WO2009039018A1 - Plastifiant - Google Patents

Plastifiant Download PDF

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Publication number
WO2009039018A1
WO2009039018A1 PCT/US2008/075912 US2008075912W WO2009039018A1 WO 2009039018 A1 WO2009039018 A1 WO 2009039018A1 US 2008075912 W US2008075912 W US 2008075912W WO 2009039018 A1 WO2009039018 A1 WO 2009039018A1
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WO
WIPO (PCT)
Prior art keywords
secondary alcohol
plasticizer
anhydride
composition
moles
Prior art date
Application number
PCT/US2008/075912
Other languages
English (en)
Inventor
Howard Lam Ho Fong
Janine Anne Toner
Original Assignee
Shell Oil Company
Shell Internationale Research Maatschappij B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Oil Company, Shell Internationale Research Maatschappij B.V. filed Critical Shell Oil Company
Publication of WO2009039018A1 publication Critical patent/WO2009039018A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters

Definitions

  • the present invention relates to plasticizers and plasticized polyvmylchlo ⁇ de compositions.
  • Plasticizers are widely used in many ways m plastics, coatings compositions, sealing compositions and rubber articles. They interact physically with thermoplastic high polymers without reacting chemically, preferably by means of their solvent and swelling capability. This forms a homogeneous system whose thermoplastic range has been shifted to lower temperatures compared to the original polymer, with the result that, for example, the ability to change shape and the elasticity are increased and the hardness is reduced.
  • plasticizers To open up wide fields of application for plasticizers, they have to fulfill a number of requirements. In the ideal case, they should be odorless, colorless, light-resistant, cold-resistant and heat-resistant. In addition, it is expected that they are resistant to water, do not burn readily, have a low volatility and are not harmful to health. Furthermore, the preparation of plasticizer should be simple and, to meet ecological demands, should be carried out without producing waste materials such as byproducts which cannot be recycled and waste water containing pollutants .
  • Polyvinylchlo ⁇ de is relatively inflexible. In order for it to be compounded into flexible and rigid forms, plasticizers are used.
  • plasticizers are the esters of dicarboxylic and polycarboxylic acids with plasticizer alcohols, i.e., unbranched or branched primary alcohols having from about 6 to 13 carbon atoms, which can be used as individual compounds or as a mixture.
  • plasticizer alcohols i.e., unbranched or branched primary alcohols having from about 6 to 13 carbon atoms
  • the preparation of the esters has been carried out by the classical process of reacting the acids or acid anhydrides with an alcohol or a mixture of different alcohols m the presence of an acid, preferably sulfuric acid, as catalyst.
  • the alcohol component is usually used m excess. Attempts have been made to counter adverse color and odor of the reaction product by targeted selection of the acid used as catalyst, by mild reaction conditions and by complicated purification measures.
  • Plasticizers comprised of phthalates based on secondary alcohols produced by direct oxidation of hydrocarbons are described in "Synthesis of Phthalates Based on Secondary Alcohols Produced by Direct Oxidation of
  • the present invention provides a plasticizer which is comprised of a secondary alcohol alkoxylate ester of a dicarboxylic or polycarboxylic acid or anhydride.
  • the secondary alcohol from which the plasticizer is made may have from 4 to 10, preferably 6 to 9, carbon atoms m the main chain.
  • the plasticizers may contain at least about 0.5, preferably about 1 to about 5, most preferably about 1 to about 2, moles of alkoxide per mole of secondary alcohol.
  • Phthalic anhydride is the preferred material to make the secondary alcohol alkoxylate ester.
  • the preferred alkoxide is ethylene oxide.
  • the present invention also provides a plasticized polyvmylchloride composition comprising a polyvmylchloride polymer and the plasticizer described above .
  • the present invention also provides a process for making the plasticizer which comprises
  • Polyvmylchloride is a thermoplastic polymer which is produced by polymerization of the monomer vmylchlo ⁇ de, usually by free radical polymerization with a peroxide initiator. Polyvmylchloride is a hard plastic which is relatively inflexible. It is made softer and more flexible by the addition of plasticizers .
  • the plasticizers of the present invention are secondary alcohol alkoxylate esters of dicarboxylic or polycarboxylic acids or anhydrides .
  • the secondary alcohols from which the plasticizers are made generally contain from 4 to 10 carbon atoms, preferably 6 to 9 carbon atoms m the mam chain.
  • These materials may be made by starting with methane as the original feedstock.
  • Synthesis gas carbon monoxide and hydrogen
  • the paraffins thus produced may first be hydrotreated to remove olefins and oxygenates. Aromatics may also be removed by extraction or extractive distillation as needed. The desired paraffins are then separated into appropriate carbon number fractions by, for example, distillation .
  • hydrocarbons paraffins
  • Fischer-Tropsch hydrocarbon synthesis the preparation of hydrocarbons (paraffins) from a mixture of carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a suitable catalyst is known as the Fischer-Tropsch hydrocarbon synthesis.
  • Catalysts in this synthesis usually comprise one or more metals from groups VIII, IX and X of the Periodic
  • Table of Elements optionally with one or more promoters, and a carrier material.
  • iron, nickel, cobalt and ruthenium are well known catalytically active metals for such catalysts and can be used in the present process. Processes and catalysts for this reaction are described m U.S. Patent Nos . 7,105,706 and 6,740,683, both of which are incorporated herein by reference in their entirety.
  • this hydrocarbon fraction may be separated into one or more hydrocarbon fractions of paraffins. The separation may involve a distillation treatment, such as fractional distillation.
  • the catalyst and conditions may be selected such that the hydrocarbon fraction obtained comprises a C 4 to Ci 0 , preferably C 6 to C 9 , hydrocarbon fraction for use m the process of the present invention .
  • Secondary alcohols may be produced from the paraffins by either oxidizing the paraffins into secondary alcohols or by first halogenating, preferably brominating, the paraffins to form the corresponding mono-alkyl halide, followed by coupling with water in the presence of a metal oxide to produce the secondary alcohol.
  • secondary alcohols which may be made herein include isobutanol, 2- butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2- heptanol, 3-heptanol, 2-octanol, 3-octanol, 2-nonanol, 2- decanol, 4-decanol, other isomers of these alcohols, and mixtures thereof.
  • the paraffins may be oxidized in the presence of a weak acid, preferably boric acid.
  • a weak acid preferably boric acid.
  • Boric acids including orthoboric acid, metaboric acid, and boric oxide, will readily form esters with secondary alcohols. This is important to prevent further oxidation of the secondary alcohols .
  • Metaboric acid is preferred but may be formed from orthoboric acid by dehydration.
  • Metaboric acid and paraffins are introduced into an oxidation reaction along with oxidizing gas which may be oxygen, air, or an inert gas such as nitrogen with a low concentration of oxygen.
  • the rate of oxidation may be controlled by limiting the amount of oxygen absorbed.
  • the oxidation reaction may be carried out at a temperature from about 150 to about 175 0 C.
  • the reaction of the secondary alcohols with the metaboric acid to form metaborate esters of the secondary alcohols is reversible. Water may be removed during the oxidation to drive the reaction to produce more esters. The oxidation reaction mixture is then distilled to remove unreacted paraffins. The next step is hydrolysis of the borate esters to form secondary alcohols and boric acid. Water is added to the borate ester and the secondary alcohols may be separated by decantation of the aqueous boric acid phase. Residual organic acids, boric acid and organic esters are removed by saponification of the secondary alcohol reaction mixture with a base. The mixture is allowed to settle and the base (aqueous) layer is removed.
  • the secondary alcohols may then be alkoxylated by reacting them with an alkylene oxide such as ethylene oxide or propylene oxide in the presence of an appropriate alkoxylation catalyst.
  • the alkoxylation catalyst may be sodium hydroxide which is commonly used commercially for alkoxylatmg alcohols.
  • the secondary alcohols may be alkoxylated using a double metal cyanide catalyst as described in U.S. Patent No. 6,977,236 which is herein incorporated by reference in its entirety.
  • the secondary alcohols may also be alkoxylated using a lanthanum-based or a rare earth metal-based alkoxylation catalyst as described m U.S. Patent Nos .
  • Secondary alcohol alkoxylates could also be made by reacting an olefin with diethylene glycol or by reacting a haloalkane with mono-, di- or polyglycols. Secondary alcohol alkoxylates may be prepared by adding to the secondary alcohol or mixture of secondary alcohols a calculated amount, for example from about 0.1 percent by weight to about 0.6 percent by weight, of a strong base, typically an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide or potassium hydroxide, which serves as a catalyst for alkoxylation .
  • a strong base typically an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide or potassium hydroxide, which serves as a catalyst for alkoxylation .
  • An amount of alkylene oxide calculated to provide the desired number of moles of alkylene oxide per mole of secondary alcohol is then introduced and the resulting mixture is allowed to react until the alkylene oxide is consumed.
  • Suitable reaction temperatures range from about 120 to about 220 0 C.
  • the secondary alcohol alkoxylates of the present invention may be prepared by using a multi-metal cyanide catalyst as the alkoxylation catalyst.
  • the catalyst may be contacted with the secondary alcohol and then both may be contacted with the alkylene oxide reactant which may be introduced in gaseous form.
  • the reaction temperature may range from about 90 0 C to about 250 0 C and super atmospheric pressures may be used if it is desired to maintain the secondary alcohol substantially m the liquid state.
  • Narrow range secondary alcohol alkoxylates may be produced utilizing a soluble basic compound of elements in the lanthanum series as the alkoxylation catalyst.
  • Lanthanum phosphate is particularly useful.
  • the alkoxylation is carried out employing conventional reaction conditions such as those described above.
  • Suitable alkylene oxide reactants for use herein include an alkylene oxide (epoxide) reactant which comprises one or more vicinal alkylene oxides, particularly the lower alkylene oxides and more particularly those in the C 2 - 4 range.
  • alkylene oxides are represented by formula (I)
  • each of the R ⁇ , R7, R8 anc ⁇ R9 moieties is individually selected from the group consisting of hydrogen and alkyl moieties.
  • Reactants which comprise ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof are more preferred, particularly those which consist essentially of ethylene oxide and propylene oxide.
  • Alkylene oxide reactants consisting essentially of ethylene oxide are considered most preferred from the standpoint of commercial opportunities for the practice of alkoxylation processes, and also from the standpoint of the preparation of products having narrow-range ethylene oxide adduct distributions.
  • the alkoxylation procedure serves to introduce a desired average number of alkylene oxide units per mole of secondary alcohol alkoxylate.
  • treatment of a secondary alcohol mixture with 1.5 moles of alkylene oxide per mole of secondary alcohol serves to effect the alkoxylation of each alcohol molecule with an average of 1.5 alkylene oxide moieties per mole of secondary alcohol moiety, although a substantial proportion of secondary alcohol moieties will have become combined with more than 1.5 alkylene oxide moieties and an approximately equal proportion will have become combined with less than 1.5.
  • the amount of alkylene oxide added to the secondary alcohol may be at least about 0.5, preferably from about 1 to about 6, most preferably from about 1 to about 2, moles of alkylene oxide per mole of secondary alcohol. It is preferred that at least about 1 mole be utilized in order to minimize the amount of unalkoxylated secondary alcohol. It is preferred that no more than about 6 moles be used because adding alkylene oxide adds carbon to the molecule and if there are too many carbon atoms in the molecule, it will be too much of a hydrocarbon and its compatibility with the polar polyvmylchloride will be inadequate.
  • Polyvmylchloride is a very polar molecule. It is theorized by adding extra molecules of oxygen to the secondary alcohol m making the secondary alcohol alkoxylate, the polarity of the plasticizer is also increased, possibly improving its compatibility and efficacy with polyvmylchloride. It is preferred that the number of carbons in the secondary alcohol molecule from which the plasticizer is made be from 4 to 10, preferably from 6 to 9. It is also preferred that the number of moles of alkylene oxide added to the secondary alcohol range from about 1 to about 6.
  • Acids and anhydrides which are suitable as reactants for producing the plasticizers of the present invention are aliphatic and aromatic carboxylic and polycarboxylic acids.
  • the aliphatic carboxylic acids may be saturated or unsaturated and may contain at least four carbon atoms. Examples of such compounds are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, maleic acid, fumaric acid and maleic anhydride.
  • Examples of the aromatic carboxylic acids are, in particular, phthalic acid, trimellitic acid and phthalic anhydride.
  • the acids or anhydrides may be used either in pure form or m the form of mixtures .
  • the esterification of the secondary alcohol alkoxylates may be carried out in any conventional manner for the esterification of alcohols or alkoxylates thereof.
  • One such process involves reacting the acids or acid anhydrides with the secondary alcohol or a mixture of secondary alcohols in the presence of an acid, such as sulfuric acid, as the catalyst.
  • the alcohol will generally be used m excess.
  • Another method for the esterification is described in U.S. Patent No. 6,310,235, which is herein incorporated by reference in its entirety.
  • esterification catalysts including titanium or zirconium metals in finely divided form are used and the esterification is carried out in two stages.
  • the first stage is carried out without the addition of a catalyst at temperatures of above about 100 0 C and a monoester of the dicarboxylic acid is formed.
  • the esterification is completed. It is carried out in the presence of the above- described catalyst at temperatures which are above those employed in the first stage (which are above about 100 0 C and preferably above about 160 0 C) and go up to about 25O 0 C.
  • the esterification of the secondary alcohol alkoxylates generally takes place in two stages.
  • the following reaction scheme illustrates the esterification.
  • the first esterification is fast and the second esterification is slow and controlled by equilibrium.
  • the water generated may be continuously removed by distillation.
  • the phthalic anhydride and the secondary alcohol may be reacted at approximately the boiling point of the mixture, i.e., from about 100 to about 170 0 C, preferably from about 110 to about 14O 0 C for from about 0.5 to about 24 hours. This accomplishes the first esterification.
  • the second esterification then takes place in the presence of from about 0.05 to about 1 percent of sulfuric acid under the same conditions for a period of from about 0.5 to about 24 hours.
  • Sulfuric acid is the most active catalyst but others such as appropriate homogeneous and heterogeneous esterification catalysts, such as p-toluenesulfuric acid, polystyrene sulfuric acid ion-exchanged resins, organo-titanates and organo-tm compounds may also be used.
  • the reaction may be continued until the anhydride is completely consumed. This can be determined by analyzing the reaction mixture with, for example, Fourier Transform Infrared Spectroscopy (FTIR) .
  • FTIR Fourier Transform Infrared Spectroscopy
  • the ester may then be purified by washing it with a base, such as a solution of sodium carbonate, sufficient to neutralize the acid. It may next be washed with a brine solution and may finally then be washed with water.
  • the diester phase may be allowed to settle and may be separated and then dried with dessicant, such as sodium sulfate, calcium sulfate, silica gel, or molecular sieves. Finally, the diester may be distilled at an appropriate temperature to remove unreacted alcohol and monoester.
  • the preferred material for reaction with the secondary alcohols or their alkoxylates is phthalic anhydride.
  • the preferred secondary alcohols include are those discussed above .
  • Secondary alcohols and secondary alcohol ethoxylate phthalic anhydride esters were made according to the following procedure. 99 grams of phthalic anhydride were reacted with the secondary alcohol or secondary alcohol ethoxylate at a 3:2 molar ratio of the alcohol or ethoxylate. These were reacted at the boiling point, approximately 120- 130 0 C for 6 hours. 2.1 grams of sulfuric acid was added and the reaction was continued at the boiling point for 16 hours until FTIR showed that the anhydride was completely consumed. The mixture was washed with a solution of 10 percent sodium carbonate, then with a brine solution, and finally with water. The diester phase was separated and dried with sodium sulfate. The product was distilled at 40 mbar .
  • the temperature of distillation was 160 to 170 0 C for the 2-octanols and 3-octanols and 290 0 C for the 2-octanol ethoxylate and 320 0 C for the 2/3-octanol ethoxylate. Both ethoxylates had about 1.5 moles of ethylene oxide. The results are shown in Table 1.
  • the volatilities of some of the above products were determined by thermogravimetric analysis (TGA) . As shown in the following Table 2, the two phthalate esters made from secondary alcohol ethoxylates had a lower volatility than those from the non-ethoxylated secondary alcohols. The volatilities were also compared to those of the primary commercial plasticizer used for polyvinylchloride, di-octyl phthalate (DOP) . The phthalate esters have a lower volatility than the commercial DOP.
  • TGA thermogravimetric analysis
  • flexible polyvinylchloride formulations were made using the four secondary alcohol-derived plasticizers shown in Table 3 below and with two commercial plasticizers, DOP and di-isonyl phthalate (DINP) .
  • the formulation utilized is shown in the following Table 4. Table 3
  • the tensile strength, tensile elongation and modulus of the four secondary alcohol-derived samples are all higher than those of the two controls utilizing the commercial products (except for the tensile elongation of Sample B) .
  • the tensile strengths and tensile modulus of the secondary alcohol ethoxylate phthalate ester compositions (C and D) are higher than those of the secondary alcohol phthalate ester compositions (A and B) .
  • Modulus retention is an indication of migration of the plastrcizer (which is to be minimized for environmental and safety reasons) .
  • a modulus retention of close to 100 is desired - it is an indication of less migration.
  • Formulation D is by far the best in terms of low migration.
  • 2-ethyl-l-hexanol, secondary octanol mixture, and an ethoxylated secondary octanol mixture were all esterified according to the following procedure.
  • 99 grams of phthalic anhydride and sufficient secondary alcohol to have a 3:2 molar ratio of phthalic anhydride to alcohol were reacted at 115 0 C until all of the alcohol or ethoxylate was reacted.
  • 0.95 grams of sulfuric acid was added and the reaction carried on at 120 or 130 0 C until a good level of conversion was achieved. The levels of reaction were monitored by acid and metric titrations.
  • Chloroform was added to the product, it was washed with a 10 percent sodium carbonate aqueous solution to a pH of about 9.0-9.5, then washed with a 10 percent sodium chloride aqueous solution, and then finally washed with distilled water until there was no evidence of an emulsion.
  • the diester phase was separated and dried with sodium sulfate.
  • the product was distilled at 26.7 mbar and treated with silica gel to improve the color by making it lighter.
  • the tensile strength of the secondary alcohol ethoxylate ester is higher than the tensile strength of the secondary alcohol ester formulation and that of DINP but lower than the tensile strength of the DOP formulation.
  • the ethoxylate ester has the highest tensile elongation and the hardness is comparable to the formulations made with the commercial plasticizers .
  • the PVC formulations were evaluated in a heat aging test. The results are shown m the following table.
  • the secondary alcohol alkoxylate ester formulation passed the 75°C rating. It's aged tensile retention is comparable to the formulations made with the commercial plasticizers . The elongation retention is higher than any of the other formulations and the hardness retention is also the best (lower is better) .
  • Example 6 In the following experiments, the reaction kinetics of the esterification reactions of 2-ethyl hexanol and experimental samples I and II were determined. The results are shown in Tables 12 through 15.
  • the reactions for achieving second esterification were done using sulphuric acid as catalysts, at 0.2% based in reacting solution.
  • temperature of the reacting solution was raised until 120 or 13O 0 C and sulphuric acid was added. Advances of the reaction were monitored taking samples and determining the acid number of the reaction solution.
  • the kinetic data shows that catalyst Fascat 2001 used at the same conditions is less active than sulfuric acid for all three materials.
  • the data shows that increasing the temperature has a greater effect in the activation of the Fascat® 2001 catalyst than it has for the activation of sulfuric acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un plastifiant qui est constitué d'un ester alcoxylate d'alcool secondaire d'un acide ou d'un anhydride dicarboxylique ou polycarboxylique.
PCT/US2008/075912 2007-09-18 2008-09-11 Plastifiant WO2009039018A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US97325607P 2007-09-18 2007-09-18
US60/973,256 2007-09-18

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WO2009039018A1 true WO2009039018A1 (fr) 2009-03-26

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130210984A1 (en) * 2010-07-16 2013-08-15 Exxonmobil Chemical Patents Inc. Secondary Alcohols and Esters Made Therefrom
CN108250424A (zh) * 2016-12-29 2018-07-06 辽宁奥克化学股份有限公司 一种季戊四醇四(10-甲基十一烷酸)酯聚氧烷基醚、其制备方法及包含该醚的增塑剂
WO2019092366A1 (fr) * 2017-11-10 2019-05-16 Arkema France Alcool secondaire alcoxylé
US11339123B2 (en) 2017-11-10 2022-05-24 Arkema France Alkoxylated secondary alcohol sulfates
US11548904B2 (en) 2017-11-10 2023-01-10 Arkema France Secondary alcohol phosphate ester

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE20021356U1 (de) * 2000-12-18 2001-02-22 Basf Ag Polyvinylchlorid mit kernhydrierten Phthalat-Weichmachern
US20060062933A1 (en) * 2004-09-20 2006-03-23 Eastman Kodak Company Protective films containing compatible plasticizer compounds useful in polarizing plates for displays and their method of manufacture
EP1728821A1 (fr) * 2004-03-26 2006-12-06 Zeon Corporation Composition de melange maitre, composition de caoutchouc contenant le meme, et vulcanisat

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE20021356U1 (de) * 2000-12-18 2001-02-22 Basf Ag Polyvinylchlorid mit kernhydrierten Phthalat-Weichmachern
EP1728821A1 (fr) * 2004-03-26 2006-12-06 Zeon Corporation Composition de melange maitre, composition de caoutchouc contenant le meme, et vulcanisat
US20060062933A1 (en) * 2004-09-20 2006-03-23 Eastman Kodak Company Protective films containing compatible plasticizer compounds useful in polarizing plates for displays and their method of manufacture

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130210984A1 (en) * 2010-07-16 2013-08-15 Exxonmobil Chemical Patents Inc. Secondary Alcohols and Esters Made Therefrom
CN108250424A (zh) * 2016-12-29 2018-07-06 辽宁奥克化学股份有限公司 一种季戊四醇四(10-甲基十一烷酸)酯聚氧烷基醚、其制备方法及包含该醚的增塑剂
WO2019092366A1 (fr) * 2017-11-10 2019-05-16 Arkema France Alcool secondaire alcoxylé
FR3073519A1 (fr) * 2017-11-10 2019-05-17 Arkema France Alcool secondaire alcoxyle
US11339123B2 (en) 2017-11-10 2022-05-24 Arkema France Alkoxylated secondary alcohol sulfates
US11485695B2 (en) 2017-11-10 2022-11-01 Arkema France Alkoxylated secondary alcohol
US11548904B2 (en) 2017-11-10 2023-01-10 Arkema France Secondary alcohol phosphate ester
US11718581B2 (en) 2017-11-10 2023-08-08 Arkema France Alkoxylated secondary alcohol sulfates

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