JPH06505042A - Method for producing alkyl and/or alkenyl sulfate paste with improved flowability - Google Patents

Abstract

Alkyl- and/or alkenylsulfate pastes with improved flowability may be produced by admixture of at least one nonionic tenside selected from the group composed of: (a) alkyl- and/or alkenylpolyethyl glycolether, (b) alkyl- and/or alkenylpolypropylene glycolether; (c) alkyl- and/or alkenylpolypropyleneglycol-ethylene glycolether; (d) alkyl- and/or alkenyl glycosides; (e) mixed ethers and/or (f) hydroxyl mixed ethers. The viscosity of the alkyl- and/or alkenylsulfate pastes is set at 15.000 mPa.s maximum at 55 C.

Description

[Detailed description of the invention] Production of alkyl and/or alkenyl sulfate pastes with improved flowability Manufacturing method The present invention improves fluidity by adding a nonionic surfactant as a viscosity control agent. Method for producing alkyl and/or alkenyl sulfate paste with improved Regarding.

Anionic surfactants of the alkyl and alkenyl sulfate type, especially C111 , anionic surfactants with alkyl or alkenyl groups have excellent detergent properties. and is suitable for the production of laundry, dishwashing and cleaning formulations.

Use of alkyl and/or alkenyl sulfates on an industrial scale, especially powders The use of water-based alkyl and The storage and transportation of alkenyl sulfate pastes and/or alkenyl sulfate pastes alone pose considerable problems. This is because there was That is, alkyl and/or or alkenyl sulfate paste, transfer it to another container at room temperature. The viscosity is so high that it is virtually impossible to use pumps or pumps. ) is large. Furthermore, mixing the paste with other detergent ingredients creates a total (heterogeneous slurry). Only lees can be obtained and further processing cannot be performed without problems.

The solution to this problem is to heat the paste to a temperature high enough for it to flow. This is possible only by controlling H and adding alkali as necessary.

Another method for reducing the viscosity of alkyl and/or alkenyl sulfate pastes The solution is to dilute the product with water to the extent that it can be pumped, but the powdered product When spray drying paste to produce This is not desirable because it leads to energy consumption.

Conventionally, many research departments have been dealing with the problems caused by the high viscosity of anionic surfactant aqueous pastes. There was a problem. As a representative of related prior art, German Patent Publication No. 3718896A1 Alkoxy as viscosity control agent for alkylbenzene sulfonate paste It is suggested that silicated alcohol be used.

According to the teaching of European Patent 0116905B1, c. alcohol ethylene Contains 1 to 15 moles of adduct of oxide and/or propylene oxide as a surfactant. By adding in an amount of 1 to 15% by weight based on the amount of alkylaryl sulfur ate paste, α-sulfo fatty acid ester paste and alkyl sulfate paste The viscosity of the top paste can be lowered to a value of 10,000♂a”s or less at 70°C. I can do that. This patent specifically describes a paste of α-sulpo fatty acid ester salts. It is related to viscosity control. However, research has shown that the alkylene oxides described Addition of adducts to alkyl and/or alkenyl sulfate pastes Although it leads to an appropriate viscosity reduction at high temperatures, it also causes a decline in detergent properties, especially detergency. It is possible. In addition, the use of alkylene oxide adducts can be used for alkyl and/or In spray drying of alkenyl sulfate pastes, increasing product conveyance, This leads to undesirable organic contamination of wastewater (blooming).

Therefore, the problem to be solved by the present invention is to improve fluidity without the above-mentioned drawbacks. A method for producing a good alkyl and/or alkenyl sulfate paste is proposed. It is to provide.

The present invention provides alkyl and/or alkenyl sulfate pigments with improved flowability. A method for producing a yeast, a) alkyl and/or alkenyl polyethylene glycol ether b) a) Alkyl and/or Alkenyl Polypropylene Glycol Ether C) Alkyl polypropylene glycol and/or alkenyl polypropylene glycol ethylene glycol ether Tell d) alkyl and/or alkenyl glycosides e) mixed ethers and/or Ruiha f) Hydroxy mixed ether At least one nonionic surfactant selected from the group consisting of the general formula! ,R 1-0-3OsX (I) [wherein R1 is an alkyl and/or alkenyl group having 10 to 22 carbon atoms] X is an alkali metal or alkaline earth metal. ] The solid content of alkyl and/or alkenyl sulfate is 30 to 70% by weight. % of the alkyl and/or alkenyl sulfate. Adjust the viscosity of the paste to 15000 mPa-5 or less at 55°C. Relating to a method of characterizing.

Surprisingly, the selected nonionic surfactants used in the present invention are and/or the viscosity of alkenyl sulfate pastes, even at low temperatures. There is a risk of decomposition (not only reducing the level to the level that it can be pumped, but also causing fluidity abnormalities). limits and therefore ports for alkyl and/or alkenyl sulfate pastes. We also found that the design of the pump and conveying line was fairly simple. The present invention The addition of nonionic surfactants makes it possible to produce homogeneous detergent slurries. It includes the knowledge that Alkyl and/or alkenyl sulfate paste The laundry, dishwashing and cleaning functions of non-ionic No adverse effects are caused by the addition of surfactants. Finally, paste is a problem Can be sprayed without any problem. In this regard, polyethylene glycols with a narrow homologous distribution range Ether has been found to be particularly useful.

Alkyl and/or alkenyl sulfates are known anionic surfactants. and is obtained by standard methods of organic chemical preparation. Generally, alkyl and/or alkenyl sulfates are saturated and/or unsaturated aliphatic Produced by the reaction of monoalcohol with sulfur dioxide. Applying the method of the invention Alkyl and/or alkenyl sulfates contain 10 to 22 carbon atoms. derived from fatty alcohols with Typical examples of such fatty alcohols are Prill alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol oleyl alcohol, palmitole alcohol, stearyl alcohol, oleyl alcohol , erucil alcohol, petroselinyl alcohol, arachine alcohol, gado Leyl alcohol, behenyl alcohol or erucyl alcohol.

A particularly rapid decrease in viscosity of the paste occurs when carbon atoms of 12 to 18, especially 16 to 18, are present. Found in the case of alkyl sulfates derived from saturated fatty alcohols with .

Furthermore, alkyl and/or alkenyl sulfates may be of natural origin, e.g. Acid derived from industrial mixtures of fatty acid methyl esters or oxo-synthesis of leylenes. It may also be derived from the industrial alcohol fraction obtained in the hydrogenation of aldehydes.

In this case, alkyls derived from industrial fatty alcohol fractions of coconut oil or tallow and/or alkenyl sulfates are preferred. These fractions are on average It is understood that primary fatty alcohols have the following carbon chain distribution:

Coconut oil fatty alcohol Tallow fatty alcohol C+o: 0-3% by weight CD: 48-58% by weight CIa: 19-24% by weight 0-3% by weight C+s: 9-12% by weight 45- 55% by weight C+a: 11-14% by weight 45-55% by weight C2゜20-3 weight% Within the scope of the present invention, nonionic surfactants are a) alkyl and/or alkyl surfactants; b) alkyl and/or alkenyl polyethylene glycol ether C) Alkyl and/or alkenyl polypropylene glycol ether Lipropylene glycol ethylene glycol ether d) alkyl and/or alkenyl glycosides e) mixed ethers and/or Ruiha f) Hydroxy mixed ether It is. All of these surfactants are known compounds and their manufacture has been described elsewhere. For example, J. Falbe, U. Ha. Hasserodt (U.) (ed.), “Kathalysatoren, ten Zuide Land Mineral Ale Aditief Z (Katalysato ren, Ten5ide und MineralQadditive) J, Thieme Verlag, Sinitou Togart, 1987, or J. Falbe (ed.), “Surfactans in Consumer* Products” ts in Consumer Pr.

ducts) J, Springer Verlag (Springer Ver. lag), Berlin, 1986.

Alkyl and/or alkenyl polyethylene used in the method of the invention The glycol ether (component a) has the general formula ■, R”-0-(CH,-CH!- 0), H(n) [wherein R1 is a straight chain or branched chain having 6 to 22 carbon atoms] is an alkyl or alkenyl group, and n is a number from 2 to 7. ] by It may be a nonionic surfactant as shown. alkyl and/or alkenyl Significant reduction in viscosity of sulfate paste, good detergent properties and In order to achieve particularly low wastewater pollution, R2 has from 10 to 18 carbon atoms. a straight-chain or branched alkyl group, where n is a number from 2 to 7, especially a number from 5 to 7. Using an alkyl polyethylene glycol ether represented by a certain general formula ■ I found that it would be best if I did this.

Another preferred embodiment of the invention provides that the remaining amount of alcohol is removed by It is shown by the general formula The use of alkyl and/or alkenyl polyethylene glycol ethers Features:

Component b) has the general formula ■, CH3 Cheers R'-0-(CHz-CH-0)-H(m) [wherein R3 is 6 to 22 carbon atoms straight-chain or branched alkyl or alkenyl group having children, m is 1 The number is ~4. ] is a group represented by the general formula m, where m is a number from 1 to 3; The use of alkyl polypropylene glycol ethers is preferred.

Component C) has the general formula ■, In formula C, R4 is straight-chain or branched alkyl having 6 to 22 carbon atoms. or an alkenyl group, p is a number from 1 to 4, and q is a number from 1 to 10.

], p is a number of 1 or 2, and q is a number of 1 to 7. , an alkyl polypropylene glycol ethylene represented by the general formula ■ Preference is given to using glycol ethers.

The alkyl polyglycol ethers forming components a), b) and C) are natural fats. fatty alcohols or synthetic oxo alcohols, ethylene oxide and/or It is an adduct of propylene oxide. Alkoxylation is a statistical reaction; Industrial alkyl polyglycol ethers are homologues with different degrees of alkoxylation and May contain unreacted fatty alcohol. homologously pure alkyl polyglycols Ethers and industrial mixtures with a wide homologous distribution range and narrow homologous distribution ranges Any of the technical mixtures may be used in the method of the invention.

Component d) has the general formula V.

R'-0-(G) yo (V) [wherein RS is an alkyl or alkenyl group having 6 to 22 carbon atoms] and G is a glycose unit derived from a sugar having 5 or 6 carbon atoms. , and X is a number from 1 to 10. ] may be an alkyl and/or alkenyl glycoside represented by

Furthermore, alkyl and/or alkenyl glycosides are may contain an amount of alcohol, but the amount may be limited to alkyl and/or alkenyl The amount does not exceed 10% by weight relative to the glycosides. In the formula, Rs is 10 to 18 It is an alkyl group having a carbon atom, G is a glucose unit, and X is 1 to 3. alkylglycosylation of the general formula V, in particular a number from 1.1 to 1.6. It is preferable to use Regarding the production of alkyl and/or alkenyl glycosides For further details, reference may be made to German patent 3723826A1.

Component e) has the general formula ■, [wherein R- is an alkyl or alkenyl group having 6 to 22 carbon atoms] Yes, R? is an alkyl group or benzyl group having 1 to 4 carbon atoms, R8 is hydrogen or a methyl group, and y is a number from 1 to 10. ] It is a mixed ether. In the formula, R6 is an alkyl group having 12 to 18 carbon atoms. , R7 is a butyl group or a benzyl group, R8 is hydrogen, and y is 4 to Preference is given to using mixed ethers represented by the general formula (1), which is a number 10.

component) is the general formula■, [Wherein, R9 is an alkyl group having 6 to 16 carbon atoms, and R1'' is 1 to an alkyl group or a benzyl group having 4 carbon atoms, and R1+ is hydrogen or It is a methyl group, and 2 is a number from 1 to 10. ] Hydroxy mixture indicated by It may be ether. In the formula, R9 is an alkyl group having 8 to 10 carbon atoms; R16 is a butyl group or a benzyl group, R1+ is hydrogen, and Z is 4 to Preference is given to using hydroxy mixed ethers represented by the general formula ■, which is a number 10. Yes. Details regarding the production of hydroxy mixed ethers can be found in German patent 372 332 3A1.

Nonionic surfactants to alkyl and/or alkenyl sulfate pastes The agents may be added individually or in combination. Wide range of mixing ratios can be changed to For example, polyglycol ethers, especially alkyl polyethylenes Glycol ether and alkyl glucoside, 10:90-90: 10%, and the free alcohol content is less than it amount% of the mixture It has been found to be particularly advantageous to use a mixture of

Determine the viscosity and yield point of alkyl and/or alkenyl sulfate pastes. In order to reduce the paste in an amount of 1 to 15% by weight based on the solid content of the paste, preferably 5 to 15% by weight, based on the solid content of the paste. It is added during or after neutralization in an amount of 12% by weight. Alkyl and/or alkyl Regarding the use of polyethylene glycol ether (component a), this non- The ionic surfactant is added in an amount of 5 to 12% by weight based on the solid content of the paste, especially at 7°. It is particularly advantageous to use amounts of 5 to 10% by weight. alkyl and/or The alkenyl sulfate and nonionic surfactant may be mixed mechanically, e.g. by stirring. or by pump, raising the temperature to 55-70°C if desired. There is no chemical reaction between the components.

The following examples serve to illustrate the invention without limiting it.

Example CI 6/l tallow fatty alcohol [Hydrenol ( Trademark) DD1 hydroxyl value 215, manufactured by Henkel KGaA] 60 0 g (2.3 mol) in 11 slits equipped with cooling jackets and gas inlet pipes. Introduced into a fonation reactor and reacted with 240 g (3 moles) of sulfur dioxide at 80°C. I let it happen. Sulfur dioxide is generated from a corresponding amount of 65% by weight oleum by heating. , diluted with nitrogen to a concentration of 5% by volume and introduced into the starting material over 60 minutes. Then coarse The sulfonated product was neutralized with a 25% by weight aqueous sodium hydroxide solution, based on the solid content. Then 1% by weight of citric acid was added as a buffer.

Product characteristic values Anionic surfactant content: 49.8% by weight Unsulfonated component: 4.0% by weight % Sodium sulphuni) + 1.4% by weight Water: 44.8% by weight The anionic surfactant content of the unsulfonated components was determined by Inheits methoden (DGF-E inheits methoden), Stuttgart, 1950-1984, H-111-10 and G-If-6 Measured according to b. Sulfate content calculated as sodium sulfate The water content was measured using the Fisher method.

The viscosity of the mixtures of the invention (Examples 1-3) and comparative mixtures (Comparative Examples 1-4) RTV type Brookfield viscometer (spindle No. 6, rotation speed 20) ) at 55-75°C. The results are shown in Table 1.

Table 1: Viscosity (Iris Pa-5) Example number Additive Concentration (wt%) Temperature (℃)? 5 70 65 60 5 5 7.5 2750 3000 3500 5500 1200010.0 22 50 2250 3250 3500 5250 Example 2 LT7 5.0 3 500 3500 4500 7500 145007.5 3000 325 0 3750 5750 1325010.0 3000 3250 3500 6500 11000 Example 3 LS3/LT5 5.0 3250 350 0 4250 6000 12500 (80:20) 7.5 3000 32 50 4000 4250 800010.0 5500 6000 6000 4750 6250 Comparative Example I TA5 5.0 2750 3000 350 0 5000 19250 Comparative example 2 TA7 5.0 3000 3000 4 000 5500 38750 Comparative example 3 TA14 5.0 3000 300 0 4000 6000 41000 Legend: LT5 = CI! Average 5 mol ethylene oxide adduct L of 71s fatty alcohol T7=C+! /Ig fatty alcohol with average 7 moles of ethylene oxide Addition LS3/LT5=CI! /+4 Fatty alcohol average 5 mos of ethylene oxide Le adduct and Cl! /l 8 fatty alcohols added with an average of 5 moles of ethylene oxide Mixture with body weight ratio of 80:20 TA5 = C1sy□8 fatty alcohol ethylene oxide average 5 mole adduct T A7 = C+sz+s fatty alcohol ethylene oxide average 7 mole adduct TA 14=C+sz+s ethylene oxide average 14 mole adduct of fatty alcohol TA20=C+az+s Addition of 20 moles of ethylene oxide on average to fatty alcohol body international search report --, --am=-11-11-. PCT/EP 92100330 front page Continuation of page (72) Inventor Kischgal, Ditmar Federal Republic of Germany Day-4019 Monheim 2, Schwanenstraasse No. 20

Claims (9)

[Claims] 1. Alkyl and/or alkenyl sulfate pastes with improved flow properties A method of manufacturing, a) alkyl and/or alkenyl polyethylene glycol ether b) a) alkyl and/or alkenyl polypropylene glycol ether c) alkyl polypropylene glycol and/or alkenyl polypropylene glycol ethylene glycol ether Tell d) alkyl and/or alkenyl glycosides e) mixed ethers and/or Ruiha f) Hydroxy mixed ether At least one nonionic surfactant selected from the group consisting of general formulas I, R 1-O-SO3X(I) [wherein R1 is alkyl and/or alkyl having 10 to 22 carbon atoms] It is a kenyl group, and X is an alkali metal or alkaline earth metal. ] by The solid content of the indicated alkyl and/or alkenyl sulfate is 30 to 70 % by weight of alkyl and/or alkenyl sulfur added to the aqueous paste. Adjusting the viscosity of the paste to 15,000 mPa・s or less at 55°C A method characterized by: 2. A general formula in which R1 is a C16-18 alkyl group and x is sodium Claim 1 characterized in that an alkyl sulfate represented by I is used. The method described in. 3. As component a) general formula II, R2-O-(CH2-CH2-O)nH(II) [wherein R2 is 6-22 carbon a straight-chain or branched alkyl or alkenyl group having an elementary atom, n is a number from 2 to 7. ] Alkyl and/or alkenyl groups represented by Claim 1 or 2, characterized in that polyethylene glycol ether is used. Method described. 4. As component b) general formula III, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, R3 is 6 to 22 carbon atoms] a straight-chain or branched alkyl or alkenyl group having atoms, m is It is a number from 1 to 4. ] Alkyl and/or alkenyl poly Claim 1 or 2, characterized in that propylene glycol ether is used. Method described. 5. As component c) general formula IV, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) [In the formula, R4 is a carbon atom of 6 to 22 straight-chain or branched alkyl or alkenyl group having children, p is 1 ~4, and q is a number from 1 to 10. ] and / or using alkenyl polypropylene glycol ethylene glycol ether. The method according to claim 1 or 2, characterized in that the method is used. 6. As component d) general formula V, R5-O-(G)x(V) [wherein R5 is an alkyl or alkenyl group having 6 to 22 carbon atoms] and G is a glycose unit derived from a sugar having 5 or 6 carbon atoms. , and x is a number from 1 to 10. ] using alkyl and/or alkenyl glycosides represented by The method according to claim 1 or 2, characterized in that: 7. As component e) general formula VI, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VII) [In the formula, R6 is 6 to 22 carbon atoms] is an alkyl or alkenyl group having 1 to 4 carbon atoms; is an alkyl group or benzyl group having , y is a number from 1 to 10. ] to use a mixed ether indicated by 3. A method according to claim 1 or 2, characterized in that: 8. As component f) one-stage VII, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VII) [In the formula, R9 is a carbon atom of 6 to 16 R10 is an alkyl group having 1 to 4 carbon atoms; or a benzyl group, R11 is hydrogen or a methyl group, and z is 1 to 10. It is a number. ] Characterized by using a hydroxy mixed ether represented by The method according to claim 1 or 2. 9. Add nonionic surfactants to alkyl and/or alkenyl sulfate pastes. A claim characterized in that it is added to the liquid in an amount of 1 to 15% by weight based on the solid content. 9. The method according to any one of 1 to 8.