CN1197449A - Reducing estrogenicity of alkoxylated compounds and products thereof - Google Patents

Reducing estrogenicity of alkoxylated compounds and products thereof Download PDF

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CN1197449A
CN1197449A CN96197148A CN96197148A CN1197449A CN 1197449 A CN1197449 A CN 1197449A CN 96197148 A CN96197148 A CN 96197148A CN 96197148 A CN96197148 A CN 96197148A CN 1197449 A CN1197449 A CN 1197449A
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carbon atom
alk
straight
branched
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M·W·梅道斯
C·贝格尔
P·贝格尔
R·克拉维
C·达维斯
K·弗里劳克斯
C·格林
吕英道
阮永交
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Witco Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
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    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C43/184—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring to a carbon atom of a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
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    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups

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Abstract

Compounds of the formula A-D-(OC2H4)x-(O-Alk)y-(OC2H4)z-OR, wherein A denotes a straight-chained or branched alkyl or alkenyl group containing 1 to 18 carbon atoms, a phenyl group, a phenyl-alkenyl group wherein the alkenyl moiety contains 1 to 4 carbon atoms, a polycyclic group containing 9 to 14 carbon atoms, a polyol, alkoxy group, or hydrogen; B denotes phenoxy, oxy, phenyl, a linear or branched alkyl or alkenyl group, an amino group, or a carbonyl group; x is 0 - 10; y is 1 - 10; z is 0 - 100; each (O-Alk) denotes straight-chained or branched propoxy, butoxy or substituted oxirane; and R is hydrogen, sulfate, sulfonate, monophosphate, diphosphate, carboxylate, monosulfosuccinate, disulfosuccinate, or a salt thereof, are useful as surfactants per se and in any application in which the corresponding purely ethoxylated surfactants are useful, and have been found to exhibit reduced or no estrogenicity in themselves and their degradation products.

Description

Emotionally act on alcoxylates that reduces and products thereof
The present invention relates to alcoxylates, include but not limited to alkylphenol such as side chain or straight chain, naphthols and naphthol derivative, bis-phenol, the dialkyl phenol of side chain and straight chain, dihydroxy-benzene, benzenetriol, resol, 1, the alcoxylates of the phenolic compound of 2-toluylene and derivative thereof and phenyl phenol and so on.The invention still further relates to alcohols, polyalcohols, fatty acid, amine, carboxylic-acid, with any alcoxylates that can oxyalkylated other material, particularly for example in various industrial application, be used as tensio-active agent and can be used as intermediate is used for preparing this alcoxylates of other related compound that serves many purposes in industry and commercial field some derivative.
It is found that alkyl phenolic alkoxy thing, particularly alkylphenol ethoxylate have purposes widely in multiple Application Areas.These are used mainly is the surfactant properties that relies on these compounds.This surfactant properties itself can be done suitably to select to regulate again by the number of multiple ethoxy unit poly-(oxyethyl group) side chain of the formation of counting to the alkyl substituent in the phenolic group with from the Sauerstoffatom that phenyl connected.For example, nonyl phenol ethoxylate is the tensio-active agent of knowing that serves many purposes; This compound is commonly referred to " nonoxynolum ", and contains the individual multiple ethoxy unit of 1-100 (or at random more) at some position of molecule.This alkylphenol ethoxylate is at makeup, washes and dresses articles for use and such as the oil film dispersion agent, the deinking tensio-active agent, metal treatment, yarn fabric is handled, milk sap forms, letex polymerization, and washing composition has purposes widely with relevant industrial application of all kinds such as sanitising agent.
Recently, scientific circles are for many common compounds, and the derivative (as nonyl phenol ethoxylate) that comprises nonyl phenol and phenol may demonstrate emotionally that effect has produced worry.Referring to: Jobling, S. etc. " detergent ingredients in the sewage has weak emotionally effect to fish: with rainbow trout (Oncorhynchus; the mykiss) in vitro tests carried out of liver cell ", " hydrocoles toxicology (Aquatic Toxicology) " 27 volumes (1993), P361-372; Soto, A.M. etc. " right-nonyl phenol: a kind of oestrogenic hormon xenobiotics that oneself " modified polystyrene " discharges ", " environmental health prospect (Env.Health Perspectives) ", 92 volumes (1991), P167-173.Therefore, many phenolic compound, their derivative, the possibility relevant with this adverse side effect with the biodegradable product of these derivatives all worried about all producers and the user of these materials.At present, for careful and responsible, ethoxylate and derivative thereof, various nonionics, negatively charged ion, positively charged ion and amphoterics must be as may the originate processing of these materials in environment, much demonstrated in them to have emotionally effect.Therefore, hope can be found such material, the final product that can be synthesized by it has the various useful qualitys that present available alkoxylate material is had, but not have to produce the danger that emotionally acts on when using, and does not also produce the estrogenicity material when biological degradation.
Widespread use and various uses in view of alkylphenol ethoxylate, and this ethoxylate can be biodegradable into, particularly biological degradation becomes to have the possibility of the corresponding alkylphenol compound or derivatives thereof of estrogenicity, to the job search of the qualified surrogate of the precursor of the estrogenicity material that confirms not to be possible be appreciated that away from the alkyl phenolic alkoxy thing.
Brief summary of the invention
Although have reason fully to expect that the oxyalkylated analogue of alkyl phenolic alkoxy thing can be degraded into alkylphenol and its derivative that may have emotionally effect, but confirm, have the following compound itself of hydrophobic part and hydrophilic segment and its degraded product and demonstrate this ideal character extremely of the emotionally effect that do not have or reduce greatly, hydrophilic segment wherein is poly-ethoxy chain, as the alkyl phenolic alkoxy thing, but it is characterized in that 1) lack block from oxyethyl chain propoxy-and/or the butoxy unit before that be positioned at that hydrophobic grouping is stretched, or 2) third oxygen and/or the unitary short block of butoxy in the insertion oxyethyl chain, or 3) be inserted into third oxygen and/or butoxy unit in the oxyethyl chain at random, or 4) be added to third oxygen and/or the butoxy unit of oxyethyl chain end, or 5) replace third oxygen and/or the butoxy unit of oxyethyl chain.
Therefore, one aspect of the present invention comprises following formula: compound,
A 1-4-D-(OC 2H 4) x-(O-AlK) y-(OC 2H 4) z-OR (1) wherein A represents the straight or branched alkyl or alkenyl that contains 1-18 carbon atom, and phenyl, alkenyl part contain the phenyl-thiazolinyl of 1-4 carbon atom, contain many cyclic groups of 8-14 carbon atom, polyvalent alcohol, alkoxyl group, or hydrogen; D represents phenoxy group, oxygen, phenyl, the alkyl or alkenyl of straight or branched, amino, or carboxyl; X is 0-10; Y is 1-10; Z is 0-100; Each (O-AlK) represents the propoxy-of straight or branched or the oxyethane of butoxy or replacement; And R is a hydrogen, sulfate radical, sulfonate radical, a phosphate radical and/or gen-diphosphate, carboxylate radical, a sulfosuccinic acid group and/or disulfo amber acid radical, or their salt.
The present invention is formula A-D-(O-AlK) on the other hand y-OH compound, wherein A.D. (O-AlK) and y as above define, and they are as the application of the raw material of synthesis type (1) compound.
Following formula product and in the method for this definition is characterized in that the alkoxy compound that forms has kept the institute's available energy as the tensio-active agent needs, and itself and degraded product thereof demonstrate the extremely ideal character that emotionally effect reduces or do not have again simultaneously.
Detailed Description Of The Invention
Above-mentioned formula (1) A-D-(OC 2H 4) x-(O-AlK) y-(OC 2H 4) z-OR compound is used to comprise many commercial application fields of tensio-active agent.Therefore, the present invention expands to any in the numerous finished product preparation that comprise this compounds itself and can comprise one or more following formula compounds.And do not mean that these preparations comprise oil field emulsifying agent and emulsion splitter, the oil film dispersion agent under the situation that limits the scope of the invention, the deinking tensio-active agent, metal treatment tensio-active agent, textile treatment tensio-active agent, the paper composition that comes unstuck, letex polymerization tensio-active agent, the tensio-active agent of used for cosmetic and emulsifying agent, wash and dress articles for use and personal-care supplies, hard surface cleaner, low-sudsing detergent, emulsifying agent and dispersion agent, wetting agent, agricultural emulsifier, coating surface promoting agent etc.
Get back in the above-mentioned formula (1) group A 1-4-D-more generally is the hydrophobic part of representation compound, and wherein D is replaced by 1-4 the group of representing as A.Therefore, A 1-4-D-can represent various possible structures.For example, A can be:
The alkyl that contains 1-18 carbon atom or the alkenyl of straight or branched, as methyl, or preferred 4-10 carbon atom, as nonyl;
Phenyl;
Phenyl-thiazolinyl, wherein alkenyl part contains 1-4 carbon atom, and the example is a benzyl;
The many cyclic groups that contain 8-14 carbon atom, these many rings can be complete saturated, undersaturated entirely, or the fractional saturation part is undersaturated, as, 2,3-indanyl, naphthalene, dihydronaphthalene, naphthane and contain the cyclohexyl that replaces phenyl ring, cyclohexenyl, their analogue of cyclopentyl or cyclopentenyl;
Hydroxyl or preferably contain the polyvalent alcohol of 2-6 carbon atom and 2-6 hydroxyl; Or
Alkoxyl group preferably contains the straight or branched alkoxyl group of 1-20 carbon atom.
For example, D can be a phenoxy group, oxygen (promptly-O-), phenyl contains the alkyl or alkenyl of the straight or branched of 1-18 carbon atom, amino, or carbonyl (promptly-C (o)-).
Preferred A 1-4-D-group comprises hydroxyl, benzyl phenyl, i.e. and residue in the dihydroxyphenyl propane, the embodiment of another preferred molecule is to contain the straight or branched alkyl of 1-18 carbon atom and/or the phenyl ring of alkenyl substituted with one, two or three, or other any group described herein.A preferably contains 4-12 carbon atom.
Will appreciate that in the nature of things, the invention still further relates to and contain two or more not cotype (1) compound compositions; For example contain the composition of certain more than one constitutional isomers of compound and contain composition with two or more different types formulas (1) corresponding compounds with given carbonatoms.Formula (1) compound also contains 1-10 oxyalkyl units of the formula of being expressed as (O-AlK), and wherein each (O-AlK) represents the propyl group of straight or branched, the oxyethane of butyl or replacement.Although containing the segment that gathers (propoxy-) and/or poly-(butoxy) part of short block or the propoxy-and/or the butoxy of random sequence is to be considered within the scope of the present invention, but in the molecule of any given corresponding formula (1), preferably each (O-AlK) unit is identical.
In the formula (1), 1-100 the ethoxy unit segment that the chain of being made up of multiple (O-AlK) unit can be optionally substituted with itself stops.Equally with the situation of the nonyl phenol ethoxylate of known being commonly referred to " nonoxynolum " can select the number of multiple ethoxy unit and the carbonatoms in the segments A, so that it is well-known in the tensio-active agent industry, be provided at needed solubleness and HLB (hydrophile-lyophile balance) in the predetermined solvent (referring to Griffin, W.C., " cosmetic chemistry man meeting will (J.Soc.Cosmetic chemists) " the 1st volume (1949), P311).The same also planning of mixture at random and oxyethyl group and propoxy-and/or the unitary block of butoxy within the scope of the present invention.
As the formula (1), poly-(oxyethyl group) alkyl phenolic alkoxy thing of sealing can be simply sealed, thereby a kind of useful nonionic surface active agent is provided with-H group.Or formula (1) compound can be used negatively charged ion such as sulfate radical, sulfonate radical, and carboxylate radical, phosphate radical or sulfosuccinic acid group and its salt are sealed, thereby form a series of useful anion surfactants.
Anionic group can be equipped with positively charged ion M such as sodium, potassium, and lithium, ammonium, or amine salt makes charge balance, or keep its sour form.The concrete selection of nonionogenic tenside and anion surfactant group is that the makers-up is adequate fully.All have and the alkylphenol ethoxylate of routine and the carboxylate salt of alkylphenol ethoxylate by the nonionogenic tenside of formula (1) and the anion surfactant of this formula, vitriol, sulfonate, the corresponding to purposes of the known applications of phosphoric acid salt and sulfosuccinate.
An importance of the present invention is the method that the applicant has found to can be used to the alkyl phenolic alkoxy thing of synthesis type (1), and this compound itself or its degraded product demonstrate the emotionally effect that does not have or reduce.
As mentioned above, this synthetic method is propoxy-and/or butoxy unit are attached in poly-(oxyethyl group) segment.Naturally, there is multiple different route of synthesis can finish needed insertion reaction.For example, but in a kind of preferred embodiment preparation formula A-D-(O-AlK) y-OH precursor, A wherein, D (O-AlK) and y such as preceding definition, changes into needed degree with its oxyethyl group subsequently, and this alkoxide can further react and obtain required vitriol, carboxylate salt, sulfonate, phosphoric acid salt or sulfosuccinate.In another preferred embodiment, initiator A-D-OH and established segment H (O-AlK) y(OC 2H 4) z-OH reaction, or sequentially with H (O-AlK) yOH and H (OC 2H 4) zThe OH reaction forms end product.
In this one side and others, experienced technician in this area be it is evident that, achievement of the present invention is a kind of synthetic method, successfully prepares the emotionally surfactant compounds of effect that itself and degraded product thereof demonstrate not to be had or reduce greatly by this method.
Any required the synthetic of specific formula (1) compound all is quite simple and the very conventional synthetic technology of use, adopts the method for known formation alcoxylates.The discovery of the source of precursor raw material and suitable reaction conditions is determined by those skilled in the art easily.As mentioned above, usually, will have the alkylphenol that replaces of the composition of wanting and position by the certain way alkoxylate, make propoxy-and/or butoxy unit prepare product among being attached to oxyethyl chain with required character.Subsequently alcoxylates is reclaimed, perhaps, if desired, alcoxylates is further processed, make sulfonate, phosphoric acid salt, vitriol, sulfosuccinate, or carboxylate salt according to known technology.For guaranteeing the complete alkoxylate of alkylphenol, preferably use excessive propylene oxide of stoichiometry and/or oxybutylene usually.The alkylphenol mole number) or higher reaction is finished generally reach about 5: 1 excessive (oxyalkylene mole number:.
Now describe the present invention with following embodiment, these embodiment only limit the scope of the present invention for usefulness being described, should not be construed as.
Embodiment 1
(right-nonylphenol+2 oxyethane)
Nonyl phenol 2.558kg and 50% aqueous sodium hydroxide solution 10.8g are packed in the reactor, be heated to 125 ℃ behind the purging.Reaction mixture dewatered 2 hours under this temperature, subsequently the oxyethane (EO) of 1.026kg was added in the reactor and in 125 ℃ of reactions 1 hour.In the mixture that forms and back is taken out from reactor.Result that the hormesis test of expressing in the trout liver cell by art-recognized standard test methods and to the vitellogenin group obtains (referring to Jobling etc., " detergent ingredients in the sewage ... " (seeing above-mentioned); And White, R etc., " the long-pending alkylphenol compound that stagnates in the environment has emotionally effect ", incretology (Endocrinology) " 135 volumes, 1,175-182) show that this compound has emotionally effect.
Embodiment 2
(right-nonylphenol+4 oxyethane)
Right-nonyl phenol 1.989kg and 50% aqueous sodium hydroxide solution 10.8g are packed in the reactor into purging post-heating to 125 ℃.This mixture dewatered 2 hours under this temperature, subsequently oxyethane 1.595kg was added in the reactor and in 125 ℃ of reactions 1 hour, in the mixture that will form and back be taken out from reactor.The result who derives from above-mentioned standard test shows that this material has emotionally effect, but needs higher concentration just can reach to resemble the emotionally effect of same degree embodiment 1 product.
Embodiment 3
(right-nonylphenol+2 propylene oxides)
Nonylphenol 2.345kg and 50% aqueous sodium hydroxide solution 10.8g are packed in the reactor into purging after heat to 125 ℃.Under this temperature,, subsequently propylene oxide (PO) 1.239kg is added in the reactor and and reacted 1 hour in 125 ℃ with this mixture dehydration 2 hours.The mixture that forms is neutralized the back and takes out from reactor.Show that with above-mentioned standard test methods test this product is not have the emotionally nonyl phenol propoxylated glycerine of effect.
Embodiment 4
(right-nonylphenol+2PO+4EO)
Nonyl phenol 2.345kg and 50% aqueous sodium hydroxide solution 10.8g are added in the reactor, with reactor purging post-heating to 125 ℃.Reaction mixture dewatered 2 hours under this temperature, subsequently propylene oxide 812.5g was added in the reactor and in 125 ℃ to react 1 hour.After propylene oxide reacts completely, add oxyethane 1.233kg reaction 1 hour with the reactor exhaust and in reactor.In the mixture that forms and back is taken out from reactor.Is that the nonyl phenol alcoxylates emotionally acts on test with above-mentioned test method to this product, found that nothing emotionally acts on.Show that through Study on degradation the degradation product of this product does not have emotionally effect.
Embodiment 5
(right-octyl phenol+4EO)
Octyl phenol 1.932kg and 50% aqueous sodium hydroxide solution 10.8g are installed in the reactor, with reactor purging post-heating to 125 ℃.Under this temperature,, subsequently oxyethane 1.652kg is added in the reactor and and reacted 1 hour in 125 ℃ with mixture dehydration 2 hours.In the mixture that forms and back is taken out from reactor.The result who derives from above-mentioned standard test methods shows that this product has emotionally effect.
Embodiment 6
(right-octyl phenol+2PO+4EO)
Octyl phenol 1.481kg and 50% aqueous sodium hydroxide solution 10.8g are added in the reactor, and with reactor purging post-heating to 125 ℃, this mixture dewatered 2 hours under this temperature, subsequently propylene oxide 836g was added in the reactor and 125 ℃ of reactions 1 hour.After propylene oxide reacts completely, will add oxyethane 1.266kg after the reactor exhaust and react 1 hour.In the mixture that forms and back is taken out from reactor.The result who derives from above-mentioned standard test shows that this product is compared with its ethoxylation analogue, and emotionally effect reduces greatly.
Embodiment 7
(neighbour-nonyl phenyl phenol+4EO)
Neighbour-nonyl phenol 1.989kg and 50% aqueous sodium hydroxide solution 10.8g are installed in the reactor purging post-heating to 125 ℃.Under this temperature,, subsequently oxyethane 1.5959kg is added in the reactor and and reacted 1 hour in 125 ℃ with mixture dehydration 2 hours.In the mixture that forms and back is taken out from reactor.Derive from above-mentioned standard test result and show that this product has emotionally effect.
Embodiment 8
(the 2-methyl, the 4-nonylphenol+4EO)
With the 2-methyl, 4-nonyl phenol 2.043kg and 50% aqueous sodium hydroxide solution 10.8g pack in the reactor, are heated to 125 ℃ behind the purging.This mixture dewatered 2 hours under this temperature, subsequently oxyethane (EO) 1.5409kg was added in the reactor and in 125 ℃ to react 1 hour.In the formed mixture and back is taken out from reactor.The result who derives from above-mentioned standard test shows that this product has emotionally effect.
Embodiment 9-12 has described the synthetic of other compound, and these compounds have the emotionally effect of reduction, and is degraded into and has the possibility that emotionally acts on product and reduce.
Embodiment 9
(the 2-methyl, the 4-nonyl phenol+2PO+4EO)
With the 2-methyl, 4-nonyl phenol 1.592kg and 50% aqueous sodium hydroxide solution 10.8g pack in the reactor, with its purging post-heating to 125 ℃.Under this temperature,, subsequently propylene oxide 790.9g is added in the reactor, and in 125 ℃ of reactions 1 hour, after propylene oxide reacts completely, was added in the reactor reaction 1 hour with the reactor exhaust and with oxyethane 1.201kg with this mixture dehydration 2 hours.In the formed mixture and back is taken out from reactor.
Embodiment 10
(right-nonylphenol+1EO+2PO)
Right-nonylphenol 2.073kg and 50% aqueous sodium hydroxide solution 10.8g are packed in the reactor, behind the reactor purging by heat to 125 ℃.Under this temperature,, add oxyethane 416g subsequently and in 125 ℃ of reactions 1 hour with this mixture dehydration 2 hours.Reacting ethylene oxide fully after with the reactor exhaust and add propylene oxide 1.201kg reaction 1 hour.In the formed mixture and back is taken out from reactor.
Embodiment 11
(right-nonylphenol+1EO+2PO+3EO)
Right-nonylphenol 1.538kg and 50% aqueous sodium hydroxide solution 10.8g are installed in the reactor, behind the purging reaction is heated to 125 ℃.Under this temperature,, in reactor, add oxyethane 308g subsequently and in 125 ℃ of reactions 1 hour with this mixture dehydration 2 hours.After reacting ethylene oxide is intact, with the reactor exhaust and add propylene oxide 812g reaction 1 hour.After propylene oxide reacts completely, with the reactor exhaust and added oxyethane 925g reaction 1 hour.In institute's formation mixture and back is taken out from reactor.
Embodiment 12
(right-nonylphenol+2PO/4EO)
Nonyl phenol 2.345kg and 50% aqueous sodium hydroxide solution 10.8g are packed in the reactor, be heated to 125 ℃ behind the purging.Under this temperature,, be added in reactor as " blended " oxide compound propylene oxide 812.5g and oxyethane 1.233kg subsequently and, will in the formed mixture and then from reactor, take out in 125 ℃ of reactions 1 hour with mixture dehydration 2 hours.
For the contrast evaluation that emotionally acts on, embodiment 13 and 14 have been finished.
Embodiment 13
(right-nonyl phenol+10EO)
The aqueous sodium hydroxide solution 10.8g of right-nonyl phenol 1.193kg and 50% is packed in the reactor into purging post-heating to 125 ℃.Under this temperature,, subsequently oxyethane 2.391kg is added in the reactor and and reacted 1 hour at 125 ℃ with mixture dehydration 2 hours.In the reaction mixture and back is taken out from reactor.
Embodiment 14
(right-nonyl phenol+2PO+10EO)
Nonylphenol 1.014kg and 50% aqueous sodium hydroxide solution 10.8g are packed in the reactor into purging post-heating to 125 ℃.Under this temperature,, in reactor, add propylene oxide 536g subsequently and in 125 ℃ of reactions 1 hour with this mixture dehydration 2 hours.After propylene oxide has reacted,, and in reactor, add oxyethane 2.034kg reaction 1 hour with the reactor exhaust.In the formed mixture and back is taken out from reactor.
Show that by the DeR that compares the material of preparation in embodiment 13 and 14 the described method for preparing above-mentioned substance has also reduced the emotionally effect of its degraded product.
The function of the counterpart that the nothing of nonoxynolum-4 and it is emotionally acted on and the assessment of physical properties show that being used for preparing this modifying function that nothing emotionally acts on analogue has no adverse effect for other functional propertys (as surfactivity) of these materials.

Claims (11)

1. formula (1) compound
A 1-4-D-(OC 2H 4) x-(O-AlK) y-(OC 2H 4) z-OR (1) wherein A representative contains the alkyl or alkenyl of the straight or branched of 1-18 carbon atom, and phenyl, alkenyl part contain the phenyl-thiazolinyl of 1-4 carbon atom, the many cyclic groups that contain 8-14 carbon atom, polyvalent alcohol contains the alkoxyl group of 1-20 carbon atom or hydrogen; D represents phenoxy group, oxygen, and phenyl contains the alkyl or alkenyl of the straight or branched of 1-18 carbon atom, amino or carbonyl; X is 0-10; Y is 1-10; Z is 0-100; Each (O-AlK) all represents the propoxy-of straight or branched, the oxyethane of butoxy or replacement; And R is a hydrogen, sulfate radical, and sulfonate radical, a phosphate radical, gen-diphosphate, carboxylate radical, a sulfosuccinic acid group, the disulfo amber acid radical, or have their salt of hydrogen, ammonium or alkali metal cation; Compare with the analogue of y=0 wherein, formula (1) compound itself and its degraded product show the emotionally effect that does not have or reduce.
2. by the compound of claim 1, wherein A is the alkyl or alkenyl that contains the straight or branched of 1-18 carbon atom, and D is a phenyl.
3. by the compound of claim 1, wherein x is zero.
4. by the compound of claim 3, wherein A is the alkyl or alkenyl that contains the straight or branched of 1-18 carbon atom, and D is a phenyl.
5. by the compound of claim 4, wherein A is a nonyl.
6. one kind is synthesized the modification method with hydrophobic part and hydrophilic segment compound, and wherein hydrophilic segment comprises the polyethoxye chain, and described improvement is included in and comprises a formula (O-AlK) between said hydrophobic part and the hydrophilic segment ySegment, thereby make this compound both have the emotionally effect of reduction, have the trend that is degraded into the estrogenicity by product of minimizing again, wherein y is 1-10, and y AlK unit all is propyl group or butyl.
7. the method for claim 6, wherein said compound has formula (1) structure
A-D-(OC 2H 4) x-(O-AlK) y-(O-C 2H 4) z-OR (1) wherein A representative contains the alkyl or alkenyl of the straight or branched of 1-18 carbon atom, and phenyl, alkenyl part contain the phenyl-thiazolinyl of 1-4 carbon atom, the many cyclic groups that contain 8-14 carbon atom, polyvalent alcohol contains the alkoxyl group of 1-20 carbon atom or hydrogen; D represents phenoxy group, oxygen, and phenyl contains the straight or branched alkyl or alkenyl of 1-18 carbon atom, amino, or carbonyl; X is 0-10; Y is 1-10; Z is 0-100; Each (O-AlK) all represents the propoxy-of straight or branched, the oxyethane of butoxy or replacement; And R is a hydrogen, sulfate radical, sulfonate radical, a phosphate radical, gen-diphosphate, carboxylate radical, a sulfosuccinic acid group, disulfo amber acid radical, or have hydrogen, their salt of ammonium or alkali metal cation.
8. the method for claim 7, its Chinese style A-C 6H 4The alkylphenol compound of-OH, wherein A is the alkyl that contains the straight or branched of 1-18 carbon atom, and is selected from propylene oxide, one or more compounds reactions of the oxyethylene of oxybutylene and replacement, production A-C 6H 4-(O-AlK) yThe OH intermediate, wherein y is that 1-10 and y AlK unit all are propyl group or butyl, and with this intermediate and reacting ethylene oxide production A-C 6H 4-(O-AlK) y-(OC 2H 4) the z-OH product, wherein z is 1-100.
9. the method for claim 8, wherein A is a nonyl.
10. the method for claim 7, its Chinese style A-C 6H 4The alkylphenol compound of-OH, wherein A is the alkyl that contains the straight or branched of 1-18 carbon atom, with formula H-(O-AlK) y-(OC 2H 4) zThe reaction of-OH compound, wherein y is that 1-10 and z are 1-100, production A-C 6H 4-(O-AlK) y-(O-C 2H 4) zThe OH compound.
11. the method for claim 10, wherein A is a nonyl.
CN96197148A 1995-08-04 1996-08-02 Reducing estrogenicity of alkoxylated compounds and products thereof Pending CN1197449A (en)

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CN102791824A (en) * 2010-03-10 2012-11-21 巴斯夫欧洲公司 Method for producing crude oil using surfactants based on butylene oxide-containing alkyl alkoxylates
CN109021227A (en) * 2018-06-25 2018-12-18 陕西科技大学 A kind of nonylphenol acrylate phenol polyethenoxy polyoxypropylene ester and preparation method thereof

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US7291582B2 (en) 2005-09-20 2007-11-06 Conopco, Inc., D/B/A Unilever Liquid laundry detergent with an alkoxylated ester surfactant
US7977284B2 (en) * 2009-07-29 2011-07-12 Oil Chem Technologies, Inc Non-estrogenic alkylphenol derivatives

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CN102791824A (en) * 2010-03-10 2012-11-21 巴斯夫欧洲公司 Method for producing crude oil using surfactants based on butylene oxide-containing alkyl alkoxylates
CN104726084A (en) * 2010-03-10 2015-06-24 巴斯夫欧洲公司 Method for producing crude oil using surfactants based on butylene oxide-containing alkyl alkoxylates
CN102791824B (en) * 2010-03-10 2016-03-02 巴斯夫欧洲公司 Use the method for the tensio-active agent exploitation mineral oil based on the alkyl alkoxylates containing oxybutylene
CN109021227A (en) * 2018-06-25 2018-12-18 陕西科技大学 A kind of nonylphenol acrylate phenol polyethenoxy polyoxypropylene ester and preparation method thereof

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NO980462L (en) 1998-03-24

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