United States Patent (19) 11 4,338,431

König et al. 45 Jul. 6, 1982

(54) PROCESS FOR THE PREPARATION OF 3,330,789 7/1967 Aylesworth et al. ................. 260/22
NEOPENTYL GLYCOL POLYESTERS AND 4,101,422 7/1978 Lamont et al. ........ ..., 260/84
CO-POLYESTERS 4,148,764 4/1979 Lamont et al. .... ... 260/22
4,152,512 5/1979 Downs ............... ... 528/272
75 Inventors: Klaus König, Leverkusen; Wolfgang FOREIGN PATENT DOCUMENTS
Reichmann, Duesseldorf; Manfred
Schönfelder, Leverkusen, all of Fed. 2390460 8/1978 France .
Rep. of Germany 1029136 5/1966 United Kingdom .
73 Assignee: Bayer Aktiengesellschaft, Primary Examiner-Lucille M. Phynes
Leverkusen, Fed. Rep. of Germany Attorney, Agent, or Firm-Gene Harsh; Lawrence S.
Pope; Thomas W. Roy
21 Appl. No.: 122,149 57 ABSTRACT
22 Filed: Feb. 15, 1980 The present invention relates to an improved process
(30) Foreign Application Priority Data for the preparation of neopentyl glycol polyesters by
Mar. 1, 1979 DE Fed. Rep. of Germany ....... 2907952 reacting neopentyl glycol with carboxylic acids or de
rivatives thereof in the presence of minor amounts of
51) Int. Cl............................................... C08G 63/22 glycols which boil at lower temperatures than neopen
52 U.S. Cl. .................................... 528/272; 528/274; tyl glycol. These low-boiling glycols obviate previous
560/76; 560/98; 560/127 difficulties relating to the sublimation of neopentyl gly
58) Field of Search................ 528/272, 274; 560/127, col. Thus, the present process offers safety advantages
560/76, 98 since neopentylglycol does not crystallize in the reac
56) References Cited tion apparatus and also provides better control over the
molecular ratio of acid groups to alcohol groups.
U.S. PATENT DOCUMENTS
3,055,869 9/1962 Wilson et al. ....................... 528/272 11 Claims, No Drawings
 1.
4,338,431 2
are used (e.g., ethylene glycol), there is an undesirable
PROCESS FOR THE PREPARATION OF loss in the resistance to hydrolysis of the end products.
NEOPENTYL GLYCOL POLYESTERS AND It was therefore an object of the present invention to
CO-POLYESTERS provide a process which could easily be carried out for
the preparation of neopentylglycol polyesters and co
BACKGROUND OF THE INVENTION polyesters preferably having average molecular
1. Field of the Invention weights of from about 400 to 6,000 without the above
This application relates to an improved process for mentioned disadvantages of the known art.
the preparation of neopentylglycol polyesters and co 10 This problem could surprisingly be solved by using
polyesters preferably having average molecular certain low-boiling glycols described in more detail
below at certain concentrations described below in the
weights in the range of from about 400 to 6,000. preparation of neopentyl glycol polyesters and co
2. Description of the Prior Art polyesters.
Neopentyl glycol polyesters and co-polyesters are
known. Polyurethanes produced from them are distin 15 SUMMARY OF THE INVENTION
guished by their optimum mechanical properties such as The present invention relates to a process for the
advantageous cold characteristics and exceptional resis preparation
tance to hydrolysis, which are important, for example, polyesters byoftheneopentyl
reaction
glycol polyesters and co
of:
in coatings of all types. -
Neopentyl glycol polyesters and co-polyesters are 20 (a)esters
carboxylic acids, their anhydrides and/or their
with monohydric alcohols with .
normally prepared by the solvent-free esterification of (b) neopentyl glycol and, optionally, other glycols
(a) polyvalent and optionally also monovalent, prefera boiling at higher temperatures than neopentylgly
bly divalent carboxylic acids on their anhydrides or col, wherein neopentyl glycol is present in an
esters with low-boiling monohydric alcohols: (b) neo amount between 20 and 100%, preferably between
pentyl glycol; and optionally (c) additional polyhydric 25 50 and 100% by weight, based on the total weight
alcohols, in particular higher boiling diols (Houben of component (b),
Weyl, Methoden der Organischen Chemie, Volume 14/2, accompanied by removal of the water of condensation
page 1 et seq., 1963). In such solvent-free esterification or of the monohydric alcohol, characterized in that the
processes, the major portion of the water of condensa reaction is carried out in the presence of a glycol prefer
tion or of the monohydric alcohol is first distilled off 30 ably having 2 or 3 carbon atoms which boils at a lower
after the starting components have been mixed, and temperature than neopentyl glycol, the lower boiling
esterification is then completed under vacuum, with glycol being used in quantities of from about 0.1-3% by
removal of the remainder of the water of condensation weight, preferably from 0.2-1% by weight, based on
or monohydric alcohol. It is well known that when the the polyester.
process is used for the preparation of neopentylglycol 35
polyesters or co-polyesters, technical difficulties arise at DETAILED DESCRIPTION OF THE
this stage, due to the physical properties of neopenty INVENTION
glycol, since it has a melting point of about 127 C. and The starting materials for the process according to
a boiling point at atmospheric pressure of about 208 C., the present invention include monobasic and/or polyba
but at pressures below 50 mbar, neopentylglycol boils 40 sic, preferably dibasic carboxylic acids or anhydrides
in the region of, or below, its melting point, i.e., it sub derived therefrom or esters of such carboxylic acids
limes. Since the temperature in the reaction vessel dur with monohydric alcohols boiling at a lower tempera
ing the vacuum phase of the preparation of neopentyl ture then neopentylglycol, e.g., 2-ethylhexanoic acid,
glycol polyesters is approximately from 200 to 220 C., oleic acid, phthalic acid anhydride, dimethyl tere
it is found that even at a comparatively slight vacuum 45 phthalate, isophthalic acid, trimellitic acid anhydride,
neopentyl glycol enters the column in considerable maleic acid anhydride, tetrahydrophthalic acid, hexa
quantities and immediately crystallizes there. This phe hydrophthalic acid dimethyl ester, succinic acid, adipic
nomenon leads to several problems. Firstly, esterifica acid, acelaic acid, suberic acid, sebacic acid and dode
tion is accompanied by an uncontrolled lowering of the cane diacid. Adipic acid is preferably used.
concentration of neopentylglycol in the reaction vessel 50 Higher boiling diols such as the following are used in
due to sublimation losses. This cause an undesirable addition to neopentylglycol in the preparation of neo
change in the prescribed molar ratio of acid to alcohol pentylglycol co-polyesters: hexanediol, diethylene gly
groups. In the course of condensation, part of the subli col, triethylene glycol, and dipropylene glycol. These
mating neopentylglycol is deposited in those parts of polyesters are preferably mixed with hexanediol-(1,6).
the apparatus where it is liable to cause blockages, so 55 In addition, polyhydric alcohols such as glycerol, tri
that the preparation of neopentyl glycol polyesters is methylol propane, pentaerythritol or sorbitol may be
also a problem from a safety point of view. Added to added as branching components.
this are the problems of environmental contamination, The following are examples of glycols having lower
in particular, the contamination of effluent by neopenty boiling points than neopentylglycol which may be used
glycol. in the process according to the present invention: ethyl
It is known that substantial quantities of glycols ene glycol, propylene glycol-(1,2) and propylene gly
which have a higher boiling point than neopentylglycol col-(1,3). Ethylene glycol is preferred.
may be used in the preparation of neopentyl glycol As already described above, losses of neopentylgly
polyesters without impairing the properties of the syn col due to sublimation occur in the preparation of neo
thetic materials produced from the polyesters. Co 65 pentyl glycol polyesters and co-polyesters by the
polyesters of, for example, adipic acid, neopentylglycol known processes of the art. This entails the disadvan
and hexanediol are therefore particularly important. If, tages already mentioned. These disadvantages are unex
however, substantial quantities of lower boiling glycols pectedly obviated by the addition of the lower boiling
 3
4,338,431
4.
glycols at the concentrations mentioned above. Due to the presence of 2 g of tin (II) chloride as a catalyst. The
the small quantities in which these glycols are added total esterification time was 25 hours. The polyester had
according to the present invention, the properties of a hydroxyl number of 224 (m. 25 C. = 2,700 mPas).
synthetic materials produced from such neopentyl gly
col polyesters and co-polyesters are not adversely af. COMPARISON EXAMPLE
fected. Solvent-free esterification was carried out using the
The process according to the present invention thus same starting components as in Example 1 and under
opens up for the future the possibility of wider technical the same conditions but without the addition of ethyl
use of neopentyl glycol polyesters. ene glycol. Heavy deposits of neopentyl glycol were
The process according to the present invention is 10 formed in the column and particularly at the head of the
carried out at the conventional temperatures (prefera column, and a large proportion of the neopentylglycol
bly in the region of from about 150' to 220 C.) and also escaped with the water of condensation into the
conventional pressures (from atmospheric pressure to receiver provided for the latter. At the end of the esteri
about 5 mbar) used for the preparation of polyesters. fication, the hydroxyl number of the polyester was not
The usual esterification catalysts such as tin or titanium 15
within the desired range, but was 157.
compounds, for example, tin (II) chloride or titanium
tetrabutylate, may be used if desired. EXAMPLE 2
The process according to the present invention is Using a procedure analogous to that described in
preferably carried out as follows: Example 1, 4,599 g of adipic acid were esterified with
The esterification components together with the gly 20
4,056 g of neopentylglycol with the addition of 50 g of
cols used according to the present invention, which ethylene glycol (0.7%, based on the polyester) within
have a lower boiling point than neopentyl glycol, are 30 hours, first at atmospheric pressure up to 200° C. and
introduced into a suitable reaction vessel under nitro then, in the presence of 200 mp of tin (II) chloride as a
gen. This reaction vessel is equipped with a distillation catalyst, at a reduced pressure (down to 20 mbar). The
column with a cooling device attached to remove the 25
hydroxyl number of the polyester was 112 (m. 25
water of condensation or monohydric alcohol formed C. = 6,900 mPa.s).
in the preparation of the polyester. The reaction mix
ture is then heated with stirring, the temperature being EXAMPLE 3
raised to about 200 to 220" C. as the water or monohy 5,190 g of adipic acid were reacted with 3,098 g of
dric alcohol is progressively removed. It is not advis 30
hexane diol-(1,6) and 1,487 g of neopentylglycol with
able to increase the temperature above this range due to the addition of 90 g of propylene glycol-(1,2) (1%,
the risk of discoloration of the reaction product. When based on the polyester) using a procedure analogous to
the bulk of the water or monohydric alcohol has been
removed, the pressure in the reaction vessel is reduced. that described in Example 1. Esterification was com
The catalyst is generally added at this stage. Esterifica 35 pleted after 30 hours. The hydroxyl number was 66 (m
tion is completed under continuous reduction of pres 75° C. = 400 mPa.s).
sure down to a final pressure of about 200-5 mbar (de Although the invention has been described in detail
pending on the average molecular weight), so that the for the purpose of illustration, it is to be understood that
residues of water or monohydric alcohol escape. The such detail is solely for that purpose and that variations
total time required for preparation of the polyester is 40 can be made therein by those skilled in the art without
from about 20 to 50 hours. The process according to the departing from the spirit and scope of the invention
present invention may be carried out batchwise or con except as it may be limited by the claims.
tinuously using the methods known in the art. What is claimed is:
The neopentyl glycol polyesters and co-polyesters 1. A process for the preparation of neopentylglycol
prepared by the process according to the present inven 45 polyesters and co-polyesters which comprises reacting:
tion may be used as starting materials for numerous (a) carboxylic acids, their anyhydrides or their esters
synthetic products, for example, for the production of with monohydric alcohols; with
polyester resins, polyurethane foams, adhesives, PUR (b) neopentyl glycol and, optionally, other glycols
thermoplasts, lacquers and coatings of all kinds. In addi boiling at higher temperatures than neopentylgly
tion to good cold characteristics, they impart to these 50 col, wherein neopentyl glycol is present in an
materials exceptional resistance to hydrolysis and resis amount between 20 and 100% by weight based on
tance to light and heat. the total weight of neopentylglycol and the higher
The examples given below serve to illustrate the boiling glycols,
present invention. All percentages given are percent accompanied by removal of the water of condensation
ages by weight unless otherwise indicated. 55 or of the monohydric alcohol, characterized in that the
EXAMPLE 1 reaction is carried out in the presence of from about
0.1-3% by weight, based on the polyester, of a glycol
An apparatus customarily used for solvent-free esteri boiling at lower temperatures than neopentylglycol.
fication, consisting of a reaction vessel, column and 2. The process according to claim 1, characterized in
attached condenser, was rinsed with nitrogen. 44.57 kg 60 that the amount of neopentyl glycol is between 50 and
of adipic acid and 48.91 kg of neopentyl glycol were 100% by weight, based on the total weight of compo
then introduced with the addition of 0.5 kg of ethylene nent (b).
glycol (0.6% based on the polyester). The reaction 3. The process according to claim 1 or claim 2, char
mixture was heated to 200 C. at atmospheric pressure, acterized in that from about 0.2-1% by weight, based
during which operation most of the water of condensa 65 on the polyester, of the low-boiling glycol is used.
tion was distilled off. Condensation was then completed 4. The process according to claim 1 or claim 2, char
with removal of the remaining water at the same tem acterized in that the low-boiling glycol used is ethylene
perature and at reduced pressure (down to 120 mbar) in glycol.
 4,338,431 6
5
5. The process according to claim 1, characterized in col, wherein neopentyl glycol is present in an
that the reaction is carried out at a temperature between amount between 20 and 100% by weight based on
about 150' to 220 C. the total weight of neopentylglycol and the higher
6. The process according to claim 1, characterized in boiling glycols,
that the reaction is carried out at a pressure between 5 accompanied by removal of the water of condensation
about 5 to 1000 mbar. or of the monohydric alcohol, characterized in that the
7. The process according to claim 1, characterized in reaction is carried out in the presence of from about
that the glycol boiling at lower temperatures than neo 0.1-3% by weight, based on the polyester, of a glycol
pentylglycol has 2-3 carbon atoms. boiling at lower temperatures than neopentylglycol.
8. A process for the preparation of neopenty glycol O 9. The process of claim 8, wherein said acid compo
polyesters and co-polyesters which comprises reacting: nent is selected from the group consisting of 2-ethyl
(a) an acid component exclusively selected from the hexanoic acid, phthalic acid, terephthalic acid, iso
group consisting of 2-ethyl hexanoic acid, oleic phthalic acid, tetrahydrophthalic acid, hexahydro
acid, phthalic acid anhydride, dimethyl terephthal phthalic acid, adipic, dodecane diacid, anhydrides of
ate, isophthalic acid, trimellitic acid anhydride, 15 these acids or esters of these acids with monohydric
maleic acid anhydride, tetrahydrophthalic acid, alcohols.
hexahydrophthalic acid dimethyl ester, succinic 10. The process of claim 8, wherein said acid compo
acid, adipic acid, azelaic acid, suberic acid, sebacic nent consists of adipic acid, adipic acid anhydride or
acid, dodecane diacid, anhydrides of these acids or esters of adipic acid with monohydric alcohols.
esters of these acids with monohydric alcohols; 20 11. The process of claim 1 or 8, wherein said glycol
with boiling at lower temperatures than neopentyl glycol
(b) neopentyl glycol and, optionally, other glycols consists of ethylene glycol.
k k i k sk
boiling at higher temperatures than neopentylgly
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