WO2015079451A1 - Alkylphenol ethoxylates and a process for preparing the same - Google Patents

Alkylphenol ethoxylates and a process for preparing the same Download PDF

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Publication number
WO2015079451A1
WO2015079451A1 PCT/IN2014/000046 IN2014000046W WO2015079451A1 WO 2015079451 A1 WO2015079451 A1 WO 2015079451A1 IN 2014000046 W IN2014000046 W IN 2014000046W WO 2015079451 A1 WO2015079451 A1 WO 2015079451A1
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WIPO (PCT)
Prior art keywords
formula
alkylphenol
group
octene
ethoxylate
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Application number
PCT/IN2014/000046
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English (en)
French (fr)
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WO2015079451A8 (en
Inventor
Rajshekhar GHOSH
Ashis Ranjan BANDYOPADHAYA
Raskshvir JSRA
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Reliance Industries Limited
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Application filed by Reliance Industries Limited filed Critical Reliance Industries Limited
Publication of WO2015079451A1 publication Critical patent/WO2015079451A1/en
Publication of WO2015079451A8 publication Critical patent/WO2015079451A8/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups

Definitions

  • the present disclosure relates to alkylphenol ethoxylates and a process for preparing the same.
  • Alkylphenol ethoxylates are non-ionic surfactants obtained by ethoxylation of alkylphenols. They are used as emulsifiers for emulsion polymerization, as detergents and in pesticides.
  • Ethoxylates are typically produced by using a base catalyst such as sodium hydroxide and potassium hydroxide.
  • a base catalyst such as sodium hydroxide and potassium hydroxide.
  • US20080132728 discloses a continuous process for the production of alkylphenol ethoxylates from an alkylphenol in the presence of a double metal cyanide (“DMC”) catalyst.
  • DMC double metal cyanide
  • NPE nonylphenol ethoxylates
  • OPE octylphenol ethoxylates
  • NPEs represent approximately 80% to 85% of the volume of APEs. NPEs, are used in a wide variety of applications including detergents, cleaners, degreasers, dry cleaning aids, petroleum dispersants, emulsifiers, defoaming agent, wetting agents and adhesives.
  • NPEs are hydrophilic ("water-attracting”) at one end of the molecule and hydrophobic ("water-avoiding”) at the opposite end.
  • the hydrophilic "head” attracts water and the hydrophobic "tail” attracts poorly soluble substances, such as oils and greases. This ability to simultaneously attract water and hydrophobic substances makes NPEs useful in the surfactant applications.
  • NPE Nonoxynol-9
  • NPEs Nonylphenol ethoxylates
  • NP Nonylphenol
  • NPEs also include alcohol ethoxylates and glucose-based carbohydrate derivatives such as alkylpolyglucoside, glucamides, and glucamine oxides.
  • R and R' are independently C 3 to C 12 straight or branched alkyl group;
  • R" is H or Ci-C 9> the sum of carbon atoms of R, R' and R" being equal to 15; and
  • n being a whole number between 1 and 100.
  • the HLB value of said ethoxylate ranges between 4 and 20.
  • the CMC value of said ethoxylate at 25°C ranges between 1 and 100 ppm.
  • the surface tension of said ethoxylate at 1% actives and 25°C ranges between 10 and 50 dynes/cm.
  • the cloud point of said ethoxylate at 1 wt % actives aqueous solution is >60
  • R and R' are independently C 3 to C 12 straight or branched alkyl group; R" is H or Ci-C 9) the sum of carbon atoms of R, R' and R" being equal tol5; and n being a whole number between 1 and 100, said process comprising the following steps:
  • C 8 stream comprising at least two octenes selected from the group consisting of 1-octene, 2-octene, 3-octene and 4-octene to dimerization or oligomarization to obtain Ci 6 -olefin;
  • R and R' are independently C 3 to C 12 straight or branched alkyl group;
  • R" is H or CrC 9 and the sum of carbon atoms of R, R' and R" being equal tol 5, and
  • the toxicity of the C 16 Alkylphenol of formula II is lesser by a factor of at least 20 as compared to nonylphenol.
  • C 16 alkylphenol of formula II is selected from the group consisting of
  • the dimerization or oligomarization is carried out in the presence of a zeolite catalyst having Si/Al ratio ranging between 12 and 80 in their H+ form.
  • the dimerization or oligomarization is carried out at a temperature ranging between 100 and 127 °C
  • the alkylation is carried out at a temperature ranging between 75 and 130 °C in the presence of a catalyst selected from the group consisting of macroreticular resins made of styrene divinylbenzene copolymers having HSO 3 functional group with a concentration of acid sites ranging between 4.5 and 5.5 eq/ g and which can tolerate operating temperature of > 125 °C in their dry form.
  • a catalyst selected from the group consisting of macroreticular resins made of styrene divinylbenzene copolymers having HSO 3 functional group with a concentration of acid sites ranging between 4.5 and 5.5 eq/ g and which can tolerate operating temperature of > 125 °C in their dry form.
  • said C 8 stream is a by-product stream containing at least two octenes obtained from a plant selected from the group consisting of a petrochemical plant and a polymer plant.
  • Figure 1 illustrates 13C NMR spectrum of alkylphenol
  • Figure 2 illustrates Distortionless Enhancement by Polarization Transfer (DEPT) spectra of alkylphenol
  • Figure 3 illustrates 13C NMR spectrum of grade 2 sample (Ci 6 alkylphenol ethoxylate) of the present disclosure.
  • hexadecylphenol The family of hexadecylphenol is less known and barely studied. Only one isomer, namely 4-hexadecylphenol (CAS NO. 2589-78-8) of this family has been studied. In 4-hexadecylphenol, hexadecyl unit is connected to the phenol by the first carbon of the alkyl chain.
  • the other known and commercially available alkylphenols are octylphenol, nonylphenol and dodecylphenol ethoxylates.
  • the present disclosure provides alkylphenol ethoxylates which are highly effective as a surfactant at low concentration compared to conventional ethoxylates such as nonylphenyl ethoxylate.
  • the corresponding alkylphenol is less toxic as compared to the conventional nonylphenol.
  • the present disclosure particularly provides hitherto unknown alkylphenol ethoxylates having a branched C; 6 alkyl unit.
  • R and R' are independently C 3 to 0 ]2 straight or branched alkyl group
  • R" is H or C r C 9; the sum of carbon atoms of R, R' and R" being equal tol5; and n being a whole number between 1 and 100.
  • Ci 6 alkylphenol ethoxylate is synthesized from a mixture of Ci 6 olefins where the double bond is present in an internal position and not using a terminal or alpha olefin.
  • octene rich stream is used to synthesize a mixture of C )6 olefins with double bond at an internal position and not an alpha olefin.
  • a mixture of octenes is converted into Ci 6 olefin having a double bond at an internal position.
  • phenol is alkylated with the obtained C
  • alkylphenol is ethoxylated to get alkylphenol ethoxylates.
  • the generated alkylphenol ethoxylates are found to exhibit enhanced surfactant properties.
  • the surfactant properties are measured and compared against nonylphenol ethoxylates.
  • CMC critical micellar concentration
  • each molecule of the surfactant of the present disclosure has low concentration of phenol unit as compared to the nonylphenol analogue, it is expected to show lower toxicity as compared to the nonylphenol counterparts.
  • the C i6 alkylphenol ethoxylates of the present disclosure are characterized by the following properties:
  • - HLB value ranging between 4 and 20; - CMC value: ranging between 10 and 25 ppm at 25°C;
  • the toxicity of the C 16 Alkylphenol is lesser by a factor of at least 20 as compared to nonylphenol.
  • novel alkylphenol ethoxylates are synthesized from an octene rich by-product stream obtained from a petrochemical plant or a polymer plant.
  • the stream used is devoid of octylphenol and nonylphenol.
  • R and R' are independently C 3 to C 12 straight or branched alkyl group; R" is H or Q-C ⁇ the sum of carbon atoms of R, R' and R" being equal to 15; and n being a whole number between 1 and 100, involves the following steps:
  • a C 8 stream comprising at least two octenes selected from the group consisting of 1 - octene, 2-octene, 3-octene and 4-octene is subjected to dimerization or oligomarization to obtain C ⁇ -olefin.
  • the dimerization or oligomarization is carried out in the presence of a zeolite catalyst having Si/Al ratio ranging between 12 and 80 in their H+ form, and at a temperature ranging between 100 0 C and 127°C.
  • zeolites examples include but are not limited to CBV712, CBV720, CBV760 and CBV780.
  • R and R' are independently C 3 to C ⁇ 2 straight or branched alkyl group; R" is H or C1-C9 and the sum of carbon atoms of R, R' and R" being equal tol5.
  • the alkylation is carried out at a temperature ranging between 75 and 130 °C in the presence of a catalyst selected from the group consisting of macroreticular resins made of styrene divinylbenzene copolymers having HSO 3 functional group with a concentration of acid sites ranging between 4.5 and 5.5 eq/Kg and which can tolerate operating temperature of > 125 °C in their dry form.
  • a catalyst selected from the group consisting of macroreticular resins made of styrene divinylbenzene copolymers having HSO 3 functional group with a concentration of acid sites ranging between 4.5 and 5.5 eq/Kg and which can tolerate operating temperature of > 125 °C in their dry form.
  • catalyst include but are not limited to Amberlyst catalysts in the dry form such as Amberlyst 15dry, Amberlyst 35dry and Amberlyst 36dry.
  • the alkylphenol is characterized by various techniques including but not limited to 13C NMR and DEPT. ( Figure 1 and figure 2)
  • the para alkylphenol in this case can be between 99% - 75% and the remaining being ortho alkyl phenol.
  • the alkyl section of the alkylphenol consists of C, CH and CH 2 units and thus leads to the structures represented below.
  • C 16 alkylphenol of formula II includes but is not limited to
  • C ! 6 alkylphenol ethoxylates of formula I are obtained by ethoxylating the Cj 6 alkylphenols using ethylene oxide.
  • Grade 1 contains 6.5 moles of EO.
  • Grade 2 contains 13.5 moles of EO (RIL AP 13.5 EO)
  • Grade 3 contains 18.8 moles of EO (RIL AP 18.8 EO)
  • APEOs are widely used in cleaning products and as industrial process aids.
  • the spectrum of applications range from dispersing agents in paper and pulp production to emulsifying agents in latex paints and pesticides formulations, flotation agents, industrial cleaners (metal surfaces, textile processing, and food industry), cold cleaners for cars, and household cleaners.
  • the majority of APEOs are used in aqueous solutions; therefore, they are discharged into municipal and industrial waste waters which enter sewage treatment plants. During the different steps of sewage treatment a complex biodegradation process of APEOs takes place, leading to the formation of several biorefractory metabolites.
  • the degradation products 4-alkylphenol diethoxylate (AP2EO), 4-alkylphenol monoethoxylate (AP1EO), [(4- alkylphenoxy)ethoxy] acetic acid (AP2EC), (4-alkylphenoxy)acetic acid (API EC), and 4-alkylphenols formed by shortening of the hydrophilic ethoxy chain are persistent, strongly lipophilic, and more toxic than the parent compounds.
  • Acute toxicity data of NP to aquatic organisms range from 0.18 to 5.0 mg L "1 dependent on species and experimental conditions. In comparison, toxicities of NP9/10EO to fish are 5.0-1 1.0 mg L "1 . The release of these highly toxic compounds via secondary effluents or sewage sludge could be harmful to the aquatic or terrestrial environment. (Thiele et al, Chem. Rev. 1997, 97, 3247-3272)
  • the toxicity of the alkylphenol of the present disclosure was measured and compared against commercially available nonylphenol.
  • the protocol used was as per OECD 203 guidelines for "Acute fish Toxicity - Fixed Dose procedure".
  • OECD 203 the total length of the fish recommended was 2.0 ⁇ 1.0 cm. All the fish obtained were allowed to acclimatize to the experimental laboratory conditions for a period of 12 days before they were used for the testing. The light cycle was of 12 to 16 hours.
  • Temperature for the appropriate species in the tank water was as per the guidelines and the oxygen concentration was at least 80 % of air saturation value.
  • C16 Alkyl Phenol at 100 mg/1 the mortality observed was less than 50 percent, within 24 hours, at 50 mg/1 dose there was one mortality within 48 hours. No mortality was observed amongst the animals administered by the dose lOmg/1 to 0.1 mg/1 even after 96 hours. Under similar test conditions in the Nonylphenol sample, at dosage level of 100 mg/1 to 5 mg /l in the sample 1 mortality observed was hundred percent within the first 24 hours. The mortality rate of Nonyl Phenol was statistically significant when compared to C16 Alkyl Phenol.
  • the oral LC 50 of the product C16 Alkyl Phenol in fish is found to be more than 100 mg/1. This indicates that the C16 alkylphenol is significantly less toxic as compared to nonylphenol by a factor of 20 or higher.
  • the present disclosure provides novel Ci 6 alkylphenol ethoxylates having enhanced surfactant properties and their corresponding Alkylphenol was found to have significantly lower toxicity.
  • Ci6 alkylphenol ethoxylates of the present disclosure can be synthesized from a mixture of octenes rather than pure alpha-olefin.
  • - C 16 alkylphenol ethoxylates of the present disclosure can be synthesized from a side or by-product octene rich stream of polymer or petrochemical plant.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/IN2014/000046 2013-11-29 2014-01-22 Alkylphenol ethoxylates and a process for preparing the same WO2015079451A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022086266A1 (ko) * 2020-10-22 2022-04-28 한국화학연구원 세정제 조성물
WO2022171871A1 (fr) * 2021-02-15 2022-08-18 Global Bioenergies Alkylphénols, leurs procédés de préparation et leurs utilisations

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039273A1 (en) * 1997-03-07 1998-09-11 Aquatrols Corporation Of America Inc. Fully compatible surfactant-impregnated water-soluble fertilizer; concentrate; and use
US20080132728A1 (en) * 2006-12-01 2008-06-05 Mcdaniel Kenneth G Continuous processes for the production of alkylphenol ethoxylates
CN103172485A (zh) * 2011-12-20 2013-06-26 Ifp新能源公司 使乙烯二聚成丁烯及丁烯二聚成辛烯来制备辛烯的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039273A1 (en) * 1997-03-07 1998-09-11 Aquatrols Corporation Of America Inc. Fully compatible surfactant-impregnated water-soluble fertilizer; concentrate; and use
US20080132728A1 (en) * 2006-12-01 2008-06-05 Mcdaniel Kenneth G Continuous processes for the production of alkylphenol ethoxylates
CN103172485A (zh) * 2011-12-20 2013-06-26 Ifp新能源公司 使乙烯二聚成丁烯及丁烯二聚成辛烯来制备辛烯的方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022086266A1 (ko) * 2020-10-22 2022-04-28 한국화학연구원 세정제 조성물
WO2022171871A1 (fr) * 2021-02-15 2022-08-18 Global Bioenergies Alkylphénols, leurs procédés de préparation et leurs utilisations

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