GLYCEROL BASED POLYMER SURFACE
ACTIVE CHEMISTRY AND PRODUCTION
Cross-Reference to Related Applications
This application is a continuation-in-part of US Patent Application
12/582,827 which was filed on October 21, 2009.
Statement Regarding Federally Sponsored Research or Development
Not Applicable.
Background of the Invention
This invention relates to compositions of glycerol (glycerin or glycerine)
based polymer surface active chemistry and methods of producing the unique chemistry
compositions. The unique surface active chemistry is branched and cyclic, and has both
alkyl ether and ester functionalities along with a beneficial co-product lactic acid and/or
lactate salt as an anti-biodegrading agent. The glycerol-based surface active products
from this chemistry are produced in a continuous process using a unique formula under a
particular low activity atmospheric environment.
Conventionally, syntheses of polyglycerol alkyl ethers and esters are based
on polyglycerols. For synthesizing polyglycerols, glycidol-based synthesis is particularly
useful in producing structured or hyperbranched polyglycerols (HBPG) and high
molecular weight HBPG, such as those described in US Patent 6,822,068 B2 and US
Published Application 2008/282579 Al. Alternatively, glycidol is used to directly react
with fatty alcohols to produce polyglycerol alkyl ethers in one step as described in US
Patent Application 2009/0239958. Unfortunately these syntheses rely on expensive
monomer glycidol which is often so expensive that in many cases their use on an
industrial scale is cost prohibitive.
A number of production processes have been developed for synthesis of
glycerol-based polyols, particularly polyglycerols, from inexpensive monomer glycerol.
However, these syntheses are mostly limited to producing linear or at least mostly linear,
low molecular weight polyglycerols (or oligoglycerols). US Patent 2,258,892 describes
various reaction conditions for synthesizing polyglycerols at reaction temperature 200 to
260 degrees Celsius employing 1% of a caustic or salt by weight as the catalyst relative to
glycerol used, but only oligomeric polyglycerol products were produced (mean molecular
weight: 116 to 314 Daltons). In US patent 5,641,816, 0.12% of LiOH or lithium soaps
under nitrogen atmosphere were used. In US patent 6,620,904 B2 0 .1% of calcium
hydroxide under vacuum was used. In WO 2007/049950 A2, 1% of a weak acid alkaline
metal salt was used. In each of these cases, however, only oligomeric polyglycerols were
produced.
Another strategy used in the prior art is the use of small amounts of strong
bases. In EP 0719752 Bl 1% of sodium hydroxide under vacuum or nitrogen was used.
JP 3717193 describes using 0.5% of sodium hydroxide under nitrogen. US Application
2008/30621 1Al describes using 0.3% or 0.4% of KOH. Again however the only major
product was oligomeric polyglycerols or olygomeric glycerol-based polyols. Other
methods are described in US Patents 3,637,774, 4,551,561, and 5,198,532, Chinese Patent
Application CN 101186696A and Scientific Article Determination of the Optimum
Conditionsfor the Condensation of Glycerin in the Presence of Potassium Hydroxide, D.
A. Zhukov, et al., Zhurnal Prikladoni Khimii, Vol. 57, No. 2, pp. 389-392 (1984).
Unfortunately these methods also only produce linear polyglycerols.
Although glycerol is not expensive, the current processes for the glycerolbased
condensation polymerizations are often inefficient. The resulting polyols are linear
and often have rather low molecular weights. Therefore, etherification or esterification of
the polyglycerols only results in linear and relative low molecular weight polyglycerol
alky ethers or esters, such as descried in US Patent 2,023,388.
Additionally in prior arts branched or hyperbranched alkyl ethers are
produced based on glycerol as described in US Patent 6,683,222 B2, and the structured
surface active products are superior to the traditional linear ones in various applications.
However, the production requires multiple steps and separations, and use hydrogen
peroxide as an epoxidation reagent which is of a safety concern in industrial scale. The
process inefficiency and safety concern of the synthesis are limiting factors for scaling up.
In US Patent Application 2006/0286052 Al, polyglycerol branched esters are synthesized
using branched fatty acid, and are superior to the linear esters in cosmetic applications.
However, the branched structured are derived only from the fatty acids used and therefore
the esters are dimensionally very limited comparing to the esters synthesized from
branched polylgycerols. In addition these prior art methods lack cyclic, crosslinked
structures and any anti-biodegrading agents. Thus there is a clear need for and utility in
an improved method of synthesizing glycerol-based polymer surface active products. The
art described in this section is not intended to constitute an admission that any patent,
publication or other information referred to herein is "prior art" with respect to this
invention, unless specifically designated as such. In addition, this section should not be
construed to mean that a search has been made or that no other pertinent information as
defined in 37 C.F.R. § 1.56(a) exists.
Brief Summary of the Invention
At least one embodiment of the invention is directed towards a method of
synthesizing glycerol-based surface active products in a continuous process under a low
reactivity atmospheric environment. The method comprises the steps of: a) reacting a
reaction mass comprising at least glycerol monomer in the presence of a strong base
catalyst of a concentration of above 2% at a temperature above 200 degrees C which
produces a first product comprising polyols which are both branched and cyclic, and a coproduct
comprising lactic acid, lactic salt, and any combination thereof, b) esterifying the
first product in presence of an acid catalyst of a concentration above 5% at a temperature
above 115 degrees C to produce a second product, c) alkylating the second product at a
temperature above 115 degrees C to form a third product, and d) crosslinking the third
product at a temperature above 115 degrees C to form an end product.
At least 0.1% of the produced polyols in the step a may be: alkylated,
esterified, crosslinked and any combination thereof. The Esterification reaction may
esterify at least 0.1% of the co-product lactic acid to the produced polyols. The
esterification reaction may be accomplished by adding at least one additional C2-C50
hydrocarbon acid in the step b. The alkylation may be accomplished by adding at least
one C4-C50 hydrocarbon alcohol or the like to the second product. The glycerol
monomer may at least in part comprise glycerol from crude glycerin and the crude
glycerin further comprises methyl esters, methanol, mong and inorganic salts and water.
The acid catalyst may be selected from the group consisting of: phosphoric
acid, sulfuric acid, p-toluenesulfonic acid, organic acid, Lewis acid and any combination
thereof. The base catalyst may be selected from the group consisting of: NaOH, KOH,
CsOH, a base stronger than NaOH, and any combination thereof. The
atmospheric environment may be an atmospheric pressure of less than 760 mm Hg and/or
a flow of an inert gas selected from the list of N2, C0 2, He, other inert gases and any
combination thereof. The flow may be at a rate of 0.2 to 1 mol of inert gas per hour per
mol of monomer (s).
The produced glycerol-based polyols in step a may be selected from the
group consisting of poly glycerols, polyglycerol derivatives, a polyol having both glycerol
monomer units and non-glycerol monomer units and any combination thereof, and the
polyols have at least two hydroxyl groups. At least a portion of the produced polyols in
step a may have both at least a 0.1 degree of branching and at least a 0.01 degree of
cyclization, and at least a portion of the end product has both a 0.1 degree of branching
and at least a 0.01 degree of cyclization. The co-product may be at least 1% by weight.
The produced glycerol-based polyols in step a may be at least 166 Daltons in molecular
weight, and the produced end product may be at least 500 Daltons in molecular weight.
The end product may have a polydispersity of at least 1. The acid catalyst may be added
portionwise in step b, step c, step d and any combination thereof. The acid catalyst may
be 8.6% to 20 .0%. The glycerol-based polymer surface active products may comprise at
least one lactic acid, fatty acid, fatty alcohol, a reaction product thereof and any
combination thereof. The glycerol-based surface active products may be produced by
steps a, b, c and d and any combination thereof.
Brief Description of the Drawings
A detailed description of the invention is hereafter described with specific
reference being made to the drawings in which:
FIG. 1 is an illustration of an inventive polymerization reaction.
FIG. 2 is an illustration of basic structural units useful with the inventive
polymerization reaction.
FIG. 3 is an illustration of an inventive continuous polymerization process.
Detailed Description of the Invention
DEFINITIONS
The following definitions are provided to determine how terms used in this
application, and in particular how the claims, are to be construed. The organization of the
definitions is for convenience only and is not intended to limit any of the definitions to
any particular category.
"Crude glycerin" means a by-product derivative from a transesterification
reaction involving triglycerides including transesterification reactions involving biodiesel
manufacturing processes, in which the by-product comprises glycerin and a least one
component selected from the list consisting of: fatty acids, esters, salt, methanol,
tocopherol, sterol, mono-glycerides, di-glycerides, and tri-glycerides.
"Degree of Branching ' or DB means the mol fraction of monomer units at
the base of a chain branching away from the main polymer chain relative to a perfectly
branched dendrimer, determined by 1 C NMR based on known literature method
described in Macromolecules, 1999, 32, 4240. Cyclic units or branched alkyl chains
derived from fatty alcohols or fatty acids are not included in the degree of branching. In a
perfect dendrimer the DB is 1 or 100%. FIG. 1 illustrates a compound with a DB of 1/7.
"Degree of cyclization" or DC means the mol fraction of cyclic structure
units relative to the total monomer units in a polymer. The cyclic structure units can be
formed by intramolecular cyclization of the polyols or any other ways to incorporate in
the polyols. The cyclic structure units comprise basic structure units (V, VI and VII of
1 FIG. 2) and the analogues thereof. The degree of cyclization may be determined by C
NM .
"Glycerol-based polyols" means any polymers containing repeating
glycerol monomer units such as polyglycerols, polyglycerol derivatives, and a polymer
consisting of glycerol monomer units and at least another monomer units to other
multiple monomers units regardless of the sequence of monomers unit arrangements.
These polymers also comprise at least two or multiple free hydroxyl groups.
"Hyperbranched" means a polymer, which is highly branched with threedimensional
tree-like structures or dendritic architecture.
"Low reactivity atmospheric environment" is an atmospheric environment
which is less reactive than the standard earth environment, which is achieved by
substituting the atmospheric environment with an inert gas such as nitrogen, C0 2, He, and
any combination thereof, and/or by reducing the atmospheric pressure to less than 760
mm Hg or even to vacuum conditions.
"Mong" means non glycerol organic material and typically consists of
soaps, free fatty acids, and other impurities.
"Solids" means all starting materials used in the reaction except for
solvents and water. Solids, includes but is not limited to products, co-products or by
products and any starting materials.
"AcyV means a group or radical having the general formula of RCOderived
from an organic acid, where R is a hydrocarbon-based substituent.
In the event that the above definitions or a definition stated elsewhere in
this application is inconsistent with a meaning (explicit or implicit) which is commonly
used, in a dictionary, or stated in a source incorporated by reference into this application,
the application and the claim terms in particular are understood to be construed according
to the definition in this application, and not according to the common definition,
dictionary definition, or the definition that was incorporated by reference.
In at least one embodiment the glycerol-based polyol used as the backbone
of the surface active polymer chemistry is synthesized according to the methods and
compositions described in US Patent Application 12/582,827. As illustrated in FIG. 1, in
at least one embodiment, a unique composition of glycerol-based polyol is produced from
glycerol using an improved method. The polyol comprises a structure including at least
two repeating units selecting from at least one of the structures listed in FIG. 2 including
but not limited to structures I and II, branched structures III, IV, and VIII, cyclic structures
V, VI, VII and any combination thereof. Any structure in FIG. 2 can be combined with
any structure or structures including itself through any free hydroxyl group functionality in
the structure. The cyclic linkages of any basic cyclic structures in FIG. 2 may contain any
structure or structures as a part or parts of linkages. In FIG. 1, FIG. 2 and Fig 3 the
numbers m, m', n, n', o, o', p, p', q, q', r and r' in each structure can independently be any
numeric number 0, 1, 2, . . .m, m' . ..r, or r'. In FIG. 1 R and R' are (CH2) and n can
independently be 1 or 0, and M can be H, metal or other counterion.
In at least one embodiment, a unique composition of glycerol-based polyol
is produced from glycerol and at least one or more other monomers. Suitable monomers
are any polyols or hydrogen active compounds such as those described in US 6,822,068
B2, such as pentaerythritol, glycols, amines, etc. capable of reacting with glycerol or any
polyglycerol structures.
In at least one embodiment the unique compositions of glycerol-based
polyol products produced by the improved method comprise branched, cyclized structure
units in the polyol and co-product lactic acid or lactate salt. In at least one embodiment
the glycerol-based polyols have at least 0. lof degree of branching, preferentially from 0.2
to 0.5, and a degree of cyclization at least 0.01, preferentially 0.02 to 0.19. In at least one
embodiment the valuable co-product lactic acid or and lactate salt produced in the
invention is at least 1%, preferentially 5% to 30%, by weight in the product solids. In at
least one embodiment the valuable co-product is subsequently used for esterification to
produce the glycerol-based polymer surface active products. The produced lactic acid or
lactic salt is particularly useful as it protects the glycerol-based polyols from bacterial and
fungal spoilage. Biochallenge experimental tests show that the polyglycerol products are
not susceptible to biological infestation such as from bacteria or fungi. Experimentally
produced samples have gone for over 2 years without biological infestation or spoilage.
In at least one embodiment the inventive method comprises particular
concentration of a strong base as the catalyst under a particular distillation environment at
high reaction temperature for a desired reaction time. In at least one embodiment the
strong base is CsOH, KOH, NaOH, any other strong base stronger than NaOH or any
combination thereof in the amount of above 2%, preferably above 3%. In at least one
embodiment the particular distillation environment is inert gas flow rates of more than 0.2
mol of inert gas per hour per mol of monomer used. In at least one embodiment the inert
gas is nitrogen, carbon dioxide, any other inert gas, or any combination thereof. In at least
one embodiment the particular distillation environment is a vacuum pressure of less than
760 mmHg. In at least one embodiment the reaction temperature is above 200 and below
300 degrees Celsius. In at least one embodiment the reaction temperature is from 230 to
260 degrees Celsius. The reaction is conducted over 2 hours to a number of hours as
desired.
In at least one embodiment, the reaction produced polyols have a
polydispersity of at least 1. In at least one embodiment, the reaction produced polyols
have a polydispersity within the range of 1 to 30. For purposes of this application the term
"polydispersity" is a term of art whose precise definition is provided in Principles of
Polymerization, 4th Edition, by George Odion Wiley-InterScience (2004), Introduction
pages 18-25.
In at least one embodiment the polyol is made at least in part from the
polymerization of crude glycerin. Crude glycerin is derived from a transesterification
reaction involving triglycerides. Biodiesel is typically made through a chemical process
called transesterification in which vegetable oil or animal fats are converted to fatty acid
alkyl esters and crude glycerin by-product. Fatty acids and fatty acid alkyl esters can be
produced from oils and fats by base-catalyzed transesterification of the oil, direct acidcatalyzed
esterification of the oil and conversion of the oil to fatty acids and subsequent
esterification to biodiesel.
The majority of fatty acid alkyl esters are produced by the base-catalyzed
method. In general, any base may be used as the catalyst used for transesterification of the
oil to produce biodiesel, however sodium hydroxide or potassium hydroxide are used in
most commercial processes.
Suitable examples of crude glycerin and its manufacture can be found in among
other places in US Patent Application 12/246,975. In the biodiesel manufacturing process,
the oils and fats can be filtered and preprocessed to remove water and contaminants. If
free fatty acids are present, they can be removed or transformed into biodiesel using
special pretreatment technologies, such as acid catalyzed esterification. The pretreated oils
and fats can then be mixed with an alcohol and a catalyst (e.g. base). The base used for the
reaction is typically sodium hydroxide or potassium hydroxide, being dissolved in the
alcohol used (typically ethanol or methanol) to form the corresponding alkoxide, with
standard agitation or mixing. It should be appreciated that any suitable base can be used.
The alkoxide may then be charged into a closed reaction vessel and the oils and fats are
added. The system can then be closed, and held at about 7 1 degrees C (160 degrees F) for
a period of about 1 to 8 hours, although some systems recommend that the reactions take
place at room temperature.
Once the reactions are complete the oil molecules (e.g. triglycerides) are
hydrolyzed and two major products are produced: 1) a crude fatty acid alkyl esters phase
(i.e. biodiesel phase) and 2) a crude glycerin phase. Typically, the crude fatty acid alkyl
ester phase forms a layer on top of the denser crude glycerin phase. Because the crude
glycerin phase is denser than the biodiesel phase, the two can be gravity separated. For
example, the crude glycerin phase can be simply drawn off the bottom of a settling vessel.
In some cases, a centrifuge may be employed to speed the separation of the two phases.
The crude glycerin phase typically consists of a mixture of glycerol, methyl esters,
methanol, mong and inorganic salts and water. Methyl esters are typically present in an
amount of about 0.01 to about 5 percent by weight.
In at least one embodiment, methanol can be present in the crude glycerin in an
amount greater than about 5 weight percent to about 30 weight percent. In at least one
embodiment, the crude glycerin comprises about 30 to about 95 weight percent of
glycerol.
The inventive method has a number of benefits. One advantage is the high
proportion of valuable lactic acid or lactate salt present in the reaction product. In at least
one embodiment, the lactic acid has been observed to be as much as at least 11% to 22%
by weight of the reaction product. The produced lactic acid is particularly useful as it
protects the polyglycerol from bacterial and fungal spoilage. Experimentally produced
samples have gone for over 2 years without biological infestation or spoilage.
In at least one embodiment the degree of cyclization of the resulting polyol
is 0.15 to 0.18.
In at least one embodiment, at least 30 to 35% of the produced
polyglycerols are branched or hyperbranched polyglycerols. Branching or hyperbranching
is particularly useful as it facilitates increased molecular weight of the polyglycerols.
Furthermore as described in US Published Application 2009/0130006 Al branched and
hyperbranched polyglycerols are also capable of reducing scale in Bayer liquor during
aluminum processing.
In at least one embodiment the inventive composition of polyols can be
used as substitute for other compositions which are used to assist in addressing a number
of industrial concerns. As examples: the inventive composition can be used as a substitute
for or additive to the humectant for a Yankee coating according to the methods and
procedures described in US Patent 8,101,045 B2. In at least one embodiment the inventive
composition can be used as a substitute for or additive to the paper brightening agent
according to the methods and procedures described in US Patent Application 12/499916.
Without being limited to theory it is believed that the beneficial effects of
the inventive process are a result of the unique conditions that the polymerization reaction
occurs within. In prior art glycerol-based condensation polymerizations either no catalyst
is used, weak bases or organic acid salts of alkaline metals are used, or a low catalyst
loading of a strong base as the catalyst, typically from 0.1to 2% is used. This results in
linear or mostly linear glycerol-based polyols, and often low molecular weight glycerolbased
polyols. In contrast the inventive process uses a higher amount of a strong base as
the catalyst under a particular distillation environment to effectively produce the branched,
cyclized glycerol-based polyols in a wide range of molecular weights with a beneficial coproduct
lactic acid or lactate as anti-biodegrading agent. Furthermore, the low reactivity
atmospheric environment removes water that forms as a reaction byproduct, which
prevents the water from inhibiting the polymerization reactions.
Referring now to FIG. 3 there is shown an embodiment in which the
polyols are used to produce glycerol-based polymer surface active products comprising
ester and alkyl ether functionalities and crosslinked structures additionally. In at least one
embodiment the esterification, alkylation and crosslinking occur in presence of particular
amount of acid(s) as the catalyst under a particular low reactivity atmospheric
environment. In a least one embodiment the particular amount of acid catalyst is at least
above 5%. In at least one embodiment the acid catalyst is 8.6% to 20.0%. In at least one
embodiment the acid catalyst comprised sulfuric acid, phosphoric acid, other inorganic
acids, ^-toluenesulfonic acid, other organic acids, Lewis acids and any combination
thereof. In at least one embodiment the polyglycerols are esterified with a portion of coproduct,
lactic acid. In at least one embodiment the polyglycerol are esterified with lactic
acid, fatty acids added and any combination thereof. In at least one embodiment above 1%
of the co-product lactic acid or its metal salt is remained in the end product as an antibiodegrading
agent. In at least one embodiment C2-C50 hydrocarbon based acids is added
and esterified with glycerol-based polyols. In at least one embodiment the esterification
occurs at above 115° C and below 200 0 C. In at least one embodiment the esterification
occurs as high a temperature as 200 C or higher. Suitable examples of polyols include
glycerol and crude glycerin which have undergone acid or base catalyzed
polycondensation or from glycidol which has undergone acid or base catalyzed living
polymerization. The glycerol, crude glycerin, and/or polyol can undergo alkylation.
In FIG. 3 the alkylation can continuously occur by reaction of the
polyglycerol esters with fatty alcohols, or other hydrocarbon alcohols and other
hydrocarbon based nucleophiles under a particular low activity atmospheric environment.
In at least one embodiment additional amount of acid catalyst is added in the alkylation
step. In at least one embodiment the alkylation occurs at above 115° C and below 200 C.
In at least one embodiment the alkylation occurs at as high a temperature as 200 C or
higher. In at least one embodiment the alkylation is accomplished by the alkoxylation
and/or the oxyalkylation (with oxyalkenes) of the glycerol, crude glycerin, and^r the
polyol. In at least one embodiment the hydrocarbon alcohols or oxylalkenes are C4-C50
hydrocarbon reagents.
In FIG. 3 the crosslinking reaction can continuously occur with or without
a crosslinking reagent under a particular low reactivity atmospheric environment. In at
least one embodiment the crosslinking occurs at temperature of above 115° C and below
200° C. In at least one embodiment the crosslinking occurs as high a temperature as 200 C
or higher. In at least one embodiment additional acid catalyst is added for the crosslinking
reaction. In at least one embodiment the crosslinking adds crosslinked structures and
increases the degree of branching. In at least one embodiment the crosslinking increases
molecular weight of the end product
FIG. 3 illustrates at least one embodiment in which the inventive
composition is synthesized by first polycondensation of suitable monomer units, second
esterification of the polymer, third alkylation of the polymer and finally crosslinking.
After the polycondensation, a lactate co-product (such as sodium lactate) is formed. In at
least one embodiment the esterification occurs at a temperature of at least 130° C and
forms a polyglycerol-lactate ester. In at least one embodiment the polyglycerol-lactate
ester then undergoes alkylation with fatty alcohols at a temperature of at least 150° C. In
at least one embodiment the polyglycerol alkyl ethers and esters are crosslinked at a
temperature of at least 150° C to form more structured high molecular weight surface
active products.
In at least one embodiment the unique surface active polymer products are
produced in a continuous process comprising polycondensation, esterification, alkylation
and crosslinking without any separations. In at least one embodiment the unique surface
active polymer products are produced y a process comprising polycondensation,
esterification, alkylation, crosslinking and any combination thereof.
One advantage of the invention is the resulting surface active products
have both ester and alkyl functionalities. The nature of different polarities from both
functionalities is a matrix to adjust the surfactancy for improving performance activities in
targeted applications. Another advantage of this invention is the cyclic structures. The
rigidity of cyclic structures in the polymer backbone uniquely extends the molecular
dimensions and increases the hydrodynamic volume, to better act interfacially. The
lipophilic nature of the cyclic structures relative to glycerol monomer better balances the
surface active property in the polymer backbone. Another advantage of this invention is
the crosslinking which increases the molecular weight and degree of branching.
In at least one embodiment the resulting surface active product has both
ester and alkyl functionalities.
An advantage of having ester and alkyl functionalities is that it provides a
desirable range of polarities for particular surface interactions.
The degree of esterification can be 0.1% to 99%. The degree of alkylation can be
0 .1% to 99%. In addition to the inventive surface active products, the resulting end
product may contain residues of the added components, and co-products such as
hydrocarbon lactate esters.
In at least one embodiment the reaction product is used as a digestion
additive for wood pulping as described for example in US Patent Application 12/720973.
This is because the alkylated glycerol-based polymer surfactants are structured and wellbalanced
lipophilically and hydrophilically, and therefore are effective at both penetrating
within masses of wood-based fibers and at reducing the native lignin in the wood-based
fibers.
EXAMPLES
The foregoing may be better understood by reference to the following
Examples, which are presented for purposes of illustration and are not intended to limit
the scope of the invention:
A number of samples of the inventive composition were created by using
various permutations of the inventive concept.
General Experimental Procedure:
100 Units (or using different amounts) of glycerol were added to a reaction vessel
followed by 3.6% of active NaOH relative to the reaction mixture. This mixture was
agitated and then gradually heated up to 240° C under a particular low reactivity
atmospheric environment. This temperature was sustained for at least three hours to
achieve the desired polyglycerol composition, while being agitated under a particular low
reactivity atmospheric environment. An in-process polyglycerol sample was drawn for
the molecular weight/composition analysis. The vessel was then allowed to cool down,
and 4 to 20% of active acid(s) was added. The mixture was again gradually heated up to
130° C-150 C and kept there for at least 30 minutes under a particular low reactivity
atmospheric environment, to achieve the desired esterification. A 5 to 40% amount of
C10-C16 alcohols was then added and the mixture was heated up to 150° C and kept there
under a particular low reactivity atmospheric environment for at least 30 minutes to
achieve the desired alkylation. The resulting reaction mixture was stirred at 150° C under
a particular low reactivity atmospheric environment for at least 30 minutes to achieve the
crosslinking to produce the desired end product. 3 to 16 Hours of the reaction time for
esterification, alkylation and crosslinking were used. The product was dissolved in water
in a desired concentration and pH was adjusted as needed. During the whole process inprocess
samples were drawn every 30 minutes to 2 hours as needed to monitor the
reaction progress in each step and determine the composition as needed.
Example I
It was done following the general procedure. 13.50% of sulfuric acid was used. The
reaction time for esterification, alkylation and crosslinking was 3 hours.
Example II
It was done following the general procedure. 15.00% of sulfuric acid was used. The
reaction time for esterification, alkylation and crosslinking was 4 hours.
Example III
It was done following the general procedure. 15.00% of sulfuric acid was used. The
reaction time for esterification, alkylation and crosslinking was 5 hours.
Table 1: Summary of the inventive examples
Note: *weight average molecular weight determined by borate aqueous SEC method and
calibrated with PEO/PEG standards; **weight average molecular weight determined by
SEC method using PLgel Guard Mixed-D column and DMSO as mobile phase, and
calibrated with polysaccharide standards; ***p-toluenesulfonic acid.
COMPARATIVE EXAMPLES
Comparative Example I
It was done following the general procedure, except for that all the reaction starting
materials were mixed together first at 100 C and then gradually heated up to 1 0 C.
2% of sulfuric acid and 2% of PTSA were used. The reaction time for esterification,
alkylation and crosslinking was 8 hours.
Comparative Example P
It was done following the general procedure, except for that all the reaction starting
materials were mixed together first at 100-1 10 C and then gradually heated up to 150
C. 1.92% of sulfuric acid and 1.81% of PTSA were used for the first four hours, followed
by another addition of 2.75% of sulfuric to run 12 hours more. The reaction time for
esterification, alkylation and crosslinking was 16 hours.
Table 2 : Summary of the comparative examples
Note: *weight average molecular weight determined by borate aqueous SEC method and
calibrated with PEO/PEG standards; **weight average molecular weight determined by
SEC method using PLgel Guard Mixed-D column and DMSO as mobile phase, and
calibrated with polysaccharide standards; ***j»-toluenesulfonic acid.
The examples demonstrate that a particular amount of acid catalyst in the
reaction formula and a particular low reactivity atmospheric environment conditions are
unique to result in the unique surface active products (Table 1) efficiently, while the prior
art conditions are inferior even with an additional organic acid catalyst and prolonged
reaction time (Table 2).
While this invention may be embodied in many different forms, there
described in detail herein specific preferred embodiments of the invention. The present
disclosure is an exemplification of the principles of the invention and is not intended to
limit the invention to the particular embodiments illustrated. All patents, patent
applications, scientific papers, and any other referenced materials mentioned herein are
incorporated by reference in their entirety. Furthermore, the invention encompasses any
possible combination of some or all of the various embodiments described herein and'or
incorporated herein. In addition the invention encompasses any possible combination that
also specifically excludes any one or more of the various embodiments described herein
and/or incorporated herein.
The above disclosure is intended to be illustrative and not exhaustive. This
description will suggest many variations and alternatives to one of ordinary skill in this
art. The compositions and methods disclosed herein may comprise, consist of, or consist
essentially of the listed components, or steps. As used herein the term "comprising"
means "including, but not limited to". As used herein the term "consisting essentially of
refers to a composition or method that includes the disclosed components or steps, and
any other components or steps that do not materially affect the novel and basic
characteristics of the compositions or methods. For example, compositions that consist
essentially of listed ingredients do not contain additional ingredients that would affect the
properties of those compositions. Those familiar with the art may recognize other
equivalents to the specific embodiments described herein which equivalents are also
intended to be encompassed by the claims.
All ranges and parameters disclosed herein are understood to encompass
any and all subranges subsumed therein, and every number between the endpoints. For
example, a stated range of " 1 to 10" should be considered to include any and all
subranges between (and inclusive of) the minimum value of 1 and the maximum value of
10; that is, all subranges beginning with a minimum value of 1 or more, (e.g. 1 to 6.1),
and ending with a maximum value of 10 or less, (e.g. 2.3 to 9.4, 3 to 8, 4 to 7), and finally
to each number 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 contained within the range.
All numeric values are herein assumed to be modified by the term "about,"
whether or not explicitly indicated. The term "about" generally refers to a range of
numbers that one of skill in the art would consider equivalent to the recited value (i.e.,
having the same function or result). In many instances, the term "about" may include
numbers that are rounded to the nearest significant figure. Weight percent, percent by
weight, % by weight, wt %, and the like are synonyms that refer to the concentration of a
substance as the weight of that substance divided by the weight of the composition and
multiplied by 100.
As used in this specification and the appended claims, the singular forms
"a," "an," and "the" include plural referents unless the content clearly dictates otherwise.
Thus, for example, reference to a composition containing "a compound" includes a
mixture of two or more compounds. As used in this specification and the appended
claims, the term "or" is generally employed in its sense including "and/or" unless the
content clearly dictates otherwise.
This completes the description of the preferred and alternate embodiments
of the invention. Those skilled in the art may recognize other equivalents to the specific
embodiment described herein which equivalents are intended to be encompassed by the
claims attached hereto.
Claims
What is claimed is:
1. A method of synthesizing glycerol-based surface active products in a continuous
process under a low reactivity atmospheric environment, comprising the steps of:
a) reacting a reaction mass comprising at least glycerol monomer in the
presence of a strong base catalyst of a concentration of above 2% at a temperature above
200 degrees C which produces a first product comprising polyols which are both
branched and cyclic, and a co-product comprising lactic acid, lactic salt, and any
combination thereof,
b) esterifying the first product in presence of an acid catalyst of a
concentration above 5% at a temperature above 115 degrees C to produce a second
product, and
c) alkylating the second product at a temperature above 115 degrees C to
form a third product, and
d) crosslinking the third product at a temperature above 115 degrees C to
form an end product.
2. The method of claim 1 in which at least 0.1% of the produced polyols in the step a
are: alkylated, esterified, crosslinked and any combination thereof.
3. The method of claim 1 in which the esterification reaction esterifies at least 0.1%
of the co-product lactic acid to the produced polyols.
4. The method of claim 1 in which the esterification reaction is accomplished by
adding at least one additional C2-C50 hydrocarbon acid in the step b .
5. The method of claim 1 in which alkylation is accomplished by adding at least one
C4-C50 hydrocarbon alcohol or the like to the second product.
6. The method of claim 1 in which the glycerol monomer is at least in part glycerol
from crude glycerin and the crude glycerin further comprises methyl esters, methanol,
mong and inorganic salts and water.
7. The method of claim 1 in which the acid catalyst is selected from the group
consisting of: phosphoric acid, sulfuric acid, p-toluenesulfonic acid, organic acid, Lewis
acid and any combination thereof.
8. The method of claim 1 in which the base catalyst is selected from the group
consisting of: NaOH, KOH, CsOH, a base stronger than NaOH, and any combination
thereof.
9. The method of claim 1 in which the atmospheric environment is an atmospheric
pressure of less than 760 mm Hg.
10. The method of claim 1 in which the atmospheric environment is a flow of an inert
gas selected from the list of 2, C0 2, He, other inert gases and any combination thereof
and the flow is at a rate of 0.2 to 15 mol of inert gas per hour per mol of monomer (s).
11. The method of claim 1 in which the produced glycerol-based polyols in step a are
selected from the group consisting of polyglycerols, polyglycerol derivatives, a polyol
having both glycerol monomer units and non-glycerol monomer units and any
combination thereof, the polyols have at least two hydroxyl groups.
12. The method of claim 1 in which at least a portion of the produced polyols in step a
has both at least a 0 .1 degree of branching and at least a 0.01 degree of cyclization, and at
least a portion of the end product has both a 0.1 degree of branching and at least a 0.01
degree of cyclization.
13. The method of claim 1 in which the co-product is at least 1% by weight.
14. The method of claim 1 in which the produced glycerol-based polyols in step a are
at least 166 Daltons in molecular weight, and the produced end product is at least 500
Daltons in molecular weight.
15. The method of claim 1 in which the glycerol-based polyols and the end product
have a polydispersity of at least 1.
16. The method of claim 1 in which the acid catalyst is added portionwise in step b,
step c, step d and any combination thereof.
17. The method of claim 1 in which the acid catalyst is 8.6% to 20.0%.
18. The method of claim 1 in which the glycerol-based polymer surface active
products comprise at least one lactic acid, fatty acid, fatty alcohol, a reaction product
thereof and any combination thereof.
19. The method of claim 1 in which glycerol-based surface active products are
produced by steps a, b, c and d and any combination thereof.