A preferred polymerizable
surfactant is SAM 186N.TM. sold by PPG Industries, Inc. of
Pittsburgh, PA. The polymerizable surfactant may be used in various
amounts. Specifically, the stabilized emulsion polymer may include
between about 0.1 and about 5 percent polymerizable surfactant
based on the monomer weight, more preferably from about 1 to about
4 weight percent, and most preferably from about 2 to about 3
weight percent.
[0021] Conventional surfactants may be used in conjunction with the
surfactant having ethylenic unsaturation described herein. Such
surfactants are preferably of the anionic and nonionic type. The
selection of these surfactants is apparent to one skilled in the
art. Preferred nonionic surfactants are selected from the family of
alkylphenoxypoly(ethyleneoxy) ethanols where the alkyl group
typically various from C.sub.7-C.sub.18 and the ethylene oxide
units vary from 4-100 moles. Various preferred surfactants in this
class include the ethoxylated octyl and nonyl phenols, and in
particular ethoxylated nonyl phenols with a hydrophobic /lipophilic
balance (HLB) of 15-19. Non-APE (alkylphenol ethoxylate)
surfactants such as ethoxylated alcohols, for example, Abex 2525,
are also preferred. Anionic surfactants can be selected from the
broad class of sulfonates, sulfates, ethersulfates,
sulfosuccinates, diphenyloxide disulfonates, and the like, and are
readily apparent to anyone skilled in the art.
[0022] An unsaturated mono- or dicarboxylic acid monomer may also
be included in the stabilized emulsion polymer. These monomers
include, but are not limited to, acrylic acid, methacrylic acid,
itaconic acid, fumaric acid, and maleic acid. Derivatives, blends,
and mixtures of the above may also be used. The unsaturated mono-
or discarboxylic acid monomer may be used in an amount ranging from
about 0 to about 15 percent based on the total monomer weight, and
more preferably from about 0 to about 5 weight percent.
[0023] Additional comonomers can be added to the stabilized
emulsion polymer. Included among such additional comonomers are
monoethylenically unsaturated substituted aliphatic hydrocarbons
such as vinyl chloride, and vinylidene chloride; aliphatic vinyl
esters such as vinyl formate, vinyl propionate, vinyl butyrate,
vinyl versatate and vinyl neodecanoate.
[0024] The stabilized emulsion polymer can include additives to
enhance its various physical and mechanical properties; the
selection of which is readily apparent to one skilled in the art.
For example, crosslinking agents can be included such as vinylic
compounds (e.g., divinyl benzene); allyllic compounds (e.g., allyl
methacrylate, diallyl maleate); multifunctional acrylates (e.g.,
di, tri and tetra (meth)acrylates); self-crosslinking monomers such
as N-methylol acrylamide, N-methylol methacrylamide and C.sub.1 to
C.sub.4 ethers of these monomers respectively (e.g.,
N-iso[butoxymethoxy] methacrylamide), acrylamido glycolic acid and
its esters, and alkyl acrylamido glycolate alkyl ethers (e.g.,
methylacrylamido glycolate methyl ether). The crosslinking agents
can be included in amounts of up to about 15 percent by weight, and
preferably from about 3 to about 8 percent by weight. Additional
monomers such as silanes can be included to improve specific
properties such as latex stability, solvent resistance, as well as
adhesion and strength and are described, for example, in U.S. Pat.
No. 5,830,934 to Krishnan, the disclosure of which is incorporated
herein by reference in its entirety.
[0025] Initiators which facilitate polymerization are typically
used and include, for example, materials such as persulfates,
organic peroxides, peresters, and azo compounds such as
azobis(isobutyronitrile) (AIBN). Persulfate initiators are
preferred and include, for example, potassium persulfate and
ammonium persulfate.
[0026] Reductants may be employed in the polymerization, and are
typically employed in combination with the initiator as part of a
redox system. Suitable reductants include sodium bisulfite,
erythorbic acid, ascorbic acid, sodium thiosulfate, sodium
formaldehyde sulfoxylate (SFS), and the like.
[0027] Other additives which may be used include other natural and
synthetic binders, fixing agents, wetting agents, plasticizers
(e.g., diisodecyl phthalate), softeners, foam-inhibiting agents,
froth aids, other crosslinking agents (e.g., melamine formaldehyde
resin, epoxies, polyisocyanates, etc.), flame retardants,
dispersing agents (e.g., tetrasodium pyrophosphate), pH adjusting
components (e.g., ammonium hydroxide), sequestering or chelating
agents (e.g., ethylene diaminetetraacetic acid (EDTA)) and other
components. The selection of any of these additives is readily
apparent to one skilled in the art.
[0028] One use of the reduced phenolic/butadiene blend is, for
example, the fabrication of filters (e.g., oil filters). In the
first or treating step, a continuous roll of paper is
conventionally impregnated with the binder in the form of an
alcohol solution. When a phenolic is used, the saturated paper is
heated to remove the alcohol (solvent). In the present invention,
the alcohol solution is not needed and this step is eliminated. The
treated paper is then corrugated for the purpose of increasing
surface area. The corrugated sheet is subsequently conveyed through
an oven in order to advance the cure of the resinous impregnate to
a fusible intermediate or B stage, and then the corrugated sheet is
made into a filter.
[0029] The following examples are provided to illustrate the
present invention, and should not be construed as limiting the
scope thereof.
EXAMPLES
Example 1
[0030] A polyvinyl alcohol stabilized butadiene emulsion is
prepared comprising the following:
1 COMPONENT GRAMS Deionized Water 2560.00 EDTA Chelating Agent 0.80
Dowfax 2A1 Surfactant 3.20 Airvol 103 PVOH 32.00 Abex 2525
Surfactant 16.00 Tamol 731A Dispersing Agent 0.80 Sam 186N
Polymerizable Surfactant 16.00 Methoxy polyethylene 32.00 glycol
methacrylate Ammonium Persulfate Initiator 0.80 Butadiene 160.00
Tertiary Dodecyl Mercaptan 6.40 Acrylonitrile 320.00 Styrene 448.00
Acrylic Acid 16.00 Methylmethacrylate 480.00 Butylacrylate 80.00
N-methylol arylamide 64.00 Diammonium Phosphate 4.00
[0031] Wet performance testing was achieved by boiling the test
samples in distilled water for 5 minutes. After the allocated time,
the samples were removed and blotted dry but kept wet during
testing by covering them with moist absorbent towels.
[0032] Tensile data was generated on substrate tested in the
machine direction. Sample size was 1".times.5", with an extension
rate of 10 inches/minute, and samples were tested on an Instron
1125.
[0033] The testing was done on No. 4 Whatman Filter Paper. Each
sheet had a 20 percent add on of the composition of Example 1 is
diluted to 22 percent total solids, was dried for 4 minutes at
225.degree. F. and was allowed to condition overnight in a constant
temperature/humidity room. Then each sheet was cured at 350.degree.
F. in a forced air oven for the cure times of the tables.
2EXAMPLE 1 Wet Tensile Strength Max Load (lbf) Max Stn (elong) Max
Str (psi) Cure Time (std. dev.) (std. dev.) (std. dev.) 1' 11.97
(1.07) 4.027 (0.686) 25.75 (7.25) 2' 13.14 (0.16) 4.210 (0.259)
27.52 (3.1) 3' 14.57 (0.47) 4.487 (0.105) 34.36 (1.25) 4' 14.04
(0.52) 4.257 (0.229) 31.59 (3.17) 5' 14.15 (0.63) 4.211 (0.298)
31.28 (4.50) 10' 13.77 (0.79) 3.846 (0.185) 27.01 (2.74)
[0034]
3EXAMPLE 1 Dry Tensile Strength Max Load (lbf) Max Stn (elong) Max
Str (psi) Cure Time (std. dev.) (std. dev.) (std. dev.) 1' 26.86
(1.57) 2.929 (0.259) 42.61 (9.17) 2' 29.50 (1.22) 3.022 (0.183)
52.95 (4.99) 3' 26.64 (1.17) 2.792 (0.229) 41.61 (6.13) 4' 27.80
(2.03) 2.747 (0.396) 46.08 (11.37) 5' 28.19 (0.68) 2.746 (0.258)
46.41 (6.43) 10' 26.83 (2.01) 2.471 (0.317) 38.80 (9.68)
Examples 2-7
[0035] Various amounts a phenolic available as Resafen 8121 from
Resana, Sao Paulo, Brazil, were added to Example 1, along with
phenolic only, and the tensile strengths measured. The amounts
added are as follows:
4 Example Amt (%) of Example 1 Amt (%) of Phenolic 2 98 2 3 96 4 4
94 6 5 92 8 6 90 10 7 50 50 8 0 100
[0036] The wet tensile strength results are as follows:
5EXAMPLE 2 Cure Time @ Max Load Max elong Max psi % add-on 350 F.
(std. dev.) (std. dev.) (std. dev.) 19.2 1' 12.11 (0.38) 4.394
(0.002) 27.12 (1.40) 19.2 2' 14.84 (0.19) 4.669 (0.105) 36.66
(1.29) 19.2 3' 15.00 (0.81) 4.441 (0.311) 34.61 (4.06) 19.6 4'
14.28 (0.44) 4.393 (0.183) 32.35 (2.13) 19.6 5' 14.38 (0.57) 4.396
(0.183) 32.89 (2.77) 19.6 10' 14.26 (0.58) 3.967 (0.107) 29.32
(1.75)
[0037]
6EXAMPLE 3 Cure Time @ Max Load Max elong Max psi % add-on 350 F.
(std. dev.) (std. dev.) (std. dev.) 19.9 1' 14.12 (0.12) 4.821
(0.28) 36.62 (2.32) 19.9 2' 15.38 (1.14) 4.898 (0.345) 39.14 (6.60)
19.9 3' 14.88 (0.27) 4.271 (0.106) 31.13 (0.99) 19.4 4' 16.35
(1.40) 4.454 (0.529) 38.14 (7.74) 19.4 5' 16.33 (0.83) 4.303
(0.184) 36.45 (5.24) 19.4 10' 16.11 (0.81) 4.027 (0.258) 31.90
(4.20)
[0038]
7EXAMPLE 4 Cure Time @ Max Load Max elong Max psi % add-on 350 F.
(std. dev.) (std. dev.) (std. dev.) 19.4 1' 14.00 (0.55) 4.897
(0.311) 36.02 (3.47) 19.4 2' 17.65 (0.97) 5.081 (0.406) 45.86
(6.85) 19.4 3' 17.52 (0.83) 4.806 (0.433) 43.47 (5.51) 19.3 4'
19.10 (0.93) 4.822 (0.280) 47.26 (4.76) 19.3 5' 18.50 (0.71) 4.577
(0.183) 43.58 (3.37) 19.3 10' 19.14 (1.10) 4.347 (0.313) 41.73
(4.38)
[0039]
8EXAMPLE 5 Cure Time @ Max Load Max elong Max psi % add-on 350 F.
(std. dev.) (std. dev.) (std. dev.) 19.4 1' 13.35 (1.08) 4.578
(0.539) 32.29 (6.96) 19.4 2' 18.63 (0.50) 5.172 (0.175) 49.29
(3.15) 19.4 3' 19.49 (0.95) 4.898 (0.405) 48.49 (5.48) 19.8 4'
20.02 (0.72) 4.668 (0.317) 48.06 (4.52) 19.8 5' 22.05 (0.70) 4.943
(0.335) 57.85 (5.97) 19.8 10' 20.79 (1.49) 4.531 (0.347) 48.06
(8.20)
[0040]
9EXAMPLE 6 Cure Time @ Max Load Max elong Max psi % add-on 350 F.
(std. dev.) (std. dev.) (std. dev.) 19.5 1' 15.84 (0.45) 5.127
(0.259) 42.05 (0.281) 19.5 2' 19.36 (0.62) 5.188 (0.212) 50.93
(4.13) 19.5 3' 20.16 (1.05) 4.623 (0.231) 48.82 (5.46) 19.3 4'
22.59 (0.69) 5.188 (0.212) 60.15 (3.89) 19.3 5' 23.05 (0.93) 4.852
(0.235) 58.31 (5.02) 19.3 10' 22.55 (0.86) 4.578 (0.150) 54.30
(3.40)
[0041]
10EXAMPLE 7 Cure Time @ Max Load Max elong Max psi % add-on 350 F.
(std. dev.) (std. dev.) (std. dev.) 19.9 1' 13.84 (0.99) 5.035
(0.57) 33.45 (4.27) 19.9 2' 21.98 (0.85) 4.669 (0.235) 54.29 (5.16)
19.9 3' 23.79 (1.74) 4.073 (0.347) 52.04 (9.66) 20.1 4' 26.68
(0.78) 3.891 (0.229) 57.95 (4.95) 20.1 5' 15.26 (0.45) 3.526
(0.092) 49.22 (2.34) 20.1 10' 26.06 (2.42) 3.066 (0.525) 44.42
(11.01)
[0042]
11EXAMPLE 8 Cure Time @ Max Load Max elong Max psi Product 350 F.
(std. dev.) (std. dev.) (std. dev.) Resafen 1' 11.72 (1.6.29) 1.466
(0.185) 6.711 (2.118) 8121 2' 13.11 (1.11) 1.190 (0.132) 6.031
(0.937) 3' 13.00 (0.70) 1.283 (0.00) 5.490 (0.509) 4' 9.7222
(1.440) 0.9778 (0.1058) 2.622 (0.618) 5' 12.24 (1.05) 1.097 (0.183)
4.955 (0.621) 10' 12.05 (0.73) 1.160 (0.104) 4.533 (0.598)
Example 9
[0043] A polyvinyl alcohol stabilized emulsion having more
N-methylol acrylamide and no butylacrylate is prepared, comprising
the following:
12 COMPONENT GRAMS Deionized Water 2560.00 EDTA Chelating Agent
0.80 Dowfax 2A1 Surfactant 3.20 Airvol 103 PVOH 32.00 Abex 2525
Surfactant 16.00 Tamol 731A Dispersing Agent 0.80 Sam 186N
Polymerizable Surfactant 16.00 Methoxy polyethylene 32.00 glycol
methacrylate Ammonium Persulfate Initiator 0.80 Butadiene 240.00
Tertiary Dodecyl Mercaptan 6.40 Acrylonitrile 320.00 Styrene 704.00
Acrylic Acid 16.00 Methylmethacrylate 176.00 N-methylol arylamide
112.00 Diammonium Phosphate 4.00
[0044] The wet tensile strength at different cure rates was as
follows:
13 Cure Time 350.degree. F. Lbf (std. dev.) Elong (std. dev.) Psi
(std. dev.) 1' 17.41 (0.42 5.310 (0.299) 45.57 (4.37) 2' 17.58
(1.08) 5.004 (0.212) 44.59 (6.09) 3' 17.47 (0.93) 4.822 (0.279)
41.23 (5.58) 4' 16.89 (0.32) 4.699 (0.106) 38.49 (2.96) 5' 17.32
(0.62) 4.699 (0.212) 40.55 (2.73) 10' 16.99 (0.58) 4.393 (0.183)
38.19 (2.37)
[0045] The above examples illustrate that compositions having no
phenolic or reduced phenolic can provide physical properties
comparable to conventional emulsion compositions having
phenolics.
[0046] The foregoing is illustrative of the present invention and
is not to be construed as limiting thereof. Although a few
exemplary embodiments of this invention have been described, those
skilled in the art will readily appreciate that many modifications
are possible in the exemplary embodiments without materially
departing from the novel teachings and advantages of this
invention. Accordingly, all such modifications are intended to be
included within the scope of this invention as defined in the
claims. Therefore, it is to be understood that the foregoing is
illustrative of the present invention and is not to be construed as
limited to the specific embodiments disclosed, and that
modifications to the disclosed embodiments, as well as other
embodiments, are intended to be included within the scope of the
appended claims. The invention is defined by the following claims,
with equivalents of the claims to be included therein.
* * * * *