U.S. patent application number 10/977988 was filed with the patent office on 2006-05-04 for material compositions for reinforcing ionic polymer composites.
Invention is credited to Lei Jong.
Application Number | 20060094800 10/977988 |
Document ID | / |
Family ID | 36228462 |
Filed Date | 2006-05-04 |
United States Patent
Application |
20060094800 |
Kind Code |
A1 |
Jong; Lei |
May 4, 2006 |
Material compositions for reinforcing ionic polymer composites
Abstract
The invention is related to the preparation of an ionic polymer
composite material comprising a protein and carbohydrate-containing
vegetable material component that serves as a reinforcement agent
for the composite. In preferred embodiments of the invention, the
vegetable seed component is selected from the group of soy spent
flakes, defatted soy flour, or soy protein concentrate with ionic
polymers and the ionic polymer is carboxylated
poly(styrene-butadiene). The composites have a significantly higher
elastic modulus when compared with base polymer.
Inventors: |
Jong; Lei; (Peoria,
IL) |
Correspondence
Address: |
USDA-ARS-OFFICE OF TECHNOLOGY TRANSFER;NATIONAL CTR FOR AGRICULTURAL
UTILIZATION RESEARCH
1815 N. UNIVERSITY STREET
PEORIA
IL
61604
US
|
Family ID: |
36228462 |
Appl. No.: |
10/977988 |
Filed: |
October 29, 2004 |
Current U.S.
Class: |
524/17 |
Current CPC
Class: |
C08L 99/00 20130101;
C08L 13/00 20130101; C08L 89/00 20130101; C08L 89/00 20130101; C08L
89/00 20130101; C08L 2666/06 20130101; Y10T 428/2982 20150115; C08L
2666/08 20130101; C08L 2666/06 20130101; C08L 2666/26 20130101;
Y10T 428/254 20150115; C08L 13/00 20130101; C08L 99/00 20130101;
C08L 51/003 20130101 |
Class at
Publication: |
524/017 |
International
Class: |
C08L 89/00 20060101
C08L089/00 |
Claims
1. A composite comprising (1) an ionic polymer and (2) a protein
and carbohydrate-containing vegetable material.
2. The composite of claim 1, wherein said composite is
characterized by having a higher modulus when compared with said
ionic polymer alone.
3. The composite of claim 1, wherein said vegetable material is an
oilseed residue remaining after removal of oil from said oil
seed.
4. The composite of claim 1, wherein said vegetable material
comprises 10-85% protein and 15-90% carbohydrate.
5. The composite of claim 1, wherein said vegetable material
comprises 20-70% protein and 30-80% carbohydrate.
6. The composite of claim 1, wherein said vegetable material is
selected from the group consisting of soy spent flake, defatted soy
flour, and soy protein concentrate.
7. The composite of claim 1, wherein said ionic polymer contains a
functional group selected from (1) carboxylic acid groups or salts
thereof; (2) sulfonic acid groups or salts thereof; and (3)
mixtures of said carboxylic acids, sulfonic acids or salts
thereof.
8. The composite of claim 7, wherein said ionic polymer comprises
polymerized monomer units, less than 30 weight percent of which
contain said functional group.
9. The composite of claim 8, wherein said ionic polymer comprises
at least 70 weight percent of hydrocarbon monomer units, in
addition to said monomer units containing said functional
group.
10. A method for making a composite comprising: a. mixing (1) an
ionic polymer and (2) a protein and carbohydrate-containing
vegetable material in the presence of water to obtain an aqueous
dispersion; b. removing at least some of said water from said
aqueous dispersion; and c. recovering said composite as a solid
from said aqueous dispersion.
11. The method of claim 10, wherein said removing of water from
said aqueous dispersion in step (b) is conducted by drying.
12. The method of claim 10, wherein said removing of water from
said aqueous dispersion in step (b) is conducted by reducing the pH
of the aqueous dispersion at least until said composite forms a
precipitate, and separating said precipitate from said
dispersion.
13. The method of claim 12, wherein said separating is conducted by
centrifugation.
14. The method of claim 13, wherein additional water is removed
from said composite by drying.
15. The method of claim 10, wherein said vegetable material is an
oilseed residue remaining after removal of oil from said oil
seed.
16. The method of claim 10, wherein said vegetable material is
selected from the group consisting of soy spent flake, defatted soy
flour, and soy protein concentrate.
17. The method of claim 10, wherein said ionic polymer contains a
functional group selected from (1) carboxylic acid groups or salts
thereof; (2) sulfonic acid groups or salts thereof; and (3)
mixtures of said carboxylic acids, sulfonic acids or salts
thereof.
18. The method of claim 17, wherein said ionic polymer comprises
polymerized monomer units, less than 30 weight percent of which
contain said functional group.
19. A product produced by the method of claim 10.
20. A product produced by the method of claim 16.
21. A product produced by the method of claim 17.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention is related to the preparation of an ionic
polymer composition comprising a protein and
carbohydrate-containing vegetable material component, such as soy
spent flakes, defatted soy flour, or soy protein concentrate. The
composite composition is formed by incorporating soy spent flakes,
defatted soy flour, or soy protein concentrate composition with
ionic polymers. The composites have a significantly higher elastic
modulus when compared with base polymer.
[0003] 2. Description of the Prior Art
[0004] Soybean is composed of approximately 20% soybean oil, 8%
hulls, and 72% defatted soy flour. Soybean also contains very
little or no starch. Traditional approaches to the art of soybean
processing involve appropriate preparation of the soybean prior to
solvent extraction. After cracking of the beans and subsequent
separation of the hull from the kernel portions, the cracked
kernels are steam conditioned in large pressure cookers called bean
conditioners that are located upstream from a flaking mill. The
flaking mill functions to squeeze and impart a slight shear to the
steam conditioned kernels resulting in the formation of a thin meal
flake having a diameter of around 0.50 inch and a thickness of
about 10-16 mils. After the meal has been flaked, the traditional
approach is to route the flaked meal to a further heat processing
step or directly to extraction processes. This further heat
processing step may occur within a jacketed screw press conveyor
with steam being injected into the working section of the conveyor.
The flakes are there steam treated and are mechanically worked. The
meal exiting the die orifices of the screw conveyor can best be
described as including dust-like particles that are combined in the
form of a pellet or pellets. After the flaked, steam treated
pellets exit the second heating step, they are sent to extraction
processes including extractors, desolventizer-toasters,
dryer-cooler, meal grinding and meal storage stations. During these
processes, the meal is mixed with a solvent, such as hexane, which
dissolves the soybean oil. The soybean oil-solvent mixture is then
separated from the meal particles. The desired soybean oil may then
be isolated from the solvent solution by conventional techniques
such as distillation, etc. The meal itself is desolventized, dried
and then ground and stored prior to use.
[0005] After the hulls are removed and soybean oil is extracted,
the remaining material is called defatted soy flour, which is
composed of soy protein and soy carbohydrate. (Protein Resources
and Technology, 1978) The defatted soy flour usually contains more
than 50 percent soy protein. The defatted soy flour can further be
processed to separate soy protein from soy carbohydrate. The
separated soy protein usually contains more than 90 percent protein
and is called soy protein isolate. Soy carbohydrate contains a
soluble fraction called whey and an insoluble fraction called spent
flakes. The defatted soy flour can be further subjected to acidic
treatment to separate the whey from the protein and insoluble
carbohydrate. The remaining material after whey removal is called
soy protein concentrate containing more than 70 percent protein.
The protein and insoluble carbohydrate is then further separated by
alkali treatment. An alternative process is to treat defatted soy
flour in alkali condition to separate the insoluble carbohydrate
first and then separate the soy protein from the whey in acidic
condition. If the alkali process is used to separate the spent
flakes (mostly soy carbohydrate), the composition of spent flake is
approximately 12% cellulose, 17% pectin, 14% protein, and 53%
insoluble polysaccharide. It is clear that the composition of soy
carbohydrate is very different from starch that contains mostly
amylose and amylopectin. The defatted soy flour, soy spent flake,
and soy protein concentrate used in this invention can be defined
as the mixture of soy protein and soy carbohydrate that contains
15-90% soy carbohydrate.
[0006] Protein, in general, has been suggested as a component in
rubber latex. For example, U.S. Pat. No. 2,056,958 discloses a
flexible floor covering composition containing casein (milk
protein) and rubber latex. U.S. Pat. No. 2,127,298 shows a
composition consisting of protein, starch, and resinous matter for
applications such as abrasive wheels and paint formulations. This
patent also discloses a composition containing soya bean meal,
lime, sodium fluoride, aluminum stearate, an oleo-resin, isopropyl
alcohol, and dispersed rubber. However, the patent does not teach
the use of soya bean meal in ionic polymers such as carboxylic acid
or sulfonic acid modified rubber for modulus reinforcement. U.S.
Pat. No. 2,931,845 teaches the composition of
rubber-protein-glyoxal for modulus reinforcement. U.S. Pat. No.
3,113,605 teaches using a mixture of protein and carbohydrate in
rubber tires to modify frictional properties, such as anti-skid
resistance. U.S. Pat. No. 5,446,078 discloses using dry reactive
melt blending of protein with polymers containing non-ionic maleic
anhydride to form covalent bonds. The patent does not teach the use
of a combination of soy protein and soy carbohydrate to achieve
synergistic reinforcement effects in a polymer matrix. The reaction
of maleic anhydride with active hydrogen functional groups from
protein can only occur in the dry state, and the alkali neutralized
maleic anhydride groups can not be used because the salt of maleic
anhydride is not reactive. The patent also fails to teach the
formation of intimate ionic complexes in aqueous phase with
neutralized carboxylic acid functional groups, where the
interaction between the reinforcing phase and the polymer matrix is
an ionic interaction instead of covalent bonding. U.S. Pat. No.
6,632,925 teaches using plant protein and a compatibilizer in
polylactide composites. However, polylactide is not an ionic
polymer because it does not contain ionic functional groups along
the polymer backbone for it to be water dispersible. Therefore,
polylactide cannot be used to form a complex with soy products in
alkali water solution and is not suitable as a polymer matrix in
the present invention. U.S. Pat. Nos. 4,812,550 and 4,607,089 teach
the grafting of various reactive monomers onto protein or modified
protein with a free-radical initiator. These patents do not teach
the formation of non-reactive ionic complex to enhance composite
modulus. U.S. Pat. No. 6,291,559 B1 teaches the use of modified or
non-modified soy protein and polyacrylate to thicken paper coating
dispersions. There is no teaching herein of using a combination of
soy protein and soy carbohydrate to achieve synergistic
reinforcement effects in a polymer matrix. U.S. Pat. No. 4,185,146
teaches composite formation by reacting diisocyanate with non-ionic
polyalkylene ether polyol and solid soybean derivatives in a dry
state since the reaction cannot occur in the presence of water.
This patent does not show the formation of an ionic complex in
water phase. None of these references teach the use of soy spent
flakes, defatted soy flour, or soy protein concentrate in the
structural reinforcement of ionic polymer materials.
SUMMARY OF THE INVENTION
[0007] I have now discovered a novel composition of matter
comprising an ionic polymer and a protein and
carbohydrate-containing vegetable material component. Of particular
interest as the vegetable material component is a soy fraction,
such as soy spent flakes, defatted soy flour, or soy protein
concentrate. The resultant composites have a significantly higher
elastic modulus when compared with base polymer, and also have
improved functional properties in comparison with composites of the
base polymer and carbon black.
[0008] In accordance with this discovery, it is an object of the
invention to reinforce ionic polymers with a biodegradable,
vegetable-based material.
[0009] It is a specific object of the present invention to provide
a method for reinforcing ionic polymers by forming a complex of soy
spent flake and ionic polymers in aqueous phase, followed by a
water removal process.
[0010] Further, it is an object of the present invention to provide
a method for reinforcing ionic polymers by forming a complex of
defatted soy flour and ionic polymers in aqueous phase, followed by
a water removal process.
[0011] In addition, it is also an object of the present invention
to provide a method for reinforcing ionic polymers by forming a
complex of soy protein concentrate and ionic polymers in aqueous
phase, followed by a water removal process.
[0012] One embodiment of the present invention includes reinforcing
ionic polymers with soy spent flakes obtained in the alkali
separation process of soy protein isolate.
[0013] Another embodiment of the present invention includes
reinforcing ionic polymers with defatted soy flour obtained in an
organic solvent separation process or a solventless process to
remove soybean oil from soybean flakes.
[0014] An additional embodiment of the present invention includes
reinforcing ionic polymers with soy protein concentrate obtained in
an acidic separation process of defatted soy flour to remove
soluble whey.
[0015] The present invention also includes ionic polymers that
either are synthesized by a copolymerization process or are
modified by a polymer modification process to include ionic
functional groups for forming an aqueous dispersion and forming
complexes with soy spent flake or defatted soy flour.
BRIEF DESCRIPTION OF THE DRAWING
[0016] FIG. 1 is a plot of shear elastic modulus vs. temperature of
composites filled with different amount of defatted soy flour (FIG.
1A), soy spent flake (FIG. 1B), soy protein concentrate (FIG. 1C),
or carbon black N339 (FIG. 1D). The significant extent of
reinforcement is demonstrated when the composite moduli are
compared with the modulus of ionic polymer with 0% of fillers.
[0017] FIG. 2 is a plot of shear elastic modulus of composites
filled with different amounts of soy spent flakes, defatted soy
flour, soy protein concentrate, soy protein isolate, or carbon
black. The plot demonstrates a significant extent of reinforcement
in the rubbery region occurring in composites reinforced with soy
spent flakes, defatted soy flour, or soy protein concentrate when
compared with the comparative examples of soy protein isolate- or
carbon black-reinforced composites.
[0018] FIG. 3 is a plot of shear elastic moduli of composites
filled with 20% defatted soy flour (FIG. 3A), soy spent flakes
(FIG. 3B), soy protein concentrate (FIG. 3C), or carbon black (FIG.
3D). The plot demonstrates the change of moduli with eight cycles
of dynamic strain at 1 Hz and 140.degree. C. (rubbery region).
[0019] FIG. 4 is a plot of shear elastic moduli of composites
filled with 30% of defatted soy flour (FIG. 4A), soy spent flakes
(FIG. 4B), soy protein concentrate (FIG. 4C), or carbon black (FIG.
4D). The plot demonstrates the change of elastic moduli with eight
cycles of dynamic strain at 1 Hz and 140.degree. C. (rubbery
region)
[0020] FIG. 5 is a plot of composites filled with different amounts
of defatted soy flour (FIG. 5A), soy spent flakes (FIG. 5B), soy
protein concentrate (FIG. 5C), or carbon black N339 (FIG. 5D). The
plot demonstrates the stress-strain behavior at 50 mm/min and
23.degree. C. (transition zone, T.sub.g+13.degree. C.).
DETAILED DESCRIPTION OF THE INVENTION
[0021] Sources of the protein and carbohydrate-containing vegetable
material for use herein include fractions or components of
vegetable seeds, particularly oil seeds, that have been processed
to remove substantially all of the oil. Typical oil processing
procedures include pressing and/or extraction with aqueous or
organic solvents, or with supercritical fluids. The residues
resulting from oil recovery steps of vegetable seeds may include
press cakes, meals, flakes, flours, protein concentrates and the
like. The residues for use herein will contain at least 10%
protein, preferably at least 20% protein, and less than 85%
protein, preferably less than 70% protein, and 15-90% carbohydrate,
preferably 30-80%, all on a dry weight basis. Examples of suitable
oilseeds include soybean, cottonseed, linseed, safflower,
sunflower, lupine, sesame, tung, canola (rapeseed) and peanut. Of
particular interest are soybeans, and especially the soy spent
flake, defatted soy flour, and soy protein concentrate.
[0022] Soy spent flakes are the residue remaining after oil,
protein, and whey extraction of flaked soybeans. When the oil is
solvent-extracted, the flakes are also treated to remove residual
solvent. Protein content of soy spent flakes is typically about
15%, on a dry weight basis.
[0023] Defatted soy flour is the ground, screened, graded product
obtained after extracting most of the oil from sound, clean,
dehulled soybeans. Soy flour is produced from finely grinding the
defatted soy flakes so that most of it passes through a number 100
screen. Grits are similarly produced, but constitute a coarser
fraction than the flour. Protein contents of defatted soy flakes
and grits ranges from about 40-60%, dry weight basis.
[0024] Soy protein concentrate is prepared from high quality sound,
clean, dehulled soybean seeds by removing most of the oil and
water-soluble, non-protein constituents. Soy protein concentrate
contains at least 65% protein, dry weight basis.
[0025] The preferred class of ionic polymers to be reinforced by
the aforementioned vegetable material are polymers with a glass
transition temperature below 150.degree. C.
[0026] Ionic polymers intended for use herein include both
synthetic and natural polymers containing a sufficient number of
ionic functional groups capable of dispersing the polymer in water
to form an aqueous emulsion. Examples of suitable ionic polymers
are carboxylated poly(styrene-butadiene), poly(ethylene-acrylic
acid), poly(butadiene-acrylic acid), sulfonated
ethylene-propylene-diene terpolymer, poly(ethylene-methacrylic
acid) . . . etc. Other examples are carboxylic acid-modified
urethane rubber, carboxylic acid-modified polybutadiene, carboxylic
acid-modified polyisoprene, carboxylic acid-modified nitrile
butadiene rubber, carboxylic acid-modified butyl rubber, carboxylic
acid-modified fluorine-based thermoplastic elastomer, carboxylic
acid-modified silicone rubber, carboxylic acid-modified
polyester-based thermoplastic elastomer, carboxylic acid-modified
polyamide-based thermoplastic elastomer, carboxylic acid-modified
fluororubber, carboxylic acid-modified epichlorohydrin rubber,
carboxylic acid-modified vinyl chloride-based thermoplastic
elastomer, carboxylic acid-modified norbornene rubber, carboxylic
acid-modified styrene-based thermoplastic elastomer, carboxylic
acid-modified olefin-based thermoplastic elastomer, carboxylic
acid-modified urethane-based thermoplastic elastomer, and
carboxylic acid-modified polysulfide rubber.
[0027] Anionic polymers made by the copolymerization of monomers
containing carboxylic acid or sulfonic acid groups are suitable to
form complexes with soy spent flake, defatted soy flour, or soy
protein concentrate. Examples of carboxylic acid-containing
monomers are methacrylic acid, acrylic acid, fumaric acid, maleic
acid, tartaric acid, itaconic acid, and crotonic acid. An examples
of sulfonic acid-containing monomers is ethylene sulfonic acid.
[0028] Anionic polymers made by chemical modification of existing
polymers are also suitable for this application. Examples of this
class of ionic polymers are the reaction products of alkali
hydrolysis of esters of the aforementioned carboxylic
acid-containing monomers. Another class of ionic polymers results
from the direct sulfonation of aromatic and/or unsaturated
polymers. Other carboxylic acid-modified polymers are carboxylic
acid-modified liquid isoprene rubber latex, carboxylic
acid-modified isoprene rubber latex, carboxylic acid-modified
styrene-butadiene rubber latex, carboxylic acid-modified natural
rubber latex, carboxylic acid-modified butadiene rubber latex,
carboxylic acid-modified acrylonitrile-butadiene rubber latex,
carboxylic acid-modified chloroprene latex, carboxylic
acid-modified acryl rubber latex, carboxylic acid-modified
acrylate-butadiene rubber latex, carboxylic acid-modified vinyl
acetate rubber latex.
[0029] Copolymerizable ethylenically unsaturated monomers useful in
producing the carboxylic acid functional copolymer are monomers
containing carbon-to-carbon, ethylenic unsaturation, including
vinyl monomers, acrylic monomers, allylic monomers, acrylamide
monomers, and mono- and dicarboxylic unsaturated acids. Exemplary
monomers are described, below. Vinyl esters include vinyl acetate,
vinyl propionate, vinyl butyrates, vinyl benzoates, vinyl isopropyl
acetates and similar vinyl esters. Vinyl halides include vinyl
chloride, vinyl fluoride, and vinylidene chloride. Vinyl aromatic
hydrocarbons include styrene, methyl styrenes and similar lower
alkyl styrenes, chlorostyrene, vinyl toluene, vinyl naphthalene,
divinyl benzoate, and cyclohexene. Vinyl aliphatic hydrocarbon
monomers include alpha olefins such as ethylene, propylene,
isobutylene, and cyclohexene as well as conjugated dienes such as
1,3 butadiene, methyl-2-butadiene, 1,3-piperylene, 2,3-dimethyl
butadiene, isoprene, cyclopentadiene, and dicyclopentadiene. Vinyl
alkyl ethers include methyl vinyl ether, isopropyl vinyl ether,
n-butyl vinyl ether, and isobutyl vinyl ether. Acrylic monomers
include monomers such as lower alkyl esters of acrylic or
methacrylic acid having an alkyl ester portion containing between 1
to 12 carbon atoms as well as aromatic derivatives of acrylic and
methacrylic acid. Useful acrylic monomer include, for example,
acrylic and methacrylic acid, methyl acrylate and methacrylate,
ethyl acrylate and methacrylate, butyl acrylate and methacrylate,
propyl acrylate and methacrylate, 2-ethyl hexyl acrylate and
methacrylate, cyclohexyl acrylate and methacrylate, decyl acrylate
and methacrylate, isodecylacrylate and methacrylate, benzyl
acrylate and methacrylate, and various reaction products such as
butyl, phenyl and cresyl glycidyl ethers reacted with acrylic and
methacrylic acids, hydroxyl alkyl acrylates and methacrylates such
as hydroxyethyl and hydroxypropyl acrylates and methacrylates.
[0030] Carboxylic acid functional polymers contemplated herein
comprise copolymerized monomers including carboxylic acid monomers
that may include methacrylic acids, acrylic acid, and olefinic
unsaturated acids. Acrylic acids include acrylic and methacrylic
acid, ethacrylic acid, alpha-chloracrylic acids, alpha-cyanoacrylic
acid, crotonic acid, and beta-acryloxy propionic acid. Olefinic
unsaturated acids include fumaric acid, maleic acid or anhydride,
itaconic acid, citraconic acid, mesaconic acid, muconic acid,
glutaconic acid, aconitic acid, hydrosorbic acid, sorbic acid,
alpha-chlorosorbic acid, cinnamic acid, and hydromuconic acid. On a
weight basis, the carboxylic acid functional polymer contains at
least 1% copolymerized carboxyl functional monomers and preferably
between 5% and 15% carboxylic acid monomers, with the balance being
other ethylenically unsaturated monomers. Carboxylic acid
functional polymers preferably are produced in bulk, either in
solvent or by emulsion/suspension polymerization.
[0031] One class of carboxyl functional polymer comprises a
polyester polymer. Polyester polymers comprise the esterification
products of glycols, diols, or polyols with excess equivalents of
dicarboxylic acid or polycarboxylic acids. Linear aliphatic glycols
are esterified with greater molar amounts of aromatic dicarboxylic
acid and/or linear saturated dicarboxylic acid having between 2 and
10 linear carbon atoms such as adipic, azelaic, succinic, glutaric,
pimelic, suberic or sebacic acid to produce polyesters.
Additionally, larger dicarboxylic acids, such as the dimer fatty
acids, dodecanedioic acid and the like can be used. Preferred and
commercially available linear saturated dicarboxylic acids are
adipic, azelaic, dodecane-dicarboxylic acid and the dimer fatty
acids. Aromatic dicarboxylic acids (anhydrides) include phthalic,
isophthalic, terephthalic, and tetrahydrophthalic. Minor amounts of
polyfunctional acid such as trimelletic acid can be added. Suitable
glycols include linear aliphatic glycols having 2 to 8 carbon
atoms, such as 1,3- or 1,4-butylene glycol, 1,6-hexane diol,
neopentyl glycol, propylene glycol, ethylene glycol and diethylene
glycol, propylene, and dipropylene glycol, and similar linear
glycols. Additionally, the larger diols such as hydrogenated
bisphenol A, and the C.sub.10 to C.sub.18 diols are suitable.
Preferred glycols are hydrophobic glycols such as neopentyl glycol
and 1,6-hexane diol and hydrogenated bisphenol A. Minor amounts of
polyols can be used such as glycerol, pentaerythritol,
dipentaerythritol, or trimethylol ethane or propane. The molar
deficiency of the glycol over the greater molar amounts of aromatic
and linear saturated dicarboxylic acid is between about 1 and 50
and preferably between about 5% and 20%. Hence, the polyester
contains a considerable excess of unreacted carboxylic groups to
provide a carboxyl polyester having an Acid No. between 5 and 300
and preferably between 20 and 100. Glycol can be esterified with
minor amounts of up to about 20% by weight of unsaturated
dicarboxylic acids (anhydrides) including maleic, fumaric or
itaconic acids; or monocarboxylic acids such as acetic, benzoic,
and higher chain aliphatic and aromatic acids up to about 12 carbon
atoms. The polyester component can be produced by solvent or bulk
polymerization although bulk polymerization is preferred. The raw
materials can be charged in bulk and esterification polymerized at
temperatures typically between 170.degree. C. to 240.degree. C.,
although moderately higher or lower temperatures can be utilized
satisfactorily with appropriate adjustment in the reaction time as
within the skill of a person in the art. An esterification catalyst
can be used, typically at less than 1% levels based on charge, such
as an organic tin compound or organic titanate.
[0032] Another class of carboxyl polymer contemplated for use in
this invention is a carboxyl functional polymer comprising acrylic
grafted polyester. Grafted copolymers of polyester and acrylics can
be produced by free-radical polymerization of ethylenically
unsaturated monomers, including acrylic and carboxyl monomers, in
the presence of a preformed molten or fluid polyester at
temperatures sufficient to induce addition copolymerization of the
monomers along with some grafting onto the polyester backbone. The
acrylic polymer component of the acrylic grafted polyester
comprises in-situ copolymerized ethylenically unsaturated monomers,
including acrylic monomers and carboxyl monomers, along with other
ethylenically unsaturated monomers if desired. Acrylic monomers
include monomers such as lower alkyl esters of acrylic or
methacrylic acid having an alkyl ester portion containing between 1
to 12 carbon atoms as well as aromatic derivatives of acrylic and
methacrylic acid. Useful acrylic monomers include, for example,
acrylic and methacrylic acid, methyl acrylate and methacrylate,
ethyl acrylate and methacrylate, butyl acrylate and methacrylate,
propyl acrylate and methacrylate, 2-ethyl hexyl acrylate and
methacrylate, cyclohexyl acrylate and methacrylate, decyl acrylate
and methacrylate, isodecylacrylate and methacrylate, benzyl
acrylate and methacrylate, and various reaction products such as
butyl, phenyl, and cresyl glycidyl ethers reacted with acrylic and
methacrylic acids, hydroxyl alkyl acrylates and methacrylates such
as hydroxyethyl and hydroxypropyl acrylates and methacrylates.
Acrylic acids include acrylic and methacrylic acid, ethacrylic
acid, alpha-chloroacrylic acid, alpha-cycanoacrylic acid, crotonic
acid, beta-acryloxy propionic acid, and beta-styryl acrylic acid.
Other ethylenically unsaturated monomers have been previously
described herein. The copolymerized monomers for the acrylic
component of the acrylic grafted polyester comprises copolymerized
monomers, on a weight basis between 1% and 100% acrylic monomer,
between 0% and 30% carboxylic acid containing monomer, with the
balance being other ethylenically unsaturated monomers. Preferred
acrylic components comprise on a weight basis between 20% and 90%
acrylic monomer, between 5% and 15% carboxyl acid monomer, with the
balance being other ethylenically unsaturated monomers. It should
be noted that the carboxyl functionality could be part of the
polyester polymer or part of the grafted acrylic polymer or both
polymers. The acrylic grafted polyester preferably comprises by
weight between 10% and 70% polyester polymer component and between
30% and 90% acrylic polymer component.
[0033] Another class of carboxyl polymers for use herein is
carboxyl functional urethanes that can be produced by co-reacting
diisocyanates with a diol or a polyol and a hydroxyl acid. Linear
polyurethanes are obtained from difunctional reactants while
branched polyurethanes are produced from the combination of
difunctional and higher functional reactants. Urethanes for
ionomeric crosslinking in composites can be prepared from any of
several available aromatic, aliphatic, and cycloaliphatic
diisocyanates and polyisocyanates. Suitable polyisocyanates can be
di- or triisocyanates such as, for example, 2,4- and 2,6-tolylene
diisocyanates, phenylene diisocyanate; hexamethylene or
tetramethylene diisocyanates, 1,5-naphthalene diisocyanate,
ethylene or propylene diisocyanates, trimethylene or triphenyl or
triphenylsulfone triisocyanate, and similar di- or triisocyanates
or mixtures thereof. The polyisocyanate can be generally selected
from the group of aliphatic, cyclo-aliphatic and aromatic
polyisocyanates such as for example hexamethylene 1,6-diisocyanate,
isophorone diisocyanate, diphenylmethane diisocyanate 2,4-tolylene
diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof,
polymethylene polyphenyl polyisocyanate, or isocyanate functional
prepolymers. Preferred diisocyanates include isophorone
diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and
the like.
[0034] A wide variety of diols and polyols can be used to prepare
urethanes with a wide range of properties. Polyethers, such as the
polytetramethylene oxides can be used to impart flexibility as well
as the polyethylene oxides and polypropylene oxides. Simple diols
that can be used include neopentyl glycol, 1,6 hexane diol, and
longer chain diols having 12-, 14- and higher carbon chains.
Branching can be introduced with polyols such as trimethylol
propane and pentaerythritol. Hydroxyl functional polyesters and
various other hydroxyl functional polymers are also suitable.
Useful polyols preferably contain two, three, or four hydroxyl
groups for co-reaction with the free isocyanate groups. Useful
polyols are: diols such as ethylene glycol, propylene glycols,
butylene glycols, neopentyl glycol, 14-cyclohexane dimethanol,
hydrogenated bisphenol A, and the like; triols such as glycerol,
trimethylol propane, trimethylol ethane; tetrols such as
pentaerythritol; hexols such as sorbitol, dipentaerythritol, and
the like; polyether polyols produced by the addition of alkylene
oxides to polyols; polycaprolactone polyols produced by the
addition of monomeric lactones to polyols, such as caprolactone;
and hydroxyl terminated polyesters.
[0035] The polyurethane copolymers suitable for use herein further
contain a co-reacted hydroxy-acid material. The hydroxy-acid
contains at least one reactive hydroxy group for co-reacting with
the isocyanate during polymer synthesis and at least one
non-reactive carboxy group which is essentially non-reactive to the
isocyanate groups during the polymer synthesis. Examples of alkyl
acids are 2,2 dihydroxymethyl propionic acid, 2,2-dihydroxymethyl
butyric acid, glycolic acid, and the like; other acids are lactic
acid, 12-hydroxy stearic acid, the product of the Diels-Alder
addition of sorbic acid to di-(2-hydroxyethyl) maleate or fumarate,
or low molecular weight (300 to 600) precondensates of polyols with
tribasic acids such as trimelletic anhydride or ricinoleic acid.
Acid functionality can be introduced with materials like
12-hydroxystearate, dimethylolpropionic acid, and various other
hydroxy acids. Monohydroxyl acids will position the acid
functionality at the end of the chain, while the diol acids will
randomly place the acid groups at intermediate positions within the
chain. When isocyanates are reacted with diols and polyols of
various types, the reaction rate may be enhanced by the use of
catalysts. Common isocyanate catalysts are suitable, and examples
include dibutyltindilaurate, dibutyltinoxide, and the like.
[0036] A different class of ionic polymer that is also suitable for
use in the current invention is the sulfonic acid-containing
polymers. These polymers can be made by copolymerizing a sulfonic
acid-containing monomers. Typical examples of sulfonate-containing
monomers suitable in the practice of the present invention include
alkali metal salts of styrene sulfonic acid, vinyl sulfonate, and
acryloamidopropane sulfonic acid. Sulfonic acid groups can also be
introduced by the direct sulfonation of aromatic and/or unsaturated
polymers. For example, the sulfonation can be made using acetyl
sulfate or a combination of acetic anhydride and sulfuric acid at
ambient or elevated temperatures. After the sulfonation, the
reaction can be terminated by alcohol or water.
[0037] Still another class of ionic polymer is the non-covalent
complex of hydrophobic polymer with surfactants that contain
carboxylic acid or sulfonic acid functional groups. The hydrophobic
polymers suitable for this class of complex are the aforementioned
ionic polymers without the incorporation of ionic monomers or ionic
functional groups. Examples of surfactants suitable for the
formation of the complex are fatty acids and their salts such as
lauric acid, mystric acid, palmitic acid, stearic acid, oleic acid,
linoleic acid, linolenic acid, or a mixture thereof. The examples
of sulfonic acid containing surfactants are linear alkylbenzene
sulfonic acid, fatty alcohol sulfate, fatty alcohol ether sulfate,
or their mixtures.
[0038] The level of addition of the vegetable material may be
greater than 2.5%, 5%, 10%, 15%, 20%, 30%, 40%, or 50% of the total
amount of vegetable material and ionic polymer on a dry weight
basis. Typically, the level of addition will be in the range of
about 10-30% by weight of the total of these two components.
[0039] For the polymer material reinforcement, it is necessary for
the reinforcing material to be more rigid than the polymer to be
reinforced. The soy products described herein, including soy spent
flake, defatted soy flour, and soy protein concentrate yield
composites having high elastic modulus and improved stress-strain
behavior, and therefore are suitable for such applications.
Relative to composites that are reinforced with carbon black or
with vegetable material comprised of at least 90% (dry weight
basis) of protein, the composites of this invention are
characterized by a higher elastic modulus.
[0040] As previously mentioned, soy spent flakes obtained from the
alkali separation process are suitable for use in the current
invention. The alkali separation process involves the dispersion of
defatted soy flour in water at alkali pH that is adjusted using
strong base, such as sodium hydroxide or potassium hydroxide. After
heat treatment at 40-60.degree. C. to disperse the soy protein, the
spent flakes can be separated by centrifugation. The dispersed soy
protein remains in the aqueous phase, while spent flakes
precipitate under the centrifugal force.
[0041] Defatted soy flour obtained from either an organic solvent
separation process or from a solventless process is suitable for
use in the current invention. For example, defatted soy flour
obtained from hexane extraction process of de-hulled and flaked
soybean to remove soybean oil, as described previously, may be
used. Soy protein concentrate obtained from the acidic separation
process of defatted soy flour by removing the water-soluble whey is
also suitable for use herein.
[0042] In making the composites of the invention, the vegetable
matter is first dispersed in water under alkaline conditions so as
to solubilize the protein. The pH conditions of the dispersion
should be adjusted to at least about pH 7.5, and more typically pH
9.0 or greater. Thereafter, the ionic polymer is thoroughly blended
into the dispersion at ambient temperature. The mixing time is
usually less than 30 minutes due to the low viscosity of the
mixture. The dispersion is then dewatered and the complex
solidified by any appropriate means as known in the art. For
instance, the dispersion can be casting into a film, bar, or the
like, during which process the water is expelled from the composite
during setting of the cast. In another embodiment of the invention,
the dispersion can be acidulated so as to coagulate the composite
material. The acid-coagulated co-precipitate is then separated from
the aqueous medium by centrifugation, screening, or the like. The
coagulated material may further be dewatered by banding on a rubber
mill or aromatic fluid bed dryer at elevated temperatures.
[0043] Other components may be added to the resultant composite
material prior to or after solidification, depending on the
prospective end-use application. These components include, but are
not limited to, biocide, colorant, surfactant, other filler,
anti-foam agent, cross-linking agent, UV-protectants, plasticizer,
oil, antioxidant, softening agent, cross-linking or vulcanization
accelerator, and the like. It is also understood that proportions,
components, and the manner and order of adding the components may
be varied over a wide range depending on a number of factors such
as the end-use application for the resulting formulation.
[0044] Biocides are important for stability of the aqueous
dispersion of vegetable matter and/or ionic polymer if the
dispersion is to be held for a substantial period of time prior to
processing. Biocides may also be important because of residual
moisture that may be initially present after solidification of the
complex, and also due to the potential for hydroscopic absorption
of moisture during storage and use of the bulk material or end
product. The biocide can be present in any effective amount to
improve the stability of aqueous dispersion or product, typically,
an amount exceeding about 0.1% by weight, and usually in the range
of 0.1% to about 1% on a dry weight basis of the solid complex. The
biocide is preferably added during the mixing process of vegetable
material with the aqueous dispersion of ionic polymers. Generally,
anionic and non-ionic types of biocide are preferred.
[0045] Examples of anionic biocides include: anionic potassium
N-hydroxymethyl-N-methyl-dithiocarbamate; an anionic blend of
N-hydroxymethyl-N-methyl dithiocarbamate (80 percent by weight) and
sodium 2-mercapto benzothiazole (20 percent by weight); an anionic
blend of sodium dimethyl dithiocarbamate, 50 percent by weight, and
(disodium ethylenebis-dithiocarbamate), 50 percent by weight; an
anionic blend of Nomethyldithiocarbamate, 60 percent by weight, and
disodium cyanodithioimidocarbonate, 40 percent by weight; an
anionic blend of methylene bis-thiocyanate (33 percent by weight),
sodium dimethyl-dithiocarbamate (33 percent by weight), and sodium
ethylene bisdithiocarbamate (33 percent by weight); sodium
dichlorophene (G-4-40 available from Givaudan Corporation); and the
like, as well as mixtures thereof.
[0046] Examples of nonionic biocides include:
2-hydroxypropylmethane thiosulfonate; 2-(thio cyanomethyl
thio)benzothiazole; methylene bis(thiocyanate);
2-bromo-4'-hydroxyacetophenone; 1,2-dibromo-2,4-dicyano-butane;
2,2-dibromo-3-nitropropionamide; N-.alpha.-(1-nitroethyl
benzylethylene diamine); dichlorophene (6-4 available from Givaudan
Corporation); 3,5-dimethyl
tetrahydro-2H-,1,3,5-thiadiazine-2-thione; a nonionic blend of a
sulfone, such as bis(trichloromethyl)sulfone and methylene
bisthiocyanate; a nonionic blend of methylene bisthiocyanate and
bromonitrostyrene; a nonionic blend of
2-(thiocyanomethylthio)benzothiazole (53.2 percent by weight) and
2-hydroxypropyl methanethiosulfonate (46.8 percent by weight); a
nonionic blend of methylene bis(thiocyanate) 50 percent by weight
and 2-(thiocyanomethylthio) benzothiazole, 50 percent by weight; a
nonionic blend of 2-bromo-4'-hydroxyacetophenone (70 percent by
weight) and 2-(thiocyanomethylthio)benzothiazole (30 percent by
weight); a nonionic blend of
5-chloro-2-methyl-4-isothiazoline-3-one (75 percent by weight) and
2-methyl-4-isothiazolin-3-one (25 percent by weight), and the like,
as well as mixtures thereof.
[0047] Examples of cationic biocides include: cationic
poly(oxyethylene (dimethylamino)-ethylene (dimethylamino) ethylene
dichloride); a cationic blend of methylene bisthiocyanate and
dodecyl guanidine hydrochloride; a cationic blend of a sulfone,
such as bis(trichloromethyl) sulfone and a quaternary ammonium
chloride; a cationic blend of methylene bis thiocyanate and
chlorinated phenols, and the like, as well as mixtures thereof.
[0048] Crosslinking agents that are frequently used in rubbers are
elemental sulfur and disulfides such as alkylphenol disulfides,
N,N'-caprolactam disulfides, 4,4'-dithiobismorpholine,
dipentamethylene thiuram disulfide, dipentamethylene thiuram
hexasulfide, dipentamethylene thiuram tetrasulfide,
dipentamethylene thiuram monosulfide, tetrabutyl thiuram disulfide,
tetraethyl thiuram disulfide, tetramethyl thiuram disulfide,
tetramethyl thiuram monosulfide, and the like. Various peroxide
compounds are also used, such as dicumyl peroxide,
t-butylperoxy-diisobutyl benzene, di(2,4-dichloro benzoyl)
peroxide, dibenzoyl peroxide, t-butylperoxy benzoate,
1,1-di(t-butylperoxy)-3,3,5-trimethyl-cyclohexane,
2,5-dimethyl-2,5-di(t-butylperoxy) hexane,
2,5-dimethyl-2,5-di(t-butylperoxy) hexyne-3, and the like.
[0049] The following examples are provided to illustrate preferred
embodiments of the invention and are not intended to restrict the
scope thereof. Unless otherwise indicated, all percentages are
expressed as weight percentages.
[0050] All references disclosed herein or relied upon in whole or
in part in the description of the invention are incorporated by
reference.
EXAMPLE 1
Preparation of 10% Soy Spent Flakes Composite.
[0051] Soy spent flakes were obtained by dispersing 154 gm of
defatted soy flour (Nutrisoy 7B, ADM) in 810 gm of water and
cooking at pH 10 and 45.degree. C. for 1 hour. The resulting
dispersion was then centrifuged at 3000 rpm and 15.degree. C. for
10 minutes. Soy protein dispersion was removed and the spent flakes
were washed with water and centrifuged again to obtain spent flakes
with a solids content of 12.2%. A 131.1 gm sample of a 7.6% aqueous
dispersion of spent flakes was mixed with 177.3 gm of 50.7%
carboxylated styrene-butadiene latex (CP620NA, Dow), and the pH was
adjusted to 9. The dispersion was first dried at 75.degree. C. to a
moisture content of 3-4% and then dried at 140.degree. C. to a
moisture content of less than 1%. After drying, the shear elastic
moduli from -40.degree. C. to 140.degree. C. were measured by a
dynamic mechanical method at 1 rad/s and 0.05% strain (Rheometric
ARES). The effect of dynamic strain is measured at 1 Hz. The
stress-strain properties are measured by INSTRON at 50 mm/min and
23.degree. C. The mechanical properties of this composite are shown
in FIG. 1B, FIG. 2, and FIG. 5B.
EXAMPLE 2
Preparation of 15% Soy Spent Flakes Composite.
[0052] Soy spent flakes were obtained by dispersing 250 gm of
defatted soy flour (Nutrisoy 7B, ADM) in 1300 gm of water and
cooking at pH 10 and 45.degree. C. for 1 hour. The resulting
dispersion was then centrifuged at 3000 rpm and 15.degree. C. for
10 minutes. Soy protein dispersion was removed and the spent flakes
were washed with water and centrifuged again to obtain spent flakes
with a solids content of 9.4%. A 209.7 gm sample of a 7.2% aqueous
dispersion of spent flakes was mixed with 167.5 gm of 50.7%
carboxylated styrene-butadiene latex (CP620NA, Dow) and the pH
adjusted to 9. The dispersion was dried in the same manner as that
in Example 1. After drying, the mechanical properties were measured
as described in Example 1. The mechanical properties of this
composite are shown in FIG. 1B, FIG. 2, and FIG. 5B.
EXAMPLE 3
Preparation of 20% Soy Spent Flakes Composite.
[0053] Soy spent flakes were obtained by dispersing 154 gm of
defatted soy flour (Nutrisoy.RTM. 7B, ADM) in 810 gm of water and
cooked at pH 10 and 45.degree. C. for 1 hour. The resulting
dispersion was then centrifuged at 3000 rpm and 15.degree. C. for
10 minutes. Soy protein dispersion was removed and the spent flakes
were washed with water and centrifuged again to obtain spent flakes
with a solids content of 12.2%. A 382.5 gm sample of a 5.2% aqueous
dispersion of spent flakes was mixed with 157.51 gm of 50.7%
carboxylated styrene-butadiene latex (CP620NA, Dow) and the pH
adjusted to 9. The dispersion was dried in the same manner as that
in Example 1. After drying, the mechanical properties were measured
as described in Example 1. The mechanical properties of this
composite are shown in FIG. 1B, FIG. 2, FIG. 3B, and FIG. 5B.
EXAMPLE 4
Preparation of 30% Soy Spent Flakes Composite.
[0054] Soy spent flakes were obtained by dispersing 250 gm of
defatted soy flour (Nutrisoy.RTM. 7B, ADM) in 1300 gm of water and
cooked at pH 10 and 45.degree. C. for 1 hour. The resulting
dispersion was then centrifuged at 3000 rpm and 15.degree. C. for
10 minutes. Soy protein dispersion was removed and the spent flakes
were washed with water and centrifuged again to obtain spent flakes
with a solids content of 9.4%. A 327.4 gm sample of a 7.3% aqueous
dispersion of spent flakes was mixed with 111.5 gm of 50.7%
carboxylated styrene-butadiene latex (CP620NA, Dow) and the pH
adjusted to 9. The dispersion was dried in the same manner as that
in Example 1. After drying, the mechanical properties are measured
as described in Example 1. The mechanical properties of this
composite are shown in FIG. 1B, FIG. 2, FIG. 4B, and FIG. 5B.
EXAMPLE 5
Preparation of 10% Defatted Soy Flour Composite.
[0055] A 10.4-gm sample of 96% defatted soy flour (Nutrisoy.RTM.
7B, ADM) was dispersed in 220 gm of water and cooked at pH 9 and
55.degree. C. for 1 hour. 177.5 gm of 50.7% carboxylated
styrene-butadiene latex (CP620NA, Dow) was added and the pH
adjusted to 9. The dispersion was dried in the same manner as that
in Example 1. After drying, the mechanical properties were measured
as described in Example 1. The mechanical properties of this
composite are shown in FIG. 1A, FIG. 2, and FIG. 5A.
EXAMPLE 6
Preparation of 15% Defatted Soy Flour Composite.
[0056] A 15.8-gm sample of 96% defatted soy flour (Nutrisoy.RTM.
7B, ADM) was dispersed in 250 gm of water and cooked at pH 9 and
55.degree. C. for 1 hour. 168 gm of 50.7% carboxylated
styrene-butadiene latex (CP620NA, Dow) was added and pH adjusted to
9. The dispersion was dried in the same manner as that in Example
1. After drying, the mechanical properties were measured as
described in Example 1. The mechanical properties of this composite
are shown in FIG. 1A, FIG. 2, and FIG. 5A.
EXAMPLE 7
Preparation of 20% Defatted Soy Flour Composite.
[0057] A 20.9-gm sample of 96% defatted soy flour (Nutrisoy.RTM.
7B, ADM) was dispersed in 230 gm of water and cooked at pH 9 and
55.degree. C. for 1 hour. 158 gm of 37.9% carboxylated
styrene-butadiene latex (CP620NA, Dow) was added and the pH
adjusted to 9. The dispersion was dried in the same manner as that
in Example 1. After drying, the mechanical properties were measured
as described in Example 1. The mechanical properties of this
composite are shown in FIG. 1A, FIG. 2, FIG. 3A, and FIG. 5A.
EXAMPLE 8
Preparation of 30% Defatted Soy Flour Composite.
[0058] A 31.5-gm sample of 96% defatted soy flour (Nutrisoy.RTM.
7B, ADM) was dispersed in 230 gm of water and cooked at pH 9 and
55.degree. C. for 1 hour. 140 gm of 50.7% carboxylated
styrene-butadiene latex (CP620NA, Dow) was added and pH adjusted to
9. The dispersion dried in the same manner as that in Example 1.
After drying, the mechanical properties were measured as described
in Example 1. The mechanical properties of this composite are shown
in FIG. 1A, FIG. 2, FIG. 4A and FIG. 5A.
EXAMPLE 9
Preparation of 30% Defatted Soy Protein Concentrate Composite.
[0059] A 150.3-gm sample of 96% defatted soy flour (Nutrisoy.RTM.
7B, ADM) was dispersed in 1200 gm of water and mixed at pH 4.5 for
0.5 hour. The dispersion was centrifuged at 3000 rpm for 10
minutes. The washing process was repeated three times to obtain a
soy protein concentrate with 21.9% solids content. 490 gm of water
was added to 137 gm of 21.9% soy protein concentrate and cooked at
pH 9 and 55.degree. C. for 1 hour. 138.6 gm of 50.7% carboxylated
styrene-butadiene latex (CP620NA, Dow) was added and the pH
adjusted to 9. The dispersion was dried in the same manner as that
in Example 1. The same process was used to prepare composites
containing 10%, 15%, and 20% of soy protein concentrate. After
drying, the mechanical properties were measured as described in
Example 1. The mechanical properties of this composite are shown in
FIG. 1C, FIG. 2, FIG. 3C, FIG. 4C, and FIG. 5C.
EXAMPLE 10
Comparative Example
Preparation of 10% Carbon Black Composite.
[0060] 100-gm of carbon black grade N-339 and 3.2 gm of sodium
lignin sulfonate (Vanisperse CB, LIGNOTECH USA) were homogenized at
10,000 rpm in 540 gm of water for 1 hour. The resulting carbon
black dispersion had a pH of 9.7 and a solid fraction of 15.9%.
63.3 gm of 15.9% carbon black dispersion was mixed with 338 gm of
26.8% carboxylated styrene-butadiene latex (CP620NA, Dow) and the
pH adjusted to 9. The dispersion was dried in the same manner as
that in Example 1. After drying, the mechanical properties were
measured as described in Example 1. The mechanical properties of
this composite are shown in FIG. 1D, FIG. 2, and FIG. 5D.
EXAMPLE 11
Comparative Example
Preparation of 15% Carbon Black Composite.
[0061] A 100-gm sample of carbon black grade N-339 and 3.2 gm of
sodium lignin sulfonate (Vanisperse CB, LIGNOTECH USA) were
homogenized at 10,000 rpm in 540 gm of water for 1 hour. The
resulting carbon black dispersion had a pH of 9.7 and a solid
fraction of 15.9%. 75.6 gm of 15.9% carbon black dispersion were
mixed with 324.6 gm of 21% carboxylated styrene-butadiene latex
(CP620NA, Dow) and the pH adjusted to 9. The dispersion was dried
in the same manner as that in Example 1. After drying, the
mechanical properties were measured as described in Example 1. The
mechanical properties of this composite are shown in FIG. 1D, FIG.
2, and FIG. 5D.
EXAMPLE 12
Comparative Example
Preparation of 20% Carbon Black Composite.
[0062] A 20.1-gm sample of carbon black grade N-339 and 0.78 gm of
sodium lignin sulfonate (Vanisperse CB, LIGNOTECH USA) was
homogenized at 10,000 rpm in 80 gm of water for 1 hour. The
resulting carbon black dispersion had a solid fraction of 20.7%.
17.6 gm of 20.7% carbon black dispersion was mixed with 190.6 gm of
37.4% carboxylated styrene-butadiene latex (CP620NA, Dow) and the
pH adjusted to 9. The dispersion was dried in the same manner as
that in Example 1. After drying, the mechanical properties are
measured as described in Example 1. The mechanical properties of
this composite are shown in FIG. 1D, FIG. 2, FIG. 3D, and FIG.
5D.
EXAMPLE 13
Comparative Example
Preparation of 30% Carbon Black Composite.
[0063] A 100-gm sample of carbon black grade N-339 and 3.2 gm of
sodium lignin sulfonate (Vanisperse CB, LIGNOTECH USA) were
homogenized at 10,000 rpm in 540 gm of water for 1 hour. The
resulting carbon black dispersion had a pH of 9.7 and a solid
fraction of 15.9%. 189.3 gm of 15.9% carbon black dispersion was
mixed with 190.7 gm of 37% carboxylated styrene-butadiene latex
(CP620NA, Dow) and the pH adjusted to 9. The dispersion was dried
in the same manner as that in Example 1. After drying, the
mechanical properties were measured as described in Example 1. The
mechanical properties of this composite are shown in FIG. 1D, FIG.
2, and FIG. 4D.
EXAMPLE 14
Comparative Example
Preparation of 10% Soy Protein Isolate Composite.
[0064] A 10.5-gm sample of 95.6% soy protein isolate (Profam 781,
ADM) was dispersed in 208 gm of water and cooked at pH 9 and
55.degree. C. for 1 hour. 181 gm of 49.7% caboxylated
styrene-butadiene latex (CP620NA, Dow) was added and the pH
adjusted to 9. The dispersion was dried in the same manner as that
in Example 1. After drying, the mechanical properties were measured
as described in Example 1. The mechanical properties of this
composite are shown in FIG. 2.
EXAMPLE 15
Comparative Example
Preparation of 15% Soy Protein Composite.
[0065] A 15.8-gm sample of 95.4% soy protein isolate (Profam 781,
ADM) was dispersed in 220 gm of water and cooked at pH 9 and
55.degree. C. for 1 hour. 172 gm of 49.7% caboxylated
styrene-butadiene latex (CP620NA, Dow) was added and pH adjusted to
9. The dispersion was dried in the same manner as that in Example
1. After drying, the mechanical properties were measured as
described in Example 1. The mechanical properties of this composite
are shown in FIG. 2.
EXAMPLE 16
Comparative Example
Preparation of 20% Soy Protein Composite.
[0066] 20.9-gm sample of 95.6% soy protein isolate (Profam 781,
ADM) was dispersed in 218 gm of water and cooked at pH 9 and
55.degree. C. for 1 hour. 161 gm of 49.7% caboxylated
styrene-butadiene latex (CP620NA, Dow) was added and the pH
adjusted to 9. The dispersion was dried in the same manner as that
in Example 1. After drying, the mechanical properties were measured
as described in Example 1. The mechanical properties of this
composite are shown in FIG. 2.
EXAMPLE 17
Comparative Example
Preparation of 30% Soy Protein Composite.
[0067] A 31.4-gm sample of 95.6% soy protein isolate (Profam 781,
ADM) was dispersed in 250 gm of water and cooked at pH 9 and
55.degree. C. for 1 hour. 140.9 gm of 49.7% caboxylated
styrene-butadiene latex (CP620NA, Dow) was added and the pH
adjusted to 9. The dispersion was dried in the same manner as that
in Example 1. After drying, the mechanical properties are measured
as described in Example 1. The mechanical properties of this
composite are shown in FIG. 2.
EXAMPLE 18
Comparative Example
Preparation of 40% Soy Protein Composite.
[0068] A 41.8-gm sample of 95.6% soy protein isolate (Profam 781,
ADM) was dispersed in 237 gm of water and cooked at pH 9 and
55.degree. C. for 1 hour. 120.7 gm of 49.7% caboxylated
styrene-butadiene latex (CP620NA, Dow) was added and the pH
adjusted to 9. The dispersion was dried in the same manner as that
in Example 1. After drying, the mechanical properties are measured
as described in Example 1. The mechanical properties of this
composite are shown in FIG. 2.
[0069] Having thus described the invention, numerous changes and
modifications thereof will be readily apparent to those having
ordinary skill in the art without departing from the spirit or
scope of the invention. For example, the compositions of the
present invention also can contain other fillers, colorants,
stabilizers, and the like.
* * * * *