CN1781591A - Anionic surfactant and detergent composition containing same - Google Patents
Anionic surfactant and detergent composition containing same Download PDFInfo
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- CN1781591A CN1781591A CN200510126786.2A CN200510126786A CN1781591A CN 1781591 A CN1781591 A CN 1781591A CN 200510126786 A CN200510126786 A CN 200510126786A CN 1781591 A CN1781591 A CN 1781591A
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Abstract
The invention provides an anionic surface active agent, which is obtained by anionizing an adduct (A') of aliphatic alcohol and oxyalkylene. The adduct (A') is obtained by directly adding the oxyalkylene (b1) onto the aliphatic alcohol (a1), and satisfying the conditions (II'), (III') and (IV). The invention also provides a detergent compound containing the anionic surface active agent and a detergent compound containing the anionic surface active agent and an amphoteric surface active agent and/or a non-ionic surface active agent.
Description
The application is that international filing date is on September 29th, 1999, and international application no is PCT/JP99/05305, and the China national application number is 99811485.5, and denomination of invention is divided an application for " surfactant, its preparation method and composition of detergent " application.
Technical field
The present invention relates to a kind of nonionic surface active agent of novelty, a kind of anionic surfactant and a kind of composition of detergent that its anionization is made.More particularly, the present invention relates to the nonionic and the anionic surfactant of non-alkyl phenol type.
Background technology
Up to now, have some and under base catalyst or acidic catalyst existence condition, oxyalkylene and aliphatic alcohol are used as various surfactants, solvent and the intermediate that chemicals is used through aliphatic alcohol oxyalkylene addition compound and its anionization product that sudden reaction obtains.Yet, compare with the nonionic surface active agent of alkyl phenolic group, hitherto known aliphatic alcohol oxyalkylene addition compound its surface-active that has in some cases is not enough, and this adduct for example emulsibility, the stability of emulsion as emulsifying agent the time is all insufficient, and foaminess is also poor.As for the anionization product of aliphatic alcohol oxyalkylene addition compound, still exist foaminess, detergency, time stability and to the problems such as excitant of human body skin.
In addition, known a kind of method (United States Patent (USP) 4,112,231) of using the perchlorate catalyst to come the addition oxyalkylene.This method because the catalytic activity of this catalyst is low, and when its consumption of raising shortens the reaction time, can produce problems still not in industrial use, and as the obviously decolouring of product of gained, outward appearance is very poor, and the aldehyde height of this product.
The inventor addresses the above problem to have carried out deep research, and the nonionic surface active agent of finding to comprise the aliphatic alcohol oxyalkylene addition compound with specific composition and specified molecular weight distribution has good emulsibility and detergency.In addition, they find that also this aliphatic alcohol oxyalkylene addition compound can use the combination of two kinds of specific catalyst and directly makes, thereby realize the present invention.And find aliphatic alcohol oxyalkylene addition compound with gained carry out product that anionization obtains have improved foaminess, detergency, product in time stability and to the excitant of human body skin.
An object of the present invention is to provide a kind of aliphatic alcohol oxyalkylene addition compound, this adduct has and the analogous surface-active of alkyl phenolic group nonionic surface active agent, and do not have to resemble the alkyl phenolic group nonionic surface active agent environment is not caused the inherent worry of destroying.
Another object of the present invention provide a kind of have improved foaminess, detergency, product in time stability and to the irritating anionic surfactant of human body skin, it makes by the aliphatic alcohol oxyalkylene addition compound is carried out anionization.
A further object of the present invention provides a kind of composition of detergent that uses above-mentioned anionic surfactant and have good detergency.
Summary of the invention
Like this, the invention provides following (I), (II), (III) and (IV).
(I) a kind of nonionic surface active agent, it comprises aliphatic alcohol oxyalkylene addition compound (A),
Described (A) directly makes by a kind of oxyalkylene (b1) is added on a kind of aliphatic alcohol (a1), and satisfies following condition (i), (ii) and (iii):
(i) it comprises the compound of a kind of following general formula (1) expression or the mixture of its two or more compounds:
R
1O-[(C
2H
4O)
m/ (AO)
n]-(C
2H
4O)
p-H (1) in following formula, R
1It is the cyclic aliphatic alkyl that contains the aliphatic hydrocarbyl of 8-24 carbon atom or contain 8-24 carbon atom; A is the alkylidene that contains at least 3 carbon atoms; M is 0 or 1 or bigger integer, and its mean value is 0-4, and n is 0 or 1 or bigger integer, its mean value is 0-3, and p is 0 or 1 or bigger integer, and its mean value is 1-80, (m+n+p) be an integer, its mean value is 3-81, and mean value (m+p)/(m+n+p) is at least 0.5.Under the situation of m ≠ 0 and n ≠ 0, [(C
2H
4O)
m/ (AO)
n] represent block addition or random addition.
(ii) weight average molecular weight (Mw) satisfies following relational expression (2) or (3) with the ratio Mw/Mn of number-average molecular weight (Mn):
Mw/Mn≤0.030 * Ln (v)+1.010 (under the situation of v＜10) (2)
(v)+1.139 (under the situation of v 〉=10) (3) at this, v represents the mean value of (m+n+p) in the above-mentioned general formula (1) to Mw/Mn≤-0.026 * Ln.
Be 1.0 or littler (iii) according to leading the distribution constant of determining from the following formula (4) of Weibull distribution law (c).Only v up to 12 situation under, require to satisfy this condition.
C=(v+n
0/ n
00-1)/[Ln (n
00/ n
0)+n
0/ n
00-1] (4) at this, the implication of v as mentioned above, n
00Be the molal quantity of aliphatic alcohol (a1) used in reaction, n
0It is the molal quantity of unreacted aliphatic alcohol (a1).
(II) a kind of method for preparing the aliphatic alcohol oxyalkylene addition compound,
This method comprises a kind of aliphatic alcohol oxyalkylene addition compound, (e) with the oxyalkylene that contains at least two carbon atoms, (b3) at base catalyst, (f) carry out addition reaction under the existence condition, described aliphatic alcohol oxyalkylene addition compound, (e) can make through following method, the oxyalkylene that contains at least two carbon atoms with average 1-2.5 mole, (b2) at catalyst, (d) add to the aliphatic alcohol that contains 1-24 carbon atom under the existence condition, (a2) on, described catalyst, (d) can make adduct according to the following formula of leading from the Weibull distribution law, the distribution constant c ' that (4 ') determined is 1.0 or littler
C '=(v '+n
0'/n
00'-1)/[Ln (n
00'/n
0')+n
0'/n
00'-1] (4 '), v ' represented the average addition molal quantity of the oxyalkylene of per 1 mole of aliphatic alcohol (a2) institute addition, n at this
00' representative molal quantity of used aliphatic alcohol (a2) in reaction, n
0' represent the molal quantity of unreacted aliphatic alcohol (a2).
(III) aliphatic alcohol oxyalkylene addition compound (A ') is carried out the anionic surfactant that anionization obtains,
Described (A ') adds to oxyalkylene (b1) on the aliphatic alcohol (a1) and directly makes, and satisfies following condition (ii '), (iii ') and (iv).
(ii ') weight average molecular weight (Mw) satisfies following relation (2 ') or (3 ') with the ratio Mw/Mn of number-average molecular weight (Mn):
Mw/Mn≤0.030 * Ln (v ")+1.010 (at v "＜10 situation under) (2 ')
Mw/Mn≤-0.026 * Ln (v ")+1.139 (at v " 〉=10 situation under) (3 ') is at this, v " represents in the following general formula (1 ') mean value of (m '+n '+p ').
(iii ') by the definite distribution constant c of following formula (4 ") " be 1.0 or littler." satisfy this condition only at v up to requirement under 12 the situation.
C "=(v "+n
0/ n
00-1)/[Ln (n
00/ n
0)+n
0/ n
00-1] (4 ") are at this, v " implication as mentioned above.n
00The molal quantity of representative used aliphatic alcohol (a1) in reaction, n
0Represent the molal quantity of unreacted aliphatic alcohol (a1).
(iv) it comprises the compound of a kind of following general formula (1 ') expression or the mixture of its two or more compounds:
R
1O-[(C
2H
4O)
M '/ (AO)
N ']-(C
2H
4O)
P '-H (1 ') in following formula, R
1It is the cyclic aliphatic alkyl that contains the aliphatic hydrocarbyl of 8-24 carbon atom or contain 8-24 carbon atom; A is the alkylidene that contains at least 3 carbon atoms; M ' is 0 or 1 or bigger integer, its mean value is 0-5, n ' is 0 or 1 or bigger integer, its mean value is 0-5, p ' is 0 or 1 or bigger integer, and its mean value is 0-10, (m '+n '+p ') be an integer, its mean value is 1-20, and the mean value of (m '+p ')/(m '+n '+p ') is at least 0.5.Under the situation of m ' ≠ 0 and n ' ≠ 0, [(C
2H
4O)
M '/ (AO)
N '] represent block addition or random addition.
(IV) comprise the composition of detergent of above-mentioned anionic surfactant.
The specific embodiment
(I) nonionic surface active agent
In the invention of above-mentioned (I), described aliphatic alcohol oxyalkylene addition compound (A) is a kind of oxyalkylene (b1) to be added to the aliphatic alcohol oxyalkylene addition compound that directly makes on the aliphatic alcohol (a1) or the mixture (in this manual, " aliphatic alcohol " is defined as and comprises aliphatic alcohol and cycloaliphatic alcohol) of its two or more adducts.
Term used herein " directly makes ", is meant under the situation of operation that need not any adduct that is used for unreacted alcohol of classification or different addition molal quantitys such as fractionation, just directly makes described adduct.Needing the adduct of progressive operation is unpractical as common nonionic surface active agent, because its process complexity.But not for the classification purpose in the adduct that shirtsleeve operation stripping low-boiling point material or unreacting alcohol obtain is not included in.
Above-mentioned (A) comprises the compound of a kind of following general formula (1) expression or the mixture of its two or more compounds:
R
1O-[(C
2H
4O)
m/ (AO)
n]-(C
2H
4O)
p-H (1) in following formula (1), R
1Be the residue of aliphatic alcohol (a1), its representative contains the aliphatic hydrocarbyl or the cyclic aliphatic alkyl of 8-24 (being preferably 12-18) carbon atom usually.If R
1In carbon atom be less than 8, then can't obtain required emulsibility, dissolving power and detergency; And if R
1In carbon atom surpass 24, be disadvantageous then, because the pour point of gained oxyalkylene addition compound improves to disposing.Above-mentioned aliphatic hydrocarbyl comprises straight or branched, saturated or undersaturated aliphatic hydrocarbyl (alkyl, alkenyl and alkadienyl); Above-mentioned cyclic aliphatic alkyl comprises cycloalkyl and multi-ring alkyl.
R
1Object lesson comprise alkyl, as octyl group, nonyl, decyl, dodecyl, tridecyl, myristyl, cetyl, octadecyl, nonadecyl, 2-ethylhexyl and 2-ethyl octyl group.The example of alkenyl is octenyl, decene base, dodecenyl succinic, tridecylene base, 15 carbene bases, oil base and gaducene base (gadoleyl group).Alkadienyl comprises inferior oleyl (linoleyl group).The example of cycloalkyl is ethyl cyclohexyl, propyl group cyclohexyl, octyl group cyclohexyl and nonyl cyclohexyl.Multi-ring alkyl for example comprises adamantyl (adamantyl group).
The present invention is used is used to provide residue R
1Aliphatic alcohol (a1) be the alcohol that contains 8-24 (being preferably 12-18) carbon atom usually, it can be natural alcohol or synthol (as Ziegler alcohol and oxo alcohol).
Its example comprises that radical of saturated aliphatic alcohol is as octanol, nonyl alcohol, decyl alcohol, tip-nip, dodecanol, tridecanol, tetradecanol, hexadecanol, octadecanol and nonadecanol; Unsaturated aliphatic alcohol is as matsutake alcohol, decenol, lanolin alcohol, tridecylene alcohol, 15 carbene alcohol, oleyl alcohol, the oily enol in the pure and mild Asia of gaducene; Cycloaliphatic alcohol such as ethyl cyclohexanol, propyl group cyclohexanol, octyl group cyclohexanol, nonyl cyclohexanol and adamantanol.Can use one or both or multiple mixture in these alcohol.In these aliphatic alcohols, better be uncle or secondary alcohol, be more preferably primary alconol.In addition, moieties can be a straight chain or branched.Good especially is dodecanol, tridecanol, tetradecanol, hexadecanol and octadecanol.
In following formula (1), form (C by addition of ethylene oxide (below be called EO)
2H
4O) part.The A representative contains at least 3 carbon atoms, better 3-8 carbon atom, the alkylidene of 3 carbon atoms especially.The oxyalkylene that contains at least 3 carbon atoms by addition forms (AO) part.As this oxyalkylene, that can address has expoxy propane (below be called PO), 1,2-or 2,3-epoxy butane, oxolane, a styrene oxide etc.Be preferably PO.
In above-mentioned general formula (1), m is 0 or 1 or bigger integer, and its mean value is generally 0-4, is preferably 0-3, and good especially is 1-3.In general, n is 0 or 1 or bigger integer, and its mean value is generally 0-3, is preferably 0,1 or 2.In general, p is 0 or 1 or bigger integer, and its mean value is 1-80, is preferably 2-70, and more preferably 3-40 is preferably 3-20.When it surpasses 80, then can't reach enough emulsification and solute effects, and can't reach required permeability because molecule is too big because hydrophily is too high.In above-mentioned general formula (1), n better is 0 or 1 or bigger integer, and its mean value is generally 1-3.
In general, (m+n+p) be an integer, its mean value is 3-81, is preferably 3-71, more preferably 3-41.If it surpasses 81, then can't reach enough emulsification and solute effects, and can't reach required permeability because molecule is too big because hydrophily is too high.(m+p)/(m+n+p) ratio is at least 0.5 usually, is preferably 0.7-0.99.This ratio can variation less than 0.5 o'clock emulsifying effectiveness.{ (C
2H
4O)
m/ (AO)
nPartly can be that the block addition is (by (C
2H
4O)
mThen (AO)
nOrder) or random addition.It better is the block addition.
The weight average molecular weight (Mw) of the aliphatic alcohol oxyalkylene addition compound (A) that obtains in the invention (I) is preferably 261-5, and 000, good especially is 300-1,200.When it is 261-5,000 o'clock, surface-active such as penetration were good especially, so this is preferred.((GPC) measures molecular weight by gel permeation chromatography, down together).
(A) weight average molecular weight (Mw) must satisfy following formula (2) or (3) with the ratio Mw/Mn of number-average molecular weight (Mn).
Mw/Mn≤0.030 * Ln (v)+1.010 (under the situation of v＜10) (2)
Mw/Mn≤-0.026 * Ln (v)+1.139 (under the situation of v 〉=10) (3)
In these relational expressions, Ln (v) represents the natural logrithm of v, the average addition molal quantity of the oxyalkylene (b1) of v representative every mole of aliphatic alcohol (a1) addition, it is equivalent to the mean value of m, n and p summation, and they are respectively the addition molal quantitys of each oxyalkylene in above-mentioned general formula (1).
If do not satisfy relational expression (2) or (3), promptly during the molecular weight distribution broad, then can't obtain enough surface-actives.
In addition, the relatively good of Mw/Mn satisfied following relation (2 ') or (3 '):
Mw/Mn≤0.031 * Ln (v)+1.000 (under the situation of v＜10) (2 ')
Mw/Mn≤-0.026 * Ln (v)+1.129 (under the situation of v 〉=10) (3 ')
And, when can (c) being not more than 1.0 according to leading when the following formula (4) of following Weibull distribution law formula (5) is determined distribution constant (c).C is preferably and is not more than 0.9, more preferably is not more than 0.7.In formula (4), the value of distribution constant (c) is more little, and promptly the amount of unreacted aliphatic alcohol is few more, and then molecular weight distribution is just narrow more.
The content that this formula is used in unreacted aliphatic alcohol (a1) is not less than the situation of detectable limit (i.e. 0.001 weight %); Under the situation of (A), its situation when the average addition molal quantity that can be used for oxyalkylene (b1) is 12 moles.
If c surpasses 1, then can't reach enough surface-actives.
v＝c×Ln(n
00/n
0)-(c-1)×(1-n
0/n
00) (5)
c＝(v+n
0/n
00-1)/[Ln(n
00/n
0)+n
0/n
00-1] (4)
In these relational expressions, Ln (n
00/ n
0) representative (n
00/ n
0) natural logrithm, v as mentioned above, n
00The molal quantity of representative used aliphatic alcohol (a1) in reaction, n
0Represent the molal quantity of unreacted aliphatic alcohol (a1).
When the n in general formula (1) is 0 situation, when promptly having only oxirane to add to situation on the aliphatic alcohol (a1), weight average molecular weight (Mw) satisfies following relational expression (6) or (7) with the ratio Mw/Mn of number-average molecular weight (Mn) is better, rather than relational expression (2) or (3).
Mw/Mn≤0.020 * Ln (v)+1.010 (under the situation of v＜10) (6)
Mw/Mn≤-0.026 * Ln (v)+1.116 (under the situation of v 〉=10) (7)
In following formula, the v representative is to the average addition molal quantity of the oxirane (b1) of every mole of aliphatic alcohol (a1) addition, and it is equivalent to the mean value of (m+p) in the above-mentioned general formula (1).
If can not satisfy relational expression (6) or (7), promptly during the molecular weight distribution broad, then can't reach enough surface-actives.
In addition, the relatively good of Mw/Mn satisfied following relational expression (6 ') or (7 '):
Mw/Mn≤0.018 * Ln (v)+1.015 (under the situation of v＜10) (6 ')
Mw/Mn≤-0.023 * Ln (v)+1.113 (under the situation of v 〉=10) (7 ')
In the surfactant that comprises aliphatic alcohol oxyalkylene addition compound of the present invention (A), in order to produce good especially emulsifying effectiveness to high hydrophobic material, better be those to comprise HLB be 5-13 (good especially be 6-12) and to the emulsification index of mineral oil be at least 8 surfactant of (A) of (good especially be at least 9).Be preferably, it is R in formula (1)
1For containing the aliphatic hydrocarbyl of 10-20 carbon atom, m average out to 1-3, n average out to 0-2, those (A) of p average out to 1-5.That good especially is its R
1For containing the aliphatic hydrocarbyl of 12-18 carbon atom, m average out to 1-3, n average out to 0-1, those (A) of p average out to 1-3.In above and following description, HLB is meant by Griffin ' s HLB:Griffin ' the s HLB=of following formula (8) definition (molecular weight of the molecular weight/surfactant of E0 part in the surfactant) * 20 (8)
Herein, using under the situation of surfactant of the present invention as emulsifying agent, described emulsification index to mineral oil is measured as follows.
It is that 70 ℃ and viscosity 25 ℃ the time are the mineral oil of 15-25mPas that 3 weight portions are contained the emulsifying agent of nonionic surface active agent and 97 weight portion aniline points; This mixture of 5 weight portions is added to covering in the graduated cylinder of 100 milliliters of deionized waters that 95 weight portion adjustment to 25 ℃ are housed.Fluctuate then graduated cylinder 20 times leaves standstill when being allowed to condition at 25 ℃ afterwards.Observe emulsified state after 60 minutes, represent emulsification index s by the grade of following benchmark evaluation.
10: the state that all is uniformly emulsify.
9: all be milky white, the oil reservoir (less than 2 millimeters) that has part to separate.
8: all be milky white, the oil reservoir (2 millimeters or thicker, but less than 5 millimeters) that has part to separate.
7: all be milky white, the oil reservoir (5 millimeters or thicker, but less than 8 millimeters) that has part to separate.
6: all be milky white, the oil reservoir (8 millimeters or thicker, but less than 10 millimeters) that has part to separate.
5: all be milky white, the oil reservoir (10 millimeters or thicker, but less than 13 millimeters) that has part to separate.
4: oil reservoir almost separates (13 millimeters or thicker), and oil reservoir is milky white, and the bottom in water-bearing layer is transparent sign.
3: oil reservoir almost separates (13 millimeters or thicker), and oil reservoir is the white of emulsus, and the Lower Half in water-bearing layer is transparent sign.
2: oil reservoir almost separates (13 millimeters or thicker), and oil reservoir is the white of emulsus, and it is transparent that whole water-bearing layer nearly all is.
1: separate fully, it is transparent that oil reservoir and water-bearing layer nearly all are.
In addition, in the surfactant that contains the present invention (A), for high water wetted material is produced good especially emulsifying effectiveness, better be those to comprise HLB be 11-19 (good especially be 12-18) and to the emulsification index of OPE be at least 8 surfactant of (A) of (good especially be at least 9).Be preferably its R in formula (1)
1For containing the aliphatic hydrocarbyl of 10-20 carbon atom, m average out to 1-4, n average out to 0-3, those (A) of p average out to 5-20.That good especially is its R
1For containing the aliphatic hydrocarbyl of 12-18 carbon atom, m average out to 1-3, n average out to 1-2, those (A) of p average out to 5-15.
Herein, using under the situation of surfactant of the present invention as emulsifying agent, described emulsification index t to OPE measures as follows.
With 40 weight portion weight average molecular weight is that 9000-10000 and acid number are the OPE of 22-24,11 parts of emulsifying agents, 0.5 part of saleratus (potassium hydrocarbon) and 48.5 parts of deionized waters, be added in the stainless steel pressure container together with 10 stainless shots, use nitrogen-sealed then, follow in 140 ℃ at 2-3kgf/cm
2Pressure under it was shaken 30 minutes, with they emulsification.Represent that by the grade of following benchmark evaluation 1% of such emulsification product that obtains contains the state of water diluent.Be that water is diluted to 1 weight % with the emulsification product, use laser diffraction and scattering type particle size distribution measurement instrument (for example LA-700 that makes by Horiba-Seisakusho) to measure granularity.
10: particle mean size is less than the emulsion of 0.2 μ m.
9: particle mean size is 0.2 μ m or bigger but less than the emulsion of 0.3 μ m.
8: particle mean size is 0.3 μ m or bigger but less than the emulsion of 0.5 μ m.
7: particle mean size is 0.5 μ m or bigger but less than the emulsion of 0.6 μ m.
6: particle mean size is 0.6 μ m or bigger but less than the emulsion of 1.0 μ m.
5: particle mean size is that UV (750nm) transmissivity of 1.0 μ m or bigger and the 1 weight % aqueous solution is at least 30% emulsion.
4: particle mean size is that UV (750nm) transmissivity of 1.0 μ m or bigger and the 1 weight % aqueous solution is less than 30% emulsion.
3: full-bodied thickener.
2: inadequate emulsification, can't in gather.
1: each component is separated.
And, in the surfactant that contains oxyalkylene addition compound of the present invention (A), in order to dispose easily under than the lower temperature of conventional aliphatic alcohol oxyalkylene addition compound and to produce the good emulsifying effect, better be those to comprise HLB be that 7-15 (good especially be 8-14) and freezing point satisfy the surfactant of (A) of following formula (9).When HLB was 8-14, emulsifying effectiveness was good especially.Be preferably its R in formula (1)
1For containing the aliphatic hydrocarbyl of 10-20 carbon atom, m average out to 1-4, n average out to 1-3, those (A) of p average out to 1-20.That good especially is its R
1For containing the aliphatic hydrocarbyl of 12-18 carbon atom, m average out to 1-3, n average out to 1-3, those (A) of p average out to 2-16.
1.61x-102≤y≤1.61x-92 (9)
C in the general formula (1) that this x representative forms by addition EO
2H
4The weight % of the unit that O represents, y represent aliphatic alcohol oxyalkylene addition compound (A) freezing point (℃).
Freezing point y is more preferably and satisfies following relational expression (9 '):
1.61x-100≤y≤1.61x-95 (9’)
In the surfactant that contains aliphatic alcohol oxyalkylene addition compound of the present invention (A), for crust such as metal, tableware and cloth are had good detergency, better be those to comprise HLB be 7-15 (good especially for 8-14) and to the detergency index that is placed on the artificial dirt on the slide (with 9.5 moles of adducts of nonyl phenol EO as 100 standardization detergency) be at least 100 surfactant of (A) of (good especially be at least 102).Be preferably its R in formula (1)
1For containing the aliphatic hydrocarbyl of 10-20 carbon atom, m average out to 1-4, n average out to 1-3, those (A) of p average out to 3-15.That good especially is its R
1For containing the aliphatic hydrocarbyl of 12-18 carbon atom, m average out to 1-3, n average out to 1-3, those (A) of p average out to 5-10.
Said detergency index is measured as follows.Below, except as otherwise noted outside, % is meant weight %.
" prescription of cleaning solution "
Nonionic surface active agent 5%
Sodium lauryl benzene sulfonate 10%
Ethanol 5%
Urea 5%
Water 75%
Amount to 100%
Press Leenerts method (JIS K3370), use cleaning solution to carry out the detergency test by above-mentioned formulated.Use six slides as dirt-to substrate, the solution of artificial dirt in chloroform that uses following composition is as the dirt component.The cleaning solution aqueous solution with 0.15% concentration washs the slide that scribbles artificial dirt as wash liquid; Determine detergency by following formula, and detergency exponential representation is as 100 index with respect to the detergency of 9.5 moles of adducts of nonyl phenol EO.
" composition of artificial dirt component "
Tallow 16.6%
Soya-bean oil 16.6%
Monoolein 0.4%
Oil red 0.2%
Chloroform 66.2%
Amount to 100%
The amount (gram) of dirt before detergency (%)=100 * [amount (gram) of the amount (gram) of dirt before the washing-washing back dirt]/washing
In the surfactant that contains aliphatic alcohol oxyalkylene addition compound of the present invention (A), in view of high thickening function with as the consideration of thickener, better be those to comprise HLB be 10-14 (good especially be 11-13) and 5% viscosity in aqueous solution index (with 8.5 moles of adducts of nonyl phenol EO as 100 standardization viscosity) be at least 50 surfactant of (A) of (good especially be at least 70).Be preferably its R in formula (1)
1For containing the aliphatic hydrocarbyl of 10-20 carbon atom, m average out to 1-4, n average out to 0-3, those (A) of p average out to 1-10.That good especially is its R
1For containing the aliphatic hydrocarbyl of 12-18 carbon atom, m average out to 1-3, n average out to 0-1, those (A) of p average out to 3-7.
Viscosity index (VI) described herein is measured as follows.
5% aqueous solution of preparation nonionic surface active agent adopts Brookfield type viscosimeter to measure its viscosity with its No. 3 rotors under the 40rpm condition at 25 ℃; Viscosity index (VI) is expressed as with respect to 5% viscosity in aqueous solution of 8.5 moles of adducts of nonyl phenol EO as 100 index.
When nonionic surface active agent of the present invention is applied to its purposes, can prepare other nonionic surface active agent, anionic surfactant, cationic surface active agent and amphoteric surfactant.Specifically, nonionic surface active agent comprises for example the present invention polyoxyalkylene (C in addition
2-8) aliphatic series (C
8-24) alcohol (degree of polymerization=1-100), polyoxyalkylene (C
2-8, the higher fatty acids (C of the degree of polymerization=1-100)
8-24) aliphatic acid (C of ester (as polyethylene glycol mono stearate (degree of polymerization=20), polyglycol distearate (degree of polymerization=30) etc.), polyhydroxy (two to ten or more a plurality of hydroxyl) alcohol
8-24) polyoxyalkylene (C of ester (as glyceryl monostearate, ethylene glycol monostearate, Arlacel-20 etc.), polyhydroxy (two to ten or more a plurality of hydroxyl) alcohol
2-8, the aliphatic acid (C of the degree of polymerization=1-100)
8-24) ester adduct (as polyoxyethylene (degree of polymerization=10) Arlacel-20, polyoxyethylene (degree of polymerization=50) two oleic acid methyl glucosides etc.), Marlamid (as 1: 1 mole cocoanut fatty acid diethanolamide, 1: 1 mole lauroyl diglycollic amide etc.), polyoxyalkylene (C
2-8, the alkyl (C of the degree of polymerization=1-100)
1-22)-phenyl ether, polyoxyalkylene (C
2-8, the degree of polymerization=1-100)-alkyl (C
8-24) amino ethers, and oxidation of alkyl (C
8-24) dialkyl group (C
1-6) amine (as oxidation lauryl dimethylamine etc.).
The example of anionic surfactant comprises C
8-24Hydrocarbyl ether carboxylic acid or its salt are (as lauryl polyoxyethylene (the ether acetic acid sodium of the degree of polymerization=1-100), lauryl polyoxyethylene (degree of polymerization=1-100) disodium sulfosuccinate etc.), C
8-24The sulfate of hydrocarbon is (as NaLS, lauryl polyoxyethylene (degree of polymerization 1-100) ether sodium sulfate, lauryl polyoxyethylene (triethanolamine salt of the ether sulfuric acid of the degree of polymerization=1-100), coconut oil fatty acid monoethanolamide polyoxyethylene (degree of polymerization=1-100) ether sodium sulfate etc.), C
8-24The sulfonate of hydrocarbon (as neopelex etc.), and C
8-24The salt of hydrocarbon phosphate is (as the lauryl sodium phosphate; lauryl polyoxyethylene (degree of polymerization 1-100) ether phosphoric acid sodium etc.); soap is (as sodium laurate; Triethanolamine lauric acid salts etc.), the amino-acid salt of acidylate is (as coco-nut oil fatty acid N-methyltaurine sodium; the coco-nut oil fatty acid sodium sarcosinate; triethanolamine coco-nut oil fatty acid sarcosinate; triethanolamine N-coco-nut oil fatty acid-L-glutamate; N-coco-nut oil fatty acid-L-sodium glutamate; lauroyl methyl-Beta-alanine sodium etc.) and other anionic surfactant (as lauroyl glycollic amide disodium sulfosuccinate polyoxyethylene (degree of polymerization=1-100) etc.).
The example of cationic surface active agent comprises quaternary (as stearyl trimethyl ammonium chloride, mountain Yu base (behenyl) trimethyl ammonium chloride, distearyl alkyl dimethyl ammonium chloride, lanolin fatty acid aminopropyl ethyl dimethyl ethyl ammonium sulfate etc.) and amine salt type (as diethyl amino yl acetamide lactate stearate, dilaurylamine (DLA) hydrochloride, oleyl amine lactate etc.).The example of amphoteric surfactant comprises betaine type amphoteric surfac-tant's (as the amino ethyl hydroxyethyl of coco-nut oil fatty acid acylamino-propyl-dimethyl betaine, lauryl dimethyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole quinoline betaine, lauryl hydroxyl sulfo betaine, lauroyl carboxymethyl betaine hydroxypropyl sodium phosphate etc.), the amino acid type amphoteric surfactant (as β-lauryl alanine sodium etc.).
Nonionic surface active agent of the present invention is being used as for example emulsifying agent (I), as as the emulsifying agent of the emulsifying agent of the emulsifying agent of the emulsifying agent of the emulsifying agent of metal processing, agricultural chemicals emulsion, cosmetics, water paint and emulsion polymerisation the time, have such as excellent properties such as emulsibility height, stability of emulsion height, foaminess are low.Specifically, they can be used as can prepare mineral oil, vegetable oil (as castor oil, soya-bean oil and olive oil), animal oil ﹠ fat (as tallow and egg oil), the O/W of monomer (as styrene and acrylate) or the emulsifying agent of W/O emulsion, and it is also unrestricted that it is used.
Except being used as emulsifying agent (I), nonionic surface active agent of the present invention also can be used for following various uses, as as solubilizer (K), house detergent such as the fabric detergent of the dispersant as pigment and fatty acid metal salts (J) of paper grade (stock), spices etc. and the washing agent (L) of dishwashing dish usefulness washing agent and industrial detergent such as mechanical metal detergent, and bleeding agent (M) or wetting agent (N).
Using under the situation of aliphatic alcohol oxyalkylene addition compound of the present invention (A) as emulsifying agent (I), dispersant (J) or solubilizer (K), the p in the formula (1) better is the integer of average out to 2-40.If p surpasses 40, then the product hydrophily of gained is not suitable for as emulsifying agent, dispersant or solubilizer too by force.In addition, in such use, Mw (A) is preferably 261-2, and 000,270-1 more preferably, 500.
(II) prepare the method for nonionic surface active agent
Described aliphatic alcohol oxyalkylene addition compound of the present invention (A) better is to make through method of the present invention (II).
In method of the present invention (II), aliphatic alcohol oxyalkylene addition compound (e) is that the oxyalkylene (b2) with average 1-2.5 mole adds to aliphatic alcohol (a2) and goes up and obtain under catalyst (d) existence condition, and it is 1.0 or littler according to leading the distribution constant c ' that determines from the following formula (4 ') of Weibull distribution law that described catalyst (d) can make adduct.To this adduct (e), just obtain the aliphatic alcohol oxyalkylene addition compound of narrow molecular weight distribution in oxyalkylene (b3) addition reaction that will contain at least two carbon atoms under base catalyst (f) existence condition.
c’＝(v’+n
0’/n
00’-1)/[Ln(n
00’/n
0’)+n
0’/n
00’-1] (4’)
At this, v ' represents the oxyalkylene (b2) of every mole of aliphatic alcohol (a2) addition and average addition molal quantity (b3), n
00' representative molal quantity of used aliphatic alcohol (a2) in reaction, n
0' represent the molal quantity of unreacted aliphatic alcohol (a2).
Aliphatic alcohol (a2) is the alcohol that contains 1-24 (better 8-24, good especially 12-18) carbon atom usually, and it can be natural alcohol or synthol (as Ziegler alcohol and oxo alcohol).Wherein, the alcohol that contains 8-24 carbon atom comprises the alcohol identical with (a1).The aliphatic alcohol that contains 1-7 carbon atom for example comprises that radical of saturated aliphatic alcohol is as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol and enanthol; Unsaturated aliphatic alcohol is as propenyl, butenol and pentenol; Cycloaliphatic alcohol such as methyl cyclohexanol.Can use in these alcohol one or both or multiple.In these aliphatic alcohols, better be uncle or secondary alcohol, be more preferably primary alconol.In addition, moieties can be a straight chain or branched.Good especially is dodecanol, tridecanol, tetradecanol, hexadecanol and octadecanol.
As oxyalkylene (b2) and (b3), having of can addressing contains at least 2, better contains 2-8, the good especially oxyalkylene that contains 2-3 carbon atom.Its example comprises EO, PO, 1,2-or 2, and 3-epoxy butane, oxolane, styrene oxide etc. can use in them two or more.When using two or more, they can block fashion or random fashion carry out addition.Wherein, better be EO and PO.
As catalyst (d), use be that to make the distribution constant c ' of the oxyalkylene addition compound of gained be 1.0 or littler catalyst.Better be that to make c ' be 0.7 or littler, being more preferably and making c ' is 0.45 or littler catalyst.
Can make c ' be 1.0 or littler catalyst for example comprise perhalogeno acid or its salt, sulfuric acid or its salt, phosphoric acid or its salt, nitric acid or its salt.There is no particular restriction to the metal that forms these salt, but better be the metal beyond the alkali metal, is more preferably divalence or trivalent metal.Be preferably Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu and Al in these metals; Be more preferably Mg, Zn, Ca, Sr, Ba and Al, that good especially is Mg, Zn and Al.Halogen in perhalogeno acid or its salt comprises chlorine, bromine and iodine, better is chlorine.Like this, catalyst (d) better is the perchlorate of divalence or trivalent metal, is more preferably the perchlorate that is selected from metal among Mg, Zn and the Al.In addition, divalence or trivalent metal alcoholates can be combined use.Per 100 weight portions (d), total consumption of metal alcoholate is the 20-200 weight portion.As the alkyl in the metal alcoholate, what can address is to be easy to be distilled remove and become the low alkyl group (containing 1-4 carbon atom) of alcohol, or the composition alkyl identical with the raw material aliphatic alcohol.Although can use a kind of in these catalyst separately, but better be two or more catalyst junction to be used altogether (magnesium perchlorate/magnesium sulfate 7 hydrate=95/5-50/50 for example, magnesium perchlorate/aluminum perchlorate=99/1-30/70 is weight ratio here).
From reaction speed and economic angle, per 100 weight portions (a2) and total amount (b2), the consumption of catalyst (d) is preferably the 0.001-1 weight portion.0.003-0.8 weight portion more preferably, good especially is the 0.005-0.5 weight portion.
Used catalyst is base catalyst (f) in oxyalkylene (b3) being added to oxyalkylene addition compound (e) (it adds to (b2) (a2) and goes up acquisition).Base catalyst (f) comprises the hydroxide of alkali metal and alkaline-earth metal, as lithium hydroxide, NaOH, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide; Wherein be more preferably potassium hydroxide and cesium hydroxide.
From reaction speed and economic angle, per 100 weight portions (e) and total amount (b3), consumption (f) is preferably the 0.0001-1 weight portion.0.001-0.8 weight portion more preferably.
As for (a2) reaction condition when (b2) reacting, the method that can address comprises mixes (a2) with (d), carry out the nitrogen substitution reaction, subsequently under 80-200 ℃ temperature at-0.8-5kgf/cm
2Pressure add down (b2), its amount reaches (b2) consumption of defined, then wears out under 80-200 ℃ temperature, the pressure in reaction system reaches balance.
In the oxyalkylene addition compound (e) that obtains like this, add base catalyst (f), by above-mentioned identical mode oxyalkylene (b3) is reacted subsequently, obtain desired aliphatic alcohol oxyalkylene addition compound.
After polymerisation of the present invention stops, the aliphatic alcohol oxyalkylene addition compound of gained itself or then just can be applied to various uses by regulating the pH value.If the words that need, catalyst can be got rid of from polymerizate, its way is to use the adsorbent such as " Kyowaad 600 " (a kind of alumina silicate type adsorbent is made by KyowaChemical Ind.) and so on to carry out adsorption treatment, carries out filter operation subsequently.In this case, can also use diatom soil type filter aid (as " Radiolite " that makes by Showa Chemical Ind.) to shorten the required time of filter operation.In addition, as record in open communique 112931/1981 of Japan Patent and Japanese patent gazette 53417/1990, come the neutralization bases catalyst with hydroxycarboxylic acid (as lactic acid).
Owing to the unreacted aliphatic alcohol content in the aliphatic alcohol oxyalkylene addition compound that makes with the inventive method (II) is lower, so the intermediate that they can be used as low smell anionic surfactant (as sulfating product and carboxy methylation product) improves smell.Certainly they can be used for, for example as the such use of emulsifying agent and dispersant.
(III) anionic surfactant
Another aspect of the present invention provides a kind ofly carries out the anionic surfactant that anionization obtains to aliphatic alcohol oxyalkylene addition compound (A '),
Described (A ') adds to oxyalkylene (b1) on the aliphatic alcohol (a1) and directly makes, and satisfies following condition (ii '), (iii ') and (iv).
(ii ') weight average molecular weight (Mw) satisfies following relation (2 ') or (3 ') with the ratio Mw/Mn of number-average molecular weight (Mn):
Mw/Mn≤0.030 * Ln (v ")+1.010 (at v "＜10 situation under) (2 ')
Mw/Mn≤-0.026 * Ln (v ")+1.139 (at v " 〉=10 situation under) (3 ')
At this, v " represents in the following general formula (1 ') mean value of (m '+n '+p ').
(iii ') by the definite distribution constant c of following formula (4 ") " be 1.0 or littler:
c″＝(v″+n
0/n
00-1)/[Ln(n
00/n
0)+n
0/n
00-1] (4″)
At this, v " implication as mentioned above.As mentioned above, " satisfy this condition up to requirement under 12 the situation only at v.n
00The molal quantity of representative used aliphatic alcohol (a1) in reaction, n
0Represent the molal quantity of unreacted aliphatic alcohol (a1).
(iv) it comprises the compound of a kind of following general formula (1 ') expression or the mixture of its two or more compounds:
R
1O-[(C
2H
4O)
m’/(AO)
n’]-(C
2H
4O)
p’-H (1’)
In following formula, R
1It is the cyclic aliphatic alkyl that contains the aliphatic hydrocarbyl of 8-24 carbon atom or contain 8-24 carbon atom; A is the alkylidene that contains at least 3 carbon atoms; M ' is 0 or 1 or bigger integer, its mean value is 0-5, n ' is 0 or 1 or bigger integer, its mean value is 0-5, p ' is 0 or 1 or bigger integer, and its mean value is 0-10, (m '+n '+p ') be an integer, its mean value is 1-20, and the mean value of (m '+p ')/(m '+n '+p ') is at least 0.5.Under the situation of m ' ≠ 0 and n ' ≠ 0, [(C
2H
4O)
M '/ (AO)
N '] represent block addition or random addition.
General formula (1) is different with general formula (1 ') on the value of m, n and p and m ', n ' and p ', although R
1With A is identical.In other words, the m ' in the general formula (1 ') is 0 or 1 or bigger integer, and its mean value is 0-5; And the m in the general formula (1) is 0 or 1 or bigger integer, and its mean value is 0-4.N ' in the general formula (1 ') is 0 or 1 or bigger integer, and its mean value is 0-5; And the n in the general formula (1) is 0 or 1 or bigger integer, and its mean value is 0-3.P ' in the general formula (1 ') is 0 or 1 or bigger integer, and its mean value is 1-10; And the p in the general formula (1) is 0 or 1 or bigger integer, and its mean value is 1-80.In the general formula (1 ') (m '+n '+p ') be an integer, its mean value is 1-20; And (m+n+p) in the general formula (1) is an integer, and its mean value is 3-81.As for (m+p)/(m+n+p), in two general formulas, equally on average be at least 0.5.
As satisfy condition (ii '), (iii ') and aliphatic alcohol oxyalkylene addition compound (iv) (A '), can be after the above-mentioned first step termination that comprises in two methods that prepare the aliphatic alcohol oxyalkylene addition compound that go on foot, and before using base catalyst, use oxyalkylene addition compound, perhaps stop the back and use oxyalkylene addition compound, (ii '), (iii ') and (iv) as long as these oxyalkylene addition compounds satisfy condition in second step.
Satisfy condition (ii '), (iii ') and aliphatic alcohol oxyalkylene addition compound (iv) (A ') are carried out the method for anionization, and there is no particular restriction, as long as terminal hydroxyl by anionization just can, method for example comprises sulphation, phosphorylation, sulfosuccinic acidifying and carboxyl etherificate.
As sulphation, what can address is that aliphatic alcohol oxyalkylene addition compound (A ') to gained itself carries out the method that sulphation then neutralizes with alkali such as NaOH.Specifically, for example have (a) that can address uses the method for chlorosulfonic acid, and (b) method of use sulfane (sulfan) (c) is used the method for sulfamic acid and the method for (d) using sulfuric acid.The nitrogen that usefulness is done when using the sulfane in (b) etc. dilutes it.
Under (a) and situation (b), reaction temperature is generally 0-70 ℃, is preferably 10-50 ℃.Under (c) and situation (d), reaction temperature is generally 50-150 ℃, is preferably 60-130 ℃.Reaction time can the visual response temperature and becomes, and is generally 0.1-10 hour, is preferably 0.5-5 hour.(A ') is generally 1.0 with the mol ratio of above-mentioned sulfur acidizing reagent: 1.2-1.0: 0.8, be preferably 1.0: 1.1-1.0: 0.9.
Under any situation of (a)-(d), reactive mode comprises successive reaction and batch reactions.
Reach the 90-110% of theoretical value by the acid number (AV) of 56100/ (molecular weight of sulfating product) expression, better during 95-105%, reach the terminal point of sulfating reaction.
In addition, can be confirmed this terminal point by measuring in conjunction with the amount of sulfuric acid, be the 90-110% that is reached theoretical value by the amount in conjunction with sulfuric acid of (80 * 100)/(molecular weight of sulfating product) expression, when being preferably 95-105%.
Phosphorylation can be undertaken by following process, with phosphorylation agent such as phosphoric acid, polyphosphoric acid, phosphoric anhydride, phosphoryl chloride phosphorus oxychloride etc. the aliphatic alcohol oxyalkylene addition compound of gained (A ') is carried out phosphorylation, then neutralizes with NaOH, KOH, amine etc.Phosphorylation is identical with Phosphation (phosphoric esterification), forms monoesters, diester etc., and all these contents all comprise within the scope of the invention.
(A ') is generally 30-150 ℃ with being reflected at of phosphoric anhydride, is preferably under 60-130 ℃ the reaction temperature to carry out in blanket of nitrogen, obtains the bisphosphate of (A '), uses subsequently with the equimolar water of phosphoric anhydride to be hydrolyzed, thereby obtains the phosplate of (A ').Reaction time can the visual response temperature and becomes, and it is generally 1-10 hour, is preferably 2-5 hour.(A ') is generally 2.0 with the mol ratio of phosphoric anhydride under the situation of phosplate: 1.15-2.0: 0.85, be preferably 2.0: 1.05-2.0: 0.95, and under the situation of bisphosphate, above-mentioned mol ratio is generally 1.0: 0.4-1.0: 0.6, be preferably 1.0: 0.45-1.0: 0.55.
Reach the 90-110% of theoretical value by the acid number (AV) of 56100/ (molecular weight of esterification products) expression, better during 95-105%, reach the terminal point of phosphorylation reaction.After this, the aqueous solution with alkali such as NaOH or amine neutralizes the acquisition objective composition to product.Degree of neutralization can be selected arbitrarily.
The sulfosuccinic acidifying is a kind of method of two-step reaction process, and it comprises (A ') and maleic anhydride (below be called MA) reaction is obtained the step of monoesters, and it carries out the step of sulfonation with sulphite or acidic sulfurous acid salt pair under the water existence condition.
(A ') is generally 50-100 ℃ with being reflected at of MA, is preferably under 60-90 ℃ the reaction temperature to carry out under blanket of nitrogen, obtains the MA monoesters of (A ').Add under the excessive situation at MA, stop the back at single-esterification and under reduced pressure, remove MA.(A ') is generally 1.0 with the mol ratio of MA: 0.9-1.0: 1.1, be preferably 1.0: 0.95-1.0: 1.05.
Reach the 90-110% of theoretical value by the acid number of 56100/ (molecular weight of esterification products) expression, better during 95-105%, reach the terminal point of single-esterification.
Subsequently, the mono-esterification product with sulphite or acidic sulfurous acid salt pair gained carries out sulfonation.Sulphite comprises for example alkali metal salt such as sodium sulfite and potassium sulfite, alkali salt such as magnesium sulfite, ammonium salt such as ammonium sulfite.Acid sulphite comprises bisulfites such as sodium hydrogensulfite, potassium bisulfite, ammonium bisulfite, magnesium bisulfite.Sulfonating reaction can be under the water existence condition with esterification products and sulphite or acidic sulfurous acid reactant salt and carry out.The mol ratio of mono-esterification product and sulphite or acid sulphite is generally 1.0: 0.9-1.0: 1.1, be preferably 1.0: 0.95-1.0: 1.05.Reaction temperature is generally 30-90 ℃, is preferably 40-80 ℃.Reaction is carried out under blanket of nitrogen usually.Visual reaction temperature of reaction time and different is generally 1-10 hour, is preferably 2-5 hour.
Reach the 90-110% of theoretical value by the amount in conjunction with sulfuric acid of (80 * 100)/(molecular weight of sulfonated products) expression, better during 95-105%, reach the terminal point of sulfonating reaction.After sulfonation stops, neutralize with organic acid such as citric acid or alkanolamine such as triethanolamine adjusting pH value.
The carboxyl etherificate can be carried out through for example following process, at caustic alkali or also have under a kind of solvent existence condition, lower carboxylic acid salt that the aliphatic alcohol oxyalkylene addition compound of gained (A ') and single halogen are replaced such as monochloro carry out condensation reaction for acetate, single monobromo-acetic acid salt, monochloro for propionate, single bromo acid salt etc. (better be monochloro for acetate, particularly monochloro is for sodium acetate).
(A ') can for example carry out under the following condition for the reaction of sodium acetate with monochloro, (A ') and monochloro are generally 1.0 for the mol ratio of sodium acetate: 0.90-1.0: 1.60, be preferably 0: 0.95-1.0: 1.50, reaction temperature is generally 30-100 ℃, be preferably 40-70 ℃, under blanket of nitrogen, use the solvent such as toluene and add NaOH gradually.Then, carry out such as the purification process of washing and separate, obtain the carboxyl etherificate product of aliphatic alcohol oxyalkylene addition compound.Again, add entry, obtain the aqueous solution of aliphatic alcohol oxyalkylene addition compound carboxyl etherificate product.
Can adopt liquid chromatography to measure degree of etherification falling in the carboxyl etherification reaction under the following conditions.
The liquid chromatography measuring condition:
Post: ODS type, 6mm φ * 15cm
Column temperature: 35 ℃
Eluate: methanol=90/10
Flow velocity: 0.8ml/min
Sample solution concentration: 10%
Pour into: 30 μ l
When degree of etherification falling reaches at least 90%, better at least 95% the time, reach terminal point.
Selection that can be different in addition to the type of above-mentioned anionization, the different type of being taked depends on the purposes of gained anionic surfactant.In the anionization product, it better is above-mentioned four types.
Better the object lesson of anionic surfactant comprises the anionization product of general formula (1) (A '), R in the formula
1Be the aliphatic hydrocarbyl that contains 8-18 carbon atom, the mean value of m ' is 0-2, and the mean value of n ' is 0-2, and the mean value of p ' is 1-3, and the mean value of m '+n '+p ' is 1-6; Good especially is the anionization product of such (A '), R in the formula
1Be the aliphatic hydrocarbyl that contains 8-14 carbon atom, the mean value of m '+n '+p ' is 1-5.
As stated above satisfy condition (ii '), (iii ') and (iv) (A ') are carried out the anionic surfactant that anionization obtains and have good forming property and detergency.In addition, (ii '), (iii ') and aliphatic alcohol oxyalkylene addition compound (iv) because satisfy condition (A ') only comprise a spot of raw material aliphatic alcohol, so, can obtain the anionic surfactant less to the human body skin excitant because the content of the anionization product of aliphatic alcohol is lower.In addition, can also reduce smell.Moreover, phosphorylation product, sulfosuccinic acidifying product and carboxyl etherificate product exist the problem (haze problem especially at a lower temperature or problem of solidification) of Long-term Storage stability under lower temperature and higher temperature up to now, and product of the present invention has improved stability significantly.In addition, anionic surfactant of the present invention also has surface-active such as permeability except having above-mentioned detergency and forming property, and it especially can be used as washing agent such as shampoo, is used for the washing agent of dish and is used for rigid surface such as the washing agent of metal.
When the anionic surfactant that will obtain like this is used for washing agent and other purposes, can prepare other nonionic surface active agent, anionic surfactant, cationic surface active agent and amphoteric surfactant.What particularly, can address is above-mentioned with regard to described those surfactants of nonionic surface active agent.
(IV) composition of detergent
Except independent use anionic surfactant of the present invention, also can be made into a kind of composition of detergent, better be that it is mixed mutually with nonionic surface active agent and/or amphoteric surfactant.The example of nonionic surface active agent and amphoteric surfactant such as above-mentioned with regard to those surfactants described in the nonionic surface active agent.Press solid content meter, the amount of allocating each surfactant activity component in the composition into is 3-60%, the anionic surfactant of the present invention of better 5-50%, better 3-60%, the nonionic surface active agent of good especially 5-50%, with better 1-50%, the amphoteric surfactant of good especially 2-30%.
In addition, in composition of detergent, can allocate hitherto known additive into.Can be with following each material together as this additive, described material is: wetting agent such as glycerine and pyrrolidones-carboxylic acid sodium; High-molecular weight compounds such as weight average molecular weight as conditioner are respectively 500-5,000,000 cationized cellulose, cationization guar gum, polyethylene glycol, Sodium Polyacrylate, hydroxyethylcellulose and protein derivatives; Siloxanes such as dimethyl polysiloxane, the modified siloxane of the various organic groups of introducing on the methyl moiety of dimethyl polysiloxane and ring-type dimethyl siloxane; Chelating agent is as 1,2-ethylenediamino tetraacetic acid sodium and 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid sodium; Lower alcohol such as ethanol, propane diols and DPG; Spices, colouring agent, anticorrisive agent, ultraviolet absorber and water.
The form of composition of detergent has liquid, thickener, solid, powder etc. usually, to this and without particular limitation, but be preferably from easy to operate angle liquid and thickener.For example, under the situation that is liquid and pasty state shampoo, the consumption of anionic surfactant of the present invention is 5-30 weight %; The total amount of surfactant is 5-50 weight %, is preferably 10-30 weight %; The consumption of high-molecular weight compounds and siloxanes is 0-5 weight %; The consumption of wetting agent, chelating agent and lower alcohol is 0-10 weight %; The consumption of water is 35-95 weight %.
Embodiment
Further specify the present invention with more following embodiment, but the present invention is not limited to these embodiment.Umber is a weight portion, and % is weight %.
Molecular weight among embodiment 1-16 and the Comparative Examples 1-13 adopts following gel permeation chromatography (below be called GPC) to measure.
" measuring condition of GPC-1 "
Device category: HLC-8120 (making) by Tosoh Corp.
Post: tsk gel SuperH4000,3000 and 2000 (all making) by Tosoh Corp.
Column temperature: 40 ℃; Detector: RI;
Solvent: oxolane; Flow: 0.6ml/min;
Sample solution concentration: 0.25%; Pour into: 10 μ l;
Standard: polyethylene glycol (TSK STANDARD POLYETHYLENE OXIDE is made by Tosoh Corp.)
Data processor: SC-8020 (making) by Tosoh Corp.
The concentration of unreacted aliphatic alcohol adopts following gas chromatography (below be called GC) to measure among embodiment 1-16 and the Comparative Examples 1-13.
" measuring condition of GC "
Device category: gas chromatograph GC-14B (making) by Shimadzu Corp.
Detector: FID
Post: glass column (internal diameter is about 3 millimeters, and length is about 2 meters)
Column material: siloxanes GE SE-305%
Column temperature: rise to 280 ℃ from 90 ℃
Firing rate: 4 ℃/minute; Carrier gas: nitrogen;
Sample: 50% acetone soln; Pour into: 1 μ l;
Measure: use and contain the aliphatic alcohol that lacks 2 or 3 carbon atoms than used aliphatic alcohol and measure as interior mark.
Embodiment 1
Have in the stainless steel autoclave of stirring and function of temperature control one, add 186 parts of (1 mole) laruyl alcohols, 0.05 part of magnesium perchlorate and 0.01 part of magnesium sulfate 7 hydrate; After the atmosphere that replaces with nitrogen in the container, (about 20mmHg) dewatered 1 hour under reduced pressure in the time of 120 ℃.Be 1-3kgf/cm in gauge pressure then in 150 ℃
2Introduce 88 parts of (2 moles) E0 under the condition.The Weibull distribution constant c ' of gained adduct is 0.42, and the amount of unreacting alcohol is 2.2% (0.032 mole).Adding 0.3 part of potassium hydroxide in this adduct, is 1-3kgf/cm in 150 ℃ in gauge pressure again
2Introduce 220 parts of (5 moles) EO under the condition.Add 3 parts " Kyowaad 600 " (a kind of alumina silicate type adsorbent is made by Kyowa Chemical Corp.) in this product, adsoption catalyst in the time of 90 ℃ filters it subsequently, obtains nonionic surface active agent of the present invention (B-1).
Adopt GPC and GC to measure the amount of molecular weight distribution and unreacted aliphatic alcohol, Mw/Mn is 1.045 and (satisfies the calculated value of the Mw/Mn upper limit of relational expression (6): 1.049), be 0.92 by the value of formula (4) dispensed constant c.
About embodiment 2-14 and Comparative Examples 1-11, adopt GPC and GC to measure the amount of molecular weight distribution and unreacted aliphatic alcohol similarly equally.Its result the results are shown in the table 1,2 and 4 together with embodiment's 1.
Embodiment 2
Press the identical mode of embodiment 1, different are to use 0.04 part of magnesium perchlorate and 0.01 part of aluminum perchlorate's nonahydrate to replace 0.05 part of magnesium perchlorate, and (the distribution constant c ' of gained adduct is 0.38, the amount of unreacting alcohol is 1.7%), and under the base catalyst existence condition, use 352 parts of (8 moles) EO to replace adding 220 parts of EO, obtain nonionic surface active agent of the present invention (B-2).
Embodiment 3
Press the identical mode of embodiment 1, different are to use barium sulfate to replace magnesium sulfate 7 hydrate, and (the distribution constant c ' of gained adduct is 0.32, the amount of unreacting alcohol is 1.1%), and under the base catalyst existence condition, use 618 parts of (14 moles) EO to replace adding 220 parts of EO, obtain nonionic surface active agent of the present invention (B-3).
Embodiment 4
Press the identical mode of embodiment 1, different is to use 1,672 part of (38 moles) EO to replace adding 220 parts of EO under the base catalyst existence condition, obtains nonionic surface active agent of the present invention (B-4).
Embodiment 5
Press the identical mode of embodiment 1, different is not use magnesium sulfate 7 hydrate, obtains the EO adduct of laruyl alcohol.The distribution constant c ' of gained adduct is 0.60, and the amount of unreacting alcohol is 4.5%.Adding 1.3 parts of potassium hydroxide in this adduct, add 116 parts of (2 moles) PO, is 1-3kgf/cm in 130 ℃ in gauge pressure again
2Introduce 176 parts of (4 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain nonionic surface active agent of the present invention (A-1).
Embodiment 6
Press the identical mode of embodiment 5, different is to use 528 parts of (12 moles) EO to replace adding 176 parts of EO under the base catalyst existence condition, obtains nonionic surface active agent of the present invention (A-2).
Embodiment 7
With embodiment 1 described identical container in add 186 parts of (1 mole) laruyl alcohols, 0.05 part of magnesium perchlorate and 0.05 part of zinc perchlorate; After the atmosphere that replaces with nitrogen in the container, in 120 ℃ under reduced pressure (about 20mmHg) dewatered 1 hour.Be 1-3kgf/cm in gauge pressure then at 120 ℃
2Introduce 116 parts of (2 moles) PO under the condition.The distribution constant c ' of gained adduct is 0.42, and the amount of unreacting alcohol is 2.0%.Adding 1.3 parts of potassium hydroxide in this adduct, is 1-3kgf/cm in 130 ℃ in gauge pressure again
2Introduce 704 parts of (16 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain nonionic surface active agent of the present invention (A-3).
Embodiment 8
Press the identical mode of embodiment 1, different is to use 0.05 part of zinc perchlorate to replace magnesium sulfate, and laruyl alcohol is dewatered.In the time of 120 ℃, be 1-3kgf/cm then in gauge pressure
2Sneak into 44 parts of (1 mole) EO and 58 parts of (1 mole) PO under the condition.The distribution constant c ' of gained adduct is 0.34, and the amount of unreacting alcohol is 1.3%.Adding 1.3 parts of potassium hydroxide in this adduct, is 1-3kgf/cm in 130 ℃ in gauge pressure again
2Introduce 704 parts of (8 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain nonionic surface active agent of the present invention (A-4).
Embodiment 9
Press the identical mode of embodiment 1, different is to use 0.03 part of zinc sulfate to replace magnesium sulfate, obtains the EO adduct of laruyl alcohol.The distribution constant c ' of gained adduct is 0.38, and the amount of unreacting alcohol is 1.7%.Adding 1.3 parts of potassium hydroxide in this adduct, is 1-3kgf/cm in gauge pressure in the time of 130 ℃ again
2Introduce 144 parts of (2 moles) 1,2-epoxy butane and 704 parts of (8 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain nonionic surface active agent of the present invention (A-5).
Comparative Examples 1
With embodiment 1 described identical container in add 186 parts of (1 mole) laruyl alcohols and 0.3 part of potassium hydroxide; After the atmosphere that replaces with nitrogen in the container, in 120 ℃ under reduced pressure (about 20mmHg) dewatered 1 hour.Be 1-3kgf/cm in gauge pressure then in 150 ℃
2Introduce 308 parts of (7 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain nonionic surface active agent I.
Comparative Examples 2
By the identical mode of Comparative Examples 1, different is to use 440 parts of (10 moles) EO to replace 308 parts of EO, obtains nonionic surface active agent II.
Comparative Examples 3
By the identical mode of Comparative Examples 1, different is introduces 88 parts of (2 moles) EO, 116 parts of (2 moles) PO and 264 parts of (6 moles) EO replace 308 parts of EO successively, obtains nonionic surface active agent III by filtering.
Comparative Examples 4
By the identical mode of Comparative Examples 3, different is to use 88 parts of (2 moles) EO, 116 parts of (2 moles) p0 and 528 parts of (12 moles) EO to replace 88 parts of (2 moles) EO, 116 parts of (2 moles) P0 and 264 parts of (6 moles) EO, obtains nonionic surface active agent IV by filtering.
Comparative Examples 5
With embodiment 1 described identical container in add 186 parts of (1 mole) laruyl alcohols; After the atmosphere that replaces with nitrogen in the container, (about 20mmHg) dewatered 1 hour under reduced pressure in the time of 120 ℃, added 0.3 part of boron trifluoride diethyl ether subsequently, then with the atmosphere in the nitrogen replacement container.In the time of 50 ℃, be 1kgf/cm then in gauge pressure
2Introduce 440 parts of (10 moles) EO under the condition.Use the alkali neutralization reaction product, obtain nonionic surface active agent V.In this Comparative Examples, observe and form about 6% accessory substance polyethylene glycol.
Comparative Examples 6
By the identical mode of Comparative Examples 5, different is to use 88 parts of (2 moles) EO, 116 parts of (2 moles) P0 and 264 parts of (6 moles) EO to replace 440 parts of EO, obtains nonionic surface active agent VI by filtering.
Table 1
| The embodiment sequence number | Nonionic surface active agent | Mw/Mn | Unreacted alcohol amount (%) | Distribution constant | |
| Measured value | The upper limit of calculating | ||||
| Embodiment 1 | B-1 | 1.045 | 1.049 | 0.02 | 0.92 |
| Embodiment 2 | B-2 | 1.052 | 1.056 | Do not detect | - |
| Embodiment 3 | B-3 | 1.041 | 1.044 | Do not detect | - |
| Embodiment 4 | B-4 | 1.019 | 1.020 | Do not detect | - |
| Embodiment 5 | A-1 | 1.067 | 1.072 | 0.006 | 0.91 |
| Embodiment 6 | A-2 | 1.065 | 1.067 | Do not detect | - |
| Embodiment 7 | A-3 | 1.061 | 1.064 | Do not detect | - |
| Embodiment 8 | A-4 | 1.071 | 1.079 | Do not detect | - |
| Embodiment 9 | A-5 | 1.071 | 1.074 | Do not detect | - |
| Comparative Examples 1 | I | 1.089 | 1.049 | 2.9 | 3.70 |
| Comparative Examples 2 | II | 1.101 | 1.056 | 0.7 | 3.26 |
| Comparative Examples 3 | III | 1.118 | 1.079 | 0.3 | 2.50 |
| Comparative Examples 4 | IV | 1.122 | 1.067 | 0.03 | 2.71 |
| Comparative Examples 5 | V | 1.082 | 1.056 | 0.04 | 1.60 |
| Comparative Examples 6 | VI | 1.096 | 1.079 | 0.04 | 1.60 |
Embodiment 10
Press the identical mode of embodiment 1, different is to use 0.01 part of magnesium sulfate to replace 0.02 part of magnesium sulfate, obtains the EO adduct of laruyl alcohol.The distribution constant c ' of gained adduct is 0.42, and the amount of unreacting alcohol is 2.2% (0.032 mole).Adding 0.3 part of potassium hydroxide in this adduct, is 1-3kgf/cm in gauge pressure again
2Introduce 61.6 parts of (1.4 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain to comprise the emulsifying agent (I-1) of nonionic surface active agent of the present invention.HLB is 8.9.
Embodiment 11
Press the identical mode of embodiment 10, different is to use 242 parts of (1 mole) cetanols to replace laruyl alcohol, and under the base catalyst existence condition, use 105.6 parts of (2.4 moles) EO to replace adding 61.6 parts of EO, obtain to comprise the emulsifying agent (I-2) of nonionic surface active agent of the present invention.HLB is 8.9.
Embodiment 12
Press the identical mode of embodiment 10, different is to use 270 parts of (1 mole) stearyl alcohols to replace laruyl alcohol, and under the base catalyst existence condition, use 127.6 parts of (2.9 moles) EO to replace adding 61.6 parts of EO, obtain to comprise the emulsifying agent (I-3) of nonionic surface active agent of the present invention.HLB is 8.9.
Comparative Examples 7
With embodiment 1 described identical container in add 186 parts of (1 mole) laruyl alcohols and 0.3 part of potassium hydroxide; After the atmosphere that replaces with nitrogen in the container, (1-5mmHg) dewatered 1 hour under reduced pressure in the time of 130 ℃.In the time of 150 ℃, be 1-3kgf/cm subsequently in gauge pressure
2Introduce 149.6 parts of (3.4 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain emulsifying agent I.HLB is 8.9.
Comparative Examples 8
By the identical mode of Comparative Examples 5, different is to use 149.6 parts of (3.4 moles) EO to replace 440 parts of EO, obtains emulsifying agent II.HLB is 8.9.In this Comparative Examples, observe and form about 4% accessory substance polyethylene glycol.
Comparative Examples 9
With embodiment 1 described identical container in add 186 parts of (1 mole) laruyl alcohols and 3.6 parts of magnesium perchlorates; After the atmosphere that replaces with nitrogen in the container, in 120 ℃ under reduced pressure (about 20mmHg) dewatered 1 hour.In the time of 150 ℃, be 1-3kgf/cm subsequently in gauge pressure
2Introduce 149.6 parts of (3.4 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain emulsifying agent III.HLB is 8.9.In this case, the smell of aldehyde is very heavy, and comprises about 3% high molecular weight material (dimer such as aldol condensate) accessory substance.The emulsifying agent III that this Comparative Examples obtains is painted very heavy, and dark brown pool is arranged.The average addition molal quantity of determining from hydroxyl value of EO is 2.5 moles.
Table 2
| The embodiment sequence number | Nonionic surface active agent | Mw/Mn | Unreacted alcohol amount (%) | Distribution constant | |
| Measured value | The upper limit of calculating | ||||
| Embodiment 10 | I-1 | 1.031 | 1.035 | 0.3 | 0.57 |
| Embodiment 11 | I-2 | 1.037 | 1.040 | 0.08 | 0.61 |
| Embodiment 12 | I-3 | 1.038 | 1.042 | 0.05 | 0.65 |
| Embodiment 11 | I-2 | 1.037 | 1.040 | 0.08 | 0.61 |
| Comparative Examples 7 | I | 1.084 | 1.035 | 10.8 | 3.13 |
| Comparative Examples 8 | II | 1.063 | 1.035 | 5.5 | 1.77 |
| Comparative Examples 9 | III | 1.058 | 1.028 | 0.5 | 0.39 |
Test example 1
The emulsifying agent I-III that uses emulsifying agent (I-1)-(I-3) that embodiment 10-12 obtains and Comparative Examples 7-9 to obtain is that 70 ℃ mineral oil is emulsified in the entry preparation O/W type emulsion with aniline point.Experimental condition is as follows.
With 3 parts of emulsifying agents each with 97 parts of mineral oil, in 100 milliliters of graduated cylinders of adding a cover of 5 parts of these mixture inputs, add the deionized water of 95 parts of adjustment to 25 ℃ more separately.Fluctuate graduated cylinder 20 times makes it leave standstill in the time of 25 ℃.
After emulsification just, respectively emulsified state is observed after 30 minutes, 60 minutes and 90 minutes, estimated by above-mentioned numerical grade system.Grade after 60 minutes is emulsibility index s.Measurement result is listed in the table 3.
Table 3
| Emulsifying agent | Emulsibility (after emulsification just) | Stability of emulsion | Height (mm) apart from liquid surface | |||
| After 30 minutes | After 60 minutes | After 90 minutes | ||||
| Embodiment | 1 2 3 | 10 10 10 | 10 10 10 | 10 10 10 | 10 10 10 | 7 5 7 |
| Comparative Examples | I II III | 9 9 9 | 5 5 5 | 4 4 4 | 3 3 3 | 22 23 19 |
It is evident that from the result of table 3, compare with Comparative Examples, each surfactant of use the present invention is 10 as the emulsibility index of the embodiment that emulsifying agent obtains, demonstrates good emulsibility and stability of emulsion, also demonstrates the foaminess less than half of Comparative Examples simultaneously.
Embodiment 13
With embodiment 1 described identical container in add 219 parts of (1 mole) Dobanol 45 (trade names, make by Mitsubishi Chemicals Corp., the mixture of C14/C15=65/35, straight chain content is about 75%), 0.05 part of magnesium perchlorate and 0.02 part of barium sulfate; After the atmosphere that replaces with nitrogen in the container, in 130 ℃ of (1-5mmHg) dehydrations 1 hour under reduced pressure.Be 1-3kgf/cm in gauge pressure then in 150 ℃
2Introduce 88 parts of (2 moles) EO under the condition.The Weibull constant of gained adduct is 0.38, and the amount of unreacting alcohol is 1.7%.Adding 1.3 parts of potassium hydroxide in this adduct, is 1-3kgf/cm in 130 ℃ in gauge pressure again
2Add 87 parts of (1.5 moles) PO and 492.8 parts of (11.2 moles) EO under the condition successively.By embodiment 1 identical mode product is carried out post processing, obtain emulsifying agent of the present invention (I-4).The cloud point of emulsifying agent (I-4) aqueous solution is 87 ℃.
Embodiment 14
Press the identical mode of embodiment 13, obtain the Weibull constant and be the EO adduct of 0.38 Dobanol 45.Adding 0.5 part of potassium hydroxide in this adduct, is 1-3kgf/cm in 130 ℃ in gauge pressure again
2Introduce 528 parts of (12 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain emulsifying agent of the present invention (I-5).The cloud point of 2% aqueous solution of emulsifying agent (I-5) is 87 ℃.
Comparative Examples 10
With embodiment 1 described identical container in add 219 parts of (1 mole) Dobanol 45 and 0.3 part of potassium hydroxide; After the atmosphere that replaces with nitrogen in the container, in 130 ℃ of (1-5mmHg) dehydrations 1 hour under reduced pressure.Be 1-3kgf/cm in gauge pressure then in 150 ℃
2Introduce 88 parts of (2 moles) EO, 87 parts of (1.5 moles) PO and 462 parts of (10.5 moles) EO under the condition successively.By embodiment 1 identical mode product is carried out post processing, obtain emulsifying agent IV.The cloud point of 2% aqueous solution of emulsifying agent IV is 87 ℃.
Comparative Examples 11
Press the identical mode of embodiment 10, Dobanol 45 is dewatered.Then, be 1-3kgf/cm in 150 ℃ in gauge pressure
2Introduce 484 parts of (11 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain emulsifying agent V.
Test example 2
Use emulsifying agent (I-4) that embodiment 13-14 obtains and (I-5) and the emulsifying agent IV and the V of Comparative Examples 10 and 11 acquisitions, also use 11 moles of adduct (HLB:13.8 of nonyl phenol EO, freezing point: 16 ℃, emulsibility index t:9) as emulsifying agent VI, under the high-temperature pressurizing condition, OPE is carried out emulsification, in order to compare emulsibility.Experimental condition is as follows.
In a stainless steel pressure container, add 40 parts of OPE (LUWX OA3, make by BASF, weight average molecular weight: 9000-10000,22-24), 11 parts of emulsifying agents, 0.5 part of potassium hydroxide and 48.5 parts of deionized waters and 10 stainless shots acid number:, after with nitrogen-sealed, be 2-3kgf/cm at pressure in 140 ℃
2Shake under the condition and carried out emulsification in 30 minutes.Measurement result is listed in the table 4.
Table 4
| The embodiment sequence number | Emulsifying agent | Mw/Mn | The amount of unreacting alcohol (%) | HLB | Freezing point (℃) | Emulsibility index t |
| Embodiment 13 | I-4 | 1.063 | Do not detect | 13.1 | 14 | 9 |
| Embodiment 14 | I-5 | 1.047 | Do not detect | 14.1 | 29 | 9 |
| Comparative Examples 10 | IV | 1.120 | 1 | 13.1 | 16 | 2 |
| Comparative Examples 11 | V | 1.104 | 0.1 | 13.8 | 32 | 4 |
The situation of relevant 1% dilute aqueous solution is estimated by said reference.
It is evident that from the result of table 4, comprise surfactant of the present invention (A) and emulsifying agent (B) (I) and have and the analogous emulsibility of nonyl phenol EO adduct, and (I-4) under the situation that keeps emulsibility, have improved low temperature flow.On the other hand, the nonionic surface active agent of conventional non-alkyl phenol type can't provide such emulsibility, although can improve its low temperature flow.
Embodiment 15
Press the identical mode of embodiment 13, different is to use 0.02 part of magnesium sulfate 7 hydrate to replace barium sulfate, obtains the EO adduct of Dobanol 45.The Weibull constant of gained adduct is 0.42, and the amount of unreacting alcohol is 2.2% (0.032 mole).In this adduct, add 1 part of potassium hydroxide; Be 1-3kgf/cm in gauge pressure again
2Introduce 88 parts of (2 moles) EO, 116 parts of (2 moles) PO and 352 parts of (8 moles) EO under the condition successively.By embodiment 1 identical mode product is carried out post processing, obtain washing agent of the present invention (L-1).HLB is 12.2.
Adopt GPC and GC to measure the molecular weight distribution of this washing agent (L-1) and the amount of unreacted aliphatic alcohol, Mw/Mn is that 1.068 (satisfy the upper limit calculated value of the Mw/Mn of relational expression (3): 1.070), the amount of unreacted aliphatic alcohol does not detect.
Comparative Examples 12
By the identical mode of Comparative Examples 11, different is to use 1.5 parts of potassium hydroxide to replace 0.3 part of potassium hydroxide, and Dobanol 45 is dewatered.Be 1-3kgf/cm in 150 ℃ in gauge pressure then
2Introduce 176 parts of (4 moles) EO, 116 parts of (2 moles) PO and 352 parts of (8 moles) EO under the condition successively.By embodiment 1 identical mode product is carried out post processing, obtain washing agent (VII).HLB is 12.2.
Adopt 6PC and GC to measure the molecular weight distribution of this washing agent (VII) and the amount of unreacted aliphatic alcohol, Mw/Mn is 1.101 and (satisfies the upper limit calculated value of the Mw/Mn of relational expression (3): 1.070), the amount of unreacted aliphatic alcohol is 0.048%, and the value of the distribution constant c that calculates by formula (4) is 2.51.
Test example 3
Washing agent (L-1), washing agent (VII) and 9.5 moles of adducts of nonyl phenol EO (HLB:13.1) that use embodiment 15 obtains (VIII) carry out the contrast test of detergency.Experimental condition as stated above described in.
Carry out the detergency test by Leenerts method (JIS K3370).Use the pair of substrates of six slides, use the dirt component of above-mentioned composition as dirt., as wash liquid the slide that scribbles artificial dirt is cleaned with the above-mentioned cleaning solution aqueous solution of 0.15% concentration; Determine detergency by above-mentioned formula, detergency exponential representation is with respect to the detergency of 9.5 moles of adducts of nonyl phenol EO (VIII) index as 100 o'clock.Measurement result is listed in the table 5.
Table 5
| Embodiment | Comparative Examples | Standard | |
| Surfactant | L-1 | VII | VIII |
| The detergency index | 103 | 98 | 100 |
| The cloud point of 2% aqueous solution (℃) | 57 | 56 | 55 |
It is evident that from the result of table 5, compare that the embodiment that uses nonionic surface active agent of the present invention to obtain as washing agent has improved detergency with Comparative Examples.
Embodiment 16
Press the identical mode of embodiment 15, the first step obtains the EO adduct of Dobanol 45.Adding 0.3 part of potassium hydroxide in this adduct, is 1-3kgf/cm in 150 ℃ in gauge pressure again
2Add 264 parts of (6 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain surfactant of the present invention (H-1).HLB is 12.3.
Adopt GPC and GC to measure the molecular weight distribution of (H-1) and the amount of unreacted aliphatic alcohol, Mw/Mn is 1.046 and (satisfies the upper limit calculated value of the Mw/Mn of relational expression (2): 1.052), the amount of unreacted aliphatic alcohol is 0.003%, and the value of the distribution constant c that calculates by formula (4) is 0.83.
Comparative Examples 13
With embodiment 1 described identical container in add 219 parts of (1 mole) Dobanol 45 and 1.0 parts of potassium hydroxide; After the atmosphere that replaces with nitrogen in the container, in 130 ℃ of (1-5mmHg) dehydrations 1 hour under reduced pressure.Be 1-3kgf/cm in gauge pressure then in 150 ℃
2Introduce 352 parts of (8 moles) EO under the condition.By embodiment 1 identical mode product is carried out post processing, obtain surfactant (IX).HLB is 12.3.
Adopt GPC and the molecular weight distribution of GC meter surface-active agent (IX) and the amount of unreacted aliphatic alcohol, Mw/Mn is 1.092 and (satisfies the upper limit calculated value of the Mw/Mn of relational expression (2): 1.052), the amount of unreacting alcohol is 1.4%, and the value of the distribution constant c that calculates by formula (4) is 3.13.
Test example 4
The surfactant (IX) that the surfactant (H-1) that use embodiment 16 obtains, Comparative Examples 13 obtain and 8.5 moles of adducts of nonyl phenol EO (HLB:12.6) are (X), measure viscosity in aqueous solution, viscosity index (VI) is expressed as with respect to the viscosity of 8.5 moles of adducts of nonyl phenol EO (X) index as 100 o'clock.Adopt Brookfield type viscosimeter under 40rpm, to measure viscosity in 25 ℃ with its No. 3 rotors.The results are shown in Table 6.
Table 6
| Embodiment | Comparative Examples | Standard | |
| Surfactant | H-1 | IX | X |
| Surfactant concentrations (%) | 5 | 5 | 5 |
| Viscosity (mPas) | 360 | 25 | 128 |
| Viscosity index (VI) | 280 | 20 | 100 |
It is evident that from the result of table 6 when the concentration identical with Comparative Examples, surfactant of the present invention has higher viscosity, thereby has improved thickening function.
In more following embodiment, anionic surfactant is described.Carry out the evaluation test of following analysis (content of molecular weight, unreacted aliphatic alcohol and anionization product) and performance as follows.
" measuring condition of GPC-2 "
Post: tsk gel G2500PWXL
Column temperature: 40 ℃; Detector: RI;
Solvent: water/methyl alcohol=70/30 (0.5% sodium acetate);
Flow: 1.0ml/min;
Sample solution concentration: 0.25 weight %; Pour into: 200 μ l;
Standard: polyethylene glycol (TSK STANDARD POLYETHYLENE OXIDE is made by Tosoh Corp.)
Data processor: SC-8020 (making) by Tosoh Corp.; Or
" measuring condition of GPC-3 "
Post: tsk gel SuperH4000,3000 and 2000 (all making) by Tosoh Corp.
Column temperature: 40 ℃; Detector: RI;
Solvent: oxolane; Flow: 0.6ml/min;
Sample solution concentration: 0.25 weight %; Pour into: 10 μ l;
Standard: polyethylene glycol (TSK STANDARD POLYETHYLENE OXIDE is made by Tosoh Corp.)
Data processor: SC-8020 (making) by Tosoh Corp.
" measuring condition of GC-2 "
Post: siloxanes GE-SE30;
Detector: FID; Injection: 280 ℃;
Firing rate: 100-250 ℃/10 ℃ min;
Interior mark: octanol;
" measuring condition of HPLC-1 "
Post: Shimapack CLC-ODS
Eluant, eluent: methanol=80/20; Flow: 1ml/min;
Pour into: 30 μ l; Detector: RI, UV
The method of testing of＜smell 〉
In 300 milliliters of glass containers, add 50 gram samples, be allowed to condition at 300 ℃ and leave standstill 1 hour post-evaluation smell.
The method of testing of＜pH value 〉
Use pH meter M-12 (making), in the time of 25 ℃, stock solution is measured by Horiba-seisakusho Corp..
The method of testing of＜solution viscosity 〉
After 2 hours, measure viscosity in aqueous solution 25 ℃ of temperature adjustments with BL type viscosimeter.
The method of testing of＜time stability (outward appearance) 〉
In 100 milliliters of vials, add composition of detergent; Outward appearance detects by an unaided eye after in the thermostatic chamber of 0 ℃, 25 ℃ and 50 ℃ it being left standstill 30 days.Outward appearance by the rough observation sample of following standard.
Standard:
Zero: transparency liquid; △: form the separation of some turbidity (vaporific)/a little degree; *: form significant turbidity (vaporific)/generation separation or curing
The method of testing of＜time stability (tone) 〉
In 100 milliliters of vials, add composition of detergent; The degree of perusal colour developing after in the thermostatic chamber of 0 ℃, 25 ℃ and 50 ℃, it being left standstill 30 days.Colour developing situation by the rough observation sample of following standard.
Standard:
Zero: the transparency liquid that does not have colour developing;
△: some colour developing is arranged;
*: serious colour developing
The method of testing of＜time stability (smell) 〉
In 100 milliliters of vials, add anionic surfactant; The degree of perusal smell after in the thermostatic chamber of 0 ℃, 25 ℃ and 50 ℃, it being left standstill 30 days.By following standard the degree that smell produces is carried out sensory evaluation.
Standard:
Zero: do not change;
△: some smells are arranged;
*: smell is serious
The method of testing of＜foaminess 〉
With juice extractor-mixer (MX-390-GM) of Toshiba the anionic surfactant aqueous solution of 200 milliliter of 0.3 weight % active component concentration was stirred for 30 seconds, the height that reads foam afterwards at once is foaminess.This numerical value is big more, and foaminess is just good more.Used water is the hard water of 15ppm (pressing CaO calculates), and test is carried out at 30 ℃.
The method of testing of＜skin irritation 〉
1.0% (active component) aqueous solution of the listed composition of preparation table 3; Carry out human blob test (closure, 48 hours, upper arm inboard) by test committee member (5 masculinity and femininities are respectively arranged), the test committee member provides mark by following standard separately, with the summation of mark as evaluation.
0: not reaction (redfree spot);
1: slight punctation;
2: punctation clearly;
3: serious punctation.
The method of testing of＜applicability 〉
Test applicability by test committee member (10 masculinity and femininities are respectively arranged), clean each one hair, by following standard evaluation " foaming ", " foam quality " and " sensation " with anionic surfactant.
Standard:
" foaming " " sensation "
Zero: good; △: general; *: poor
" foam quality "
Zero: butyrous; △: general; *: coarse
Embodiment 17
In a glass container, move into first step EO adduct (the Weibull distribution constant c ': 0.42), drip 120 parts of (1.03 moles) chlorosulfonic acids gradually, temperature is remained on 20 ℃ simultaneously of the laruyl alcohol of embodiment 1 preparation.Carrying out dehydrochlorination reaction under this temperature after 2 hours,, obtaining to contain the anionic surfactant of 25% active component with the aqueous solution neutralisation of sulphuric acid product that is dissolved in 41.2 parts of (1.03 moles) NaOH in 1110 parts of water.
Adopt the measuring condition-2 of GPC and the measuring condition-1 of HPLC to measure the molecular weight distribution of anionic surfactant and the amount of unreacted sulfated lauryl alcohol, Mw/Mn is 1.020, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (3 '): 1.031), the amount of unreacted sulfated lauryl alcohol is 2.3 weight % (0.030 mole) (distribution constant c "=0.41).
Embodiment 18
In a glass container, move into the nonionic surface active agent (B-2) that embodiment 2 makes, be added dropwise to 80 parts of (1.0 moles) sulfanes gradually, temperature is remained on 20 ℃ simultaneously.After continuing to stir 2 hours under this temperature,, obtain to contain the anionic surfactant of 25% active component with the aqueous solution neutralisation of sulphuric acid product that is dissolved in 40.0 parts of (1.0 moles) NaOH in 1374 parts of water.
Adopt the measuring condition-2 of GPC and the measuring condition-1 of HPLC to measure the molecular weight distribution of anionic surfactant and the amount of unreacted sulfated lauryl alcohol, Mw/Mn is 1.040, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (3 '): 1.052), the amount of unreacted sulfated lauryl alcohol is 1.50 weight % (0.0242 mole) (distribution constant c "=1.10).
Comparative Examples 14
By the identical mode of Comparative Examples 1, different is to use 88 parts of (2 moles) EO to replace 308 parts of EO, obtains laruyl alcohol EO adduct.
The Mw/Mn that adopts the measuring condition-2 of GPC to measure product is 1.07, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (3 '): 1.0308), adopting the measuring condition-2 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 38.0 weight % (0.560 mole) (distribution constant c "=11.15).
In a glass container, move into product, drip 120 parts of (1.03 moles) chlorosulfonic acids gradually, temperature is remained on 20 ℃ simultaneously.Carrying out dehydrochlorination reaction under this temperature after 2 hours,, obtaining to contain the anionic surfactant of 25% active component with the aqueous solution neutralisation of sulphuric acid product that is dissolved in 41.2 parts of (1.03 moles) NaOH in 1110 parts of water.
Adopt the measuring condition-2 of GPC and the measuring condition-1 of HPLC to measure the molecular weight distribution of anionic surfactant and the amount of unreacted sulfated lauryl alcohol, Mw/Mn is 1.070, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (3 '): 1.0308), the amount of unreacted aliphatic alcohol sulfate is 38.0 weight % (0.496 mole) (distribution constant c "=7.59).
Use the anionic surfactant of embodiment 17 acquisitions and the anionic surfactant that Comparative Examples 14 obtains, carry out performance evaluation.The results are shown in Table 7.
It is evident that from the result content of the unreacting alcohol sulfate of anionic surfactant of the present invention (sulfate) is lower, it all is being good aspect smell, foaminess and the skin irritation.
Table 7
| Embodiment 17 | Embodiment 18 | Comparative Examples 14 | |
| Unreacting alcohol (sulfate) content | 2.3 weight % (0.030 mole) | 1.50 (0.0242) | 38.0 (0.496) |
| Smell | Be destitute of smell | Be destitute of smell | Frowziness |
| Foaminess | 155mm | 150 | 130 |
| Excitant to skin | 0 | 0 | 15 |
Embodiment 19
In stainless steel autoclave, add 186 parts of (1 mole) laruyl alcohols, 0.32 part of magnesium perchlorate and 0.03 part of magnesium hydroxide with stirring and function of temperature control; After the atmosphere that replaces with nitrogen in the container, in 120 ℃ under reduced pressure (about 20mmHg) dewatered 1 hour.Be 1-3kgf/cm in gauge pressure then in 150 ℃
2Add 88 parts of (2 moles) EO under the condition.The required time of EO addition polymerization is 10 hours.In the product of gained, add 1.3 parts of potassium hydroxide, introduce 44 parts of (1 mole) EO in 130 ℃ again.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.037, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.043), adopting the measuring condition-1 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 2.35 weight % (0.040 mole) (distribution constant c "=0.910).
In a glass container, add 216 parts of (0.68 mole) product and 48 parts of (0.34 mole) phosphoric anhydrides, reacted the acquisition esterification products 8 hours in 65 ℃.Add 6 parts of (0.34 mole) water then, make to be reflected at 65 ℃ and to carry out 2 hours, obtain the mono-esterification product.
Subsequently, in 675 parts of water, then to the above-mentioned mono-esterification product that wherein adds 270 parts 60 ℃, regulating the pH value is 6.5, obtains about 30% aqueous solution of phosphate ester salt of the present invention with 54 parts of dissolution of sodium hydroxide.
Embodiment 20
Press the identical mode of embodiment 19, the first step EO adduct of preparation laruyl alcohol (before using potassium hydroxide catalyst).
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.020, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.031), adopting the measuring condition-2 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 3.98 weight % (0.0586 mole) (distribution constant c "=0.558).
In a glass container, add 207 parts of (0.76 mole) product and 54 parts of (0.38 mole) phosphoric anhydrides, reacted the acquisition esterification products 7 hours in 80 ℃.Add 7 parts of (0.38 mole) water then, make to react on 80 ℃ and carried out 2 hours, obtain the mono-esterification product.
Subsequently, in 673 parts of water, then to the above-mentioned mono-esterification product that wherein adds 268 parts 70 ℃, regulating the pH value is 6.5, obtains about 30% aqueous solution of phosphate ester salt of the present invention with 60 parts of dissolution of sodium hydroxide.
Embodiment 21
Press the identical mode of embodiment 5, the first step EO adduct of preparation laruyl alcohol (before using potassium hydroxide catalyst).In the product of gained, add 1.3 parts of potassium hydroxide, introduce 58 parts of (1 mole) expoxy propane (below be called PO) and 44 parts of (1 mole) EO react in 130 ℃ subsequently.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.036 and (satisfies the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.052), adopt the measuring condition-2 of GC to measure that the amount of unreacted laruyl alcohol is 0.21 weight % in the total overall reaction product.
In a glass container, add 226 parts of (0.60 mole) product and 43 parts of (0.30 mole) phosphoric anhydrides, reacted 7 hours, obtain esterification products at 90 ℃.Add 5 parts of (0.28 mole) water then, make to be reflected at 80 ℃ and to carry out 2 hours, obtain the mono-esterification product.
Subsequently, with 48 parts of (1.2 moles) dissolution of sodium hydroxide in 678 parts of water, then in the time of 50 ℃ to wherein adding 274 parts of above-mentioned mono-esterification products, regulating pH value is 6.5, about 30% aqueous solution of acquisition phosphate ester salt of the present invention.
Comparative Examples 15
By Comparative Examples 1 identical mode laruyl alcohol is dewatered.Be 1-3kgf/cm in 150 ℃ in gauge pressure then
2Introduce 176 parts of (4 moles) EO under the condition.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.07, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.043), adopting the measuring condition-2 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 18.0 weight % (0.308 mole) (distribution constant c "=4.75).
In a glass container, add 216 parts of (0.68 mole) product and 48 parts of (0.34 mole) phosphoric anhydrides, reacted 8 hours, obtain esterification products at 65 ℃.Add 6 parts of (0.34 mole) water then, make to be reflected at 65 ℃ and to carry out 2 hours, obtain the mono-esterification product.Subsequently, with 54 parts of dissolution of sodium hydroxide in 675 parts of water, then 60 ℃ to wherein adding 270 parts of above-mentioned mono-esterification products, regulating pH value is 6.5, about 30% aqueous solution of acquisition phosphate ester salt of the present invention.
Comparative Examples 16
Prepare laruyl alcohol EO adduct by Comparative Examples 14 identical modes.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.07, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.0308), adopting the measuring condition-2 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 38.0 weight % (0.560 mole) (distribution constant c "=11.15).
In a glass container, add 207 parts of (0.76 mole) product and 54 parts of (0.38 mole) phosphoric anhydrides, reacted 7 hours, obtain esterification products at 80 ℃.Add 7 parts of (0.38 mole) water then, make to be reflected at 80 ℃ and to carry out 2 hours, obtain the mono-esterification product.Subsequently, with 60 parts of dissolution of sodium hydroxide in 673 parts of water, then 70 ℃ to wherein adding 268 parts of above-mentioned mono-esterification products, regulating pH value is 6.5, about 30% aqueous solution of acquisition phosphate ester salt of the present invention.
The anionic surfactant and Comparative Examples 15 and 16 anionic surfactant that obtain that use embodiment 19-21 to obtain carry out performance evaluation.The results are shown in Table 8.
It is evident that from the result, anionic surfactant of the present invention can provide viscosity lower and on the time stability under foaminess, the high temperature, skin irritation and applicability all good aqueous solution.
Table 8
| Embodiment 19 | Embodiment 20 | Embodiment 21 | Comparative Examples 15 | Comparative Examples 16 | ||||
| PH value (stock solution) | 6.5 | 6.5 | 6.4 | 6.5 | 6.5 | |||
| Viscosity in aqueous solution (cps) | 400 | 500 | 200 | 6900 | 7800 | |||
| Time stability | 0℃ | Outward appearance | ○ | ○ | ○ | Solidify * | Solidify * | |
| Tone | ○ | ○ | ○ | ○ | ○ | |||
| Smell | ○ | ○ | ○ | ○ | ○ | |||
| 25℃ | Outward appearance | ○ | ○ | ○ | Solidify * | Solidify * | ||
| Tone | ○ | ○ | ○ | ○ | ○ | |||
| Smell | ○ | ○ | ○ | ○ | ○ | |||
| 50℃ | Outward appearance | ○ | ○ | ○ | Solidify * | Solidify * | ||
| Tone | ○ | ○ | ○ | △ | △ | |||
| Smell | ○ | ○ | ○ | △ | △ | |||
| Foaminess (mm) | 140 | 140 | 140 | 100 | 110 | |||
| Skin irritation | Point 0 | Point 0 | Point 0 | Point 8 | Point 9 | |||
| Applicability | Foaming | ○ | ○ | ○ | × | × | ||
| Foam quality | ○ | ○ | ○ | × | × | |||
| Sensation | ○ | ○ | ○ | × | × | |||
Embodiment 22
At the first step EO of laruyl alcohol adduct (Weibull distribution constant c ': add 1.3 parts of potassium hydroxide 0.42), then add 44 parts of EO and react at 130 ℃.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.037, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.043), adopting the measuring condition-2 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 2.35 weight % (0.040 mole) (distribution constant c "=0.910).
In a glass container, add 176 parts of (0.55 mole) product and 57 parts of (0.58 mole) maleic anhydrides, reacted 8 hours, obtain the mono-esterification product at 65 ℃.Then 77 parts of (0.61 mole) sodium sulfites are dissolved in 690 parts of water, then 60 ℃ to wherein adding 233 parts of above-mentioned mono-esterification products, they were reacted under this temperature about 5 hours, obtain sulfonated products.Regulating the pH value with citric acid or triethanolamine subsequently is 6.5, obtains about 30% aqueous solution of sulfosuccinate.
Embodiment 23
Press the identical mode of embodiment 19, preparation laruyl alcohol EO adduct.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.020, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.031), adopting the measuring condition-2 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 3.98 weight % (0.0586 mole) (distribution constant c "=0.558).
In a glass container, add 165 parts of (0.60 mole) product and 62 parts of (0.63 mole) maleic anhydrides, reacted 8 hours, obtain the mono-esterification product at 65 ℃.Then 84 parts of (0.67 mole) sodium sulfites are dissolved in 689 parts of water, then 60 ℃ to wherein adding 227 parts of above-mentioned mono-esterification products, they were reacted under this temperature about 5 hours, obtain sulfonated products.Regulating the pH value with citric acid or triethanolamine subsequently is 7.0, obtains about 30% aqueous solution of sulfosuccinate of the present invention.
Embodiment 24
Press the identical mode of embodiment 21, preparation laruyl alcohol PO-EO adduct.
The Mw/Mn that adopts the measuring condition-2 of GPC to measure product is 1.036 and (satisfies the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.052), adopt the measuring condition-2 of GC to measure that the amount of unreacted laruyl alcohol is 0.21 weight % in the total overall reaction product.
In a glass container, add 188 parts of (0.54 mole) product and 52 parts of (0.53 mole) maleic anhydrides, reacted 8 hours, obtain the mono-esterification product at 65 ℃.Then 69 parts of (0.55 mole) sodium sulfites are dissolved in 691 parts of water, then 60 ℃ to wherein adding 240 parts of above-mentioned mono-esterification products, they were reacted under this temperature about 5 hours, obtain sulfonated products.Regulating the pH value with citric acid or triethanolamine subsequently is 7.5, obtains about 30% aqueous solution of sulfosuccinate of the present invention.
Comparative Examples 17
By the identical mode of Comparative Examples 16, preparation laruyl alcohol EO adduct.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.10, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.052), adopting the measuring condition-2 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 11.0 weight % (0.214 mole) (distribution constant c "=2.26).
In a glass container, add 185 parts of (0.51 mole) product and 53 parts of (0.54 mole) maleic anhydrides, reacted 8 hours, obtain the mono-esterification product at 65 ℃.Then 71 parts of (0.56 mole) sodium sulfites are dissolved in 691 parts of water, then 60 ℃ to wherein adding 238 parts of above-mentioned mono-esterification products, they were reacted under this temperature about 5 hours, obtain sulfonated products.Regulating the pH value with citric acid or triethanolamine subsequently is 6.5, obtains about 30% aqueous solution of sulfosuccinate of the present invention.
Comparative Examples 18
By the identical mode of Comparative Examples 14, different is to use 0.6 part of potassium hydroxide to replace 0.3 part of potassium hydroxide, makes the laruyl alcohol dehydration.Be 1-3kgf/cm at 130 ℃ in gauge pressure then
2Add 88 parts of (2 moles) EO, 58 parts of (1 mole) PO and 44 parts of (1 mole) EO under the condition successively.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.12, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.079), adopting the measuring condition-2 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 7.3 weight % (distribution constant c "=2.97).
In a glass container, add 188 parts of (0.50 mole) product and 52 parts of (0.53 mole) maleic anhydrides, reacted 8 hours, obtain the mono-esterification product at 65 ℃.Then 69 parts of (0.55 mole) sodium sulfites are dissolved in 691 parts of water, then 60 ℃ to wherein adding 240 parts of above-mentioned mono-esterification products, they were reacted under this temperature about 5 hours, obtain sulfonated products.Regulating the pH value with citric acid or triethanolamine subsequently is 6.5, obtains about 30% aqueous solution of sulfosuccinate of the present invention.
The anionic surfactant and Comparative Examples 17 and 18 anionic surfactant that obtain that use embodiment 22-24 to obtain carry out performance evaluation.The results are shown in Table 9.
It is evident that from the result, anionic surfactant of the present invention can provide viscosity lower and on smell, time stability, foaminess, skin irritation and applicability all good aqueous solution.
Table 9
| Embodiment 22 | Embodiment 23 | Embodiment 24 | Comparative Examples 17 | Comparative Examples 18 | ||||
| PH value (stock solution) | 6.5 | 7.0 | 7.5 | 6.5 | 6.5 | |||
| Viscosity in aqueous solution (cps) | 50 | 100 | 50 | 6500 | 1000 | |||
| Time stability | 0℃ | Outward appearance | ○ | ○ | ○ | Solidify * | Pasty state * | |
| Tone | ○ | ○ | ○ | ○ | ○ | |||
| Smell | ○ | ○ | ○ | ○ | ○ | |||
| 25℃ | Outward appearance | ○ | ○ | ○ | Solidify * | Solidify * | ||
| Tone | ○ | ○ | ○ | ○ | ○ | |||
| Smell | ○ | ○ | ○ | ○ | ○ | |||
| 50℃ | Outward appearance | ○ | ○ | ○ | Solidify * | Solidify * | ||
| Tone | ○ | ○ | ○ | △ | ○ | |||
| Smell | ○ | ○ | △ | ○ | ||||
| Foaminess (mm) | 145 | 145 | 145 | 100 | 105 | |||
| Skin irritation | Point 0 | Point 0 | Point 0 | Point 8 | Point 5 | |||
| Applicability | Foaming | ○ | ○ | ○ | × | × | ||
| Foam quality | ○ | ○ | ○ | × | × | |||
| Sensation | ○ | ○ | ○ | × | × | |||
Embodiment 25
Press the identical mode of embodiment 19, preparation laruyl alcohol EO adduct.In this product, add 1.3 parts of potassium hydroxide, add 44 parts of EO at 130 ℃ subsequently.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.037, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.043), adopting the measuring condition-2 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 2.35 weight % (0.40 mole) (distribution constant c "=0.910).
In a glass container, add 240 parts of (0.75 mole) product, 97 parts of (0.83 mole) monochloros for sodium acetate and 293 parts of toluene, gradually pressure is reduced to the vacuum of 75mmHg subsequently, temperature is remained on 50 ℃ simultaneously.Then in 2 hours, add 38 parts of (0.94 mole) granular NaOH, under reduced pressure, dewater simultaneously.Aging 6 hours again.Measuring reaction speed (degree of etherification falling) with above-mentioned liquid chromatography is 96%.
After adding 300 parts of water, with hydrochloric acid product is carried out acidifying, separate liquid phase, desalination is also removed toluene.Subsequently with 30 parts of (0.75 mole) dissolution of sodium hydroxide in 700 parts of water, then in the time of 60 ℃ to wherein adding above-mentioned carboxyl etherificate product, regulating the pH value is 6.5, obtains about 30% aqueous solution of carboxyl etherificate product of the present invention.
Embodiment 26
Press the identical mode of embodiment 19, preparation laruyl alcohol EO adduct.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.020, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.031), adopting the measuring condition-2 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 3.98 weight % (0.0586 mole) (distribution constant c "=0.558).
In a glass container, add 232 parts of (0.85 mole) product, 109 parts of (0.93 mole) monochloros for sodium acetate and 284 parts of toluene, gradually pressure is reduced to the vacuum of 80mmHg subsequently, temperature is remained on 50 ℃ simultaneously.Then in 2 hours, add 42 parts of (1.06 moles) granular NaOH, under reduced pressure, dewater simultaneously.Aging 6 hours again.Measuring reaction speed (degree of etherification falling) with above-mentioned liquid chromatography is 97%.After adding 300 parts of water, with hydrochloric acid product is carried out acidifying, separate liquid phase, desalination is also removed toluene.Subsequently with 35 parts of (0.85 mole) dissolution of sodium hydroxide in 700 parts of water, then 60 ℃ to wherein adding above-mentioned carboxyl etherificate product, regulating the pH value is 6.5, obtains about 30% aqueous solution of carboxyl etherificate product of the present invention.
Embodiment 27
Press the identical mode of embodiment 24, preparation laruyl alcohol PO-EO adduct.
In a glass container, add 247 parts of (0.66 mole) these product, 84 parts of (0.72 mole) monochloros for sodium acetate and 302 parts of toluene, gradually pressure is reduced to the vacuum of 75mmHg subsequently, temperature is remained on 45 ℃ simultaneously.When then under reduced pressure, dewatering, in 2 hours, add 33 parts of (0.82 mole) granular NaOH, wore out 6 hours more subsequently.Measuring reaction speed (degree of etherification falling) with above-mentioned liquid chromatography is 96%.
After adding 300 parts of water, with hydrochloric acid product is carried out acidifying, separate liquid phase, desalination is also removed toluene.Subsequently with 26 parts of (0.66 mole) dissolution of sodium hydroxide in 700 parts of water, then in the time of 60 ℃ to wherein adding above-mentioned carboxyl etherificate product, regulating the pH value is 6.5, obtains about 30% aqueous solution of carboxyl etherificate product of the present invention.
Comparative Examples 19
By the identical mode of Comparative Examples 15, preparation laruyl alcohol EO adduct.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.07, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.043), adopting the measuring condition-2 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 18.0 weight % (0.308 mole) (distribution constant c "=4.75).
In a glass container, add 240 parts of (0.75 mole) product, 97 parts of (0.83 mole) monochloros for sodium acetate and 293 parts of toluene, gradually pressure is reduced to the vacuum of 75mmHg subsequently, temperature is remained on 50 ℃ simultaneously.Then in 2 hours, add 38 parts of (0.94 mole) granular NaOH, under reduced pressure, dewater simultaneously.Aging 6 hours again.Measuring reaction speed (degree of etherification falling) with above-mentioned liquid chromatography is 96%.
After adding 300 parts of water, with hydrochloric acid product is carried out acidifying, separate liquid phase, desalination is also removed toluene.Subsequently with 30 parts of (0.75 mole) dissolution of sodium hydroxide in 700 parts of water, then 60 ℃ to wherein adding above-mentioned carboxyl etherificate product, regulating the pH value is 6.5, obtains about 30% aqueous solution of carboxyl etherificate product of the present invention.
Comparative Examples 20
By the identical mode of Comparative Examples 14, preparation laruyl alcohol EO adduct.
The Mw/Mn that adopts the measuring condition-3 of GPC to measure product is 1.07, and (satisfy the upper limit calculated value of the Mw/Mn of relational expression (2 '): 1.0308), adopting the measuring condition-1 of GC to measure in the total overall reaction product amount of unreacted laruyl alcohol is 38.0 weight % (0.560 mole) (distribution constant c "=11.15).
In a glass container, add 232 parts of (0.85 mole) product, 109 parts of (0.93 mole) monochloros for sodium acetate and 284 parts of toluene, gradually pressure is reduced to the vacuum of 80mmHg subsequently, temperature is remained on 50 ℃ simultaneously.When then under reduced pressure, dewatering, in 2 hours, add 42 parts of (1.06 moles) granular NaOH, aging 6 hours subsequently.Measuring reaction speed (degree of etherification falling) with above-mentioned liquid chromatography is 97%.
After adding 300 parts of water, with hydrochloric acid product is carried out acidifying, separate liquid phase, desalination is also removed toluene.Subsequently with 35 parts of (0.85 mole) dissolution of sodium hydroxide in 700 parts of water, then 60 ℃ to wherein adding above-mentioned carboxyl etherificate product, regulating the pH value is 6.5, obtains about 30% aqueous solution of carboxyl etherificate product of the present invention.
The anionic surfactant and Comparative Examples 19 and 20 anionic surfactant that obtain that use embodiment 25-27 to obtain carry out performance evaluation.The results are shown in Table 10.
It is evident that from the result, anionic surfactant of the present invention can provide viscosity lower and on smell, time stability, foaminess, skin irritation and applicability all good aqueous solution.
Table 10
| Embodiment 25 | Embodiment 26 | Embodiment 27 | Comparative Examples 19 | Comparative Examples 20 | ||||
| PH value (stock solution) | 6.8 | 6.7 | 6.4 | 6.5 | 6.5 | |||
| Viscosity in aqueous solution (cps) | 400 | 500 | 200 | 5500 | 6800 | |||
| Time stability | 0℃ | Outward appearance | ○ | ○ | ○ | Solidify * | Solidify * | |
| Tone | ○ | ○ | ○ | ○ | ○ | |||
| Smell | ○ | ○ | ○ | ○ | ○ | |||
| 25℃ | Outward appearance | ○ | ○ | ○ | Solidify * | Solidify * | ||
| Tone | ○ | ○ | ○ | ○ | ○ | |||
| Smell | ○ | ○ | ○ | ○ | ○ | |||
| 50℃ | Outward appearance | ○ | ○ | ○ | Solidify * | Solidify * | ||
| Tone | ○ | ○ | ○ | △ | △ | |||
| Smell | ○ | ○ | ○ | △ | △ | |||
| Foaminess (mm) | 142 | 142 | 140 | 112 | 112 | |||
| Skin irritation | Point 0 | Point 0 | Point 0 | Point 6 | Point 5 | |||
| Applicability | Foaming | ○ | ○ | ○ | × | × | ||
| Foam quality | ○ | ○ | ○ | × | × | |||
| Sensation | ○ | ○ | ○ | × | × | |||
Press the composition of detergent of formulation embodiment 28-36 shown in table 11 and 12 and Comparative Examples 21-23.Performance evaluation to composition of detergent is listed in the table 13.Carry out benchmark test by preceding method.Determine the detergency index of anionic surfactant as follows.
(measuring method of anionic surfactant detergency index) at this, % is meant weight %
" prescription of cleaning solution "
Anionic surfactant 10%
Coco-nut oil fatty acid acylamino-propyl-dimethyl beet 5% alkali
Coco-nut oil fatty acid diethanol acyl 1% amine of 1: 1 mole of type
Water 84%
Amount to 100%
Press Leenerts method (JIS K3370), use cleaning solution to carry out the detergency test by above-mentioned formulated.Use six slides as a pair of dirt substrate, use the chloroformic solution of artificial dirt to apply as the dirt component with following composition.The cleaning solution aqueous solution with 0.3% concentration washs the slide that scribbles artificial dirt as wash liquid; Determine detergency by following formula, detergency exponential representation is that the detergency of 2 moles of adducts of laruyl alcohol EO of obtaining with respect to Comparative Examples 14 is as 100 index.
" composition of artificial dirt component "
Myristic acid 15%
Oleic acid 15%
Tristearin 15%
Triolein 15%
Cholesteryl stearate 2%
Paraffin 10%
Squalene 10%
Cholesterine 8%
Bovine serum albumin 10%
Amount to 100%
The amount (gram) of dirt before detergency (%)=100 * [amount (gram) of the amount (gram) of dirt before the washing-washing back dirt]/washing
Table 11
| Embodiment | |||||||
| 28 | 29 | 30 | 31 | 32 | 33 | 34 | |
| The sulfate of embodiment 17 | 20 | 13 | |||||
| The sulfate of embodiment 18 | 13 | ||||||
| The phosphate of embodiment 19 | 13 | ||||||
| The phosphate of embodiment 20 | 13 | ||||||
| The sulfosuccinate of embodiment 22 | 13 | ||||||
| The sulfosuccinate of embodiment 23 | 13 | ||||||
| Cocoanut fatty acid diethanolamide | 2 | 0 | 2 | 7 | 2 | 2 | |
| The lauryl dimethyl betaine | 5 | 7 | 5 | 0 | 5 | 5 | |
| Water | 80 | 80 | 80 | 80 | 80 | 80 | 80 |
| Amount to | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
Numerical value is represented active component (weight %)
Table 12
| Embodiment | Comparative Examples | Standard | ||||
| 35 | 36 | 21 | 22 | 23 | ||
| The carboxyl ether of embodiment 25 | 13 | |||||
| The carboxyl ether of embodiment 26 | 13 | |||||
| The sulfate of Comparative Examples 14 | 13 | |||||
| The phosphate of Comparative Examples 15 | 13 | |||||
| The phosphate of Comparative Examples 16 | ||||||
| The sulfosuccinate of Comparative Examples 17 | 13 | |||||
| The carboxyl ether of Comparative Examples 19 | 13 | |||||
| Cocoanut fatty acid diethanolamide | 2 | 2 | 2 | 2 | 2 | |
| The lauryl dimethyl betaine | 5 | 5 | 5 | 5 | 5 | |
| Water | 80 | 80 | 80 | 80 | 80 | 80 |
| Amount to | 100 | 100 | 100 | 100 | 100 | 100 |
Table 13
| The embodiment sequence number | Stability in time | Foaminess | Skin irritation | Applicability | The detergency index | |||
| Outward appearance | Smell | Foaming | Foam quality | Sensation | ||||
| Embodiment 28 | ○ | ○ | 142 | 0 | ○ | ○ | ○ | 122 |
| Embodiment 29 | ○ | ○ | 145 | 0 | ○ | ○ | ○ | 120 |
| Embodiment 30 | ○ | ○ | 145 | 0 | ○ | ○ | ○ | 119 |
| Embodiment 31 | ○ | ○ | 142 | 0 | ○ | ○ | ○ | 115 |
| Embodiment 32 | ○ | ○ | 142 | 0 | ○ | ○ | ○ | 116 |
| Embodiment 33 | ○ | ○ | 143 | 0 | ○ | ○ | ○ | 110 |
| Embodiment 34 | ○ | ○ | 142 | 0 | ○ | ○ | ○ | 112 |
| Embodiment 35 | ○ | ○ | 145 | 0 | ○ | ○ | ○ | 120 |
| Embodiment 36 | ○ | ○ | 145 | 0 | ○ | ○ | ○ | 120 |
| Comparative Examples 21 | × | △ | 130 | 2 | △ | △ | × | 98 |
| Comparative Examples 22 | △ | △ | 125 | 2 | △ | × | × | 92 |
| Comparative Examples 23 | △ | × | 129 | 3 | △ | △ | × | 95 |
| Standard | × | △ | 135 | 3 | △ | △ | × | 100 |
It is evident that from the result composition of detergent of the present invention has higher detergency index, and is lower to the excitant of skin, and have improved outward appearance and smell and good applicability, thereby can be used as washing agent well.
Commercial Application
Nonionic surface active agent of the present invention has surface-active, such as emulsibility, dissolving power, detergency and penetration. Therefore, they can be used in the purposes of various surfactants, for example emulsifying agent, the emulsifying agent of agricultural chemicals emulsion, the emulsifying agent of cosmetics, the emulsifying agent of water paint and the emulsifying agent of emulsion polymerisation of the processing of emulsifying agent such as metal; The dispersant of paper grade (stock) material such as pigment and soap; The solubilizer of spices etc.; House detergent such as fabric washing agent and the washing agent of washing dish usefulness washing agent and industrial detergent such as mechanical metal detergent; Bleeding agent; Wetting agent and defoamer.
Owing to already pointed out, alkyl phenolic group nonionic surface active agent commonly used has pair environment to cause the worry of stimulation (environment is caused inherent destruction) in these purposes so far, and nonionic surface active agent of the present invention (being non-alkyl phenolic group nonionic surface active agent) has good performance, so they can be used as the substitute of existing surfactant in various uses.
In addition, anionic surfactant of the present invention has good surface-active such as detergency, foaminess and penetration. Therefore, except the purposes of above-mentioned nonionic surface active agent, they can also be used as the washing agent of shampoo, dishwashing dish and be used for the washing agent of crust such as metal. Owing to improved low-temperature stability, smell and excitant by anionization, so they especially can be used as washing agent, for example shampoo and cosmetic washing agent because before anionization in the aliphatic alcohol oxyalkylene adduct content of unreacted aliphatic alcohol lower.
Claims (7)
1. anionic surfactant, it is to obtain by aliphatic alcohol oxyalkylene addition compound (A ') is carried out anionization,
Described (A ') adds to oxyalkylene (b1) on the aliphatic alcohol (a1) and directly makes, and satisfies following condition (ii '), (iii ') and (iv):
(ii ') weight average molecular weight (Mw) satisfies following relation (2 ') or (3 ') with the ratio Mw/Mn of number-average molecular weight (Mn):
Mw/Mn≤0.030 * Ln (v ")+1.010 (at v "＜10 situation under) (2 ')
Mw/Mn≤-0.026 * Ln (v ")+1.139 (at v " 〉=10 situation under) (3 ')
V wherein " represents in the following general formula (1 ') mean value of (m '+n '+p ');
(iii ') by the definite distribution constant c of following formula (4 ") " be 1.0 or littler, only at v " up to requiring to satisfy this condition under 12 the situation:
C "=(v "+n
0/ n
00One 1)/[Ln (n
00/ n
0)+n
0/ n
00-1] (4 ")
V wherein " implication as mentioned above.n
00The molal quantity of representative used aliphatic alcohol (a1) in reaction, n
0Represent the molal quantity of unreacted aliphatic alcohol (a1);
(iv) it comprises the mixture of the compound of two or more following general formula (1 ') expressions:
R
1O-[(C
2H
4O)
m’/(AO)
n’]-(C
2H
4O)
p’-H (1’)
R wherein
1It is the cyclic aliphatic alkyl that contains the aliphatic hydrocarbyl of 8-24 carbon atom or contain 8-24 carbon atom; A is the alkylidene that contains at least 3 carbon atoms; M ' is 0 or 1 or bigger integer, its mean value is 0-5, n ' is 0 or 1 or bigger integer, and its mean value is 0-5, and p ' is 0 or 1 or bigger integer, its mean value is 0-10, (m '+n '+p ') is an integer, and its mean value is 1-20, and the mean value of (m '+p ')/(m '+n '+p ') is at least 0.5, under the situation of m ' ≠ 0 and n ' ≠ 0, { (C
2H
4O)
M '/ (AO)
N 'Represent block addition or random addition.
2. anionic surfactant as claimed in claim 1, wherein said anionization is a sulphation.
3. anionic surfactant as claimed in claim 1, wherein said anionization is a phosphorylation.
4. anionic surfactant as claimed in claim 1, wherein said anionization are the carboxyl etherificates.
5. anionic surfactant as claimed in claim 1, wherein said anionization are the sulfosuccinic acidifyings.
6. composition of detergent, it comprises anionic surfactant as claimed in claim 1.
7. composition of detergent, it comprises anionic surfactant as claimed in claim 1 and amphoteric surfactant and/or nonionic surface active agent.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP274563/98 | 1998-09-29 | ||
| JP27456398 | 1998-09-29 | ||
| JP120300/99 | 1999-04-27 | ||
| JP146489/99 | 1999-05-26 | ||
| JP254772/99 | 1999-09-08 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998114855A Division CN1272418C (en) | 1998-09-29 | 1999-09-29 | Surfactant, process for producing the same, and detergent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1781591A true CN1781591A (en) | 2006-06-07 |
| CN100381547C CN100381547C (en) | 2008-04-16 |
Family
ID=36772442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101267862A Expired - Fee Related CN100381547C (en) | 1998-09-29 | 1999-09-29 | Anionic surfactant and detergent composition containing same |
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|---|---|
| CN (1) | CN100381547C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471479A (en) * | 2009-08-04 | 2012-05-23 | 花王株式会社 | Production method for nonionic surfactant |
| CN109126622A (en) * | 2017-06-27 | 2019-01-04 | 华南师范大学 | A kind of anionic surfactant, detergent and detergent composition |
| CN112759754A (en) * | 2020-12-28 | 2021-05-07 | 上海东大化学有限公司 | Low-foam biodegradable nonionic surfactant and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6029370B2 (en) * | 1977-03-30 | 1985-07-10 | 株式会社日本触媒 | Method for producing alkylene oxide adducts |
| EP0043963A1 (en) * | 1980-06-30 | 1982-01-20 | Union Carbide Corporation | Improved process for ethoxylation of broad-range primary alcohols |
| US4737314A (en) * | 1985-02-08 | 1988-04-12 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Stabilized alkylene oxide adduct containing lactic acid or a lactate |
| JP2800164B2 (en) * | 1992-10-02 | 1998-09-21 | ライオン株式会社 | Low foaming nonionic surfactant |
| DE4421576A1 (en) * | 1994-06-21 | 1996-01-04 | Hoechst Ag | Alkoxylation product mixtures with a narrow alkoxyl distribution |
-
1999
- 1999-09-29 CN CNB2005101267862A patent/CN100381547C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471479A (en) * | 2009-08-04 | 2012-05-23 | 花王株式会社 | Production method for nonionic surfactant |
| CN102471479B (en) * | 2009-08-04 | 2014-05-28 | 花王株式会社 | Production method for nonionic surfactant |
| CN109126622A (en) * | 2017-06-27 | 2019-01-04 | 华南师范大学 | A kind of anionic surfactant, detergent and detergent composition |
| CN112759754A (en) * | 2020-12-28 | 2021-05-07 | 上海东大化学有限公司 | Low-foam biodegradable nonionic surfactant and preparation method thereof |
| CN112759754B (en) * | 2020-12-28 | 2023-06-27 | 上海东大化学有限公司 | Low-foam biodegradable nonionic surfactant and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100381547C (en) | 2008-04-16 |
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