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United States Patent (19) 11) Patent Number: 4,521,548

Christen et al. 45 Date of Patent: Jun. 4, 1985


54 PREPARATION OF POLYETHER POLYOLS 3,919,174 11/1975 Taller .................................... 528/80
3,943,075 3/1976 Fishbein et al. ... 521/1.74
(75) Inventors: Jimmie D. Christen, Lake Jackson; 3,951,822 4/1976 Brown et al. ..... ... 252/.609
Henry B. Taylor, III, Angleton, both 4,025,466 5/1977 Jourquin et al. .. ... 521/15
of Tex. 4,029,879 6/1977 Muzzio .............. ... 536/4
4,066,580 1/1978 Falkenstein et al. ... 521/130
(73) Assignee: The Dow Chemical Company, 4,098,732 7/1978 Yukuta et al. ..... ... 521/125
Midland, Mich. 4,107,069 8/1978 Keller et al. ...... ... 252/82
21) Appl. No.: 484,132 4, 110,268 8/1978 Longley et al. ... ... 521/177
4,125,505 11/1978 Critchfield et al. ...... ... 524/317
22 Filed: Apr. 12, 1983 4,148,980 4/1979 Narayan ................... ... 521/115
4,150,206 4/1979 Jorquin et al. ........................ 521/51
51) Int. Cl. .............................................. C08G 18/14 4,166, 164 8/1979 Cenker et al. ..... ... 521/125
52) U.S. Cl. .................................... 521/167; 521/176; 4,191,815 3/1980 Jourquin et al. ...................... 521/51
568/621 4,200,699 4/1980 Treadwell ..... ... 521/124
58) Field of Search ................. 521/167, 176; 568/621 4,209,609 6/1980 Hass ....... ... 528/421
4,223,098 9/1980 Treadwell ..... ... 521/16
56) References Cited 4,228,310 10/1980 Speranza et al. . ... 568/620
U.S. PATENT DOCUMENTS 4,256,841 3/1981 Horacek et al. ...................... 521/51
4,260,728 4/1981 Turley et al. . 528/57
2,934,505 4/1960 Gurgiolo ............................. 528/413 4,273,910 6/1981
Lederer ................................. 528/48
2,983,763 5/1961 Krause .... ... 568/621 4,277,571 7/1981
Falkenstein et al. ..... ... 521/164
3,000,963 9/1961 Speramza .......... ... 568/62 4,282,330 8/1981
Austin ............... ... 521/118
3,016,404 1/1962 Beauchamp et al ... 568/62 4,284,728 8/1981 Denou et al. ... 521/155
3,030,426 4/1962 Moseley et al. ... ... 568/621 4,302,551 11/1981 Horn et al. .......................... 521/163
3,299,151 1/1967 Wismer et al..... ... 568/621
3,342,747 9/1976 Mindick et al. ... ... 252/313 S FOREIGN PATENT DOCUMENTS
3,373,122 3/1968 Porter et al. ...... ... 521/12 1344,038 1/1974 United Kingdom .
3,385,806 5/1968 Critchfield et al. ... 521/112
3,390,027 6/1968 Olberg et al. ..... ... 149/19.4 Primary Examiner-John Kight
3,395,108 7/1968 Stanley et al......... ... 524/871 Assistant Examiner-Marvin L. Moore
3,446,771 5/1969 Matsubayashi et al. .............. 524/98 Attorney, Agent, or Firm-Paul D. Hayhurst
3,626,023 12/1971 Brizgys ... ... 427/383.1
3,793,240 2/1974 Smith ............. ... 521/108 57 ABSTRACT
3,803,064 4/1974 Fishbein et al. ... 521/107 In the production of polyether polyols, the neutraliza
3,865,806 2/1975 Knode .......... ... 536/120
3,884,849 5/1975 Molbert. ... 521/124 tion of alkaline catalysts using formic acid such that no
3,892,685 7/1975 Pusey ...... ... 521/121 precipitate forms.
3,897,410 7/1975 Olstowski et al. .................. 524/792
3,914,269 10/1975 Nersasian ..................... 260/453 PH 19 Claims, No Drawings
4,521,548
1. 2
ene oxide-polyhydroxy initiator adduct is described in
PREPARATION OF POLYETHER POLYOLS U.S. Pat. No. 3,299,151. Said patent teaches the use of
an amount of formic acid sufficient to precipitate sub
BACKGROUND OF THE INVENTION stantially all of said catalyst, and requires the subsequent
This invention relates to a process for producing removal of the precipitate in order to obtain a polyol
polyether-containing compounds. More specifically, it which would be suitable for use in the production of
pertains to a process of neutralizing alkaline catalysts flexible polyurethane foams. The excess acid was re
used in the production of polyether polyols, and to moved by stripping means.
polyols produced by said process. The use of oleic acid, either alone or in combination
Polyether polyols prepared from alkylene oxides 10 with certain sulfonic acids, to neutralize basic catalysts
have been utilized in lubricants, emulsifiers, plasticizers, in polyols prepared using polyhydric alcohol initiators
solvents, and as intermediates in the preparation of is described in U.S. Pat. No. 4,110,268. The resulting
polyurethane and polyurethane-modified polyisocyanu salt is not removed from the polyol, and the salt acts as
rate foams.
15
a strong catalyst for the reaction in which the polyol is
The production of a polyether polyol from alkylene typically employed. A polyol having a high degree of
oxides is ordinarily carried out by the addition of the inherent catalytic activity due to such a salt is undesir
alkylene oxides to an initiator compound in the presence able for use in many applications. For example, intricate
of an alkaline catalyst at temperatures of from about 70 molds may be employed in the preparation of detailed
C. to about 160° C. The alkaline catalyst is usually pres parts from polyurethane and polyurethane-modified
ent in quantities of about 0.05 percent to about 1 percent 20
polyisocyanurate foams. The use of such molds makes it
by weight of the reactants. A typical production desirable to employ a polyol/polyisocyanate mixture
method involves the reaction of propylene oxide with which has a relatively long foam time so that the mold
propylene glycol in the presence of potassium hydrox may be completely filled before the mixture sets up as a
ide. The resulting crude polyol contains potassium hy foam. Clearly, it would be undesirable to employ a
droxide. The potassium hydroxide is typically removed 25
polyol having a high degree of inherent catalytic activ
so that the polyol will not react erratically with an ity in such an application.
isocyanate in polyurethane production. In view of the disadvantages of the methods of the
Various methods have been utilized to reduce the
level of residual alkaline materials in the final polyol prior art, it would be desirable in the production of
product. Among these methods are included the neu 30 polyols to have an efficient and inexpensive method of
tralization of the alkaline materials with hydrochloric neutralizing alkaline catalysts, which would not pro
acid followed by separation of precipitated alkali metal duce solid precipitates, which would not employ a toxic
salts and removal of excess acid. This method is de and corrosive neutralizing agent such as hydrochloric
scribed in U.S. Pat. No. 3,016,404. For some applica acid, and which would not produce a polyol having a
tions, the neutralization method employing hydrochlo 35 high degree of inherent catalytic activity. ..."

ric acid was an improvement over neutralization meth SUMMARY OF THE INVENTION
ods employing sulfuric acid, phosphoric acid, carbon
dioxide, and the like. The hydrochloric acid method is The present invention is such a method which com
advantageous in that effective neutralization occurs bines many of the advantages of known neutralization
rapidly and excess acid can be removed by gas stripping 40 methods and obviates at least one of the disadvantages
means. The hydrochloric acid method is disadvanta associated with the method of the prior art. The inven
geous in that hydrochloric acid is toxic and corrosive. tion is a process for the preparation of polyether-con
This method has another important disadvantage. Since taining polyols which are useful in the production of
determination of the exact amount of acid necessary to polyurethane-containing polymers, such as, for exam
neutralize the residual catalyst is extremely difficult, an 45 ple, polyurethane foams and polyurethane-modified
excess of acid is conventionally used. Thus, excess acid polyisocyanurate foams. More specifically, the inven
must be readily removable from the polyether polyol, tion is a process for neutralizing an alkaline catalyst in a
because if excess acid remains in the final polyol prod crude polyether-containing polyol by contacting said
uct, the presence of said acid may lead to undesirable polyol with formic acid under reaction conditions such
consequences. For example, excess acid may tend to 50 that the reaction products of the formic acid and the
degrade the polyether chains and may adversely affect catalyst are soluble in the polyol.
materials, such as surfactants and alkaline catalysts, In another aspect, the present invention is a polyeth
which are typically added to the polyol in the prepara er-containing polyol composition which includes:
tion of polyol master batch formulations. (a) the reaction product of at least one initiator com
Another method for effectively neutralizing the re 55 pound and at least one alkylene oxide; and
sidual alkaline materials and removal of same involves (b) the reaction product of formic acid and an alkaline
the use of solid organic acids. This method is described catalyst used to prepare the reaction product of (a);
in U.S. Pat. No. 3,000,963. Solid organic acids such as said reaction product of (b) being soluble in the reaction
oxalic, benzoic, citric, succinic, fumaric, phthalic, and product of (a).
the like were utilized to neutralize the residual alkaline 60 Further, the invention relates to polyurethane-con
materials in the crude polyether polyol. Excess acid and taining polymers, especially foams, prepared using a
the precipitated alkali metal salt were subsequently polyol prepared by the process of the present invention.
removed by filtration. One of the requirements of the Surprisingly, it has been discovered that polyols neu
solid organic acid utilized in this method is that the tralized using formic acid have a lower degree of auto
organic acid, and the salt of the acid and the alkaline 65 catalytic activity than do polyols neutralized using oleic
catalyst, be insoluble in the polyether polyol. acid or other carboxylic acids having more than one
The use of an excess of formic acid to neutralize an carbon atom. Thus, an advantage of the process of the
alkali metal hydroxide catalyst in a crude lower alkyl present invention is that polyols produced by this pro
4,521,548 4
3
cess may be used in making complex polyurethane-con The hydroxyl number is further defined by the fol
taining foam parts while leaving a foam maker maxi lowing equation:
mum flexibility with respect to the choice and concen
tration of additional catalysts to be employed in the OH-56,100/EW
formations used to make said foam parts. Additional 5
advantages of the present invention include consider wherein EW is the average equivalent weight of the
able savings of time and money resulting from the omis polyol, and wherein OH is as defined hereinbefore.
sion of filtration or centrifugation steps, which may Alkaline catalysts which may be used for the prepara
entail appreciable loss of polyol. tion of polyether polyols are well-known, and illustra
10 tive references to said catalysts include U.S. Pat. No.
DETAILED DESCRIPTION OF THE 4,209,609, U.S. Pat. No. 4,110,268, and the references
INVENTION cited therein. The teachings of these patents are incor
The process of the present invention requires formic porated herein by reference. Any alkaline catalyst
acid and a polyether-containing polyol which contains 15 known in the art may be neutralized using the process of
an alkaline catalyst. the present invention. Preferably, the alkaline catalyst
The process of the present invention is generally which is to be neutralized is a metal-containing alkaline
applicable to polyether-containing polyols which are catalyst. More preferred catalysts are those metal-con
prepared using an alkaline catalyst. Methods for the taining alkaline catalysts in which the metal is an alkali
preparation of the polyols are well-known and gener 20 metal, and of these, the alkali metal hydroxides are
ally involve the reaction of at least one alkylene oxide preferred. Examples of more preferred catalysts include
with an active-hydrogen-containing initiator compound those containing an alkali metal hydroxide or an alka
in the presence of an alkaline catalyst. Polyols suitable line earth metal hydroxide. Potassium hydroxide is the
for use in the present invention include, for example, most preferred catalyst.
polyester polyols as well as linear and branched chain 25 The formic acid may be employed in any form which
polyether polyols having aliphatic or aromatic-aliphatic neutralizes the alkaline catalyst, such as liquid anhy
character. The polyols may be prepared from known drous formic acid, aqueous formic acid, or gaseous
active-hydrogen-containing initiators used in the prepa formic acid. It is preferred to use aqueous formic acid.
ration of polyols such as amines and polyhydroxy com The formic acid is employed in an amount which is
pounds. The alkylene oxide is typically a vicinal alkyl 30 sufficient to neutralize the alkaline catalyst. Typically,
ene oxide such as ethylene oxide, propylene oxide or at least about 1 equivalent of formic acid per equivalent
butylene oxide. Alkylene oxides may be employed as of alkaline catalyst is employed, with the use of about 1
mixtures.
to about 1.1 equivalents being common. Preferably, 1
Polyether polyols and methods for their preparation equivalent of formic acid is employed.
The neutralization of the alkaline catalyst may be
are, as previously stated, well-known, and illustrative 35 accomplished by adding the formic acid to the polyol at
referenees to said polyols and methods include U.S. Pat. or near the end of the alkoxylation step in a manner such
No. 3,865,806, U.S. Pat. No. 4,125,505, U.S. Pat. No. that the formic acid is distributed evenly throughout the
4,209,609, and the references cited therein. The teach polyol. Typically, even distribution of the acid is ac
ings of these patents and references are incorporated complished by methods such as, for example, stirring or
herein by reference. 40 inert gas bubbling. Preferably, the formic acid is added
The key requirement of any polyol to be used in the to the polyol when the concentration of unreacted al
process of the present invention is that the neutralized kylene oxide in the reaction mixture is 100 ppm or less.
alkaline catalyst be soluble in the polyether polyol. For The time required to complete the neutralization is a
the purposes of the present invention, the term soluble function of the mass of the polyol to be neutralized, the
means soluble to such an extent that no precipitate 45 rate of addition of formic acid, the rate and type of
forms under the reaction or storage conditions normally mixing, the temperature, and the like.
applied to the specific polyol under consideration. Pre The temperature and pressure employed during the
ferred polyols for use in the process of the present in neutralization step is not critical so long as the amount
vention are those having a hydroxyl number of at least of formic acid employed is sufficient to completely
about 175. The most preferred polyols have a hydroxyl 50 neutralize the alkaline catalyst in the polyol. For exam
number of at least about 230. ple, when liquid formic acid is employed, the combina
As used herein, the hydroxyl number is determined tion of temperature and pressure is such that the acid
by, and defined as, the number of milligrams of potas does not vaporize to such a degree that the alkaline
sium hydroxide required for the complete neutralization catalyst is not completely neutralized. Typically, the
of the hydrolysis product of the fully acylated deriva 55 temperature of the polyol is between about 20 and
tive prepared from one gram of polyol or mixture of about 150° C. Preferably, the temperature is between
polyols. The hydroxyl number is a dimensionless quan about 50° C. and 100 C. Below 20 C. the neutralization
tity which is also defined by the following equation will proceed slowly, if at all. Above 150° C. polymer
which reflects its relationship with the functionality and degradation may occur.
molecular weight of the polyol reactant: 60 When the neutralization is complete, the reaction
mass is stripped to remove therefrom any remaining
OH=(56. x 1000x f/MW) volatiles, such as H2O, formic acid or unreacted alkyl
ene oxides.
wherein In the finished form, the polyol may be suitably re
OH = hydroxyl number of the polyol; 65 acted with a polyisocyanate to prepare a polyurethane
f= average functionality, that is, average number of containing polymer. The various methods for the prepa
hydroxyl groups per molecule of polyol; and ration of polyurethane-containing polymers, such as
MW = average molecular weight of the polyol. ppolyurethane foams and polyurethane-modified
4,521,548
5 6
polyisocyanurate foams, are well-known. For a refer EXAMPLE 2
ence to said methods and to various catalysts, blowing
agents, other additives, and polyisocyanates, see U.S. A polyurethane-containing foam is prepared using
Pat. No. 4,209,609 and the references cited therein; said the following formulation of components:
references and the teachings of U.S. Pat. No. 4,209,609 A. 35 g polyol of Example l;
are hereby incorporated herein by reference. For a B. 1 g DC 1931;
reference to catalysts suitable for promoting isocyanu C. 20 g R-1 12; and
rate group formation and the use of said catalysts, see D. 65 g Polymeric MDI3.
U.S. Pat. No. 4,302,551, the teachings of which, with DC 193 is a commercial silicone surfactant available from Dow Cor
respect to said catalysts and their use, are incorporated 10 ning Corporation.
herein by reference. R-11 is a CCl3F-type blowing agent which optionally includes a free
radical scavenger.
The polymeric methylene diphenylene diisocyanate employed is a
SPECIFIC EMBODIMENTS multifunctional polyisocyanate having an isocyanate functionality of
about 2.7. Polymeric methylene diphenylene diisocyanate is commer
The following examples are given to illustrate the cially available from several sources including e.g., Rubicon Chemicals,
invention, but these examples should not be construed 15 Inc. under the brand name RUBINATE M.
as limiting its scope. All parts and percentages are by Components A, B and C are premixed, then the pre
weight unless otherwise indicated. mix is blended with Component D for approximately 10
EXAMPLE 1.
seconds in an open cup using a high speed air driven
mixer. Some reactivity data for the resulting foam are
Toluene diamine (228 g, 1.87 moles) is melted and is given in Table I.
added to a reaction vessel having a temperature record COMPARATIVE EXPERIMENTS 3-4
ing and control means, a means for stirring, a pressure
recording and control means and a means for purging These are not embodiments of the present invention.
with inert gas. Then, 2.5g of an aqueous 50 percent by Foams are prepared using the formulation and
weight solution of KOH is added to the vessel. Ethyl 25 method of Example 2, except that the polyols are those
ene oxide (423 g, 9.61 moles) is added to a closed stor of Comparative Experiments 1 and 2, respectively.
age vessel, then propylene oxide (577 g, 9.95 moles) is Some reactivity data for the foams are given in Table I.
added to the closed storage vessel, which is at room
temperature. The ethylene oxide and propylene oxide TABLE
are then thoroughly mixed. The reaction vessel is 30
heated to 120° C.-125 C. and the mixture of vicinal FOAMS PREPARED USING POLYOLS
alkylene oxides is slowly introduced into the reaction INITIATED FROMAMINES
vessel over a period of approximately 7 hours. The Ex. 2 C.E. 3 C.E. 4
mixture in the reaction vessel is then allowed to digest, Catalyst-neutralizing formic acetic oleic
or react, until it is observed that the pressure in the 35 Acid ...t-
reaction vessel decreases until it stabilizes at from 5 to Reaction Profile (in seconds)
15 psig, The pH of the resulting polyol, Polyol A, is Cream time 88 65 4.
Gel time 280 210 75
10.5. Tack-free time 580 520 480
The reaction vessel is cooled to 90 C., and an aque Foam time 345 335 220
ous solution (1.2 g of 89.4 percent formic acid) is added 40
to the reaction vessel in order to neutralize the residual
KOH in the 1208 g of crude polyol. The contents of the Interestingly, the results summarized in Table I indi
reactor are stirred for approximately 2 hours at 90° C. cate that neutralization of amine-initiated polyols using
Then, the reaction vessel is subjected to subatmospheric formic acid provides a polyol with a lower level of
pressure to remove any remaining volatile materials, 45 inherent catalytic activity than does neutralization using
such as water or unreacted alkylene oxide(s) or formic higher molecular weight organic acids which may also
acid, to give a finished polyol product having a pH of leave soluble reaction products in a polyol.
9.2. EXAMPLE 3
COMPARATIVE EXPERIMENT 1. 50 Glycerine (7.5 pounds) is added to a reaction vessel
This is not an embodiment of the present invention. similar to that of Example 1. Then, 80 g of an aqueous
The procedure of Example 1 is repeated with the 50 percent by weight solution of KOH is added to the
following exceptions: 3 g of glacial acetic acid are vessel. The resulting mixture is heated to 110° C. under
added to 1377.8 g of a crude polyol. The pH of the reduced pressure until the mixture contains less than 0.1
finished polyol is 9.1. 55 percent water. The mixture is then cooled to ambient
COMPARATIVE EXPERIMENT 2.
temperature. Sucrose (13 pounds) is then added to the
reaction vessel. The resulting mixture is then heated to
This is not an embodiment of the present invention. 110° C. Then, 60 pounds of propylene oxide is added to
The procedure of Example 1 is repeated with the the reaction vessel over a period of approximately 12
following exceptions: 7.1 g of food grade oleic acid are 60 hours. The contents of the reaction vessel are then al
added to 1411.7 g of crude polyol. The pH of the fin lowed to digest for approximately 4 hours. The vessel is
ished polyol is 9.3. cooled to 90° C., then 100 g of an aqueous solution of
For each finished polyol, i.e., the polyol of Example formic acid (90 percent acid) is added to the vessel and
1, the polyol of Comparative Experiment 1 and the the contents are stirred for approximately 2 hours at 90
polyol of Comparative Experiment 2, the residual acid 65 C. The vessel is then heated to 110° C. under reduced
ity of the polyol is not detectable by titration, and the pressure until the contents contain less than 0.05 percent
residual alkalinity of the polyol is very low, as deter water. The pH of the product is 6.5. The hydroxyl
mined by titration. number of the polyol is 393.
4,521,548 8
7
COMPARATIVE EXPERIMENT 5 TABLE III
Approx. Formate
This is not an embodiment of the present invention. Polyol Concen
The procedure of Example 3 is repeated with the 5 Run #
Hydroxyl
No.
tration
(ppm)
Precipi-
tation
Observed
pH
following exceptions: glacial acetic acid (115 g) is em
ployed as the neutralizing acid. The pH of the finished 14
2:
57
57
6000
1000
yes
yes
4.4
4.3
polyol is 7.3. 3-k 92 6000 yes 8.4
4: 92 1000 yes 8.1
EXAMPLE 4 10 54 144 6000 yes 8.6
The method of Example 2 is repeated except that the 6. 144 1000 very slight 8.3
7. 74 6000 yes 8.8
following formulation is employed: 8 174 000 O 8.2
A. 50g polyol of Example 3; 9 174 1000 C} 3.8
0. 202 6000 yes 8.7
B. 0.75 g DC 193; 11 202 1000 O 8.2
C. 15 g R-11; and 15 12 202 1000 O 3.7
D. 50g polymeric MDI. 13 232 6000 O 4.6
14 232 6000 Ild 3.8
Some reactivity data are shown in Table II. 5 232 1000 O 4.5
COMPARATIVE EXPERIMENT 6 16 232 1000 O 3.8
17 383 6000 no 3.9
20
This is not an embodiment of the present invention. 18
19
383
667
1000
6000
IO
O
3.8
3.8
A foam is prepared using the formulation of Example 20 667 1000 no 3.7
4, except that the polyol is that of Comparative Experi *Not an embodiment of the present invention.
ment 5. Some reactivity data are shown in Table II.
TABLE II 25 The data of Table III indicate that precipitation is
FOAMS USING POLYOLS INITIATED influenced by the hydroxyl number of the polyol and
FROM HYDROXYL-CONTAINING COMPOUNDS the concentration of formate. Additionally, other fac
Ex. 4 C.E. 6 tors may affect the formation of a precipitate. An exam
Catalyst-neutralizing formic acetic 30 ple of such a factor is the cation of the formate salt. In
Acid
any case, the process of the present invention applies to
Reaction Profile (in seconds) polyether-containing polyols under conditions such that
Crean time 275 215 the reaction products of the formic acid and the catalyst
Gel time 350 30 are soluble in the polyol.
Tack-free time 500 475 As mentioned previously, the preceding examples
Foam time 510 465 35 serve only to illustrate the invention and its advantages,
and they should not be interpreted as limiting since
The results summarized in Table II indicate that neu further modifications of the disclosed invention will be
tralization of hydroxyl-initiated polyols using formic apparent to those skilled in the art. All such modifica
tions
acid gives a finished polyol having a lower level of 40 as defined are deemed to be within the scope of the invention
by the following claims.
inherent catalytic activity than does neutralization using What is claimed is:
higher molecular weight organic acids. 1. A process for neutralizing an alkaline catalyst in a
GENERAL PROCEDURE FOR crude polyether-containing polyol comprising contact
DETERMINATION OF PRECIPITATE 45 ing a polyol having a hydroxyl number of at least about
175 with formic acid under reaction conditions such
FORMATION
that the reaction products of the formic acid and the
Polyols are prepared according to the method of catalyst are soluble in the polyol.
Example 3 except that the mass of KOH, the mass of 2. The process of claim 1 wherein the catalyst is a
formic acid, and the mass of propylene oxide are varied, so metal-containing alkaline catalyst.
3. The process of claim 2 wherein the metal is an
Then, some of the finished polyols are further treated
with additional formic acid. The polyols are observed alkali metal or an alkaline earth metal.
visually in order to determine the presence of any pre 4. The process of claim 3 wherein the alkaline catalyst
cipitated material. The results of several runs are sum is an alkali metal hydroxide.
marized in Table III. 55 5. The process of claim 4 wherein the alkaline catalyst
The "observed pH” in Table III is the pH at which is potassium
6. The
hydroxide.
process of claim 1 wherein the formic acid is
the polyol is observed to determine whether there is employed as aqueous formic acid.
precipitation. The pH is measured using the following 7. The process of claim 1 wherein the polyol has at
procedure. Place 60 ml of a 10:1 by weight methanol:- 60 least one alkylene oxide chain having a random distribu
water solution in a 100-ml beaker. Add to the beaker 10 tion of units of ethylene oxide and units of at least one
g of the polyol to be tested. Mix until a complete solu higher molecular weight alkylene oxide.
tion is formed. Determine the pH at 25 C. using glass 8. The process of claim 7 wherein the randon chain
combination electrodes and a prestandardized pH meter is formed using ethylene oxide and propylene oxide.
such as, for example, a Leeds and Northrup Model 7401 65 9. The process of claim 8 wherein the initiator com
with electrodes No. 1199-30 and No. 1199-31. The hy prises at least one aromatic amine.
droxyl number of each polyol is determined according 10. The process of claim 9 wherein the initiator com
to ASTM D-2849-69. prises toluene diamine.
4,521,548
9 10
11. The process of claim 9 wherein the initiator com- said reaction product of (b) being soluble in the reaction
prises methylene dianiline. product of (a).
12. The process of claim 1 further comprising remov- 17. A composition of claim 16 having a hydroxyl
ing water and unreacted formic acid. number of at least about 230.
13. The process of claim 12 wherein the removal is by 5 18. A polyurethane-containing polymer prepared
stripping means. using at least one polyether-containing composition of
14. The process of claim 13 wherein the stripping is claim 16.
carried out utilizing an inert gas stream. 19. A process for the preparation of polyether-con
15. A polyurethane-containing polymer prepared taining polyols comprising:
using at least one polyol prepared using the process of 10 (a) contacting at least one initiator compound with at
claim 1. least one alkylene oxide in the presence of an alka
16. A polyether-containing composition comprising: line catalyst under reaction conditions such that a
(a) the reaction product of at least one initiator com- crude polyether-containing polyol is formed; and
pound and at least one alkylene oxide, the product (b) contacting the crude polyol with an amount of
having a hydroxyl number of at least about 175; 15 formic acid which is sufficient to neutralize the
and alkaline catalyst under reaction conditions such
(b) the reaction product of formic acid and a metal- that the reaction products of the formic acid and
containing alkaline catalyst used to prepare the the catalyst are soluble in the polyol.
reaction product of (a); ck k k k sk
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