Process for alkoxylation with a boron-containing catalyst

Details Process for alkoxylation with a boron-containing catalyst Process for alkoxylation with a boron-containing catalyst

2001-01-19

2003-07-15

Keys, Rosalynd (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S678000

Reexamination Certificate

active

06593500

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a process for making alkoxylated organic compounds of narrow molecular weight distribution. More particularly, the invention relates to a process for alkoxylation with alkylene oxides in the presence of a boron-containing catalyst.
2. Background of the Invention
Nonionic surfactants are industrially manufactured by reaction of a organic compound with ethylene oxide using a base as catalyst e.g. sodium or potassium hydroxide. Nonionic surfactants are commonly manufactured from the ethoxylation of fatty alcohols.
When a relatively low degree of ethoxylation, i.e. one to four moles, is desired, an undesirably broad molecular weight product distribution is obtained. The broad distribution is due to the similar basicity of the alcohol and ethoxylate. Additive ethoxylation proceeds at the expense of ethoxylation of alcohol. Consequently, low mole ethoxylate products typically have relatively large amounts of unreacted alcohol. Residual alcohol in the product presents odor problems and reduces the smoke point. A low smoke point is especially problematic during the spray-drying of powdered detergents containing ethoxylated nonionic surfactants, when a low smoke point may result in undesirable volatilization of the surfactants.
In addition to higher smoke points and lower odor, ethoxylates of narrow molecular weight distribution have performance advantages over ethoxylates of broad molecular weight distribution. They include the following: (i) lower viscosity and pour point for easier handling; (ii) higher cloud point; (iii) higher initial foaming and less foam stability; (iv) better wetting properties; (v) increased interfacial surface tension reduction compared to paraffin; and (vi) higher surface tension than conventional ethoxylates.
Various processes have been proposed in the base catalysis art to reduce the molecular weight distribution of alkoxylates. Such art is seen, for example, in U.S. Pat. Nos. 3,471,411; 3,969,417; 4,112,231; 4,210,764; 4,223,163; 4,223,164; 4,239,917; 4,278,820; 4,302,613; 4,306,093; 4,360,698; 4,396,779; 4,453,022; 4,465,877; 4,453,023; 4,456,773; 4,456,697; 4,721,817; 4,727,199; 4,754,075; 4,764,567; 4,775,653; 4,885,009; 4,832,321 and 5,220,046, which are incorporated herein by reference. However, the art has to date failed to propose a base catalysis process for making alkoxylates of sufficiently narrow molecular weight distribution.
One means for making alkoxylates of narrower molecular weight distribution is to employ acid catalysis to effect polymerization. Acid catalysis has been generally disfavored, however, in the art because of the formation of relatively high levels of undesirable by-products. For instance, polyoxyethylene is formed by competing dehydration reactions and dioxane and 2-methyldioxolane are formed by competing cyclization reactions.
Processes for making alkoxylates of narrow molecular weight range with catalysts of perfluorosulfonic acid derivatives have been proposed. U.S. Pat. No. 4,483,941 discloses the use of catalyst mixtures of boron fluorides and metal alkoxides. U.S. Pat. No. 4,762,952 discloses the use of boron salts of perfluorosulfonic acid polymer. U.S. Pat. No. 4,409,403 relates to the use of a polyfluorosulfonic acid catalysts. U.S. Pat. No. 4,543,430 relates to the use of trifluoromethane sulfonic acid with Group II metals, specifically aluminum, cobalt, nickel, zirconium and tin.
It would be desirable to have a new and effective process for making alkoxylates of still narrower molecular weight distribution. Further, it would be desirable to have a process which afforded a still lower degree of residual active hydrogen organic starting material. Still further, it would be desirable to have a process which afforded a lower degree of undesirable by-products.
SUMMARY OF THE INVENTION
It is an object of the present invention to produce alkoxylated organic compounds of narrow molecular weight distribution.
It is a further object of the present invention to produce alkoxylated organic compounds and leave relatively low proportions of residual starting materials.
It is still a further object of the present invention to produce alkoxylated organic compounds with relatively low proportions of undesirable by-products.
It is still a further object of the invention to have a process for making alkoxylates of active hydrogen organic compounds requiring (a) providing an active hydrogen organic compound having an alkyl group of about 8 to about 20 carbon atoms and (b) alkoxylating the organic compound with an alkylene oxide in the presence of a catalytically effective amount of a catalyst compound corresponding to formula (I) and formula (II):
B(&phgr;)
3
  (I)
H
+
B(&phgr;)
4
−
  (II)
wherein B is a boron atom and H is a hydrogen atom; &phgr; is a phenyl moiety having substituents selected from the group consisting of 1 to 5 fluorine atoms, 1 to 5 CF
3
moieties, 1 to 5 OCF
3
or SCF
3
moieties or OR; wherein C is a carbon atom, O is an oxygen atom, S is a sulfur atom and F is a fluorine atom; wherein R is a hydrogen atom or an alkyl or aryl group having from 1 to 22 carbon atoms. The process affords a product of very narrow molecular weight distribution with a low degree of both residual active hydrogen organic starting material and undesirable by-products.
DETAILED DESCRIPTION OF THE INVENTION
In the process of the present invention, it was found surprising that alkoxylates of narrow molecular weight distribution could be prepared using certain boron catalysts. It was also surprising that such alkoxylates could be prepared leaving a relatively low degree of residual active hydrogen organic starting material and undesirable by-products.
The present process employs a catalyst compound corresponding to either formula (I) or formula (II):
B(&phgr;)
3
  (I)
H
+
B(&phgr;)
4
−
  (II)
wherein B is a boron atom and H is a hydrogen atom; &phgr; is a phenyl moiety having substituents selected from the group consisting of 1 to 5 fluorine atoms, 1 to 5 CF
3
moieties, 1 to 5 OCF
3
or SCF
3
moieties or OR; wherein C is a carbon atom, O is an oxygen atom, S is a sulfur atom and F is a fluorine atom; wherein R is a hydrogen atom or an alkyl or aryl group having from 1 to 22 carbon atoms.
Representative catalyst compounds corresponding to formula (I) include tris(pentafluorophenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(4-fluorophenyl)borane, tris(3,5 di(trifluoromethyl)phenyl)borane and tris(3,5-difluorophenyl)borane. The preferred catalyst compound is tris(pentafluorophenyl)borane.
Representative catalyst compounds corresponding to formula (II) include HB(C
6
F
5
)
3
OH and HB(C
6
F
5
)
3
OCH
3
. Others include tetrakis(pentafluorophenyl) borate (HB(C
6
F
5
)
4
) and tetrakis(2,4-di(trifluoromethyl)phenyl) borate (HB(C
6
H
3
(CF
3
)
2
)
4
.
A most preferred catalyst is tris(pentafluorophenyl)borane. Tris(pentafluorophenyl)borane has the following structure:
The catalyst is employed in the process at about 1.0×10
−6
M to about 1.0×10
−1
M based on the organic compound.
The active hydrogen organic compound employed in the present process has from 1 to 22 carbon atoms. Useful active hydrogen organic compounds include alcohols, amines, mercaptans and amides. Preferred compounds are hydrophobic and have from 1 to 22 carbon atoms. Preferred compounds are also hydroxylated. Preferred hydroxylated compounds include fatty alcohols. Fatty alcohols can be obtained from natural sources such as fats and oils or may be derived synthetically from petroleum. Natural alcohols are prepared from natural fatty acids derived from coconut oil, palm kernel oil, palm oil, tallow, soya, sperm oils and the like. Useful fatty alcohols include octanol, nonanol, decanol, dodecanol, palmityl alcohol, octadecanol, eicosanol, behenyl alcohol, and stearyl alcohol and mixtures or blends of the foregoing. A preferred fatty alcohol is dodecanol. Unsaturated alcohols such as oleoyl, linoleic and linole

Affiliated with

Also associated with

Rating

Process for alkoxylation with a boron-containing catalyst does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Process for alkoxylation with a boron-containing catalyst, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for alkoxylation with a boron-containing catalyst will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3082495