US 5,488,180 AGrant
Complex Hydrophobe Compounds
Issue Date:1996-01-30
•10 Claims
Abstract
This invention relates to complex hydrophobe compounds and to alkoxylation products, i.e., condensation reaction products of alkylene oxides and complex hydrophobe compounds having at least one active hydrogen. This invention also relates to alkoxylation products that have beneficial, narrow molecular weight ranges.
Metadata
Assignee
- Union Carbide Chemicals & Plastics Technology Corporation
Inventors
- Richard D. Jenkins
- David R. Bassett
- Danny E. Smith
- John N. Argyropoulos
- James E. Loftus
- Gregory D. Shay
Application Information
Application Number:US 8876487
Filing Date:1992-05-29
Priority Date:1992-05-29
Art Unit:126
Classifications
IPC:
C07C 4313C07C 43205C07C 43164C07C 4319
Field of Search:
568558564556609;613;617;622;623;624;625;45;46;47;48;325;326;327;32826;33;34355;428;433489
Patent Drawings
This patent does not have any drawings.
Description
RELATED APPLICATIONS
The following are related, commonly assigned applications, filed on an even date herewith:
U.S. Patent Application Serial No. (07/887,647, now U.S. Pat. No. 5,292,843); U.S. patent application Ser. No. (07/887,646); U.S. patent application Ser. No. (07/887,642); U.S. patent application Ser. No. (07/887,673); U.S. patent application Ser. No. (07/887,672); U.S. patent application Ser. No. (07/887,641, now U.S. Pat. No. 5,292,828); U.S. patent application Ser. No. (07/887,643); U.S. patent application Ser. No. (07/887,645); U.S. patent application Ser. No. (07/887,644); and U.S. patent application Ser. No. (07/887,671); all of which are incorporated herein by reference.
BRIEF SUMMARY OF THE INVENTION
Technical Field
This invention relates to complex hydrophobe compounds and to alkoxylation products, i.e., condensation reaction products of alkylene oxides and complex hydrophobe compounds having at least one active hydrogen. This invention also relates to alkoxylation product mixtures that have beneficial, narrow molecular weight ranges.
Background of the Invention
A variety of products such as surfactants, functional fluids, glycol ethers, polyols, and the like, are commercially prepared by the condensation reaction of alkylene oxides with organic compounds having at least one active hydrogen, generally, in the presence of an alkaline or acidic catalyst. The types and properties of the alkoxylation products depend on, among other things, the active hydrogen compound, the alkylene oxide, and the mole ratio of alkylene oxide to organic compound employed, as well as the catalyst. As a result of the alkoxylation, a mixture of condensation product species are obtained having a range of molecular weights. In many applications of alkoxylated products, certain of the alkoxylation species provide much greater activity than others.
It has long been desired to provide superior alkoxylation products which are highly efficient for various end-use applications, particularly alkoxylation products that are selective to those desired alkoxylation species.
DISCLOSURE OF THE INVENTION
This invention relates to compounds represented by the formula: ##STR1## wherein R.sub.1 and R.sub.2 are the same or different and are hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue, R.sub.3 is a substituted or unsubstituted divalent or trivalent hydrocarbon residue, each R.sub.4 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, each R.sub.5 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, R.sub.6 is hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent, a and b are the same or different and are a value of 0 or 1, and x and y are the same or different and are a value of 0 or greater; provided (i) at least two of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are a hydrocarbon residue having greater than 2 carbon atoms in the case of R.sub.1, R.sub.2 and R.sub.6 or having greater than 2 pendant carbon atoms in the case of R.sub.3, R.sub.4 and R.sub.5, (ii) at least one of R.sub.4 and R.sub.5 is other than --CH2CH.sub.2 -- when R.sub.1 and R.sub.2 are nonylphenyl, R.sub.3 is >CH--, R.sub.6 is hydrogen or SO.sub.3, a is a value of 1, b is a value of 1, and at least one of x and y is a value of 1 or greater, and (iii) R.sub.4 is --CH2CH.sub.2 -- and x is a value of at least 2 when R.sub.1 is hexadecyl R.sub.2 is tetradecyl, R.sub.3 is >CH--, at least one R.sub.5 is --CH2CH(tetradecyl)--, R.sub.6 is hydrogen, y is a value of 1 or greater, a is a value of 1, and b is a value of 0.
This invention also relates to compounds represented by the formula: ##STR2## wherein R.sub.7 and R.sub.8 are the same or different and are hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue, R.sub.11 and R14 are the same or different and are hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent, R.sub.9 and R.sub.12 are the same or different and are a substituted or unsubstituted divalent or trivalent hydrocarbon residue, each R.sub.10 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, each R.sub.13 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, R.sub.15 is a substituted or unsubstituted divalent hydrocarbon residue, d and e are the same or different and are a value of 0 or 1, and f and g are the same or different and are a value of 0 or greater; provided at least two of R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14 and R.sub.15 are a hydrocarbon residue having greater than 2 carbon atoms in the case of R.sub.7, R.sub.8, R.sub.11 and R.sub.14 or having greater than 2 pendant carbon atoms in the case of R.sub.9, R.sub.10, R.sub.12, R.sub.13 and R.sub.15.
This invention further relates to alkoxylation product mixtures which can have relatively narrow alkoxylation product distributions. These product mixtures are relatively free from large amounts of substantially higher alkoxylation moieties, i.e., those having at least three more alkoxyl groups than the average peak alkoxylate specie. Advantageously, these narrow distributions can be obtained where the most prevalent alkoxylation moiety has four or greater alkoxy units, that is, in the regions which generally have a relatively wide range of alkoxylation species.
DETAILED DESCRIPTION
Illustrative substituted and unsubstituted monovalent hydrocarbon residues contain from 1 to about 50 carbon atoms or greater and are selected from alkyl radicals including linear or branched primary, secondary or tertiary alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, amyl, sec-amyl, t-amyl, 2-ethylhexyl and the like; aryl radicals such as phenyl, naphthyl and the like; arylalkyl radicals such as benzyl, phenylethyl, tri-phenylmethylethane and the like; alkylaryl radicals such as octylphenyl, nonylphenyl, dodecylphenyl, tolyl, xylyl and the like; and cycloalkyl radicals such as cyclopentyl, cyclohexyl, cyclohexylethyl and the like. The permissible hydrocarbon residues may contain fluorine, silicon, or other non-carbon atoms.
Preferably, the substituted and unsubstituted hydrocarbon residues are selected from alkyl and aryl radicals which contain from about 1 to 30 carbon atoms or greater. More preferably, the alkyl radicals contain from 1 to 18 carbon atoms, while the aryl, arylalkyl, alkylaryl and cycloalkyl radicals preferably contain from 6 to 18 carbon atoms or greater.
In a preferred embodiment of this invention, R.sub.1, R.sub.2, R.sub.7 and R.sub.8 can individually be a hydrocarbon radical represented by the formula: ##STR3## wherein R.sub.16 and R.sub.17 are as defined for R.sub.1, R.sub.2, R.sub.7 and R.sub.8 above, h and i are the same or different and are a value of 0 or 1, and R.sub.18 is as defined for R.sub.3 above. For compounds represented by formulae (i) and (ii), it is understood that each formula (iii) radical in a given compound may be the same or different and the R.sub.16 and/or R.sub.17 groups may themselves be a formula (iii) radical to provide complex hydrophobes of a dendritic or of a cascading nature as described below. Further, R.sub.4, R.sub.5, R.sub.10 and R.sub.13 can individually be a hydrocarbon radical represented by the formula:
wherein R.sub.19 is as defined for R.sub.4, R.sub.5, R.sub.10 and R.sub.13 above, R.sub.20 is as defined for R.sub.6, R.sub.11 and R.sub.14 above, and j is a value of 0 or greater.
Illustrative ionic substituents for R.sub.6, R.sub.11, R.sub.14 and R.sub.20 include cationic and anionic substituents such as sulfates, sulfonates, phosphates and the like. R.sub.6, R.sub.11, R.sub.14 and R.sub.20 may preferably be an organic residue containing 1 or more hydroxyls or nitrogen derivatives or epoxides or other reactive groups which may or may not contain unsaturation.
Other illustrative terminal groups which are described by R.sub.6, R.sub.11, R.sub.14 and R.sub.20 include, for example, hydrocarbon residues which may contain allylic or vinylic unsaturation, acrylic or methacrylic functionality, styryl or alpha-methylstyryl functionality, and the like, such as the reaction product between the terminal alcohol (R.sub.6, R.sub.11, R.sub.14 and R.sub.20 =H) and glycidyl methacrylate, isocyanatoethyl methacrylate, alpha, alpha-dimethyl-m-isopropenyl benzyl isocyanate (m-TMI), and the like. Other examples of terminal groups may include hydrocarbon residues of alkyl, aryl, aralkyl, alkaryl, and cycloalkyl radicals which may or may not be substituted with one or more of the following: hydroxyl, carboxyl, isocyanato, amino, mono- or disubstituted amino, quaternary ammonium, sulfate, sulfonate, phosphate, epoxy, and the like and may or may not contain other non-carbon atoms including silicon or fluorine. Also included can be divalent siloxy radicals. Other nonhydrocarbon terminal groups may include sulfates, phosphates, and the like.
Illustrative divalent hydrocarbon residues represented by R.sub.3, R.sub.4, R.sub.5, R.sub.9, R.sub.10, R.sub.12, R.sub.13, R.sub.15, R.sub.18 and R.sub.19 in the above formulae include substituted and unsubstituted radicals selected from alkylene, -alkylene-oxy-alkylene-, -arylene-oxy-arylene-, arylene, alicyclic radicals, phenylene, naphthylene, phenylene-(CH.sub.2).sub.m (Q).sub.n (CH.sub.2)m-phenylene- and naphthylene-(CH.sub.2).sub.m (Q).sub.n (CH.sub.2)m-naphthylene-radicals, wherein Q individually represents a substituted or unsubstituted divalent bridging group selected from --CR.sub.21 R.sub.22 --, --O--, --S--, --NR.sub.23 --, --SiR.sub.24 R.sub.25 -- and --CO--, wherein R.sub.21 and R.sub.22 individually represent a radical selected from hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, tolyl and anisyl; R.sub.23, R.sub.24 and R.sub.25 individually represent a radical selected from hydrogen and methyl, and each m and n individually have a value of 0 or 1. More specific illustrative divalent radicals represented by R.sub.3, R.sub.4, R.sub.5, R.sub.9, R.sub.10, R.sub.12, R.sub.13, R.sub.15, R.sub.18 and R.sub.19 include, e.g., 1,1-methylene, 1,2-ethylene, 1,3-propylene, 1,6-hexylene, 1,8-octylene, 1,12-dodecylene, 1,4-phenylene, 1,8-napthylene, 1,1'-biphenyl-2,2'-diyl, 1,1'-binaphthyl-2,2'-diyl, 2,2'-binaphthyl-1,1'-diyl and the like. The alkylene radicals may contain from 2 to 12 carbon atoms or greater, while the arylene radicals may contain from 6 to 18 carbon atoms or greater. Preferably, R.sub.3, R.sub.4, R.sub.5, R.sub.9, R.sub.10, R.sub.12, R.sub.13, R.sub.15, R.sub.18 and R.sub.19 are an alkylene or arylene radical. The permissible divalent hydrocarbon residues may contain fluorine, silicon, or other non-carbon atoms.
Illustrative trivalent hydrocarbon residues represented by R.sub.3, R.sub.9, R.sub.12 and R.sub.18 in the above formulae include substituted and unsubstituted radicals selected from >CH--, >C(R.sub.26)--, >CR.sub.27 -- and the like, wherein R.sub.26 is a substituted or unsubstituted monovalent hydrocarbon residue as described herein and R.sub.27 is a substituted or unsubstituted divalent hydrocarbon residue as described herein.
Of course, it is to be further understood that the hydrocarbon residues in the above formulae may also be substituted with any permissible substituent. Illustrative substituents include radicals containing from 1 to 18 carbon atoms such as alkyl, aryl, aralkyl, alkaryl and cycloalkyl radicals; alkoxy radicals; silyl radicals such as --Si(R.sub.28).sub.3 and --Si(OR.sub.28).sub.3, amino radicals such as --N(R.sub.28).sub.2 ; acyl radicals such as --C(O)R.sub.28 ; acyloxy radicals such as --OC(O)R.sub.28 ; carbonyloxy radicals such as --COOR.sub.28 ; amido radicals such as --C(O)N(R.sub.28).sub.2 and --N(R.sub.28)COR.sub.28 ; sulfonyl radicals such as --SO.sub.2 R.sub.28 ; sulfinyl radicals such as --SO(R.sub.28).sub.2 ; thionyl radicals such as --SR.sub.28 ; phosphonyl radicals such as --P(O)(R.sub.28).sub.2 ; as well as halogen, nitro, cyano, trifluoromethyl and hydroxy radicals and the like, wherein each R.sub.28 can be a monovalent hydrocarbon radical such as alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicals, with the provisos that in amino substituents such as --N(R.sub.28).sub.2, each R.sub.28 taken together can also compromise a divalent bridging group that forms a heterocyclic radical with the nitrogen atom, in amido substituents such as --C(O)N(R.sub.28).sub.2 and --N(R.sub.28)COR.sub.28, each R.sub.28 bonded to N can also be hydrogen, and in phosphonyl substituents such as --P(O)(R.sub.28).sub.2, one R.sub.28 can by hydrogen. It is to be understood that each R.sub.28 group in a particular substituent may be the same or different. Such hydrocarbon substituent radicals could possibly in turn be substituted with a permissible substituent such as already herein outlined above.
Referring to the general formulae (i) and (ii) above, it is appreciated that when R.sub.1, R.sub.2, R.sub.7 and/or R.sub.8 are a hydrocarbon residue of formula (iii) above, the resulting compound may include any permissible number and combination of hydrophobic groups of the dendritic or cascading type. Such compounds included in the above general formulae should be easily ascertainable by one skilled in the art.
In a preferred embodiment of this invention, the structure shown in formula (iii) can be a residue of the reaction product between epichlorohydrin and an alcohol, including those alcohols whose residues can be described by formula (iii), or a phenolic, or a mixture thereof. The structures which result can be described as complex hydrophobes of a dendritic or of a cascading nature. Pictorially, they can be described as shown below: ##STR4##
Illustrative starter components useful for making the complex hydrophobe compounds of this invention include those compounds having active hydrogens such as alcohols (mono-, di- and polyhydric alcohols), phenols, carboxylic acids (mono-, di- and polyacids), and amines (primary and secondary). Frequently, the organic compounds contain up to about 100 or 150 carbons (in the case of polyol polymers) and can contain aliphatic and/or aromatic structures. Most often, the starter compounds are selected from the group of mono-, di- and trihydric alcohols having up to about 30 carbon atoms or greater. The organic compounds having active hydrogens can be the product of hydroformylation/hydrogenation reactions. Other useful starters can include the reaction products between epichlorohydrin and the above mentioned starter compounds.
Particularly preferred starter alcohols are primary and secondary monohydric alcohols which are branched chain such as ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, isopropyl alcohol, 2-ethylhexanol, sec-butanol, isobutanol, 2-pentanol, 3-pentanol and isodecanol. Particularly suitable alcohols are linear and branched primary alcohols (including mixtures) such as produced by the "Oxo" reaction of C.sub.3 to C.sub.20 olefins. The alcohols may also be cycloaliphatic such as cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, as well as aromatic substituted aliphatic alcohols such as benzyl alcohol, phenylethyl alcohol, and phenylpropyl alcohol. Other aliphatic structures include 2-methoxyethanol and the like.
Phenols include alkylphenyls of up to 30 carbons such as phenol, methylphenol, ethylphenol, butylphenol, heptylphenol, octylphenol, nonylphenol, dinonylphenol and decylphenol. The aromatic radicals may contain other substituents such as halide atoms.
Alcohols (polyols) having 2 or more hydroxyl groups, e.g., about two to six hydroxyl groups and have 2 to 30 carbons, include glycols such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, neopentylene glycol, decylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol. Other polyols include glycerine, 1,3-propanediol, pentaerythritol, galactitol, sorbitol, mannitol, erythritol, trimethylolethane and trimethylolpropane.
The complex hydrophobe compounds can be prepared using a number of different methods. Three methods are described below, but synthesis of these structures is not limited to just these methods.
The first method involves reaction of an unsubstituted or substituted alcohol or phenol, such as nonylphenol for example, with an epoxide-containing hydrocarbon residue, such as nonylphenol glycidyl ether. The reaction can be carried out under anhydrous conditions in the presence of at least 0.1 weight % but not more than 20 weight % of a suitable catalyst based on the starting weight of alcohol or phenol. Such a suitable catalyst can be, for example, potassium hydroxide. Use of a suitable azeotroping solvent, such as toluene or cyclohexane, can aid in removal of water from the system. The reaction temperature should be at least about 60.degree. C. and at most the boiling point of the solvent, unless the reaction is done under pressure. The reaction can be carried out under vacuum or in the absence of a solvent. The catalyst and the alcohol can be added to the solvent, and essentially all water can be removed, typically through azeotroping. Once the reaction temperature is reached, the epoxide can be added. The product can be isolated by removal of solvent. An example of this type of procedure for producing a complex hydrophobe is described in Example 1.
A second method involves reaction of a polymerizable cyclic ether, such as an epoxide, with a suitable polymerization catalyst like boron trifluoride in the presence of an initiating alcohol or phenol, referred to as the starter. The reaction can be done in a suitable polymerization solvent such as cyclohexane, which can be dried prior to polymerization/oligomerization through its azeotrope. The reaction can be carried out in the absence of a solvent. In a typical preparation, the catalyst, usually added at a level of from 0.1 mole % to 50 mole %, preferably from 0.1 mole % to 10 mole % based on the starting epoxide, and the starter, usually added at a level of from 5.0 mole % to 100 mole %, preferably from 5.0 mole % to 50 mole %, based on the starting epoxide, can be added to the solvent. The reaction temperature can be as low as -78.degree. C. to as high as the reflux temperature of the solvent at atmospheric pressure, but more preferably from 25.degree. C. to 75.degree. C. The cyclic ether can then be added to the catalyst solution and polymerized. An example of this type of procedure for producing a complex hydrophobe is described in Example 5.
A third method involves the reaction of an unsubstituted or substituted alcohol or phenol, such as nonylphenol or hexadecanol, with a functional epoxide, such as epichlorohydrin. The starting alcohol or phenol can be added to a suitable reaction solvent, such as toluene, along with potassium hydroxide, a tetraalkyl ammonium halide, such as tetraethylammonium iodide, and water. The reaction can be carried out in the absence of a solvent. The reaction temperature can be regulated at about 65.degree. C. at which time the epichlorohydrin can be added. Varying the amount of epichlorohydrin and other ingredients can result in the formation of various dendritic-like molecules. An example of this type of procedure for producing a complex hydrophobe is described in Example 8.
The alkylene oxides which provide random or block oxyalkylene units in the alkoxylated products include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2- and 2,3-pentylene oxide, cyclohexylene oxide, 1,2-hexylene oxide, 1,2-octylene oxide, 1,2-decylene oxide, and higher alpha-olefin epoxides; epoxidized fatty alcohols such as epoxidized soybean fatty alcohols and epoxidized linseed fatty alcohols; aromatic epoxides such as styrene oxide and 2-methylstyrene oxide; and hydroxy- and halogen-substituted alkylene oxides such as glycidol, epichlorohydrin and epibromohydrin. The preferred alkylene oxides are ethylene oxide and propylene oxide. Also included can be hydrocarbon residues from substituted and unsubstituted cyclic esters or ethers such as oxetane and tetrahydrofuran. It is understood that the compounds represented by formulae (i) and (ii) herein can contain random and/or block oxyalkylene units as well as mixtures of oxyalkylene units. It is further understood that each R.sub.4, R.sub.5, R.sub.10, R.sub.13 and R.sub.19 group in a particular substituent for all positive values of x, y, f, g and j respectively can be the same or different.
The values of x, y, f, g and j are not narrowly critical and can vary over a wide range. For example, the values of x, y, f, g and j can range from 0 to about 200 or greater, preferably from about 0 to about 100 or greater, and more preferably from about 0 to about 50 or greater. Any desired amount of alkylene oxide can be employed in the compounds of this invention, for example, from 0 to about 90 weight percent or greater based on the weight of the compound.
The alkoxylation is conducted using a catalytically-effective amount of a catalyst, e.g., about 0.01 to 10, often about 0.5 to 5, weight percent based on the weight of a starter component, e.g., a complex hydrophobe compound having at least one active hydrogen. The catalysts should retain their activities during the alkoxylation, regardless of the amount of alkylene oxide employed. Thus, the amount of catalyst can be based on the amount of starter provided to the alkoxylation zone and not the degree of alkoxylation to be effected.
Illustrative alkoxylation catalysts useful in this invention include, for example, potassium hydroxide, diethylaluminum fluoride, oxides and hydroxides of barium and strontium, basic salts of alkaline earth metals especially calcium, calcium oxide (quicklime), calcium hydroxide (slaked line), calcium sulfate, and the like. Preferred catalysts for obtaining alkoxylation product mixtures having a narrow molecular weight distribution are disclosed in U.S. Pat. No. 4,754,075, the disclosure of which is incorporated herein by reference. This invention is not intended to be limited in any manner by the permissible catalysts.
Normally, the catalyst and the starter component are admixed and then the alkylene oxide is added at the reaction temperature until the desired amount of alkylene oxide has been added, then the product is neutralized and can be finished, if desired, in any procedure including stripping unreacted starter material from the product mixture, filtration, or further reaction.
The temperature of the alkoxylation is sufficient to provide a suitable rate of reaction and without degradation of the reactants or reaction products. Often, the temperatures range from between about 50.degree. C. and 270.degree. C., e.g. from about 100.degree. C. to 200.degree. C. The pressure may also vary widely, but when low-boiling alkylene oxides such as ethylene oxide and propylene oxide are employed, a pressurized reactor is preferably used.
The alkoxylation reaction medium is preferably agitated to ensure a good dispersal of the reactants and catalyst throughout the reaction medium. Also, the alkylene oxide is usually added at a rate approximating that which it can be reacted.
Neutralization may assist in the recovery of the catalyst from the alkoxylation product mixture. When neutralizing, acids that may tend to form catalyst-containing gel structures or solids that clog filtering apparatus should be avoided. Conveniently, sulfuric acid, phosphoric acid, propionic acid, benzoic acid and the like are used.
The above procedure represents but one of many equally viable versions of suitable alkoxylation processes. Other versions are possible through combinations of the options available in the various process steps.
The catalytic alkoxylation reactions of this invention can be effected, for example, by conventional methods such as (1) batch processes; (2) continuous fixed-bed processes; and (3) continuous fluidized reactor processes. In a batch reactor, the catalyst is kept suspended in the reactant by shaking or stirring. In a fluidized reactor, the catalyst is at a particular original level. As the velocity of the reactant stream is increased, the catalyst bed expands upward to a second level, and at a critical velocity it enters into violent turbulence. The fluidized reactor is particularly useful for removing or supplying the heat necessary to maintain a fixed catalyst temperature. The fluidized reactor can usually be employed only on a rather large scale since good fluidization requires a reactor larger than about 1.5 inches in diameter.
As indicated above, the end groups described by R.sub.6, R.sub.11, R.sub.14 and R.sub.20 can be a variety of structures including sulfates. The sulfation of a hydroxyl containing end group can be carried out using one of several methods, such as with SO.sub.3 or sulfamic acid.
In the sulfation reaction using sulfamic acid, a complex hydrophobe alkoxylate, for example ethoxylated 1,3-bis(nonylphenoxy)-2-propanol, is dried at high temperature, at or about 100.degree. C. for example, and low pressure, at or below 50 mmHg for example. The ethoxylate is cooled to a reaction temperature at or about 60.degree. C., for example, and. sulfamic acid is charged. The reaction temperature is kept at or about 110.degree. C. Once the reaction is complete, an amount of a mono- or disubstituted alkanolamine can be added to remove residual acid, and prevent hydrolysis upon introduction of water. A diluting solvent, such as ethanol and/or water, can be added along with the alkanolamine. An example of a preparation of a sulfate using sulfamic acid is shown in Example 11.
The alkoxylation products produced by the alkoxylation processes of this invention, including the complex hydrophobe compounds having at least one active hydrogen, can undergo further reaction(s) to afford desired derivatives thereof. Such permissible derivatization reactions can be carried out in accordance with conventional procedures known in the art. Illustrative derivatization reactions include, for example, esterification, etherification, amination, alkylation, hydrogenation, dehydrogenation, reduction, acylation, condensation, carboxylation, oxidation, silylation and the like, including permissible combinations thereof. This invention is not intended to be limited in any manner by the permissible derivatization reactions or permissible derivatives of alkoxylation products and complex hydrophobe compounds.
More particularly, the hydroxyl-terminated alkoxylation products and complex hydrophobe compounds of this invention can undergo any of the known reactions of hydroxyl groups illustrative of which are reactions with acyl halides to form esters; with ammonia, a nitrile, or hydrogen cyanide to form amines; with alkyl acid sulfates to form disulfates; with carboxylic acids and acid anhydrides to form esters and polyesters; with alkali metals to form salts; with ketenes to form esters; with acid anhydrides to form carboxylic acids; with oxygen to form aldehydes and carboxylic acids; ring-opening reactions with lactones, tetrahydrofuran; dehydrogenation to form aldehydes, isocyanates to form urethanes, and the like.
Alkoxylation product mixtures prepared by the processes of this invention comprise alkoxylation species that can be represented by the formulae (i) and/or (ii) above.
The alkoxylation product mixtures of this invention can be characterized as the condensation reaction products of alkylene oxides and complex hydrophobe compounds having at least one active hydrogen in which the mole ratio of reacted alkylene oxide per active hydrogen is at least about 4, say, about 4 to 16 or 24, preferably about 5 to 12. The product mixtures can have at least one alkoxylation moiety which constitutes at least about 10, say, about 20 to 30 or 40, and most often about 20 to 30, weight percent of the composition. The alkoxylation mixtures of this invention also can have a relatively symmetrical distribution. Hence, the portion of the product mixture having three or more oxyalkylene unit groups (per active hydrogen site of the complex hydrophobe compound) than the peak alkoxylation specie is relatively minor, e.g., often less than about 12, say, less than 10, and often about 1 to 10, weight percent of the mixture. Similarly, the alkoxylation species having fewer oxyalkylene groups (per active hydrogen site of the complex hydrophobe compound) by three or more oxyalkylene groups from the average peak alkoxylation species is usually relatively minor, e.g., less than about 15, say, less than about 10, often about 0.5 to 10, weight percent of the composition. Generally, the one oxyalkylene unit higher and the one oxyalkylene unit lower alkoxylates in respect to the most prevalent alkoxylation specie are present in a weight ratio to the most prevalent alkoxylation specie of about 0.6:1 to 1:1.
The preferred alkoxylation product mixtures of this invention correspond to the formula:
wherein n is the number of oxyalkylene groups per reactive hydrogen site for an alkoxylation specie (n must equal at least one) of the composition, n is the weight average oxyalkylene number, A is the weight percent of the most prevalent alkoxylation specie in the mixture and P.sub.n is, within plus or minus two percentage points, the weight percent of the alkoxylation specie having n oxyalkylene groups (per active hydrogen site) in the mixture. This distribution relationship generally applies where n is between the amount of n minus 4 to the amount of n plus 4.
For purposes herein, the average peak alkoxylation specie is defined as the number of oxyalkylene groups (per active hydrogen site) of the most prevalent alkoxylation specie when the next higher and lower homologs are each present in a weight ratio to the most prevalent alkoxylation specie of less than 0.9:1. When one of the adjacent homologs is present in a weight ratio greater than that amount, the average peak alkoxylation specie has an amount of oxyalkylene groups equal to the number average of those of the two species. The weight average oxyalkylene number is the weight average of the oxyalkylene groups of the alkoxylation species in the mixture (including unreacted alcohol), i.e., n equals the sum of (n)(P.sub.n) for all the species present divided by 100.
Among the most commercially important alkoxylation products are those which utilize an alcohol (monols, glycols, potyols, etc.) as starter and ethylene oxide, propylene oxide, or an ethylene oxide/propylene oxide mixture as the 1,2-alkylene oxide monomer. Such alcohol ethoxylates encompass a myriad of structures, compositions and molecular weights intended for service in a diversity of applications ranging from heavy duty industrial end uses such as solvents and functional fluids to ultra-sophisticated, consumer-oriented end uses such as in pharmaceutical, personal care and household goods. The surfactants of this invention are useful as emulsifiers in emulsion or suspension polymerization of various monomers to produce an aqueous suspension of polymer particles.
The compounds of this invention can be used wherever there is a need to increase surface activity. They are particularly valuable where process conditions demand the greatest efficiency from water, e.g., in wetting, penetrating, emulsifying, lubricating and dispersing. Illustrative applications include, for example, agriculture, e.g., emulsifiers and wetters, herbicidal adjuvants and fruit washes; cleaners, e.g., household detergents, dry cleaning detergents, industrial hand cleaners, detergent/sanitizers, solvent degreasers, metal cleaners, hard surface cleaners, commercial laundry detergents and car wash detergents; dust wetting, e.g., coal mines, ceramic industries and foundries; leather, e.g., hidesoaking, degreasing, fatliquor stabilization, tanning and dyeing; paint, e.g., emulsion polymerization of latexes, latex stabilization, pigment wetting and dispersion; paper, e.g., pulping, absorbent papers, de-inking waste water, wet-felt washing and adhesives; and textiles, e.g., greige goods scouring, bleaching, carbonizing of wool, scouring of cotton, wool and polyester/cotton blends, wetting and rewetting agents, desizing of cotton and polyester/cotton blends, polyethylene softener emulsifiers, mineral oil and solvent emulsifiers, fiber lubricant emulsifiers, emulsion polymerization, dyeing and finishing of synthetics, naturals and blends, dye leveling agents and resin bath additives.
Additionally, the compounds of this invention may be useful as components of sanitizing solutions for use on food-processing equipment and utensils and on beverage containers, including milk containers and equipment; emulsifiers and/or surface active agents in the manufacture of articles or components of articles intended for use in producing, manufacturing, packing, processing, preparing, treating, packaging, transporting or holding food; inert (or occasionally active) ingredients for use in formulations applied to growing crops or to raw agricultural commodities after harvest; and inert (or occasionally active) ingredients for use in formulations applied to animals.
As used herein, the term "complex hydrophobe" is contemplated to include all permissible hydrocarbon compounds having 2 or more hydrophobe groups, e.g., bis-dodecylphenyl, bis-nonylphenyl, bis-octylphenyl and the like.
For purposes of this invention, the term "hydrocarbon" is contemplated to include all permissible compounds having at least one hydrogen and one carbon atom. In a broad aspect, the permissible hydrocarbons include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic organic compounds which can be substituted or unsubstituted.
As used herein, the term "substituted" is contemplated to include all permissible substituents of organic compounds unless otherwise indicated. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, alkyl, alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl, halogen and the like in which the number of carbons can range from 1 to about 20 or more, preferably from 1 to about 12. The permissible substituents can be one or more and the same or different for appropriate organic compounds. This invention is not intended to be limited in any manner by the permissible substituents of organic compounds.
This invention can be illustrated by certain of the following examples.
EXAMPLE 1
Preparation of 1,3-Bis(nonylphenoxy)-2-propanol
To a five neck, two liter round bottom flask equipped with an addition funnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and a decanting head with a water-cooled condenser were added 220 grams (1.00 mole) of nonylphenol and 250 milliliters of cyclohexane. The solution was then heated to reflux and 2.8 grams (1.3 wt. % based on nonylphenol) of potassium hydroxide in 10 milliliters of water was slowly added to the flask. After essentially all the water was recovered in the decanting head (10 milliliters+1 milliliter formed), 250.7 grams (0.91 mole) of nonylphenyl glycidyl ether as added dropwise. During the addition of the glycidyl ether, the reaction temperature was maintained between 60.degree. and 80.degree. C. After the addition was complete, the solution was refluxed for four hours. The contents of the flask were then washed with a five percent aqueous solution of phosphoric acid, and the organic layer was separated from the water layer and washed twice with deionized water. The reaction mixture was then placed in a one liter round bottom flask, and the remaining cyclohexane and unreacted nonylphenol were recovered by distillation, first at atmospheric pressure, then under vacuum at 0.2 mm Hg. The kettle temperature was not allowed to exceed 180.degree. C. during the distillation to prevent discoloration of the product. The concentrated solution was then refiltered to give 425 grams of a pale-yellow liquid. End-group MW analysis gave a molecular weight of 506.8 (theoretical MW=496.8). Ir and nmr spectra were identical to previously recorded spectra for the compound.
EXAMPLE 2
Preparation of 1,3-(Bis(nonylphenoxy)-2-propanol
To a five neck, two liter round bottom flask, equipped with an addition funnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and a decanting head with a water-cooled condenser, were added 300 milliliters of cyclohexane and 451.7 grams (2.05 mole) of nonylphenol. The solution was then heated to reflux and 58.9 grams (1.05 mole) of potassium hydroxide in 60 milliliters of water was slowly added via the addition funnel. After essentially all the water was recovered in the decanting head (60 milliliter+19 milliliters formed), the reaction was cooled to 40.degree. C., and 92.5 grams (1.00 mole) of epichlorohydrin was slowly added. During the addition, the reaction temperature was maintained below 60.degree. C. by controlling the rate of epichlorohydrin addition. After all the epichlorohydrin was added, the solution was allowed to stir for one hour, and then brought to reflux for an additional three hours. The reaction mixture was then filtered under vacuum through a steam-jacketed Buchner funnel to remove the potassium chloride formed as a by-product. The filtration process was performed a total of three times to remove the majority of the salts. The reaction mixture was then placed in a one liter round bottom flask, and the remaining cyclohexane and unreacted nonylphenol were recovered by distillation, first at atmospheric pressure, then under vacuum at 0.2 mm Hg. The kettle temperature was not allowed to exceed 180.degree. C. during the distillation to prevent discoloration of the product. The concentrated solution was then refiltered to give 275 grams of a pale-yellow liquid. End-group MW analysis gave a molecular weight of 459.7 (theoretical MW=496.8). Ir and nmr spectra were identical to previously recorded spectra for the compound.
EXAMPLE 3
Preparation of 5 Mole Ethoxylate of 1,3-Bis(nonylphenoxy)-2-propanol
To a 500 milliliter, stainless steel, high pressure autoclave was charged 200 grams (0.40 mole) of 1,3-bis(nonylphenoxy)-2-propanol, which contained a catalytic amount of the potassium salt of the alcohol as described in Example 1. After purging the reactor with nitrogen, the alcohol was heated to 130.degree. C. with stirring, and 86.9 grams (2.0 mole) of ethylene oxide was added over a two hour period. The reaction temperature and pressure were maintained from 130.degree. C. to 140.degree. C. and 60 psig during the course of the reaction. After the addition of ethylene oxide was complete, the reaction mixture was held at 140.degree. C. for an additional hour to allow all the ethylene oxide to cook out. The reaction mixture was dumped while hot, under nitrogen, and neutralized with acetic acid to yield 285 grams of a pale-yellow liquid.
EXAMPLE 4
Preparation of Adduct of Nonylphenyl Glycidyl Ether and 5 Mole Ethoxylate of 1,3-Bis(nonylphenoxy)-2-propanol
To a five neck, one liter, round bottom flask equipped as in Example 1 was added 119.8 grams (0.17 mole) of the 5 mole ethoxylate of 1,3-bis(nonylphenoxy)-2-propanol and 100 milliliters of cyclohexane. The mixture was refluxed (100.degree. C.) for one hour to remove residual water, and then cooled to 50.degree. C. under nitrogen to add 0.5 grams of BF.sub.3 /Et.sub.2 O. Nonylphenyl glycidyl ether (46.0 grams, 0.17 mole) was then added to the flask over a one hour period, and the reaction was heated to reflux. After three hours at reflux, the reaction mixture was transferred to a separatory funnel, while hot, and washed with a saturated aqueous solution of sodium bicarbonate. The organic layer was separated from the water layer, and washed twice with hot deionized water. The washes were performed at 50.degree. C. to facilitate the separation of the two layers. The water and cyclohexane were then evaporated from the organic layer, under vacuum, to yield 145 grams of a pale-yellow, viscous liquid. End-group molecular weight analysis gave a molecular weight of 880 (theoretical molecular weight=993).
EXAMPLE 5
Preparation of Poly(nonylphenol glycidyl ether)
To a 500 milliliter round bottom equipped with an overhead stirrer, nitrogen inlet, reflux condenser, additional funnel, and temperature controller was charged 1.9 grams of ethanol (22 mmoles) and 200 grams of cyclohexane. The solution was brought to 50.degree. C. Once heated, 0.5 milliliters (4 mmoles) of BF.sub.3 /Et.sub.2 O was added using a 2 milliliter syringe. Once the acid was added, 100.0 grams of nonylphenol glycidyl ether (362 mmoles) was added dropwise so as to maintain a reaction temperature of 45.degree. C.-55.degree. C. Once the glycidyl ether was added, the solution is refluxed for 3 hours, then cooled to about 50.degree. C.
While hot (<60.degree. C.) the organic was transferred to a separatory funnel and was washed once with 100 milliliters of 5% sodium bicarbonate solution. The aqueous layer was drained and the organic was washed two more times with 100 milliliter portions of deionized water. The aqueous layers were decanted and the organic was dried for at least 1 hour over magnesium sulfate. Once dry the magnesium sulfate was filtered from the organic which was stripped of solvent using a rotary evaporator. The final yield of viscous polymer was 100 grams. The GPC molecular weight was Mw=2600 and the Mn=1700 based on monodisperse polystyrene standards.
EXAMPLE 6
Ethoxylation of Poly(nonylphenol glycidyl ether)
To a 500 milliliter stainless steel Zipperclave was added 60.0 grams (0.035 moles based on an approximate molecular weight of 1700 gram/mole) of the resin prepared in Example 5 along with 0.5 grams of potassium hydroxide. The vessel was attached to an automated ethoxylation unit and was heated to 50.degree. C. The vessel was continuously purged with nitrogen for 15 minutes and was then heated to 100.degree. C. where it was again continuously purged with nitrogen for another 15 minutes. The vessel was then heated to 140.degree. C. and was given a series of 6 purges by pressuring the vessel up to 80 psi, and then venting. Once the venting process was complete, the vessel was pressured to 20 psi with nitrogen.
The ethylene oxide lines were opened to the motor valves along with the main feed line on the Zipperclave. The feed was continued and the vessel pressure was regulated at 55 psi and a temperature of 140.degree. C. The automation was designed to hold the temperature and the pressure within safe operating limits while addition of ethylene oxide proceeded through a pair of motor control valves. The feed was allowed to continue until 60.0 grams of ethylene oxide (1.362 moles) was added based on a difference weight of the feed cylinder. After the feed was complete, the reaction was allowed to continue for 1 hour after which the vessel was cooled to 60.degree. C., purged 4 times with nitrogen to 80 psi and was dumped to a container. The final product yield was 115 grams with a theoretical yield of 120 grams. The GPC molecular weight of the product was Mw=3550 and the MN=2930 based on monodisperse polystyrene standards.
EXAMPLE 7
Preparation of Poly(phenyl glycidyl ether)
To a 500 milliliter round bottom equipped with an overhead stirrer, nitrogen inlet, reflux condenser, addition funnel, and temperature controller was charged 47.06 grams of phenol (500 mmoles) and 100 grams of toluene. The solution was brought to 50.degree. C. Once heated, 1.0 milliliter (8 moles) of BF.sub.3 /Et.sub.2 O was added using a 2 milliliter syringe. Once the acid was added, 68.18 grams of phenyl glycidyl ether (454 moles) was added dropwise so as to maintain a reaction temperature of 45.degree. C.-55.degree. C. Once the glycidyl ether was added, the solution is refluxed for 3 hours, then cooled to about 50.degree. C.
While hot (<60.degree. C.) the organic was transferred to a separatory funnel and was washed once with 100 milliliters of 5% sodium bicarbonate solution. The aqueous layer was drained and the organic was washed two more times with 100 milliliter portions of deionized water. The aqueous layers were decanted and the organic was dried for at least 1 hour over magnesium sulfate. Once dry the magnesium sulfate was filtered from the organic which was stripped of solvent using a rotary evaporator. The final yield of viscous polymer was 90.3 grams (with 11% unreacted phenol). The GPC molecular weight was Mw=470 and the Mn=310 (on average a trimer) based on monodisperse polystyrene standards.
EXAMPLE 8
Preparation of 1,3-Bis(phenoxy)-2-propanol using the Cascading Polyol Technique
To a 1 liter round bottom flask equipped with an overhead stirrer, nitrogen inlet, reflux condenser, addition funnel, and temperature controller was charged 94.11 grams of phenol (1 mole), 12.86 grams of tetraethylammonium iodide (0.05 moles), 3.00 grams of water (0.17 moles), 42.08 grams of potassium hydroxide (0.75 moles), and 250 grams of toluene. To a 100 milliliter additional funnel was charged 23.13 grams of epichlorohydrin (0.25 moles) and 50 grams of toluene. The solution was brought to 65.degree. C. at which time the epichlorohydrin solution was added over a period of 15 minutes while maintaining a reaction temperature of 65.degree. C..+-.5.degree. C. The reaction was allowed to proceed for 48 hours.
After 48 hours, the solution was cooled down to room temperature. The toluene solution was washed with two 250 milliliters portions of deionized water. The aqueous layers were drained off, and the toluene was removed along with unreacted phenol using a rotary evaporator. The final yield of product was 64.5 grams which was 106% of theory (residual is phenol). Final product purity was about 95% as shown by GPC.
EXAMPLE 9
Dimerization of 1,3-Bis(phenoxy)-2-propanol using the Cascading Polyol Technique
To a 250 milliliter round bottom flask equipped with an overhead stirrer, nitrogen inlet, reflux condenser, additional funnel, and temperature controller was charged 20.03 grams of 1,3-bis-(phenoxy)-2-propanol prepared in Example 8 (82 mmoles), 2.06 grams of tetraethylammonium iodide (8 mmoles), 0.49 grams of water (27 mmoles), 6.51 grams of potassium hydroxide (116 mmoles), and 125 grams of toluene. To a 100 milliliter addition funnel was charged 3.61 grams of epichlorohydrin (39 mmoles) and 25 grams of toluene. The solution was brought to 65.degree. C. at which time the epichlorohydrin solution was added over a period of 15 minutes while maintaining a reaction temperature of 65.degree. C..+-.5.degree. C. The reaction was allowed to proceed for 48 hours.
After 48 hours, the solution was cooled down to room temperature. The toluene solution was washed with two 250 milliliter portions of deionized water. The aqueous layers were drained off, and the toluene was removed using a rotary evaporator. The final yield of product was 21.6 grams which was 101% of theory. GPC showed two major components of the product. The first was the starting material at about 41% (Mn=220) and the second was the coupled product at about 59% (Mn=520).
EXAMPLE 10
Preparation of 1,3-Bis(hexadecyloxy)-2-propanol using the Cascading Polyol Technique
To a 500 milliliter round bottom flask equipped with an overhead stirrer, nitrogen inlet, reflux condenser, additional funnel, and temperature controller was charged 60.61 grams of hexadecanol (0.25 moles), 6.18 grams of tetraethylammonium iodide (0.024 moles), 1.44 grams of water (0.082 moles), 20.20 grams of potassium hydroxide (0.36 moles), and 125 grams of toluene. To a 100 milliliter addition funnel was charged 11.10 grams of epichlorohydrin (0.12 moles) and 25 grams of toluene. The solution was brought to 65.degree. C. at which time the epichlorohydrin solution was added over a period of 15 minutes while maintaining a reaction temperature of 65.degree. C..+-.5.degree. C. The reaction was allowed to proceed for 48 hours.
After 48 hours, the solution was cooled down to room temperature. The toluene solution was washed with two 250 milliliter portions of deionized water. The aqueous layers were drained off, and the toluene was removed using a rotary evaporator. The final yield of product was 70.9 grams which is 109% of theory (residual is hexadecanol).
EXAMPLE 11
Sulfation of 1,3Bis(nonylphenoxy)-2-propanol-block-(propylene oxide) .sub.10 -block-(ethylene oxide).sub.10
To a 250 milliliter round bottom flask equipped with an overhead stirrer, a temperature controller, and a vacuum adapter was added 75.0 grams of the material from Example 13 (49 mmoles). The kettle was then evacuated to <20 mmHg and heated to 100.degree. C. to remove any water. After 1 hour, the kettle was cooled to 60.degree. C. while under vacuum. When reaching 60.degree. C., vacuum was broken with nitrogen and 5.3 grams of sulfamic acid (54 mmoles) was added. After charging the sulfamic acid, the kettle was heated to 110.degree. C. and evacuated to <20 mmHg. The reaction was allowed to proceed for 3 hours.
At the end of the hold period, the kettle was cooled to 85.degree. C. and vacuum was broken with nitrogen. 1.2 grams of diethanolamine (11 mmoles) was slowly added under a blanket of nitrogen. This solution was stirred for 30 minutes. 10 grams of ethanol was added to the kettle and the temperature was regulated to 55.degree. C. This solution was stirred for 30 minutes. The heat was removed from the kettle and 30 grams of water along with 20 grams of ethanol were added while maintaining good agitation. The solution was stirred for 15 minutes or until cooled to room temperature (<35.degree. C.).
The pH was checked by dissolving 2 grams of the product solution in 18 grams of deionized water. If the pH was below 6.5, 0.2 gram increments of diethanolamine was added until the pH is between 6.5 and 7.5.
EXAMPLE 12
Preparation of 1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene oxide).sub.10
To a 500 milliliter stainless steel Zipperclave was added 100.0 grams (0.202 moles) of 1,3-bis(nonylphenoxy)-2-propanol prepared in Example 1 along with 0.7 grams of potassium hydroxide. The vessel was attached to an automated unit and was heated to 50.degree. C. The vessel was continuously purged with nitrogen for 15 minutes and was then heated to 100.degree. C. where it was again continuously purged with nitrogen for another 15 minutes. The vessel was then heated to 140.degree. C. and is given a series of 6 purges by pressuring the vessel up to 80 psi, and then venting. Once the venting process was completed, the vessel was pressured to 20 psi with nitrogen.
Lines connected to a cylinder which had been precharged with 117.0 grams of propylene oxide (2.02 moles) were opened to the motor valves along with the main feed line on the Zipperclave. The feed was continued and the vessel pressure was regulated at 55 psi and a temperature of 140.degree. C. The automation was designed to hold the temperature and the pressure within safe operating limits while addition of ethylene oxide proceeded through a pair of motor control valves. The feed was allowed to continue until all of the propylene oxide had been fed. After the feed was complete, the reaction was allowed to continue for 1 hour after which the vessel was cooled to 60.degree. C., purged 4 times with nitrogen to 80 psi and was dumped to a container. The final product yield was 211 grams with a theoretical yield of 277 grams. The GPC molecular weight of the product was Mw=650 and the Mn=490 based on monodisperse polystyrene standards.
EXAMPLE 13
Preparation of 1,3 -Bis(nonylphenoxy)-2-propanol-block-(propylene oxide).sub.10 -block-(ethylene oxide).sub.10
To a 500 milliliter stainless steel Zipperclave was added 75.0 grams of the propoxylate prepared in Example 12 (0.070 moles) along with 0.3 grams of potassium hydroxide. The vessel was attached to an automated ethoxylation unit and was heated to 50.degree. C. The vessel was continuously purged with nitrogen for 15 minutes and was then heated to 100.degree. C. where it was again continuously purged with nitrogen for another 15 minutes. The vessel was then heated to 140.degree. C. and was given a series of 6 purges by pressuring the vessel up to 80 psi, and then venting. Once the venting process was completed, the vessel was pressured to 20 psi with nitrogen.
The ethylene oxide lines were opened to the motor valves along with the main feed line on the Zipperclave. The feed was continued and the vessel pressure was regulated at 55 psi and a temperature of 140.degree. C. The automation was designed to hold the temperature and the pressure within safe operating limits while addition of ethylene oxide proceeded through a pair of motor control valves. The feed was allowed to continue until 30.7 grams ethylene oxide (0.696 moles) was added based on a difference weight of the feed cylinder. After the feed was complete, the reaction is allowed to continue for 1 hour after which the vessel was cooled to 60.degree. C., purged 4 times with nitrogen to 80 psi and was dumped to a container. The final product yield was 99 grams with a theoretical yield of 106 grams.
EXAMPLE 14
Preparation of Bis(nonylphenoxy) Adduct of 1,4-Butanediol Diglycidyl Ether
To a five neck, two liter round bottom flask equipped with an addition funnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and a decanting head with a water-cooled condenser were added 506.8 grams (2.30 mole) of nonylphenol and 350 milliliters of cyclohexane. The solution was heated to reflux, and 6.5 grams (1.3 weight percent based on nonylphenol) of potassium hydroxide in 15 milliliters of water was slowly added to the round bottom flask. After all the water was recovered in the decanting head (15 milliliters+2 milliliters formed), 220 grams (1.09 mole) of 1,4-butanediol diglycidyl ether was added dropwise between 60.degree. and 80.degree. C. After the addition was complete, the solution was refluxed for four hours. The contents of the flask were then washed with a five percent aqueous solution of phosphoric acid, and the organic layer was separated from the water layer and washed twice with deionized water. The reaction mixture was then placed in a one liter round bottom flask, and the remaining cyclohexane and unreacted nonylphenol were recovered by distillation, first at atmospheric pressure, then under vacuum at 0.2 mm Hg. The kettle temperature was not allowed to exceed 180.degree. C. during the distillation to prevent discoloration of the product. The concentrated solution was then refiltered to give 710 grams of a pale-yellow liquid. Molecular weight by end-group MW analysis was 689.9 (theoretical MW=643.0). Ir and nmr spectra were consistent with the expected structure of the product.
EXAMPLE 15
Preparation of 3 Mole Ethoxylate of 1,3-Bis(nonylphenyoxy)-2-propanol
To a five hundred milliliter Zipperclave reactor were charged, under nitrogen, 200.1 grams (0.43 mole) of 1,3-bis(nonylphenoxy)-2-propanol prepared in Example 2 and 0.20 grams (0.1 weight percent) of BF.sub.3.Et.sub.2 O. The reaction mixture was heated to 80.degree. C., and 55.1 grams (1.25 mole) of ethylene oxide was fed to the reactor over a two hour period. After all the ethylene oxide was fed, the reaction mixture was allowed to cook out for one hour and then dumped hot, under nitrogen, into a jar containing 160 milliliters of a one percent aqueous solution of sodium hydroxide. The organic layer was separated from the water layer and washed twice with deionized water. The washes were performed at 90.degree. C. to facilitate the separation of the two layers. The product was then dried by azeotropic removal of the water, using cyclohexane (300 milliliters) as the entrainer. The cyclohexane was stripped off under vacuum to give a pale-yellow liquid with a molecular weight by end-group MW analysis of 601.7 (theoretical MW=629). Ir and nmr spectra were consistent with the expected structure of the product.
EXAMPLE 16
Preparation of 8 Mole Ethoxylate of Bis(nonylphenoxy) Adduct of 1,4-Butanediol Diglycidyl Ether
To a five hundred milliliter Zipperclave reactor were charged, under nitrogen, 150.2 grams (0.22 mole) of bis(nonylphenoxy) adduct of 1,4-butanediol diglycidyl ether prepared in Example 14 and 0.30 grams (0.2 weight percent) of BF.sub.3. Et.sub.2 O. The reaction mixture was heated to 80.degree. C., and 77.5 grams (1.76 mole) of ethylene oxide was fed to the reactor over a two hour period. After all the ethylene oxide was fed, the reaction mixture was allowed to cook out for one hour and then dumped hot, under nitrogen, into a jar containing 160 milliliters of a one percent aqueous solution of sodium hydroxide. The organic layer was separated from the water layer and washed twice with deionized water. The washes were performed at 90.degree. C. to facilitate the separation of the two layers. The product was then dried by azeotropic removal of the water, using cyclohexane (300 milliliters) as the entrainer. The cyclohexane was stripped off under vacuum to give a pale-yellow liquid with a molecular weight by end-group MW analysis of 1047 (theoretical MW=995). Ir and nmr spectra were consistent with the expected structure of the product.
EXAMPLE 17
Preparation of Macromonomer Compound
Into a 1 liter round bottom reaction flask equipped with a heating mantle, dean stark trap, condenser, thermometer, nitrogen bubbler, nitrogen purge line and stirrer was charged 300 grams of toluene and 63 grams of a surfactant identified as S-1 in Table A below. With nitrogen purge, the resulting solution was heated to reflux at approximately 110.degree. C. and azeotroped to remove trace water to dryness. The solution was subsequently cooled to 90.degree. C., and 1.5 grams of bismuth hex chem 28% bismuth octoate catalyst (Mooney Chemical, Inc., Cleveland, Ohio) was charged and allowed to mix well, after which a stoichiometric amount of 95% m-TMI aliphatic isocyanate (American Cyanamid, Stamford, Conn.) was charged. After the reaction proceeded at 90.degree. C. for 1.3 hours, the resulting product was cooled to 70.degree. C. and 0.03 grams of 2,6-di-tert-4-methyl phenol (BHT) preservative was added. The mixture was poured into a stainless steel pan with large surface area to facilitate drying. The final product was a waxy material, and is designated herein as macromonomer M-1.
EXAMPLES 18-34
Preparation of Macromonomer Compounds
In a manner similar to that described in Example 17, other macromonomers were prepared using stoichiometric amounts of the surfactants and unsaturated compounds identified in Table B below.
EXAMPLE 35
Preparation of Alkali Soluble Thickener
A monomer mixture (300 grams) was prepared by charging ethyl acrylate (Aldrich), methacrylic acid (Aldrich), macromonomer M-1, 13 grams of a 75% solution of Aerosol.RTM. OT surfactant (American Cyanamid, Stamford, Conn.), and 3 grams of distilled deionized water to a bottle, and dispersing the contents with vigorous shaking. The ethyl acrylate, methacrylic acid and macromonomer M-1 were added in amounts identified in Table C below. A catalyst feed mixture comprised of 0.53 grams of sodium persulfate (Aldrich) and 52.47 grams of water was prepared in another container. To a 2 liter resin flask that had been immersed in a thermostated water bath and equipped with a 4-bladed stainless steel mechanical stirrer, Claisen connecting tube, water condenser, nitrogen sparge and bubble trap, thermometer and monomer and catalyst addition inlets, 1.20 grams of the sodium salt of vinyl sulfonic acid and 658.5 grams of water were charged. The monomer mixture was charged to a 1-liter graduated monomer feed cylinder, and the catalyst solution was charged to a 125 milliliter graduated catalyst feed cylinder. Under nitrogen purge, the reactor was heated to 70.degree. C., whereupon 33 milliliters of the monomer mixture and 3 milliliters of the catalyst feed mixture were charged to the reaction vessel. The reaction vessel was subsequently heated to 80.degree. C. After allowing the monomers to react for 20 minutes to form a seed product, the monomer End catalyst feed mixtures were conveyed to the reaction vessel by FMI pumps via 1/8" teflon tubing at a rate of 1.94 and 0.27 milliliters/minute, respectively, under continuous stirring at a reaction temperature held between 76.degree.-82.degree. C. The reaction was allowed to proceed for another hour, after which the product was cooled and filtered with a 200 mesh nylon cloth. The coagulum was collected from the reaction vessel and filter cloth. Thickening ability of the resulting product was monitored by Brookfield viscosity at 6 rpm by diluting the latex to 0.25%, 0.50% and 0.75% solids, and subsequently neutralizing the product to phi9.0 with a 95% solution of 2-amino-2-methyl-l-propanol (AMP-95, Angus Chemical Company). The results are given in Table C.
EXAMPLES 36-131
Preparation of Alkali Soluble Thickener
In a manner similar to that described in Example 35, other alkali soluble thickeners were prepared using the monomers identified in Tables C-J below in the amounts identified in Tables C-J. Table C illustrates the influence of m-TMI-containing macromonomer concentration and ethoxylation on thickening efficiency. Table D illustrates the influence of mixing m-TMI-containing macromonomers of various ethoxylations on thickening efficiency. Table E illustrates the influence of unsaturation type of urethane-containing macromonomers on thickening efficiency. Table F illustrates the influence of macromonomer ester structure and ethoxylation on thickening efficiency. Table G illustrates the influence of acid type and concentration on thickening efficiency. Table H illustrates the influence of polymer glass transition temperature and water solubility on thickening efficiency. Table I illustrates the influence of cross-linkable monomer concentration on thickening efficiency. Table J illustrates the influence of mercaptan on thickening efficiency. As used in Tables C-J below, the following abbreviations have the indicated meanings: MM=Macromonomer; EA=Ethyl Acrylate; MAA=Methacrylic Acid; AA=Acrylic Acid; MA=Methyl Acrylate; t-BA=t-Butyl Acrylate; n-BA=n-Butyl Acrylate; MMA=Methyl Methacrylate; 2-EHP=2-Ethylhexyl Propionate Mercaptan; and 2-HEA =2-Hydroxy Ethyl Acrylate.
Although the invention may have been illustrated by certain of the preceding examples, it is not to be construed as being limited thereby; but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof.
Claims
We claim:
1. A compound represented by the formula selected from the group consisting of: ##STR6## wherein R.sub.1 and R.sub.2 are the same or different and are hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue, R.sub.3 is a substituted or unsubstituted divalent or trivalent hydrocarbon residue, each R.sub.4 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, each R.sub.5 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, R.sub.6 is hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent, a and b are the same or different and are a value of 0 or 1, and x and y are the same or different and are a value of 0 or greater; provided (i) at least two of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are a hydrocarbon residue having greater than 2 carbon atoms in the case of R.sub.1, R.sub.2 and R.sub.6 or having greater than 2 pendant carbon atoms in the case of R.sub.3, R.sub.4 and R.sub.5, (ii) at least one of R.sub.4 and R.sub.5 is other than --CH.sub.2 CH.sub.2 -- when R.sub.1 and R.sub.2 are nonylphenyl, R.sub.3 is >CH--, R.sub.6 is hydrogen or SO.sub.3, a is a value of 1, b is a value of 1, and at least one of x and y is a value of 1 or greater, (iii) R.sub.4 is --CH.sub.2 CH.sub.2 -- and x is a value of at least 2 when R.sub.1 is hexadecyl, R.sub.2 is tetradecyl, R.sub.3 is >CH--, at least one R.sub.5 is --CH.sub.2 CH(tetradecyl)--, R.sub.6 is hydrogen, y is a value of 1 or greater, a is a value of 1, and b is a value of 0; (iv) at least one of R.sub.1 and R.sub.2 is other than CH.sub.3 (CH.sub.2).sub.1-5 OCH.sub.2 CH(OH)CH.sub.2 -- when R.sub. 6 is CH.sub.3 (CH.sub.2).sub.1-5 --, a is a value of 1, b is a value of 1, y is a value of 0, x is a value of 1, R.sub.4 is --CH.sub.2 CH(OH)CH.sub.2 -- and R.sub.3 is >CH--; (v) R.sub.1 is other than CH.sub.3 (CH.sub.2).sub.1-5 OCH.sub.2 CH(OH)CH.sub.2 -- when a is a value of 1, b is a value of 0 and R.sub.6 is CH.sub.3 (CH.sub.2).sub.1-5 --; (vi) at least one of R.sub.1 and R.sub.2 is other than CH.sub.3 (CH.sub.2).sub.1-5 OCH.sub.2 CH(OH)CH.sub.2 -- when R.sub.6 is CH.sub.3 (CH.sub.2).sub.3 CH.sub.2 CH(OH)CH.sub.2 --, a is a value of 1, b is a value of 1, x is a value of 0, y is a value of 0 and R.sub.3 is >CH--; and (vii) at least one of R.sub.4 and R.sub.5 is other than --CH.sub.2 CH.sub.2 -- when R.sub.1 and R.sub.2 are the same and are an aromatic hydrocarbon residue, R.sub.3 is >CH--, R.sub.6 is hydrogen, a is a value of 1, b is a value of 1 and at least one of x and y is a value of 1 or greater; and ##STR7## wherein R.sub.7 and R.sub.8 are the same or different and are hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue, R.sub.9 and R.sub.12 are the same or different and are a substituted or unsubstituted divalent or trivalent hydrocarbon residue, each R.sub.10 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, each R.sub.13 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, R.sub.11 and R.sub.14 are the same or different and are hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent, R.sub.15 is a substituted or unsubstituted divalent hydrocarbon residue, d and e are the same or different and are a value of 0 or 1, and f and g are the same or different and are a value of 0 or greater; provided at least two of R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14 and R.sub.15 are a hydrocarbon residue having greater than 2 carbon atoms in the case of R.sub.7, R.sub.8, R.sub.11 an R.sub.14 or having greater than 2 pendant carbon atoms in the case of R.sub.9, R.sub.10, R.sub.12, R.sub.13 and R.sub.15.
2. The compound of claim 1 wherein R.sub.1, R.sub.2, R.sub.7 and R.sub.8 are selected from substituted or unsubstituted monovalent alkyl, aryl, alkylaryl, arylalkyl, cycloalkyl and mixtures thereof.
3. The compound of claim 1 wherein R.sub.1, R.sub.2, R.sub.7 and R.sub.8 are selected from dodecylphenyl, nonylphenyl, octylphenyl and mixtures thereof.
4. The compound of claim 1 wherein at least one of R.sub.1, R.sub.2, R.sub.7 and R.sub.8 is a hydrocarbon radical represented by the formula: ##STR8## wherein R.sub.16 and R.sub.17 are the same or different and are hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue, R.sub.18 is a substituted or unsubstituted divalent or trivalent hydrocarbon residue, and h and i are the same or different and are a value of 0 or 1.
5. The compound of claim 1 wherein at least one of R.sub.4, R.sub.5, R.sub.10 and R.sub.13 is a hydrocarbon radical represented by the formula: wherein each R.sub.19 is the same or different and is a substituted or unsubstituted divalent hydrocarbon residue, R.sub.20 is hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent, and j is a value of 0 or greater.
6. The compound of claim 1 wherein each R.sub.4, R.sub.5, R.sub.10 and R.sub.13 is selected from --CH.sub.2 CH.sub.2 --, --CH.sub.2 CH(CH.sub.3)-- and mixtures thereof.
7. The compound of claim 1 wherein R.sub.6, R.sub.11 and R.sub.14 are hydrogen.
8. The compound of claim 1 wherein the values of x, y, f and g are from 0 to about 200 or greater.
9. The compound of claim 1 wherein R.sub.15 is selected from --phenylene--(CH.sub.2).sub.m (Q).sub.n (CH.sub.2).sub.m -phenylene-- and --naphthylene--(CH.sub.2).sub.m (Q).sub.n (CH.sub.2).sub.m --naphthylene--, wherein Q individually represents a substituted or unsubstituted divalent bridging group selected from --CR.sub.21 R.sub.22 --, --O--, --S--, --NR.sub.23 --, --SiR.sub.24 R.sub.25 -- and --CO--, wherein R.sub.21 and R.sub.22 individually represent a radical selected from hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, tolyl and anisyl; R.sub.23, R.sub.24 and R.sub.25 individually represent a radical selected from hydrogen and methyl, and each m and n individually have a value of 0 or 1.
10. The compound of claim 1 wherein R.sub.1 is the residue of nonylphenol, R.sub.2 is the residue of nonylphenol, R.sub.3 is >CH--, R.sub.4 is --CH.sub.2 CH.sub.2 --, R.sub.5 is --CH(CH.sub.3)CH.sub.2 --, R.sub.6 is hydrogen, a is a value of 1, b is a value of 1, x is a value of 20 and y is a value of 20.
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