CZ2000789A3 - High disperse emulsions and stable aqueous dispersions of polymers containing hydroxy groups - Google Patents

Abstract

A composition comprising either a) a highly dispersed emulsion; which is water dispersion medium and thermoplastic polyether s hydroxy groups disperse phase; and b) stable aqueous dispersing the thermoplastic polyether with hydroxy groups; provides an adhesive thermoplastic coating with an excellent barrier against oxygen and carbon dioxide, and where the properties of the barrier does not affect water contact. In the method of preparation stable aqueous dispersions of polyether with hydroxy groups dissolve the polyether with hydroxy groups in a solvent or it melts to form a solution or melt that is sufficient water-immiscible so it can be prepared high a dispersion emulsion with a polyether solution as a dispersion phase a water as a dispersion medium, while being highly dispersed the emulsion is diluted with water to form a stable aqueous dispersion.

Description

BACKGROUND OF THE INVENTION Field of the Invention

In I, creating a barrier against water, oxygen and carbon dioxide. The wettability of the paper surface is reduced by the use of sizing agents, whereas gas barriers can be created by coating the paper with a continuous film of a suitable material. Examples of barrier film materials are paraffin wax, polyethylene, ethylene-vinyl acetate copolymer, and polyvinylidene chloride (PVDC). Of these, PVDC has the best properties as a water, steam and oxygen barrier substance. Moreover, unlike substances that are a great barrier to oxygen, PVDC is water resistant. However, due to the high chlorine content of PVDC, the production equipment tends to corrode, thereby increasing operating costs.

It would be advantageous in the art to prepare a chlorine-free latex which can be used to prepare a coating that is effective as a small molecule barrier but whose properties do not adversely affect contact with water. Furthermore, it would be advantageous to apply a coating to the substrate without auxiliary adhesives. Furthermore, it would be advantageous in certain applications for the coating to be biodegradable and for the product to be composted immediately after its intended use.

The present invention is a composition comprising either: a) a highly dispersion emulsion comprising water as a dispersion medium and a thermoplastic polyether with hydroxy groups as a phase dispersion; or (b) a stable aqueous dispersion of a thermoplastic polyether with hydroxy groups, the structural units of which are represented by formulas I and II:

OC-R ¹ -C-OR ³ OR ⁴ OR ³ (I) or

OH

O-CH ₂ -C-CH ₂

R ⁵ »

Β CCC © »Β Β Β Β

OH x - ch ₂ - c - ch ₂ R ⁵ (H) wherein R ¹ is predominantly a hydrocarbon group; R ⁵ is independently hydrogen or an alkyl group; a is 0 or 1; R ³ is

OH CH ₂ OH

------------------- CH ₂ ——c — ch ₂ ---------------- or ----- 9 -------------------------- R ⁵ R ⁵ and R ⁴ is

wherein R ² is predominantly a hydrocarbon group or, H / H

CH ₂ f-CH-CH ₂ -O-CH ₂ -O-CH ₂ -C ₁₀ -O-CH ₂ -CH-C wherein R ⁶ is predominantly a hydrocarbon group; R ⁷ is independently hydrogen or methyl; X is

NR ⁸ z

or

R ^B · · · · · · o

OF \ \ /

R ⁸ or

-NR ⁸ -NR ⁸ R ⁸ zz wherein R ⁸ is independently a C 2 -C 20 hydrocarbon group; Z is independently hydrogen, alkylamide, hydroxyl, alkoxy, alkylcarbonyl, aryloxy, arylcarbonyl, halogen or cyano; Y is predominantly a hydrocarbon group; each m is independently from 0 to 100.

A second aspect of the present invention is a process for preparing a stable aqueous dispersion of a polyether with hydroxy groups, comprising the steps of

a) dissolving the polyether with hydroxy groups in the solvent or melting the polyether to form either a solution or a melt that is sufficiently immiscible with water so that a highly dispersion emulsion can be prepared with the polyether solution as the disperse phase and water as the dispersion medium;

b) continuously converging into the dispenser, in the presence of an emulsifying and stabilizing amount of a surfactant, wherein the water inflow rate is r _1t and the inflow rate of the polyether with hydroxy groups is r ₂ ;

c) mixing the inflow streams with a sufficient amount of shear to form a highly dispersed emulsion.

• 99 · ··············· · j · 0004 4 4 4 · · • 4 4 · · J

4 4 · · · · 4 · 4 ·· ··

d) diluting the highly dispersed emulsion with water to form a stable aqueous dispersion; and

e) removing the solvent from the highly dispersed emulsion;

wherein the polyether with hydroxy groups has structural units which are either of formula I:

OC-or ³ or ⁴ o (I) or formula II

OH OH

wherein R ¹ is predominantly a hydrocarbon group; R ⁵ is independently hydrogen or alkyl; a is 0 or 1; R ³ is _f

OH ch ₂ oh

where R ² is predominantly a hydrocarbon group, or

H

_{O-CHO-CH-C-CH2} N CH CH _2-0-CH- V -CH ₂ -O-CH ₂ - C wherein R ⁶ is predominantly a hydrocarbon group; R ⁷ is independently hydrogen or methyl; X is

ΜΙ

L z

or

R ⁸

OF \

-Ν N \ /

R ⁸ or

-NR ⁸ -NR ⁸ R ⁸ zz where ^R8 is independently each occurrence C2'C2o hydrocarbon group; Z is, independently of the occurrence of hydrogen, an alkylamide group, a hydroxyl group, an alkoxy group, an alkylcarbonal group, an aryloxy group, an arylcarbonyl group, a halogen or a cyano group; Y is predominantly a hydrocarbon group; each m is independently from 0 to 100; and wherein the ratio of feed rates r ₂ : r ₁ is such that the mean particle size of the highly dispersed emulsion is not greater than 3 microns.

The present invention addresses the needs of the art that require an adhesive thermoplastic coating that provides an excellent oxygen and carbon dioxide barrier, and the barrier properties do not adversely affect contact with water. In some embodiments, the composition provides a biodegradable coating that is particularly useful in applications where paper is used as packaging material and where it does not degrade food and where biodegradability is desired.

Giant. 1 is a graph polvdisperzitv (Dy / D _n) and the mean volume particle size (microns), the feeding rate polvmeru solution: water.

4 '4 4 ·

4 4 04 9

The thermoplastic hydroxyether polyether used for the highly dispersed emulsions or stable aqueous dispersions of the present invention has structural units which are either of formula I:

oc r -c-- ¹ or ³ or ⁴ R ³ R N o- or Formula II

OH OH / I \ Ω-CHo— —C-— ch ₂ - + -x — ch ₂ - I \ - C-CH ₂ -j— 0— Y R ⁵ \ L / _n R ^{5 n} (Π)

wherein X is preferably 2-hydroxyethylimino, 2-hydroxypropylimino, piperazenyl, N, N'-bis (2-hydroxyethyl) -1,2-ethylenediimino; Y is preferably isopropylidenediphenylene, 1,3-phenylene, or 1,4-phenylene; R ³ is

OH ch ₂ oh

II ch ₂ c ch ₂ or

R ⁵ R ⁵ and R ⁴ are

or

H

-CH ₂ f- CH ₂ - or ch ₂ - o ₂ - c

R ⁷ wherein R ⁵ is preferably hydrogen and preferably each m is independently from 0 to 10.

As used herein, the term "predominantly hydrocarbon group" means a divalent group which is predominantly a hydrocarbon, but may contain minor amounts of heteroatoms, or hetero groups such as oxygen, sulfur, imino, sulfonyl, and sulfoxyl.

Representative hydrocarbon groups used as R ¹ , R ² and R ⁶ are unsubstituted and hydroxyl-substituted hydrocarbons such as alkylene, cycoalkylene, alkylenarylene, poly (alkyleneoxyalkylene), alkylenthioalkylene, alkylenesulfonyl-alkylene, arylene, dialkylenarylene a diarylene sulfonyl group, a diarylene oxide group, and a diarylene sulfide group.

More preferably, in the polyethers with hydroxy groups, independently of one another, R ¹ , R ² and R ^{6 are} methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethylene, okamethylene, nonamehylene, decamethylene, dodecamethylene,

1,4-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclohexylene, p-phenylene, m-phenylene, o-phenylene, 2,6-naphthalene, diphenylene-isopropylidene, sulfonyldiphenylene, carbonyldiphenylene, or 9,9-fluorenediphenylene .

The poly (hydroxy ester ethers) which are represented by the general formula (I) can be prepared by reacting diglycidyl esters of aliphatic or aromatic diacids, such as diglycidyl terephthalate, or diglycidic ethers of dihydroxy benzenes or aliphatic diols with aliphatic or aromatic acids such as adipic or terephthalic acid. as described in US 5,171,820 or 5,496,910.

The poly (hydroxy amino ethers) represented by the general formula II (where n = 1) can be prepared by reacting one or more dihydroxy benzenes diglycidyl ethers with an amine having two hydrogen atoms on nitrogen atoms under conditions sufficient to react the amine groups and epoxy groups to form a polymer chain in which the amine bond, the ether bond, and the attached hydroxyl groups. These polyethers are described in U.S. Pat. No. 5,275,853. These polymers can also be prepared by reacting diglycidyl ethers or epihalohydrins with diamines.

Poly (hydroxy amino ethers), which are represented by the general formula II (where n = 0), by reaction of diglycidyl ethers or a combination with diglycidyl ethers with dihydroxybenzene or a combination of dihydroxybenzenes as described in U.S. Pat. No. 5,164,472. Alternatively, the hydroxy group may be prepared by reacting dihydroxybenzene or a combination of dihydroxybenzenes with epihalohydrin as described by Reinking, Barnabeo and Hale in Journal of Applied Polymer Science, vol. 7, pp. 2Λ35 (1963). ___________________________

A more preferred hydroxyether polyether comprises the structural units formed by the reaction of diglycidyl ether of biphenol A and adipic acid.

The preferred average molecular weight of the hydroxy group polyether (as determined by gel permeation chromatography) is not less than 1000 Daltons, more preferably not less than 10,000 Daltons, and most preferably not less than 20,000 Daltons and preferably not more than 250,000 Daltons and more preferably not more than 100,000 Daltons.

The stable aqueous dispersion of the polyether with hydroxy groups may be prepared by any suitable method as described in U.S. Pat. patents 3,360,599; 3,503,917; 4,123,403; 5,037,864 and 5,539,021. Advantageously, a highly dispersed emulsion is prepared first which, by dilution with water, results in a stable aqueous dispersion of the hydroxy-functional polyether.

A highly dispersed emulsion of a polyether with hydroxy groups may also be prepared by any suitable method as described in US patents 4,018,426; 5,250,576; and 5,539,021. Preferably, the highly dispersed emulsion is prepared by continuously filling the dispenser in the presence of an emulsifying and stabilizing amount of a surfactant, at a water flow rate of n, a polyether hydroxy group feed rate of r ₂ , and mixing the feeds with sufficient shear. The ratio of the feed rates is r ₂ ; ri, preferably within such a range that the polydispersity of the highly dispersed mixture, which is defined as the ratio of the mean particle size to the average particle size (D _v / D _n ), is not more than 3, more preferably greater than 2 and most preferably not greater than 1.3; or the mean particle size volume, as measured using a Coulter LS230 particle size analyzer (Coulter Instrumets), b. · <····· • · · · * ·. Is not more than 3 microns, more preferably not more than 1 microns, and most preferably not more than 0.5 microns.

From Figure 1, which shows the dependence of polydispersity (dotted lines, solid circles) and particle size (solid lines, bounded circles) on the dosing ratio (polymer solution: water), the dosing ratio giving the best results is not less than 3.5 , more preferably not less than 3.8, and not more than 4.5, and more preferably not more than 4.4. The polymer solution is 45 wt. a polyhydroxy ether ester (prepared as described in the Examples, Part B) in a mixture of toluene; and

1-butanol (60:40 ratio). It is surprising that aqueous dispersions of polyether with hydroxy groups, which are polydisperse and whose particles are of small size, can be prepared in the absence of grafted functional groups, such as those containing carboxylic acids.

The hydroxyether polyether is preferably dissolved in an organic solvent or solvent mixture such that the flow containing the hydroxyether polyether has a sufficiently low viscosity to be pumped through a duct. Alternatively, the otherwise non-pumpable polyether with hydroxy groups may be pumped after heating. Preferably, the polyether with hydroxy groups is dissolved in a solvent or solvent mixture. The solvent or solvent mixture must satisfy the condition that a polymer solution that is sufficiently immiscible with water to form a highly dispersed emulsion of the polymer solution in water. Preferred solvents are glycol ethers such as propylengylycol methyl ether acetate; a preferred solvent mixture is a mixture of a non-polar solvent and a C 1 -C 5 alcohol such as a combination of toluene and α-butanol.

The surfactants used to stabilize the highly dispersed emulsion are preferably anionic or nonionic, or a mixture thereof. A preferred nonionic surfactant is of formula IV:

-i n ’

--R ³ OCCHCHCO - R ° O »· ··.

- · · »·

•. .. · · ft ft ft ft ft ft ft ft ftft ··

R ⁹ R ¹⁰

X '(IV)

Wherein R ⁶ and R ³ are as defined above; R 0 is alkylene, preferably C 2 -C 12 alkylene, more preferably ethylene, propylene or butylene, most preferably ethylene; R ⁹ and R ¹⁰ are independently hydrogen, C1-C20 alkyl or C1-C20 alkenyl group, preferably hydrogen, C1-C12 alkyl or alkenyl group CrCl _2, most preferably hydrogen or 2-dodecane-1-yl; n 'and x' are positive integers; and R ⁶ is preferably diphenylene-isopropylidene.

The polymeric surfactant of formula (IV) may be prepared by reacting a polyoxyalkylene glycol, preferably polyoxyethylene glycol, with an anhydride in a 1: 2 molar ratio of glycol: anhydride to form a diacid intermediate that reacts with diglycidyl ether, preferably diglycidyl ether biphenol A using a diglycidyl molar ratio. The following reaction scheme illustrates this preparation.

A more preferred surfactant is the combination of a polymeric surfactant of formula (IV) with an anionic surfactant such as sulfonates and sulfates of ethoxylated phenols such as poly (oxy-1,2-ethanediyl) a-sulfonononylphenoxy) ammonium salt (available as Rhodapex ™ co 436, trademark of Rhone Poulenc); or dialkyl esters ii

9 * 4 · ·· ·

• sodium sulfosuccinate such as dioctyl ester of sodium sulfosuccinate (available as \

Aerosol OT 75, Cytec Industries inc., Division of American Cyanamide). Preferably, the molar ratio of the anioactive surfactant to the polymeric surfactant is not more than 2: 1, more preferably not more than 1: 1.

The highly dispersed emulsions can be simply diluted with water, preferably with stirring to form a stable aqueous dispersion. If an organic solvent is present, it can advantageously be removed from the stable aqueous dispersion by any suitable water dispersion. jar \ uc vor \ uuva ucouiacc.

The following examples are illustrative only and in no way limit the invention.

DETAILED DESCRIPTION OF THE INVENTION

Example 1- Preparation of a stable aqueous dispersion of a polyether with hydroxy groups by a continuous process

A. Preparation of a polymeric surfactant

In a multi-necked flask equipped with a mechanical stirrer, condenser and nitrogen inlet was added polyethylene glycol 400 (MW 400, 319.5 mmol), polyethylene glycol 4500 (MW 4500, 28.5 mmol) and succinic anhydride (696) with stirring. mmol). The reactants were heated at 90 ° C for 2 hours and then A1 catalyst (400 ppm 70% methanolic ethyltriphenylphosphonium acetate solution) and DER ™ 330 (trademark of The Dow Chemical Company, 330.5 mmol) were added over 90 minutes at 150 ° C. mass equivalent of epoxy compound 180). The mixture was further heated at 150 ° C for 3.5 hours after which methyl p-toluenesulfonate (280 ppm) was added. The solution was cooled and the polymeric surfactant was obtained as a yellow wax.

B. Preparation A stable aqueous dispersion using a polymeric surfactant.

The polyether with hydroxy groups was prepared from approximately equimolar amounts of bifenol A digyleidylether and adipic acid (using the same procedure as described above).

9 4 4

4 '4

No. 4,444 has been described in U.S. Pat. No. 5,496,910, paragraph 6, lines 14-25). The polymer solution was prepared by combining a hydroxyether polyether (45 g) with a polymeric surfactant (4.5 g) soaked in Part A in 65 g toluene-butanol (60:40, by weight). The polymer solution was pumped through a 1.27 cm (0.5 inch) inner diameter arm attached to the first T at a rate of 35 g / min. At the same time, the Aerosol OT 75 was pumped with a 0.32 cm (0.125 inch) inner diameter of polytetrafluoroethylene which was attached to the first T at a rate of 0.7 g / min. The water was pumped through a second arm with a 0.32 cm (0.125 inch) diameter of polytetrafluoroethylene at a rate of 7.2 g / min, which was connected through a tube with an inner diameter of 1.27 cm (0.5 inch) to the second T with a drain from the first T .

A highly dispersed polymer emulsion in water as in the dispersion medium was prepared by converging and stirring the polymer-Aerosol OT 75 flow and water flow using a 10 cm centrifugal pump at 1200 rpm. Then, the highly dispersed emulsion is passed through a second centrifugal pump together into an aqueous solvent to form a stable aqueous dispersion (latex). The organic solvents were removed from the latex in vacuo to give a 50% latex. The mean bulk particle size of the latex was measured by Coulter LS230 and was 0.569 microns (D _v / D _a = 1.3)

Industrial applicability

Stable aqueous dispersions of the polyether with hydroxy groups can be used to prepare non-chlorine coatings, are thermoplastic and have low transfer rates for oxygen and carbon dioxide. Coatings prepared from stable aqueous dispersions of poly (hydroxyester ethers) are particularly useful in applications where biodegradability is desired. Such coatings are applicable to food packaging paper or milk and juice packaging where it is desired to keep the food fresh and to compost the empty packaging.

Claims (18)

PATENT CLAIMS A composition characterized in that it comprises either a highly dispersion emulsion in which the dispersion medium is water and the dispersion phase is a thermoplastic polyether with hydroxy groups; or a stable aqueous dispersion of a thermoplastic polyether with hydroxy groups, whose structural units are represented by formulas I and II: wherein R ¹ is predominantly a hydrocarbon group; R ⁵ is independently hydrogen or alkyl; n is 0 or 1; R ³ is OH ch ₂ oh ch ₂ c ch ₂ - or 9 θ ^Η 2 r ⁵ R ⁵ and R ⁴ is where R ² is predominantly a hydrocarbon group or —ch ₂ ch — ch ₂ —o-Vch — ch ₂ —o — ch ₂ -C H ch ₂ -ch — c00 * Wherein R ⁶ is predominantly a hydrocarbon group; R ⁷ is independently hydrogen or methyl; Xje NR ⁸ z or R ° From \ N \ / ^N ' R ⁸ ___or_ -N-nR ⁸ z R ⁸ Z wherein R ⁸ is independently a C ² O 20 hydrocarbon group; Z is, independently of the occurrence of hydrogen, an alkylamide group, a hydroxyl group, an alkoxy group, an alkylcarbonal group, an aryloxy group, an arylcarbonyl group, a halogen or a cyano group; Y is predominantly a hydrocarbon group; each m is independently from 0 to 100. Composition according to claim 1, characterized in that in the highly dispersed emulsion the dispersion medium is water and the polyether with hydroxy groups is the dispersed phase. A composition according to claim 2 wherein R ⁴ is OH \ ¹ O ₂ CCH ₂ or R ^{5 2} -J- / mm is 0; R ^{1 is} ethylene, propylene, hexamethylene, p-phenylene or m-phenylene; R ² is p-phenylene, m-phenylene or diphenylene-isopropylidene; and R ⁵ is hydrogen. 9 ♦ 6 β Composition according to claim 2, characterized in that the polyether with hydroxy groups has structural units of the general formula I: O II C-OR ³ OR ⁴ OR ³ (I) wherein R ¹ is 1,4-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclohexylene, p-phenylene, m-phenylene, o-phenylene, 2,6-naphthalene, diphenylene-isopropylidene, sulfonyldiphenylene. carbonyldiphenylene, oxydiphenylene or 9,9-fluorenediphenylene; R ⁶ is methylene, ethylene, propylene, butylene, _t pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene. The composition of claim 3, wherein R ¹ is diphenylene-isopropylidene; R ⁶ is tetramethylene; and the average molecular weight of the polyether is greater than 10,000 Daltons and less than 250,000 Daltons. A composition according to claim 2, characterized in that it is prepared by the following steps a) dissolving the polyether with hydroxy groups in the solvent or melting the polyether to form either a solution or melt which is sufficiently immiscible with water so that a highly dispersion emulsion can be prepared with the polyether solution as the disperse phase and water as the dispersion medium; b) continuously converging into the dispenser, in the presence of an emulsifying and stabilizing amount of a surfactant, wherein the water inflow rate is η, and the inflow rate of the polyether hydroxy group solution is r ₂ ; and c) mixing the inflow streams with a sufficient amount of shear to form a highly dispersed emulsion wherein the feed ratio is r ₂ : r ₁ such that the particle size of the highly dispersed emulsion is less than 3 microns. * 16 »» · ¹ · '· · φ 7. A composition according to claim 6 wherein the surfactant comprises an anionic surfactant and a polymeric nonionic surfactant of Formula IV. CH ₂ OR ⁶ O — r ³ occhchco — R ° O — CCHCHCOR ³ OR ⁶ O — CH -i n ’ R ^{, L} R 'R ^{, at} x' (IV) wherein -R ⁶ is predominantly a hydrocarbon; and R ³ is_____________________________________ OH CH ₂ OH CH ₂ CH ₂ or C R ⁵ R ⁵ wherein each R ⁵ is independently hydrogen or an alkyl group; R c is C ₂ C ₂ alkylene; R ⁹ is hydrogen, alkyl alkenyl; n 'and x' are positive integers. The composition of claim 7, wherein the anionic surfactant is sulfonates and sulfates of ethoxylated phenols or dialkyl esters of sodium sulfosuccinate such as dioctyl ester of sodium sulfosuccinate; R ⁶ is diphenylene isopropylide; R ⁸ is ethylene, propylene or butylene; R ⁹ is hydrogen, C ₂ -C ₁₂ alkyl or C 2-12 alkylene; and wherein the molar ratio of the anioactive surfactant to the polymeric surfactant is less than 2: 1. The composition of claim 8, wherein the anionic surfactant is dioctyl ester sulfosuccinate; R ⁹ is 2-dodecan-1-yl or hydrogen; and ^R8 JR ethylene; and wherein the molar ratio of the anioactive surfactant to the polymeric surfactant is greater than 1: 1. 10. The composition of claim 1 comprising a stable aqueous dispersion of a thermoplastic polyether with hydroxy groups. Composition according to claim 1, characterized in that the polyether having hydroxy groups has the structural units of the general formula II: OH OH I I -O-CH ₂ -C-CH ₂ -X- CH ₂ --c _{--O-CH2-Y-Ιδ} r \ K i where X is -nch ₂ ch ₂ oh or -ch ₂ chch ₃ OH or And Y is isopropylidenediphenyl, 1,3-phenylene or 1,4-phenylene, and the average molecular weight of the polymer is greater than 1000 and less than 100,000 Daltons. Composition according to claim 1, characterized in that the polyether having hydroxy groups has structural units of the general formula: 4 «é -OCH ₂ CHCH ₂ y OH where Y is isopropylidendifenyl, 1,3-phenylene or 1,4-phenylene average polymer molecular weight is greater than 1000 a and less than 100,000 Daltons. 13. A composition according to claim 12 which is formed by reacting biphenol with dyglycidyl ether or epihalohydrin. A process for preparing a stable aqueous dispersion of a polyether with hydroxy groups, comprising the steps of: a) dissolving the polyether with hydroxy groups in the solvent or melting the polyether to form either a solution or a melt that is sufficiently immiscible with water so that a highly dispersion emulsion can be prepared with the polyether solution as the disperse phase and water as the dispersion medium; b) continuous convergence into the dispenser, in the presence of an emulsifying and stabilizing amount of a surfactant, where the water inflow rate is η, and the inflow rate of the hydroxy group polyether solution is Γ2Ι c) mixing the inflow streams with a sufficient amount of shear to form a highly dispersed emulsion. d) diluting the highly dispersed emulsion with water to form a stable aqueous dispersion; and e) removing the solvent from the highly dispersed dispersion; wherein the polyether with hydroxy groups of the structural units which are either ^one of the following formulas: oc — R ¹⁰ o c -— OR ³ OR ⁴ OR ³ (I) ·· c ··· · ··· fr · · · · · · I »; • · · < or of formula II OH OH wherein R ¹ is predominantly a hydrocarbon group; R ⁵ is independently hydrogen or alkyl; n is 0 or 1; R ³ is OH ---------------------------------------------------------------------------------------------------------------- CH _{2 -} c-CH ₂ Ø ⁵ or ch ₂ oh ---------------------------------- c — ch ₂ r ⁵ where R ⁴ is or H ckde R ² is predominantly a hydrocarbon group or a CH ₂ / CH -CH ₂ CH-CH ₂ W Η / CH ₂ - cis-1- O - CH ₂ - and ₇ CHι7 R ^{7 and} R ⁷ wherein R ⁶ is predominantly a hydrocarbon group; R ⁷ is independently hydrogen or methyl; X is -nR ⁸ I z or • ♦ · ♦ · ♦ 4 · 'é * / \ -Ν N \ 8 ^Z R ⁸ or -NR 1 - R ⁸ -N- | AND Ø ⁸ Ø ⁸ ZZ wherein R ^{8 '} is independently a CFC 6 hydrocarbon group; Z is, independently of the occurrence of hydrogen, an alkylamide group, a hydroxyl group, an alkoxy group, an alkylcarbonal group, an aryloxy group, an arylcarbonyl group, a halogen or a cyano group; Y is predominantly a hydrocarbon group; each m is independently from 0 to 100; and wherein the ratio of the feed rates is such that the mean volume of the particle size in the highly dispersed emulsion is not greater than 3 microns. The method of claim 14 wherein R ⁴ is wherein m is 0; R ¹ is ethylene, propylene, hexamethylene, p-phenylene or m-phenylene; R ² is p-phenylene or m-phenylene or diphenylene-isopropylidene; and R ⁵ is hydrogen; the average molecular weight of the polyether with hydroxy groups is greater than 10,000 and less than 100,000 Daltons. ¹⁶ 16. The method of claim 15, wherein the surfactant combines sodium dioctyl ester sulfosuccinate and a polymeric nonionic surfactant of formula (IV). CH ₂ OR ⁶ Or ³ occhchcoR ¹⁰ O • 0000 »0 · o ·. 23 -R ° OCHCHCOR ³ OR ⁶ O -I n ’ R ⁹ R ¹⁰ CH 11.1 '(IV) wherein R ⁶ is diphenylene-isopropylidene; and R ^J is OH ch ₂ oh ch _{2 —} c — ch ₂ R ⁵ or c-ch ₂ R ⁵ wherein each R ⁵ is hydrogen; R c is ethylene; R ⁹ and R ¹⁰ are hydrogen, C 2 -C 12 alkyl or C 2 -C 12 alkylene; n 'and x' are positive integers; and wherein the molar ratio of sodium dioctyl ester sodium sulfosuccinate to polymeric surfactant is less than 1: 1. 17. The process of claim 16 wherein the solvent comprises a mixture of 1-butanol and toluene or a glycol ether. The method of claim 16, wherein the glycol ether is propylene glycol methyl methyl acetate.