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Патент USA US3092650

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United States Patent 0 "
1
CC
3,092,640v
Patented June 4, 1963
2
ordinarily require fimther puri?cation as by recrystalliza
3,092,640
tion. However, lower concentrations of the reactants or
slightly higher concentrations of the reactants may be em
fiployed if desired for some reason.
PROCESSES FOR PREPARING BIS(HYDROXYNEO
PENTYLIDENE)
Gerald J. Mantel! and Francis R. Galiano, Kansas City,
5
Mo., and David Rankin, Kansas City, Kane, assignors
.
The reaction can be carried on by following Ia batch or
:a continuous procedure. A particularly e?icient and
to Spencer Chemical Company, Kansas City, Mo., a
‘convenient reaction set-up is a modi?ed batch procedure
corporation of Missouri
wherein the reaction mixture is continuously circulated
No Drawing. Filed Feb. 1, 1961, Ser. No. 86,296
for removal of formed product and by redntroduction
8 Claims. (Cl. 260—340.7)
10 thereof to the reaction vessel latter removal of the formed
product. lit is desirable that the reaction mixture be
This invention relates to novel methods of producing
stirred or ‘agitated during the reaction.
pentaerythritol condensation compounds. More particu
The reaction is usually conducted at an elevated temper
larly, it relates to novel processes for preparing bis(hy
ature of \at least about 40 ° C. It has been found desired to
droxyneopentylidene) pentaerythritol (also referred to in
the art as ‘8,5,5’,,6'-tetramethyl-2,4,8,l0atetraonaspiro-(5, 15 conduct the reaction at a- tempenature in the range of about
50° C. to about 100° C. with a presently preferred reac
5)-undecane-3,9-diethanol), represented by the ‘following
tion temperature being in the range of about 65° C. to
formula:
about ‘85° C. It has been iiound ‘that a highly e?icient
OH; H OHQO
01120 H CH3
reaction providing optimal yields is customarily obtained
\ /
20 when the react-ion is conducted at about 75° C. The re
\
action is conducted at one of the above temperatures for
H3
OHaC
C1120
a time sut?cient to provide reasonable yields of the de
This diol is known in the prior art; for example, it is
sired diol. It is apparent ‘that the length of the reaction
disclosed by John R. Caldwell and Benjamin S. Meeks, Jr,
period will vary dependent upon the reaction temperature
in U.S. Patent No. 2,945,008 to be useful in preparing
certain linear polyester, polyurethane, and polycarbonate 25 employed and the concentration of the reactants. Em
condensation polymers.
ploying the preferred reaction temperatures, it has been
Previously, as described in the above reference, the diol
was prepared by condensation of pentaerythritol and
reaction period, with about four to live hours presently
pentaldol (alternatively termed hydroxypivalaldehyde)
found that about two to six hours is usually a sufficient
deemed su?icient to provide a near optimum yield em
30
ploying preferred conditions, for example, employing a.
employing an organic solvent :as (the reaction medium,
reaction temperature of about 75° C. and a concentration
from which water could be .azeotropically removed. It
of pentaldol of about 20 to 30 grams per 100 ml. of re
was found following these known procedures that it was
action medium, on the basis that the theoretical ratio of
highly desired to maintain the reaction mixture as Water
the reactants is employed.
free as possible. lllustratively, in the above reference
In the reaction medium, a catalytic amount of a con
patent, it was thought that the preferred solvents were 35
densation catalyst is incorporated to promote the forma
toluene and other volatile aromatic hydrocarbon sol
tion of the desired diol from the reactants. Common
vents, which would permit the water of reaction to be re
catalysts which have been found functional in the art as
moved easily by yazeotropic distillation.
As is iapaprent, such employment of organic solvent in 40 condensation catalysts, such as sulfonic acids, for exam
ple, p-toluenesulfonic acid, can be used. Enough of the
the preparation of the diol has certain inherent dis
acid catalyst should be employed to acidify the reaction
advantages. The reaction solvents are expensive and rela
mixture. About 0.1 to about 2 grams of p-toluenesul—
tively unsafe to handle. The equipment required in the
fonic acid per 100 ml. of reaction solvent has been found
use of the organic solvents is comparatively expensive and
to
provide a satisfactory catalytic effect.
inconvenient to use, particularly ‘the mechanisms required 45
'llhe
provided ‘diol precipitates from the reaction mix
for the removal of water of reaction.
ture and, thus, can be recovered from the reaction mix
An object of this invention is to provide novel methods
of preparing bis(hydroxyneopentylidene) pentaerythritol
ture simply by following conventional ?ltration, decanta
highly e?icient method of preparing the bis(hydroxyneo~
pentylidene) pentaerythritol diol by the condensation of
the medium by evaporation. The separated crystalline
product is normally highly pure, particularly if the pre
tion, or centri?ugation procedures. If necessary or de
employing an aqueous reaction medium. Other objects
of this invention will be apparent from this disclosure. 50 sired, the separation of the diol from the aqueous reaction
medium can be augmented las by removal of part of
Accordingly, provided by this invention is a surprisingly
ferred ‘temperatures and concentrations of reactants are
pentaldol and pentaerythritol at an elevated reaction tem
perature employing ‘an aqueous medium. Pentaldol and 55 employed in its preparation, ‘and thus, as previously noted
herein, for most requirements will not require recrystal
pentaerythritol reactants are ‘added to Water in required
lization.
However, if concentrations of reactants lap
amounts in view of the fact that two mols of pentaldol
proaching saturation of the aqueous medium are em
(the usual commercial form is as its dimer) and one mol
ployed, the products of diol often do not attain the high
of pentaerythritol combine to form one mol of the diol.
‘degree
of purity obtainable using the preferred concentra
However, some excess of either reactant can be employed, 60
tions.
If it is ‘desired to recrystallize the product, re
especially the pentaldol reactant. Additionally, it has
crystallizing solvents such as a lower allcanol (e.~g., iso
been found that for the most e?‘icient formation of the
propanol), lower alkanol-water mixtures, acetone, or
diol, the higher concentrations of reactants in the aqueous
toluene,
can be employed. The produced diol can be
medium are preferred. lllustratively speaking, on rthe
washed ‘and dried if desired prior to use.
basis that the theoretical ratios of the reactants and pre
ferred reaction temperatures are employed to provide the 65 The following illustrative examples are in further ex
planation of the invention but are not in limitation thereof:
diol, for best results from ‘about 20 to about 35 grams on
the basis of pentaldol per 100 ml. of the aqueous reac
EXAMPLE I
tion medium are employed. At these higher concentra
Preparation
of
Bis(hydroxyneopentylidene)
tions ofreactants, normally :a highly pure diol product is 70
Pentaerythritol
formed during the preferred reaction periods, which prod
uct 'for use in polymer formation and other use will not
To 500 ml. of water are added 1136 grams (1.34 mols)
3,092,640
3
'4
.
rythritol having about the purity of the product of Ex
of pentaldol as its dimer (representing 27.2 g./ 100 ml. of
medium), and 91 grams (0.167 mol) of pentaerythritol,
iample I.
1
What is clamied is:
and ‘1.0 gram of p-toluenesulfonic {acid hydrate as catalyst.
1. A method of preparing bis(hydroxyneopentylidene)
pentaerythritol by the condensation of pentaldol and pen
The reaction mixture is heated ‘and maintained at about
73 ° C. for 4.5 hours. The desired product which crystal
lizes out is removed ‘by ?ltration, is washed one time
with water, and is dried in vacuo. The product consisting
of his (hydroxyneopentylidene) pentaerythritol is a white,
rcaerythritol at an elewated reaction temperature employ
ing an aqueous reaction medium.
2. The'process according to claim 1 wherein the reac-\
tion temperature employed is in the range of about 50° C.
202—203° (as determined using a Fisher-Johns melting 10 to about 100° C.
highly pure crystalline product having a melting point of
3. The process according (to claim 1 wherein the reac
point apparatus). Yield: 70%. Elemental analysis—
'Oa-lculated: C, 59.29%, H, 9.27%. Found: C, ‘59.47%,
H, 9.25%.
tion temperature employed is in the range of about 65°
stantially ‘unchanged, demonstrating the initial high purity.
C. to about 85° C. and the reaction medium contains a
catalyzing amount of a sulfonic acid condensation cata
C. to about ‘85 ° C.
4. The process according to claim 1 wherein the reac
An infrared absorption analysis using ‘a mineral oil mull
confirms the ‘formation of the desired compound. When 15 ‘ tion temperature employed is about 75 ° C.
5. The process according to claim 1 wherein the reac
the product as obtained directly from the process is re
tion temperature employed is in the range of about ‘65°
crystallized from isopropanol, the melting point is sub
EXAMPLE II
successively repeating the procedure of Example 1 us
20
ing reaction temperatures of 53 ° C. ‘and 90° C., the yields
obtained were 40 percent ‘and 43 percent of theoretical
yields, respectively.
lyst.
6. The process according to claim 1 wherein, on the
basis the theoretical ratio of reactants is employed, the
pen’naldol concentration is from about 20 to about 35
g. per 1100 ml. of the reaction medium.
EXAMPLE III
a
25' 7. The process according to claim 1 wherein, on th
basis the theoretical ratio of reactants is employed, the
pentaldol concentration is from about 20 to about 35
grams per 100 ml. of the reaction medium, and the re
action temp'erature employed is in the range of about
Repeating the procedure of Example I with the excep
tion that 13.6 g. of pentaldol/ 100 ml. of reaction medium
was ‘employed and the pentaerythritol concentration was
‘65° C. to about i85 ° C.
proportionally reduced, the yield obtained was 6.8 g. (34 30 '8. The process according to claim 1 wherein, on the
percent of theory).
basis the theoretical ratio of reactants is employed, the
pentaldol concentration is from 1about 20 to about ‘35 g.
per 100 ml. of the reaction medium, and wherein the
Repeating the procedure of Example -I with the excep
tion that 36.2 :g. of pentaldol/ 100 ml. of reaction medium 35 ‘formed bis(hydroxyneopentyli-dene) pentaerythritol is re
covered.
was employed and the pentaerythritol concentration was
proportionally increased, the yield obtained
49.1 g.
References Cited in the ?le of this patent
(78 percent of theory). This product was recrystallized
EXAMPLE IV
"from an isopropanol-water mixture (70:30 parts by
weight) to provide bis(hydroxyneopentylidene) pentae
UNITED STATES PATENTS
40
2,945,008
Caldwell et a1. ________ __ July 12, 1960
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