WO1990014327A1 - Liquid surfactant polymers of tetrahydrofuran and ethylene oxide - Google Patents

Liquid surfactant polymers of tetrahydrofuran and ethylene oxide Download PDF

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Publication number
WO1990014327A1
WO1990014327A1 PCT/US1990/002909 US9002909W WO9014327A1 WO 1990014327 A1 WO1990014327 A1 WO 1990014327A1 US 9002909 W US9002909 W US 9002909W WO 9014327 A1 WO9014327 A1 WO 9014327A1
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thf
liquid surfactant
mer units
polymer product
product according
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PCT/US1990/002909
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French (fr)
Inventor
James H. Merrifield
Mohamed M. Hashem
Robert B. Login
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Rhone-Poulenc Surfactants And Specialties, L.P.
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Publication of WO1990014327A1 publication Critical patent/WO1990014327A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/20—Tetrahydrofuran
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106

Definitions

  • This invention relates to copolymers of tetrahydrofuran (THF) and ethylene oxide (EO), and, more particularly, to liquid surfactant polymers of THF and EO having a vide range of molecular weight and monomer content.
  • Surfactants based upon copolymers of THF and EO are disclosed as alternatives to nonionic surfactants.
  • Block copolymers of these monomers have a well-defined hydrophilic and hydrophobic structure and exhibit useful surface active properties.
  • block copolymers are pastes or solids at ambient temperatures which makes them very difficult to handle.
  • R-X hydrophobic portion, R, was provided by the long chain hydrocarbon radical of the alcohol, and the hydrophilic end, X, was provided by the reaction product of the THF and EO monomers.
  • Random copolymers of THF and EO are liquids, but they do not exhibit the effective surface active properties which are characteristic of the corresponding block copolymers. Random copolymers of THF and EO are produced by copolymerizing a mixture of the monomers, or by adding one monomer to the other at a substantially constant feed rate.
  • Pruckmayr in U.S. Patent 4,139,567, for example, described the preparation of random copolymers of THF and EO using acidic resins as catalysts for the
  • the disclosed process involved precharging THF and the resin catalyst and then slowly bubbling in gaseous EO at a substantially constant feed rate over a two-hour period while holding the reaction mixture at 25oC.
  • Patent 4,195,167 disclosed the formation of gradient copolymers of ethylene oxide and propylene oxide which were considered as intermediate between block and random copolymers. Such gradient copolymers of ethylene oxide and propylene oxide were produced by a process in which one of the premixed
  • concentrations of the primary and secondary polymerizable monomer feed compositions was continuously changed during the polymerization.
  • a suitable process for preparing liquid copolymers of tetrahydrofuran and ethylene oxide having effective surfactant properties was not disclosed.
  • surfactant properties i.e. surface tension reduction, low pour points, good defoaming action, and effective
  • an object of the invention is to provide liquid surfactant polymers of THF and EO which are effective surfactants over a wide molecular weight range, and, particularly, which exhibit substantial surface tension reduction, low foaming, low pour points, and useful lubricity surfactant properties.
  • Another object of the invention is to provide a process for making such liquid surfactant polymers.
  • the present invention provides a liquid surfactant polymer product which is substantially a copolymer of THF and EO monomers (mer) units.
  • the polymer structure comprises:
  • transition THF-EO copolymer segments extending outwardly from the central copolymer segment characterized by a continuously increasing EO mer unit content relative to the THF mer units therein, and
  • the liquid surfactant polymers of the invention have useful surfactant properties, including surface tension reduction, low foaming, low pour points, and effective lubricity, within a polymer molecular weight range of about 500 to 10,000, and, preferably, about 1,500 to 5,000.
  • the invention also provides a multi-stage process for making the liquid surfactant polymer product described herein. In this process, predetermined amounts of EO are added successively to a charge of THF at selected rates. Polymerization is carried out in a predetermined manner at the various stages of the process to form the desired segments of the polymer.
  • the FIGURE is a graphical illustration of the process of the invention, shoving the rate of addition of EO to a charge of THF at each stage of the process.
  • a 3-stage process is provided for preparing the liquid surfactant polymer product of the invention. During the several stages of the process, three segments of the polymer are provided, each with a predetermined monomer content.
  • the process is carried out by first charging a reactor with THF monomer reactant and a small amount of a starter compound for the polymerization.
  • the starter will enable linear polymerization of the monomers in one or more directions, depending upon the number of reactive hydrogens in the starter.
  • the starter is added in an amount of about 0.1-10 mol % of all monomers present in the reaction.
  • Representative starter compounds include monohydric or polyhydric alcohols, alcohol, such as
  • glycerol pentaerythritol, bis-phenol A, nonyl phenol, polyethylene glycol, polypropylene glycol,
  • polytetrahydrofuran and the like, and monobasic and polybasic acids, such as acetic acid, stearic acid,
  • reaction temperature is set above the boiling point of EO (10oC.) and below about 80oC, preferably about
  • a polymerization catalyst then is added, such as a Lewis acid, of which BF 3 -etherate is one example.
  • the EO monomer reactant then is introduced slowly into the charged reactor at a low EO pressure, as shown by stage A in the FIGURE.
  • the EO pressure does not exceed about 2 psig, and preferably less than 1 psig.
  • reaction temperature gradually increases, generally, from about 45oC. to about 50o-60oC.
  • Copolymerization is thereby effected between the charged THF reactant and the small amount of added EO to form the hydrophobic central segment of the polymer which contains predominately THF mer units.
  • the EO addition is continued until about 1/2 to 2/3 of the THF charge is consumed.
  • This segment preferably includes, relatively, about 10-20 THF mer units to about 2-4 EO mer units.
  • transition THF-EO copolymer segments of the polymer which extend outwardly from the central copolymer segment.
  • transition segments are characterized by a continuously increasing EO mer unit content relative to the THF mer units therein.
  • the rate of EO addition is increased slowly, for example, up to about 5-8 psig., over a period of about an hour, as shown in the graph.
  • the EO addition during this stage may be carried out in one step, shown as step B', or, in two successive steps, B'' and B'''.
  • the EO reaction pressure is increased to the desired level (during step B'') and then it is held constant (during step B''') for a given period of time at the reaction temperature.
  • the transition segments preferably include, relatively, about 4-15 THF mer units to about 4-30 EO mer units.
  • the EO mer unit content in these segments continuously increase outwardly and away from the central segment.
  • the transition segments Upon determination by analysis that substantially all the THF charge has been consumed in stage B, the transition segments then are capped with hydrophilic EO polymer termini segments during stage C of the process.
  • stage C also is carried out in two steps, namely, step C, in which the EO pressure is increased substantially, e.g. to about 20 psig, and step C'', wherein the remainder of the EO reactant is added.
  • the termini segments preferably contain about 3-40 EO mer units, although lower and higher amounts also may be present.
  • the reactor then is purged with nitrogen, cooled, e.g. to about 35oC, and the reaction product is
  • reaction product mixture then is
  • the polymer product obtained thereby is a clear, colorless viscous liquid, containing, relatively, about 14-35 THF mer units to about 9-100 EO mer units.
  • the molecular weight of the polymer product suitably is about 500 to about 10,000, and preferably about 1,500 to 5,000.
  • the product exhibits excellent surfactant properties of substantial surface tension reduction, low foaming, low pour points, and effective lubricity.
  • a dry, stainless steel reactor was charged with 256 g. (2.85 moles) of butanediol and 8,616 g. (119 moles) of THF (maximum water content of 0.01%). The reactor was sealed, purged with nitrogen and warmed to 45oC. Then a solution of 10 g. of boron trifluoride-etherate in 15 ml. of diethyl ether was added. Ethylene oxide (3,258 g., 74 moles) then was slowly pumped into the reactor at a slov rate such that the reaction pressure was about 1 psig. This pressure
  • the rate of EO addition then was slowly increased during about an hour so that a reaction pressure of about 5-8 psig was reached. Thereafter, the reaction mixture is maintained at this pressure for 3 hours while the reaction temperature was controlled at 60oC.
  • the rate of EO addition then was increased within a period of about 15 minutes until the reaction pressure reached about 20 psig. Meanwhile, the reaction temperature was controlled at 60oC. The remaining EO reactant then was added for about 2-1/2 hours. Then the mixture was stored for an hour.
  • the reaction product was then purged with nitrogen for 15 minutes, cooled to 35oC, and discharged.
  • Magnasol 50 g. was added and the mixture was stirred for 2 hours at 65oC.
  • the Magnasol was removed by filtration and the product was vacuum stripped at 60oC. with a slight nitrogen sparge.
  • the product was a clear, colorless, viscous fluid.
  • Example 1 The procedure of Example 1 was followed using different amounts of the THF monomer reactant, initiator and catalyst, and EO rate of addition.
  • the products obtained were liquid surfactant polymers of varying
  • the molecular veights, surfactant and other physical properties of the polymers of the invention are shovn in Table 2 below.
  • surfactant properties as evidenced by the substantial surface tension reduction.
  • these surfactants exhibit low foaming, low pour point and excellent lubricity properties.

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Abstract

Liquid surfactant polymer products of tetrahydrofuran and ethylene oxide, and process for making the same, are provided herein. The polymers comprise a hydrophobic central segment, transition copolymer segments extending outwardly from the central segment characterized by a continuously increasing EO mer unit content relative to the THF mer units therein, and hydrophilic termini segments of substantially EO mer units.

Description

LIQUID SURFACTANT POLYMERS OF
TETRAHYDROFURAN AND ETHYLENE OXIDE
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to copolymers of tetrahydrofuran (THF) and ethylene oxide (EO), and, more particularly, to liquid surfactant polymers of THF and EO having a vide range of molecular weight and monomer content.
2. Description of the Prior Art
Surfactants based upon copolymers of THF and EO are disclosed as alternatives to nonionic surfactants.
Block copolymers of these monomers have a well-defined hydrophilic and hydrophobic structure and exhibit useful surface active properties. Unfortunately, block copolymers are pastes or solids at ambient temperatures which makes them very difficult to handle.
Kuwamura et al., in the J. of Am. Oil Chem. Soc. 51, 29-34 (Feb., 1971), described block copolymers of ethylene oxide and polyoxytetramethylene glycols prepared by cationic polymerization of tetrahydrofuran as being solids with surfactant properties albeit with rather high pour points and poor defoaming action. Grief et al., in U.S. Patent 4,038,296, described modified block copolymers of THF and EO which included a long chain (C8-C21) alcohol. Their product was defined as R-X in which the hydrophobic portion, R, was provided by the long chain hydrocarbon radical of the alcohol, and the hydrophilic end, X, was provided by the reaction product of the THF and EO monomers. These copolymers were disclosed to be useful as textile auxiliaries and surfactants.
Random copolymers of THF and EO, on the other hand, are liquids, but they do not exhibit the effective surface active properties which are characteristic of the corresponding block copolymers. Random copolymers of THF and EO are produced by copolymerizing a mixture of the monomers, or by adding one monomer to the other at a substantially constant feed rate.
Pruckmayr, in U.S. Patent 4,139,567, for example, described the preparation of random copolymers of THF and EO using acidic resins as catalysts for the
polymerization. The disclosed process involved precharging THF and the resin catalyst and then slowly bubbling in gaseous EO at a substantially constant feed rate over a two-hour period while holding the reaction mixture at 25ºC.
Langdon et al., in U.S. Patent 4,183,821, disclosed random-block copolymers of THF and EO which were prepared by a two-stage process. The first stage of the process comprised forming the random hydrophobic portion of the polymer by reacting a mixture of THF and SO in the presence of a Lewis acid catalyst. The hydrophobic segment then was capped with a hydrophilic block of ethylene oxide units by a base-catalyzed reaction with EO. The product was a random-block copolymer characterised by an abrupt break between its hydrophobic segment and its hydrophilic cap. Demulsifying properties were observed for such polymers but it was not apparent that they had effective surfactant properties. Knopf et al., in U.S. Patent 4,195,167, disclosed the formation of gradient copolymers of ethylene oxide and propylene oxide which were considered as intermediate between block and random copolymers. Such gradient copolymers of ethylene oxide and propylene oxide were produced by a process in which one of the premixed
concentrations of the primary and secondary polymerizable monomer feed compositions was continuously changed during the polymerization. However, a suitable process for preparing liquid copolymers of tetrahydrofuran and ethylene oxide having effective surfactant properties was not disclosed.
The following references are also of interest in this field: U.S. Patents: 3,133,095; 3,194,772; 3,254,056; 3,344,088; 3,359,332; 3,425,999; 3,644,567; 3,834,935;
4,065,520; 4,118,326; 4,198,464; 4,259,405; and 4,299,993; Brit. Pat. No. 854,958; Japan Patent Announcement No.
213-1977; and an article by Murbach, W. and Adicoff, A. in Ind. & Eng. Chem., 52, 7725 (1960).
None of the above cited references, however, disclose, describe or suggest a suitable method for
preparing copolymers of THF and EO which are liquids at ambient temperatures, and which exhibit effective
surfactant properties, i.e. surface tension reduction, low pour points, good defoaming action, and effective
lubricity, and wherein such copolymers exhibit these advantageous surfactant properties over a wide range of molecular weights and monomer content.
Accordingly, an object of the invention is to provide liquid surfactant polymers of THF and EO which are effective surfactants over a wide molecular weight range, and, particularly, which exhibit substantial surface tension reduction, low foaming, low pour points, and useful lubricity surfactant properties.
Another object of the invention is to provide a process for making such liquid surfactant polymers.
These and other objects and features of the invention will be made apparent from the following summary and description of the invention.
SUMMARY OF THE INVENTION
The present invention provides a liquid surfactant polymer product which is substantially a copolymer of THF and EO monomers (mer) units. The polymer structure comprises:
(1) a hydrophobic central THF-EO copolymer segment containing predominately THF mer units,
(2) transition THF-EO copolymer segments extending outwardly from the central copolymer segment characterized by a continuously increasing EO mer unit content relative to the THF mer units therein, and
(3) hydrophilic termini polymer segments of substantially EO mer units.
The liquid surfactant polymers of the invention have useful surfactant properties, including surface tension reduction, low foaming, low pour points, and effective lubricity, within a polymer molecular weight range of about 500 to 10,000, and, preferably, about 1,500 to 5,000. The invention also provides a multi-stage process for making the liquid surfactant polymer product described herein. In this process, predetermined amounts of EO are added successively to a charge of THF at selected rates. Polymerization is carried out in a predetermined manner at the various stages of the process to form the desired segments of the polymer.
BRIEF DESCRIPTION OF THE DRAWING
The FIGURE is a graphical illustration of the process of the invention, shoving the rate of addition of EO to a charge of THF at each stage of the process.
DETAILED DESCRIPTION OF THE INVENTION
As illustrated in the FIGURE, a 3-stage process is provided for preparing the liquid surfactant polymer product of the invention. During the several stages of the process, three segments of the polymer are provided, each with a predetermined monomer content.
CHARGE
The process is carried out by first charging a reactor with THF monomer reactant and a small amount of a starter compound for the polymerization. The starter will enable linear polymerization of the monomers in one or more directions, depending upon the number of reactive hydrogens in the starter. Suitably, the starter is added in an amount of about 0.1-10 mol % of all monomers present in the reaction. Representative starter compounds include monohydric or polyhydric alcohols, alcohol, such as
butanol, ethylene glycol, butanediol, decanediol ,
glycerol, pentaerythritol, bis-phenol A, nonyl phenol, polyethylene glycol, polypropylene glycol,
polytetrahydrofuran, and the like, and monobasic and polybasic acids, such as acetic acid, stearic acid,
succinic acid, oxalic acid, gluaric acid, benzoic acid, and the like, although others known in the art may be used as well, including primary and secondary amines, hydroxyl amines, and water. The reactor is then sealed, purged with nitrogen, and warmed to a reaction temperature. Suitably, the reaction temperature is set above the boiling point of EO (10ºC.) and below about 80ºC, preferably about
45º-60ºC. A polymerization catalyst then is added, such as a Lewis acid, of which BF3-etherate is one example.
HYDROPHOBIC CENTRAL SEGMENT
The EO monomer reactant then is introduced slowly into the charged reactor at a low EO pressure, as shown by stage A in the FIGURE. Suitably, the EO pressure does not exceed about 2 psig, and preferably less than 1 psig.
During introduction of the EO monomer, in this stage of the process, the reaction temperature gradually increases, generally, from about 45ºC. to about 50º-60ºC.
Copolymerization is thereby effected between the charged THF reactant and the small amount of added EO to form the hydrophobic central segment of the polymer which contains predominately THF mer units. The EO addition is continued until about 1/2 to 2/3 of the THF charge is consumed. This segment preferably includes, relatively, about 10-20 THF mer units to about 2-4 EO mer units. TRANSITION COPOLYMER SEGMENTS
Substantially all of the remaining THF reactant then is copolymerized with newly added EO, in stage B, to form the transition THF-EO copolymer segments of the polymer which extend outwardly from the central copolymer segment. These transition segments are characterized by a continuously increasing EO mer unit content relative to the THF mer units therein.
To form the transition segments, the rate of EO addition is increased slowly, for example, up to about 5-8 psig., over a period of about an hour, as shown in the graph. The EO addition during this stage may be carried out in one step, shown as step B', or, in two successive steps, B'' and B'''. In the latter pathways, the EO reaction pressure is increased to the desired level (during step B'') and then it is held constant (during step B''') for a given period of time at the reaction temperature. At the conclusion of stage B, substantially all of the
remaining THF charge is consumed to provide the transition segments. Generally, the transition segments preferably include, relatively, about 4-15 THF mer units to about 4-30 EO mer units. The EO mer unit content in these segments continuously increase outwardly and away from the central segment.
HYDROPHILIC TERMINI SEGMENTS
Upon determination by analysis that substantially all the THF charge has been consumed in stage B, the transition segments then are capped with hydrophilic EO polymer termini segments during stage C of the process.
These caps are provided by feeding EO into the reactor at an increased rate. Generally, stage C also is carried out in two steps, namely, step C, in which the EO pressure is increased substantially, e.g. to about 20 psig, and step C'', wherein the remainder of the EO reactant is added. The termini segments preferably contain about 3-40 EO mer units, although lower and higher amounts also may be present.
ISOLATION OF PRODUCT
The reactor then is purged with nitrogen, cooled, e.g. to about 35ºC, and the reaction product is
discharged. The reaction then is terminated by complexing the catalyst for example, with a diatomaceous earth or by ion-exchange. The reaction product mixture then is
stirred, filtered and vacuum stripped of volatiles. The polymer product obtained thereby is a clear, colorless viscous liquid, containing, relatively, about 14-35 THF mer units to about 9-100 EO mer units.
The molecular weight of the polymer product suitably is about 500 to about 10,000, and preferably about 1,500 to 5,000. The product exhibits excellent surfactant properties of substantial surface tension reduction, low foaming, low pour points, and effective lubricity.
The invention will now be described by reference to the following examples.
EXAMPLE 1
A dry, stainless steel reactor was charged with 256 g. (2.85 moles) of butanediol and 8,616 g. (119 moles) of THF (maximum water content of 0.01%). The reactor was sealed, purged with nitrogen and warmed to 45ºC. Then a solution of 10 g. of boron trifluoride-etherate in 15 ml. of diethyl ether was added. Ethylene oxide (3,258 g., 74 moles) then was slowly pumped into the reactor at a slov rate such that the reaction pressure was about 1 psig. This pressure
corresponds to an EO flow rate of approximately 300 g. of EO per hour. During the addition, the reaction temperature gradually increased to about 50º-60ºC. After 4 hours, approximately 1200 g. of EO had been added for
copolymerization with the charged THF reactant.
The rate of EO addition then was slowly increased during about an hour so that a reaction pressure of about 5-8 psig was reached. Thereafter, the reaction mixture is maintained at this pressure for 3 hours while the reaction temperature was controlled at 60ºC.
The rate of EO addition then was increased within a period of about 15 minutes until the reaction pressure reached about 20 psig. Meanwhile, the reaction temperature was controlled at 60ºC. The remaining EO reactant then was added for about 2-1/2 hours. Then the mixture was stored for an hour.
The reaction product was then purged with nitrogen for 15 minutes, cooled to 35ºC, and discharged. Magnasol (50 g.) was added and the mixture was stirred for 2 hours at 65ºC. The Magnasol was removed by filtration and the product was vacuum stripped at 60ºC. with a slight nitrogen sparge. The product was a clear, colorless, viscous fluid.
EXAMPLES 2 - 10
The procedure of Example 1 was followed using different amounts of the THF monomer reactant, initiator and catalyst, and EO rate of addition. The products obtained were liquid surfactant polymers of varying
molecular weights having effective surfactant and other physical properties.
The process parameters of Examples 1-10 are shown in Tables 1 and 2 below.
Figure imgf000012_0001
The molecular veights, surfactant and other physical properties of the polymers of the invention are shovn in Table 2 below.
Figure imgf000014_0001
The results in Table 2 show that the liquid surfactant polymers of the invention have excellent
surfactant properties, as evidenced by the substantial surface tension reduction. In addition, these surfactants exhibit low foaming, low pour point and excellent lubricity properties.
Although the invention has been described with reference to certain embodiments thereof, it will be understood that changes and modifications may be made which are within the skill of the art.

Claims

WHAT IS CLAIMED IS:
1. A liquid surfactant polymer product consisting essentially of:
(a) a hydrophobic central THF-EO copolymer segment containing predominately THF mer units,
(b) transition THF-EO copolymer segments extending outwardly from said central copolymer segment characterized by a continuously increasing EO mer unit content relative to the THF mer units therein, and
(c) hydrophilic termini polymer segments of substantially EO mer units.
2. A liquid surfactant polymer product according to claim 1 vherein (a) includes, relatively, about 10-20 THF mer units to about 2-4 EO mer units; (b) includes, relatively, about 4-15 THF mer units to about 4-30 EO units, and (c) includes about 3-40 EO mer units.
3. A liquid surfactant polymer product according to claim 2 vherein the polymer includes, relatively, about 14-35 THF mer units to about 9-100 EO mer units.
4. A liquid surfactant polymer product according to claim 1 having a molecular weight of about 500 to about 10,000.
5. A liquid surfactant polymer product according to claim 4 having a molecular weight of about 1,500 to about 5,000.
6. A liquid surfactant polymer product according to claim 1 wherein (a) segment includes a starter compound.
7. A liquid surfactant polymer product according to claim 6 vherein said starter compound is selected from a monohydric or polyhydric alcohol and a monobasic or
polybasic acid.
8. A liquid surfactant polymer product according to claim 7 wherein said starter is butanediol, glycerol, butanol or decanediol.
9. A liquid surfactant polymer product according to claim 1 which is a colorless viscous liquid.
10. A liquid surfactant polymer product according to claim 1 which exhibit substantial surface tension reduction, low foaming, a low pour point, and good
lubricity properties.
11. A process for making the liquid surfactant polymer product of claim 1 which comprises:
(a) copolymerizing a charge of THF with a predetermined amount of EO to form a hydrophobic central copolymer segment containing predominately THF mer units,
(b) copolymerizing substantially the remainder of the THF charge with an increased amount of EO to form transition copolymer segments extending outwardly from the central copolymer segment and characterized by a continuously increasing EO mer unit content relative to the THF mer units therein, and
(c) forming hydrophilic termini polymer segments containing substantially EO mer units.
12. A process according to claim 11 wherein step (b) is carried out with an increasing amount of EO monomer reactant.
13. A process according to claim 11 wherein step (b) is carried out by increasing the amount of EO monomer reactant and then holding at a given level for a
predetermined period.
14. A process according to claim 11 vherein step (a) is carried out in the presence of a starter compound.
15. A process according to claim 14 vherein said starter compound is selected from a monohydric or
polyhydric alcohol and a monobasic or polybasic acid.
PCT/US1990/002909 1989-05-26 1990-05-23 Liquid surfactant polymers of tetrahydrofuran and ethylene oxide WO1990014327A1 (en)

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WO2004031260A1 (en) * 2002-09-12 2004-04-15 Basf Aktiengesellschaft Method for producing monoesters and diesters of polytetrahydrofuran and of tetrahydrofuran copolymers
WO2005030345A2 (en) * 2003-09-26 2005-04-07 Invista Technologies S.A.R.L. Alloy blends of polyurethane and latex rubber
US8765904B2 (en) 2010-09-10 2014-07-01 INVISTA North America S.à r.l. Polyetheramines, compositions including polyetheramines, and methods of making
US9193654B2 (en) * 2004-10-06 2015-11-24 Nof Corporation Cosmetic bases and cosmetics containing the same

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EP0788470A1 (en) * 1994-10-27 1997-08-13 Mobil Oil Corporation Polyether lubricants
EP0788470A4 (en) * 1994-10-27 1998-03-04 Mobil Oil Corp Polyether lubricants
WO2004031260A1 (en) * 2002-09-12 2004-04-15 Basf Aktiengesellschaft Method for producing monoesters and diesters of polytetrahydrofuran and of tetrahydrofuran copolymers
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WO2005030345A2 (en) * 2003-09-26 2005-04-07 Invista Technologies S.A.R.L. Alloy blends of polyurethane and latex rubber
WO2005030345A3 (en) * 2003-09-26 2005-12-29 Invista Tech Sarl Alloy blends of polyurethane and latex rubber
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US7537814B2 (en) 2003-09-26 2009-05-26 Invista North America S.A.R.L. Alloy blends of polyurethane and latex rubber
US9193654B2 (en) * 2004-10-06 2015-11-24 Nof Corporation Cosmetic bases and cosmetics containing the same
US8765904B2 (en) 2010-09-10 2014-07-01 INVISTA North America S.à r.l. Polyetheramines, compositions including polyetheramines, and methods of making

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AU5810990A (en) 1990-12-18
IL94498A0 (en) 1991-03-10
CA2016096A1 (en) 1990-11-26

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