Title of Invention

A PROCESS FOR TREATING A COMPOSITION HAVING A TRIMETHYLOLALKANE BIS-MONOLINEAR FORMAL

Abstract A process for treating a composition having trimethylolalkane bis-monolinear formal,comprising subjecting trimethylopropane monocyclic formal (tmp-mcf) or trimethlolethane monocyclic formal (tme-mcf) to a transalcoholysis reaction with excess monohydric or dihydric alcohol having from 1 to 6 carbon atoms at an elevated temperature and in the presence of an acid catalyst to produce trimethylolpropane (tmp)or trimethylolpropane (tme)respectvely,and an acetal by-product,wherein less than 15 of the acid catalyst in the reaction results in a ph of the reaction of less than 4.
Full Text TREATMENT OF A COMPOSITION CQMPRISING A TRIMETHYLOLAKANE
BIS-MONOLINEARFORMAL
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Serial No. 09/324,435 filed June 1,
1999.
BACKGROUND OF THE INVENTION
Field of the Invention
The invention relates to a novel process for treating a composition comprising a
trimethylolalkane bis-monolinear formal such as that obtained as a heavy ends residue from
the purification of a crude trimethylolalkane product, to obtain useful compounds.
Description of the Related Art
Trimethylolpropane (TMP) and trimethylolethane (TME) are well-known chemical
commodities used as intermediates in the production of a wide variety of products, e.g.,
varnishes, alkyd and polyester resins, synthetic drying oils, urethane foams and coatings,
silicone lube oils, lactone plasticizers, textile finishes, surfactants, epoxidation products, etc.
TMP and TME are made by reacting one mole of n-butyraldehyde or propionaldehyde
respectively with an amount in excess of 3 moles of formaldehyde in an aqueous medium and
in the presence of an alkaline condensation agent. However, these conditions result in the
formation of not only TMP or TME, but also various higher boiling impurities. Thus it is
necessary to subject the crude TMP or TME product obtained from the reaction to a
purification process including distillation and solvent extraction steps, not only to separate
relatively pure TMP or TME from excess formaldehyde, water, and basic condensation agent,
but also from the higher boiling impurities.
A critical step in the purification process for obtaining relatively pure TMP or TME
from the crude product of the reaction is a vacuum distillation or "flashing" of the bulk of the
TMP or TME produced in the reaction, which is thus removed as a vapor from the higher
boiling impurities remaining behind as a liquid heavy ends residue. While the residue may
still contain some TMP or TME, the percentage of such desirable compound is fairly low and
is difficult to recover economically. Furthermore, several of the high boiling impurities
produced by the reaction in fairly large amounts have only limited commercial value. Thus,
any expedient for treating the heavy ends residue, or any compound present in such residue in
large amount, so as to convert at least a portion of such compound to TMP or TME and/or
other more valuable compounds, would be very desirable.
U.S. Patent No. 3,076,854 issued February 5,1963 to Klein, discloses the purification
of crude TMP product by a process comprising extracting the reaction liquor with a water
immiscible solvent for TMP, e.g., n-butanol or amyl alcohol, subjecting the extract to further
extraction with water to obtain a re-extract containing TMP contaminated with metal formate
and polyhydric by-products; separating the aqueous re-extract from the stripped solvent,
heating the contaminated TMP with methanol or other lower alkanol and a mineral acid to
convert the metal formate to a salt of the added acid, and further treating the aqueous TMP
re-extract with an acidic cation-exchange resin to remove metal ions from the solution.
British Patent No 1,290,036 discloses a process for removing trimethylpropane
monomethyl formal from a crude TMP product by treating the product with a sulfonic acid
cation exchange resin. The trimethylolpropane monomethyl formal decomposes to form
trimethylolpropane monocyclic formal and methanol.
German Democratic Republic Patent No. 142184 discloses a process for the recovery
of TMP from higher boiling residues comprising adding water and methanol to the residues
such that they contain at least 15 wt.% of water or 10-40 wt.% of methanol, pretreating the
residues with a cation exchange resin to remove traces of condensation agent contained in the
residues, treating the residues under distillation conditions with a highly acidic, highly
crosslinked cation-exchange resin with a polystyrene base, and recovering the TMP formed
by conventional separation means.
BRIEF SUMMARY OF THE INVENTION
As part of the invention disclosed herein, it has been discovered that a major
proportion of the heavy ends residue obtained after removing the bulk of the TMP or TME,
excess formaldehyde, water, and basic condensation agent, is a trimethylolalkane
bis-monolinear formal having the formula,
where R is ethyl in the case of trimethylolpropane bis-monolinear formal (TMP-BMLF) CA
Index Namel,3-Propanediol, 2,2"-[methylenebis(oxymethylene)]bis[2-ethyl-], CAS No.
[93983-16-5] or methyl in the case of trimethylolethane bis-monolinear formal (TME-BMLF)
CA Index Name 1,3-Propanediol, 2,2"-[methylenebis(oxymethylene)]bis[2-methyl-], CAS
No. [636073-72-5]. Thus, in accordance with the broadest aspect of the invention, a
composition comprising a substantial percentage, e.g., at least about 40 wt.%, of TMP-BMLF
or TME-BMLF, no more than about 5 wt.% of water, and no more than about 0.5 wt.% of
methanol, all percentages based on the total weight of the composition, is contacted with a
strong acid catalyst at an elevated temperature and a sufficient period of time to convert a
significant amount of said TMP-BMLF or TME-BMLF to TMP or TME and the
corresponding trimethylolalkane monocyclic formal having the following formula,
where R is ethyl in the case of trimethylolpropane monocyclic formal (TMP-MCF) CA Index
Name l,3-Dioxane-5-methanol, 5-ethyl, CAS No. [5187-23-5] or methyl in the case of
trimethylolethane monocyclic formal (TME-MCF) CA Index Name l,3-Dioxane-5-methanol,
5-methyl, CAS No. [1121-97-7]. The additional TMP and TMP-MCF or TME and
TME-MCF produced by the process have considerably greater value than the TMP-BMLF or
TME-BMLF consumed. In many instances the composition treated is a heavy ends residue
obtained from a crude TMP or TME product in the course of a purification treatment after the
bulk of water, excess formaldehyde, basic condensation agent, and purified TMP or TME
have been separated.
DETAILED DESCRIPTION OF THE INVENTION
The composition subjected to the acid treatment of this convention will in many
instances contain, for example, at least about 10 wt.%, preferably at least about 20-30 wt.% of
TMP-BMLF or TME-BMLF, generally anhydrous to no more than about 5 wt.%, preferably
no more than about 1.0 wt.% of water, and no more than about 0.5 wt.%, preferably no more
than about 0.1 wt.% of methanol. In addition, the composition being treated will usually
contain no more than about 5 wt.%, preferably no more than about 0.6 wt.% of any
compound in free form having an atmospheric boiling below that of water, such as
formaldehyde. The composition is contacted at an elevated temperature, e.g., about 30°C to
about 300°C preferably about 90°C to about 220°C, with a strong acid catalyst, for a period
of time, e.g., of about 2 to about 8 hours, preferably about 1 to about 6 hours, sufficient to
convert a significant amount of the TMP-BMLF or TME-BMLF to TMP and TMP-MCF or
TME and TME-MCF respectively.
Any strong acid can be used as a catalyst for the process of the invention. While such
acid may be an inorganic acid such as sulfuric or phosphoric, it is preferred in most instances
to employ an alkanesulfonic acid such as methanesulfonic acid, an arylsulfonic acid such as
toluenesulfonic acid, or a sulfonated cation-exchange resin in acid form, e.g., a sulfonated
polystyrene-based cation exchange" resin. The amount of acid may vary widely, but is often
in an amount such that the acidity of conversion reaction is in the range, for example,
equivalent to the acidity contributed by the strong acid, less than about 15 wt.% , preferably
about 0.3 to about 1.3 wt.%.
Generally a strong acid is added in sufficient amount to result in a pH range of the
reaction of less than about 4, and preferably between about 2 and 3, purified BMLF has been
found to optimally convert to TMP at about 102°C, pH of about 2.35 in about 4 hours:
As suggested previously, a small amount of water under 5 wt.% may be present in the
composition subjected to the acid treatment of this invention. Furthermore, an additional
amount of water is produced by the conversion of TMP-BMLF or TME-BMLF to TMP-MCF
or TME-MCF respectively. Although not necessary to obtain the advantages of the process,
it may be desirable in some instances to keep the amount of water at a lower level than would
ordinarily occur. For this purpose a minor amount, e.g. less than about 15 wt.% preferably
less than about 10 wt% based on the weight of the composition, of a compound which forms
a low boiling azeotrope with water and is substantially immiscible with any of the
components of the composition, may be added prior to the initiation of the reaction. Such
compound is preferably a hydrocarbon, e.g., cyclohexane, toluene or benzene.
As stated, the process of the invention results in the conversion of a significant
amount of the TMP-BMLF or TME-BMLF in the initial composition to TMP and TMP-MCF
or TME and TME-MCF respectively. For example, in the case ofTMP, it has been found
that the product resulting from the acid treatment of the process of the invention may contain
at least about 5 wt.%, more TMP-MCF than was present in the initial composition subjected
to such acid treatment, based on the weight of the total composition.
Conversely, for example, the amount of TMP-BMLF in the product was found to be
reduced by at least about 70 wt.%, of that in the initial composition based on the weight of
TMP-BMLF before the acid treatment.
As described previously, the composition subjected to the acid treatment of this
invention will in many instances be obtained as a heavy ends residue from a process for
producing TMP or TME by reaction of n-butyraldehyde or propionaldehyde with
formaldehyde in an aqueous system in the presence of a basic condensation agent such as
sodium hydroxide. Such a residue is obtained from the purification of the product of the
reaction including the following steps: 1) removal of excess formaldehyde; 2) removal of
water; 3) separation of TMP or TME and higher boiling impurities from the liquid being
purified, and the basic condensation agent and, 4) heating the crude TMP under vacuum to
flash off and recover the TMP or TME having a high degree of purity. The remaining residue
is the heavy ends residue containing high boiling impurities contemplated for acid treatment
under this invention.
When the composition being treated is the heavy ends residue from a TMP process as
described previously, such composition usually contains, in addition to TMP-BMLF, TMP in
an amount, e.g. less than about 60 wt.%, typically often about 8 to about 20 wt.%; less than
about 15 wt.%, typically about 7 to about 10 wt.% of di-trimethylpropane (Di-TMP). The
amount of TMP-MCF present in said heavy ends residue is generally lower than the latter
compounds, usually less than about 0.1 wt.% and often non-detectable.
In accordance with another aspect of the invention, TMP-MCF or TME-MCF in the
composition resulting from the process of the invention is subjected to a transalcoholysis
reaction with an excess of a monohydric or dihydric alcohol, e.g., containing 1 to about 6
carbon atoms, at an elevated temperature, e.g., about 30°C to about 300°C, in the presence of
an acid catalyst, e.g., any of the same acids disclosed previously in connection with the acid
treatment of TMP-BMLF or TME-BMLF, to produce additional TMP or TME and an acetal
by-product which is often commercially desirable. Thus, for example, the TMP-MCF or
TME-MCF in the composition resulting from the acid treatment of the invention may be
reacted with excess methanol to produce additional TMP or TME and methylal, useful as a
solvent, in organic synthesis, in perfumes, in adhesives, etc., while TMP-MCF or TME-MCF
may be reacted with excess ethylene glycol to produce additional TMP or TME and 1,3-
dioxolane, useful as low-boiling solvent and extractant for oils, fats, waxes, dyes and
cellulose derivatives.
In addition to their use an intermediate in transalcoholysis reactions to produce
additional TMP or TME and other useful compounds, TMP-MCF and TME-MCF may be
used to produce useful products by other reactions. Thus, as disclosed in U.S. Patents
4,076,727; 4,207,155 and 4,876,368, acrylate and methacrylate esters of TMP-MCF and
TME-MCF may be prepared which are useful as reactive monomers in the preparation of
coating compositions, plastic films, fibers, plastic coatings and, in particular, as diluents in
various unsaturated systems, especially ultraviolet curable coating compositions.
The following examples further illustrate the invention. Small amounts of water were
removed from the system utilizing cyclohexane as an azeotroping agent.
Examples 1 and 1A
In Example 1, a round-bottom flask, equipped with an overhead stirrer, Dean Stark
trap with condenser, and a heating system, was charged at ambient temperature with 91.30
grams of a previously analyzed, heavy ends residue obtained from the purification of a crude
TMP product as described hereinbefore, 12.53 grams of cyclohexane, and 0.25 grams of
methanesulfonic acid as a catalyst. The charge was heated to 98°C over a period of 90 min.,
and a sample of product withdrawn and analyzed.
In Example 1 A, the procedure of Example 1 was repeated, except that the charge was
heated to 110°C over a period of 275 min.
The compositions of the initial heavy ends residue feed and the treated compositions
of Examples 1 and 1A in terms of weight percentages of the most significant components
based on the weight of the total composition are shown in Table I.
Example 2
The procedure of Example 1 and 1A was followed, except that the initial charge was
462.00 g of heavy ends residue, 69.19 g of cyclohexane and as catalyst, 69.19 g of sulfonated
acrylic-polystyrene based cation exchange resin in acid form sold as "Amberlyst 36 (dry)" by
Rohm and Haas Co. In employing the solid resin catalyst of this example, the experimental
apparatus was modified as follows: The resin was weighed and poured into a "mesh-wire
stainless steel basket" which was attached to the stirring shaft. This basket was shaped like
an "X" and had four components which were filled with resin. Once filled, the basket was
connected to the overhead stirrer motor. Each side of the "basket" had a length of-7.5 cm, a
width of 4 cm and a depth of 1.5 cm and was made using wire with ~42 mesh size. The
design and use of the basket allowed heavy ends residue to have intimate contact with the
solid acid resin as well as preventing degradation of the solid catalysts due to "grinding" from
the stirrer blade.
The charge was heated from 25 to 99.6°C in 190 min. and kept between 99.5 °C and
99.8"C for an additional period of 180 min. (total heating time 370 min.). The composition of
withdrawn samples at various time intervals and temperatures are shown in Table II. "N/D"
means non-detectable.
Example 3
The procedure of Example 2 was followed, except that the initial charge consisted of
709.43g of heavy ends residue, 96.00g of cyclohexane and as catalyst, 67.35g of sulfonated
acrylic-polystyrene based cation exchange resin in acid form sold as "Amberlyst 35 (dry)" by
Rohm and Haas Co.
The charge was heated from 25°C to 95.7°C in 295 min. and the composition of
withdrawn samples at various time intervals and temperatures are shown in Table III.
Example 4
The procedure of Example 1 was followed, except that the initial charge consisted of
157.85 grams of heavy ends residue, 24.58 grams of cyclohexane, and, as catalyst, 0.86 gram
of a modified toluenesulfonic acid sold as "Witco TX Acid" by Witco Chemical Corp.,
containing 1.0 wt.% of moisture and 2.0 wt.% of sulfuric acid, and having a melting point
under 15°C, a specific gravity at 254"C of 1.30 and an acid number of 330. The charge was
heated from 25 °C to 200°C in 182 min. and the compositions of withdrawn samples at
various time intervals and temperatures are shown in Table IV.
Example 5
The procedure of Example 4 was followed, except that the initial charge consisted of
186.54 grams of heavy ends residue, 24.82 grams of cyclohexane and 0.92 grams of modified
toluenesulfonic acid catalyst. The charge was heated to 1210C in 138 minutes and kept
between 12TC and 133°C for an additional 265 min. for a total heating time of 403 min. The
composition of withdrawn samples at various time intervals and temperatures are shown in
Table V.
As indicated in the data shown in the foregoing tables of Examples 1-5, an acid
treatment under the conditions of the invention of a heavy ends residue obtained from the
purification of a crude TMP product containing a substantial percentage of TMP-BMLF
results in the conversion of the bulk of the TMP-BMLF to TMP and TMP-MCF. A
corresponding acid treatment of the heavy ends residue obtained from the purification of a
crude TME product results in a similar transformation of the TME-BMLF in such residue to
TME and TME-MCF.
As stated previously, TMP-MCF or TME-MCF in a composition.resulting from the
process of the invention may be subjected to a transalcoholysis reaction wjth an excess of a
monohydric or dihydric alcohol in the presence of an acid catalyst to produce additional TMP
or TME and a valuable acetal by-product. The reaction may be carried out at a temperature,
for example, of about 20"C to about 400°C, preferably about 25°C to about 300"C and more
preferably about 35°C to 210°C, and may be carried out for a period, for example, of about 0
to about 300 minutes, preferably about 60 to about 240 minutes.
The monohydric or dihydric alcohol reacted with TMP-MCF or TME-MCF may
contain, for example, 1 to about 6 carbon atoms, such as methanol to produce methylal,
ethylene glycol to produce 1,3-dioxolane, 1-propanol to produce di-1-propoxymethane,
2-propanol to produce di-2-propoxymethane, or 2-bromopropanol to produce
di-2-bromopropoxymethane, each in addition to TMP or TME. As also mentioned
previously, the acid catalyst for this reaction may be any of the strong liquid or solid acid
catalysts disclosed as suitable for catalyzing the reaction between TMP-BMLF or
TME-BMLF to form TMP-MCF or TME-MCF and additional TMP or TME respectively.
The reaction of TMP-MCF with ethylene glycol (EG) to produce 1,3-dioxolane and
additional TMP, for example, proceeds in accordance with the following equation:
The amount of monohydric or dihydric alcohol may be in the range, for example, of
slightly above the stoichiometric amount necessary to react with TMP-MCF or TME-MCF to
produce additional TMP or TME and an acetal by-product, i.e. two moles of a monohydric
alcohol or one mole of a dihydric alcohol per mole of TMP-MCF or TME-MCF, or up to
about 5-20 fold excess above such stoichiometric amount. The actual amount utilized
depends on various factors known to those of skill in the art, for example, the alcohol used,
and concentration of reactants in the process stream, among other factors.
The TMP-MCF or TME-MCF reacted with the monohydric or dihydric alcohol may
be relatively pure material, such as that obtained by further distilling the TMP-MCF or the
TME-MCF containing material obtained by the acid treatment under this invention of the
TMP-BMLF or TME-BMLF containing heavy ends residue remaining after the separation of
the bulk of the TMP or TME, excess formaldehyde, water and b"asic condensation agent from
the reaction product of n-butyraldehyde or propionaldehyde with formaldehyde. Such a
conversion of relatively pure TMP-MCF with ethylene glycol (EG) is illustrated in Example
Example 6
To apparatus as described in Examples I and IA was first charged EG (50.5 grams,
0.82 moles), then TMP-MCF (30.25 grams, 0.21 mole) and finally methanesulfonic acid
(MSA) as a 70 wt.% solution (0.13 gram, 0.001 mole). Then the reaction was slowly heated
to about 205°C.
The composition of the initial charge at room temperature (25.5°C) before the addition
of MSA was found by gas chromatography (GC) to be 1.39 wt.% of H2O, 63.59 wt.% of EG
and 36.95 wt.% of TMP-MCF with no detectable quantity of 1,3-dioxolane, TMP or di-TMP.
The temperature and composition of withdrawn samples after the addition of MSA at various
time intervals, in terms of weight percents of the most significant components determined by
GC, are shown in Table VI where "ND" means "not detected."
The reaction solution right after the addition of MSA was colorless. At 150 min. of
reaction time the color of the reaction solution was pale yellow. After 180 min. of reaction,
the Dean Stark Trap (DST) commenced filling up. At 360 min. the reaction solution was
brown.
The Dean Stark Trap (DST) was emptied after 480 min. and the liquid collecting in
the DST formed two phases after 510 min. After completion of the reaction, the reaction
solution was found by GC to contain 0.92 wt.% of H2O, 9.03 wt.% of EG, 3.34 wt.% of
TMP-MCF, 10.59 wt.% of TMP and 0.97 wt.% of di-TMP.
At conclusion, the DST bottom phase weighed 6.72 grams and contained by GC 56.24
wt.% of H2O and 24.56 wt.% of 1,3-dioxolane; and the DST top phase weighed 4.28 grams
and contained 3.97 wt.% of H2O and 27.2 wt.% of 1,3-dioxolane, while the DST contents
removed after 480 min. reaction time weighed 10.55 grams and contained 13.16 wt.% of H2O
and 78.75 wt.% of 1.3-dioxolane.
Based on the GC analysis the total amount of the 1,3-dioxolane collected was 11.12
grams, (0.15 mole). However, based on the water analysis, the amount of 1,3-dioxolane
produced was 16.21 grams (0.21 mole). This discrepancy can be in part attributed to the
factors used in the GC method. Since there were no other components observed in the gas
chromatogram method, the accountability based on the water analysis is believed to be more
accurate. The amount of TMP left in the reaction mixture at the end of the experiment was
determined to be 2.46 grams, (0.018 mole). However, during the course of producing the
1,3-dioxolane, the amount of TMP was found to be 7.42 grams (0.53 mole). The high
reaction temperatures readily explain the low amount of TMP formed.
Although the TMP-MCF or the TME-MCF for the foregoing transalcoholysis reaction
with a rhonohydric or dihydric alcohol to produce TMP or TME and an acetal by-product, has
been described as obtained by treating the TMP-BMLF or TME-BMLF resulting from the
reaction of n-butyraldehyde or propionaldehyde with formaldehyde, to produce TMP or
TME, such TMP-MCF or TME-MCF for the transalcoholysis may in fact be obtained from
any source.
In the course of purifying the TMP or TME containing TMP-MCF or TME-MCF
respectively, obtained as a result of the acid treatment of a TMP-BMLF or TME-BMLF
containing residue, a light ends overhead stream is obtained from a distillation finishing
treatment of a crude TMP or TME, such light ends containing some TMP or TME as well as
a minor amount of TMP-MCF or TME-MCF respectively. However, the latter compounds
have been found to be acid washed color forming bodies, i.e., they color the TMP or TME
when the latter are subject to contact with an acid in certain applications. While it is
relatively easy to separate the TMP-MCF or TME-MCF from the TMP or TME by
distillation, this results in some loss of TMP or TME recycled to the system. Thus, in
accordance with another aspect of the invention, the light ends overhead stream is subjected
to a treatment with an excess of monohydric or dihydric alcohol in the presence of an acid
catalyst to transalcoholyze at least some of the TMP-MCF or TME-MCF present in the
stream resulting in the formation of additional TMP or TME and a valuable acetal
by-product.
The light ends overhead fraction subjected to the transalcoholysis treatment generally
contains an amount of TMP or TME, for example, about 70 wt.%, preferably about 50 to
about 60 wt.%, and TMP-MCF or TME-MCF in an amount, for example, of about 1-15
wt.% preferably about 2 to about 10 wt.%. The conditions of time and temperature and
examples of suitable acid catalysts are the same as those set out previously for the
transalcoholysis of relatively pure TMP-MCF or TME-MCF. The transalcoholysis of
TMP-MCF in a light ends overhead TMP stream using MSA as catalyst and ethylene glycol
(EG) as reacting alcohol is illustrated in Examples 7 and 8.
Example 7
Apparatus as described in Examples 1 and 1A was charged with 121.9 grams of a
TMP light ends overhead fraction, including 4.15 wt.% of TMP-MCF (5.06 grams, 0.035
mole), 36.55 wt.% of TMP and 0.12 wt.% of H2O, determined by GC, then EG (8.31 grams,
0.13 mole) and finally MSA as a 70% solution (0.201 gram, 0.0002 mole)!
Then, the reaction was slowly heated to about 190"C. The temperature and
composition in terms of weight percents determined by GC of significant components of
samples withdrawn after various time intervals following the addition of MSA, are shown in
Table VII where "ND" means "not detected".
Essentially no 1,3-dioxolane was detected in any of the withdrawn samples. The DS
trap started filling with liquid after 120 min., and the liquid collected after reaction
completion contained 2.55 wt.% of H2O, 5.74 wt.% of 1,3-dioxolane which was substantially
all the 1,3-dioxolane produced in the reaction, and less than 0.21 wt.% of EG, as determined
by GC.
At the end of the reaction, based on the water analysis, the amount of 1,3-dioxolane
collected in the DS trap was 1.30 grams (0.018 mole). As in Example 6, the discrepancy
between the GC and water analysis can be in part attributed to the factors used in the GC
method and for similar reasons, the accountability based on the water analysis is believed to
be more accurate. The amount of TMP left in the reaction mixture at the end of the
experiment increased by 1.03 grams.
Example 8
In an attempt to verify and optimize the reaction of the TMP light ends overhead
described in the previous example, with EG, the overhead material was spiked with a
relatively pure TMP-MCF. Apparatus as described in Examples 1 and 1A was charged with
250.0 grams of TMP light ends overhead containing TMP-MCF (10.38 grams, 0.07 mole),
followed by EG (18.10 grams, 0.29 mole) and finally MSA as a 70% solution (0.59 gram,
0.004 mole) and the mixture was slowly heated. When the temperature reached about 150°C
an additional 10.91 grams (0.18 mole) of EG was added and the mixture was then heated to
about 207°C. Results obtained in the manner described in Examples 6 and 7 are shown in
Table VIII.
The DS trap began filling with liquid after about 60 min. of reaction time and the
liquid in the DS trap separated into two phases after about 270 min. Additional EG was
added after about 90 min. of reaction time.
The liquid in the bottom or top phase in the DS trap was withdrawn at various
temperatures between 203 °C and 207°C and its weight and weight percent of 1,3-dioxolane
and H2O determined by GC. Results are shown in Table IX.
Based on the GC analysis, about 3.1 grams (0.04 mole) of 1,3-dioxolane was formed
in this example. The results of Examples 7 and 8 indicate that the process of this invention
for treating light ends overhead is effective in the production of 1,3-dioxolane by-product and
additional TMP indicating a reduction of total TMP-MCF in the system.
In accordance with still another aspect of the invention, the previously described acid
treatment of a composition containing a substantial percentage of TMP-BMLF or
TME-BMLF, e.g. heavy ends residue containing TMP-BMLF or TME-BMLF, obtained in
the course of producing and purifying TMP or TME by reacting n-butyraldehyde or
propionaldehyde with formaldehyde, is carried out in the presence of a monohydric or
dihydric alcohol to produce a greater amount of additional TMP or TME than would be
obtained by the acid treatment in the absence of the monohydric or dihydric alcohol, and, in
addition, an acetal by-product. In some instances, this process can be substituted for, or used
in conjunction with the previous described and separately carried out acid treatment of the
TMP-BMLF or TME-BMLF containing heavy residue in the absence of monohydric or
dihydric alcohol, and the subsequent treatment of a resulting TMP-MCF or the TME-MCF
containing stream with the monohydric or dihydric alcohol.
The TMP-BMLF or TME-BMLF containing heavy ends residue and the conditions of
the acid treatment, e.g. time, temperature and nature of the acid catalyst are the same as
described previously for the acid treatment in the absence of a monohydric or dihydric
alcohol, and the nature and amount of excess of the latter alcohol which is added to the heavy
ends residue are the same as described previously as suitable for reaction with TMP-MCF or
the TME-MCF; note that the stoichiometric amounts of alcohol necessary for complete
reaction are at least two moles of a monohydric alcohol or one mole of a dihydric alcohol per
mole of TMP-BMLF or TME-BMLF in the residue.
Examples 9 and 10 illustrate the treatment with ethylene glycol (EG) of a
TMP-BMLF containing heavy ends residue having the composition shown in Table I as
"Initial Feed".
Example 9
Apparatus as described in Examples 1 and 1A was charged first with 404.28 grams of
heavy ends residue, followed by excess EG (48.0 grams, 0.77 mole), and finally by MSA
catalyst as a 70% solution (1.48 gram, 1.08x10-2 mole). Conditions and results obtained in a
manner similar to those given in the previous examples, including weight percents
determined by GC of various components in withdrawn samples, are shown in Table X where
"NR" means "GC analyses not run".
Condensation of liquid in the DST commenced at 237 min. and the total liquid in the
DST at the end of the experiment separated into two phases, no H2O or 1,3-dioxolane was
detected in any of the withdrawn samples and the entire amounts of these compounds are
assumed to have been collected in the DST, the bottom phase of which weighed 12.41 grams
and contained by GC determination 73.59 wt.% of H2O, 9.28 wt.% of 1,3-dioxolane, and 2.93
wt.% of TMP-MCF, and the top phase of which weighed 8.69 grams and contained 2.37 wt.%
of H2O, 19.64 wt.% of 1,3-dioxolane, and 4.41 wt.% of TMP-MCF.
Example 10
The procedure of Example 9 was generally followed except that the charge was
202.14 grams of heavy residue, followed by excess EG (24 grams, 0.39 moles) and finally
MSA catalyst as a 70% solution (0.74 grams, 5.38X10-3 moles). Prior to the addition of
MSA, at a temperature of 26.7°C, the reaction solution contained, as determined by GC,
22.93 wt.% of EG, 25.71 wt.% of TMP, 4.42 wt.% of di-TMP and 17.75 wt.% of
TMP-BMLF. No TMP-MCF was detected. Conditions and result of the reaction are shown
in Table XI where "ND" means "not detected by GC".
Condensation in the DST commenced at 65 min. and liquid was collecting and
separating into two phases at 185 min. At the conclusion of the reaction, the DST bottom
phase weighed 23.31 grams and contained 10.74 wt.% of 1,3-dioxolane and 3.14 wt.% of
TMP-MCF, while the DST top phase weighed 38.73 grams and contained 25.04 wt.% of
1,3-dioxolane and 2.51 wt.% of TMP-MCF. The results of Examples 9 and 10 show that the
acid-catalyzed treatment of a TMP heavy ends residue containing TMP-BMLF in the
presence of ethylene glycol is effective in producing 1,3-dioxolane by-product and additional
TMP and reducing or eliminating the TMP-BMLF in the residue.
WE CLAIM:
1. A process for treating a composition having trimethytolakane bic-
monoRnear formal, comprising subjecting trim ethylopropane monocyclic
formal (TMP-MCF) or trimethytolethane monocycllc formal (TME-MCF) to
a transalcohorysie reaction with excess monohydric or dihydric alcohol
having from 1 to 6 carbon atoms at an elevated temperature and in the
presence of an acid catalyst to produce trimethylolpropane (TMP) or
trimethytolethane (TME) respectively, and an acetal by-product, wherein
less than 15 wt% of the acid catalyst In the reaction results in a pH of the
reaction of less than 4.
2. The process as claimed in claim 1, wherein said monohydric or dihydric
alcohol is selected from the group consisting of ethytene glycol, methanol,
1-propanol, 2-propanol, and 2-bromopropanol and said acetal by-product
is a 1,3-dioxolane, methylal, di-1-propoxymethane, di-2-propoxymethane
or dl-2-bormopropoxymethane respectively.
3. The process as claimed in claim 1, wherein said acid catalyst is selected
from the group consisting of an alkanesulfonic acid, an arylsulfonic acid, a
sulfonated cation-exchange catalyst In acid form sulfuric acid and
phosphoric acid.
4. The process as claimed in claim 1, wherein the TMP-MCF or TME-MCF is
obtained from a process comprising contacting a composition containing
at least 5 wt% trimethylolpropane bis-monolinear format (TMP-BMLF) or
trimethylolethane bis-monolinear bis-monolinear formal (TME-BMLF), no
more than 5:1% water, and no more than 0.5 wt% methanol with a strong
acid catalyst at an elevated temperature and for a sufficient period of time
to convert at least 70 wt% of the TMP-BMLF or TME-BMLF to
trimethlotproparie (TMP) and trimethyloipropane mono cyclic formal (TMP-
MCF); or trimethylolethane (TME) and trimethylolethane monocyclic
formal (TME-MCF).
5. The process as claimed in claim 1, wherein the TMP-MCF or TME-MCF is
obtained from a light ends overhead stream resulting from a finishing
treatment of crude TMP or TME.
6. The process as claimed in claim 5, wherein said monohydrlc or dihydrlc
alcohol is selected from the group consisting of ethylene glycol, methanol,
1-propanol, 2-propanol, and 2-bromopropanol and said acetai by-product
is a 1,3-dioxolane, methylal, di-1-propoxymethane, di-2-propxymethane or
di-2-bromopropoxymethane respectively.
7. The process as claimed In claim S, wherein said light ends contains 1 to
15 Wt% Of TMP-MCF Of TME-MCF.
8. The process as claimed in claim 5, wherein said acid catalyst is selected
from the group consisting of an aikaneeulfonic acid, an aryisuifonic acid, a
suifonated cation-exchange catalyst in acid form suffurte acid and
phosphoric acid.
9. The process as claimed m claim 4, wherein said composition is a heavy
ends residue obtained by removing the bulk of water, excess from
aldehyde, basis condensation agent, and purified TMP or TME
in the course of purifying a crude TMP or TME product obtained by
reacting n—buryaldehyde or proptionaldehyde respectively with
formaldehyde in an aqueous medium and in the presence of an
alkaline condensation agent.
10. The process as claim ed in Claim 9 wherein said elevated temperature is
from 30 C to 300 C and said period of time is form 2 to 8
hours.
11. The process as xclaimed in Claim 9, wherein said catalyst is selected
from the group consisting of an alkanesulfonic acid, an
arylsulfonic acid, a sulfonated cation-exchange catalyst in acid
form, sulfuricacid, and phosphoric acid.
12. The process as claimed in Claim 3,8 or 11 wherein said acid catalyst is
a toluenesulforic acid.
13. The process as claimed in claim 3, 8 or 11 wherein said acid catalyst
is a sulfonated polystyrene-based cation exchange resin in acid
form.
14. The process as claimed in Claim 3, 8 or 11 wherein said acid catalyst
is present in an amount such that the acidity of the composition
is equivalent to that contributed in the range of 0.1 to 15 wt%
of methanesulfonic acid.
15. The process as claimed in Claim 9 wherein less than 15 wt.% based upon
the weight of the total composition of a compound which forms a
low boiling azetrope with water and is substantially immiscible
with any of the components of the composition, is added to said
heavy ends residue feed to said process.
16. The process as claimed in Claim 5 wherein said alcohol is methanol and
said acetal by product is methylal.
A process for treating a composition having trim ethy lolalkane bia-monolinear
formal, comprising subjecting trimethylopropane monocyclic formal (TMP-MCF)
or trimethytolethane monocyclic formal (TME-MCF) to a transalcoholysis reaction
with excess monohydric or dihydric alcohol having from 1 to 6 carbon atoms at
an elevated temperature and in the presence of an acid catalyst to produce
trlmethytolpropane (TMP) or trimethytolethane (TME) respectively, and an acetal
by-product, wherein less than 15 wt% of the acid catalyst in the reaction results
in a pH of the reaction of less than 4.

Documents:

in-pct-2001-01218-kol-granted-abstract.pdf

in-pct-2001-01218-kol-granted-claims.pdf

in-pct-2001-01218-kol-granted-correspondence.pdf

in-pct-2001-01218-kol-granted-description (complete).pdf

in-pct-2001-01218-kol-granted-form 1.pdf

in-pct-2001-01218-kol-granted-form 13.pdf

in-pct-2001-01218-kol-granted-form 18.pdf

in-pct-2001-01218-kol-granted-form 2.pdf

in-pct-2001-01218-kol-granted-form 3.pdf

in-pct-2001-01218-kol-granted-form 5.pdf

in-pct-2001-01218-kol-granted-letter patent.pdf

in-pct-2001-01218-kol-granted-pa.pdf

in-pct-2001-01218-kol-granted-reply to examination report.pdf

in-pct-2001-01218-kol-granted-specification.pdf


Patent Number 210366
Indian Patent Application Number IN/PCT/2001/01218/KOL
PG Journal Number 40/2007
Publication Date 05-Oct-2007
Grant Date 03-Oct-2007
Date of Filing 21-Nov-2001
Name of Patentee CELANESE INTERNATIONAL CORPORATION
Applicant Address 1601 WEST LBJ FREEWAY,DALLAS,TEXAS 75234 US
Inventors:
# Inventor's Name Inventor's Address
1 CAROLYN SUPPLEE 4901, SARATOGA 628,CORPUS CHRISTI, TX 78413,UNITED STATE OF AMERICA
2 MARKS.TOBIN,J 2300 CENTRAL PARK AVENUE,EVANSTON,IL 60201(US).
3 SLIKKARD,WILLIAM,E. 4521 SHEFFIELD,CORPUS CHRISTI,TX 78411.US
4 ZEY,EDWARD,G 522 EVERGREEN,CORPUS CHRISTRI,TX78412.US
5 BROUSSARD,JERRY,D 7505 VENICE DRIVE,CORPUS CHRISTI,TX 78413.US
PCT International Classification Number C07C 29/0,C07C29/128
PCT International Application Number PCT/US00/14643
PCT International Filing date 2000-05-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 USSN09/324,435 1999-06-01 U.S.A.
2 PCT/US00/14643 2000-05-26 U.S.A.