WO2013050149A1 - Procédé d'extraction au solvant pour l'élimination de siloxanes cycliques (cyclométhicones) dans des produits à base de silicone - Google Patents

Procédé d'extraction au solvant pour l'élimination de siloxanes cycliques (cyclométhicones) dans des produits à base de silicone Download PDF

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Publication number
WO2013050149A1
WO2013050149A1 PCT/EP2012/004154 EP2012004154W WO2013050149A1 WO 2013050149 A1 WO2013050149 A1 WO 2013050149A1 EP 2012004154 W EP2012004154 W EP 2012004154W WO 2013050149 A1 WO2013050149 A1 WO 2013050149A1
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WIPO (PCT)
Prior art keywords
signifies
residues
residue
chl
polymerization
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PCT/EP2012/004154
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English (en)
Inventor
Pascal Steffanut
Geraldine Primazot
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Clariant International Ltd
Clariant Specialty Fine Chemicals (France)
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Application filed by Clariant International Ltd, Clariant Specialty Fine Chemicals (France) filed Critical Clariant International Ltd
Publication of WO2013050149A1 publication Critical patent/WO2013050149A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/32—Post-polymerisation treatment
    • C08G77/34—Purification

Definitions

  • Siloxanes are used in a wide range of industrial applications, such as resins, elastomers, fuel additives, automotive polishes, waxes, and antifoaming agents, as well as in personal care products and biomedical devices. Cyclic siloxanes are the building blocks for many of these silicones polymers.
  • decamethylcyclopentasiloxane (D 5 ) and dodecamethylcyclohexasiloxane (D 6 ) are collectively known as "volatile siloxanes”.
  • these siloxanes are characterized by the -Si(CH 3 ) 2 -0- repeating unit so called "D".
  • D 3 contains 3 of these units
  • D 4 contains 4 of these repeating units closed in a cycle
  • D 5 and D 6 respectively contain 5 and 6 of them.
  • INCI International Nomenclature of Cosmetic Ingredients
  • Blends of D 4 , D 5 and D& in variable proportions are named cyclomethicones.
  • Shampoos, conditioners and stick deodorants are the main cosmetic products in which siloxanes are used.
  • D 4 's main use is as a monomer in the manufacturing of polymeric silicones or as dry-cleaning solvent in closed system. It also has a minor but essential use in cosmetic applications.
  • D 5 is also used as a monomer in the manufacturing of polymeric silicones but is mainly present as solvent in cosmetic applications.
  • these cyclic siloxanes D , D 5 and D 6 are chosen for their low toxicity, lack of skin smoothness and ease of formulation. They bring benefits to personal care products like silkiness in conditioners, volume in lip gloss and ease of application to deodorants. .
  • siloxanes are used in many products including consumer products and have been so for many years, there is relatively little information available about their toxicity apart from the information provided by the Siloxane Research Program. However, siloxanes have generally been regarded as safe in consumer products, but new uses, e.g. in breast implants and focus on reproductive toxicity and possible endocrine disrupting effects have focussed attention on this group of substances.
  • D 4 is on Annex I to the Substance Directive (67/548/EEC) with a health classification as toxic to reproduction in category 3.
  • D 4 is also on the list of potential PBT and vPvB (very persistent and very bioaccumulative) substances selected on the basis of screening criteria in the EU (DEPA 2003).
  • PBT and vPvB very persistent and very bioaccumulative substances selected on the basis of screening criteria in the EU (DEPA 2003).
  • Subacute and subchronic toxicity studies show that the liver is the main target organ for D 4 which also induces hepatocellular enzymes. This enzyme induction contributes to the elimination of the substance from the tissues.
  • Primary target organ for D 5 exposure by inhalation is the lung.
  • D 5 has a similar enzyme induction profile as D 4 .
  • the critical effects of the siloxanes are impaired fertility (D ) and potential carcinogenic effects (uterine tumours in females) (D 5 ).
  • the present invention relates to a process for the removal of cyclic siloxane residual monomers from a polysiloxane oil and also to a recycling process that involves such a process.
  • the invention describes a method for stripping and later recycling residual cyclic siloxane monomer from a polysiloxane type polymer after the polymerization or the polycondensation step leading to this polysiloxane.
  • This method describes the use of specific solvents able, first, to be dissolved in the reaction mixture and in a second step, to strip the residual cyclic siloxanes from the polymer where they are brought into.
  • These solvents are capable of forming azeotropic mixtures with the impurities that can then easily be removed by azeotropic distillation.
  • the solvents are organic solvents from the family of alkyl acetals of glyoxal. These solvents are produced by acetalization of glyoxal by the corresponding alcohol.
  • the invention is based on the surprising observation that the addition of only low amounts of these solvents followed by a mild distillation step facilitates the removal of the cyclic siloxanes still present in the polysiloxane oil after the polymerization step or introduced on purpose to the polysiloxane oil or reformed by the back-biting reaction during the polymer ageing. Consequently, the purification process of polysiloxane oils becomes more flexible, less energy-consuming, less expensive and leads to final commercial products having cyclic siloxane impurities largely under the classification requirement of 1000 ppm.
  • Ri represents the same or different monovalent Ci to C-
  • R' signifies a bivalent hydrocarbon radical with 1 to 8 carbon atoms
  • e signifies 0 or 1
  • R" signifies hydrogen or a monovalent
  • Ci-2o-hydrocarbon radical represents a residue of the following formula (h)
  • R'-(NH-CH 2 CH 2 )eNH-R" (h) represents a residue of the following formula (i)
  • R' signifies a bivalent hydrocarbon radical with 1 to 8 carbon atoms
  • e signifies 0 or 1
  • R" signifies hydrogen or a monovalent
  • Ci-20-hydrocarbon radical and R'" represents a residue of the following formula (j)
  • R 0 signifies hydrogen or a C -2 o-hydrocarbon radical
  • u signifies an integer not exceeding 50
  • v signifies 0 or an integer not exceeding 50.
  • R 2 represents Ri and/or OH or ORi
  • m has an average value of from 1 to 500 and
  • n has an average value of from 0 to 1500.
  • C C ⁇ hydrocarbon residues Ri include alkyl residues, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert.-butyl, n-pentyl, neo-pentyl, tert.-pentyl residues, hexyl residues, heptyl residues, such as n-heptyl residue, octyl residues and iso-octyl residues, such as 2,2,4-trimethylpentyl residue, nonyl residues, such as n-nonyl residue, decyl residues, such as n-decyl residue, dodecyl residues, such as n-dodecyl residue, cycloalkyi residues, such as cyclopentyl, cyclohexyl, cycloheptyl residues and methylcyclohexyl
  • alkenyl residues such as vinyl, allyl, 5-hexen-1-yl,
  • E-4-hexen-l-yl, Z-4-hexen-1-yl, 2-(3-cyclohexenyl)ethyl and cyclododeca-4,8- dienyl residues Preferred residues with an aliphatic double bond are the vinyl, allyl and 5-hexen-1-yl residues.
  • C 1 -C18 hydrocarbon residues substituted with fluorine, chlorine or bromine atoms include the 3,3,3-trifluoro-n-propyl residue, the
  • amino containing residues R1 examples include amino-propyl amino-ethyl
  • Ci-Ci 8 hydrocarbon residues R 2 are saturated linear or branched- chain or cyclic alkyl residues, such as methyl and ethyl residues as well as propyl, butyl, pentyl, hexyl, 2-methylpropyl, cyclohexyl and octadecyl residues, alkyl residues bonded through an oxygen atom or hydroxy residue. All the examples stated for alkyl residues also apply to alkoxy residues.
  • amino containing residues R2 examples include amino-propyl amino-ethyl
  • R3 and R4 may be equal or different from each other and stay for a Ci to Cis
  • C1-C18 hydrocarbon residues R3 and R4 include alkyl residues, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert.-butyl, n-pentyl, neo-pentyl, tert.-pentyl residues or hexyl residues.
  • alkyl residues such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert.-butyl, n-pentyl, neo-pentyl, tert.-pentyl residues or hexyl residues.
  • alkyl residues such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert.-butyl
  • R3 and R4 stay for a Ci to Cis linear hydrocarbon residue
  • R3 and R4 are equal and stay for a Ci to C 2 hydrocarbon residue.
  • the polyorganosiloxanes of the formula (I) or (II) that are purified by stripping may be characterized by typical parameters which are customary per se, for example by their average molecular weight and the content of amine nitrogen, and also by their viscosity.
  • the average molecular weight of the polyorganosiloxanes of the formula (I) or (II) can vary in broad ranges.
  • the average molecular weight of the included aminopolyorganosiloxanes and their amine value can vary in broad ranges
  • the polyorganosiloxanes of the formula (I) or (II) advantageously have a viscosity in the range of from 30 to 30,000, principally 30 to 20,000, preferably 30 to 10000 cP (Brookfield rotational viscometer RV, spindle No. 5, at 20 °C).
  • the polyorganosiloxanes of the formula (I) or (II) having an amine functionality may have an amine number in the range from 0.05 to 5.
  • the amine number (the concentration of amine in mmol per gram also called AZ in our examples) is determined by a potentiometric titration comprising neutralization of amine functions by perchloric acid in an acid environment.
  • Protocol In a 150 ml beaker, between 0.2 g and 1 g of the amino-siloxane oil are weighed. 50 ml of THF are added to solubilize the oil and 50 ml of acetic acid are also added to make an acid environment. The mixture is stirred for
  • the polyorganosiloxanes of the formula (I) or (II) may be produced in a manner known per se or analogously to known methods, for example by hydrosilylation reaction on Si-bonded hydrogen atoms, by aminoalkylation of polysiloxanes containing reactive Si-bonded hydrogen atoms, or principally by copolymerization of various functional silanes with corresponding nonionogenic silanes or
  • the present invention is in still another respect a process for recovering a cyclic siloxane monomer from a crude reaction solution removing a mixture of vaporized solvent and cyclic siloxane monomer and then separating the cyclic siloxane from the solvent.
  • This process is a cost-effective, efficient method for recovering the cyclic siloxane monomers from a crude reaction solution. Because of this, subsequent high temperature distillation steps can be reduced or avoided.
  • the process can also produce polysiloxane polymer of formula (I) and (II) having low levels of impurities, and in particular low levels of low molecular weights siloxanes.
  • the present process starts with a crude reaction solution containing the
  • polysiloxane polymer (as described more fully below), a solvent and reaction by- products of cyclic siloxane types, the nature of which will depend on the particular process that is used.
  • solvent is determined by the particular starting monomer
  • Particularely suitable solvents from the acetal family include tetraethoxyethane (so-called TEE, Highsolv ® E99 from Clariant) or tetramethoxyethane (so-called TME, Highsolv P99 also from Clariant) but should not be limited to both examples.
  • Preferred solvents from the acetal family have boiling temperatures (at
  • atmospheric pressure between 130 °C and 200 °C, may be substantially immiscible or miscible in water.
  • Especially preferred solvents from the acetal family are less volatile than water, and are thus allowing first the easy removal from water from the reaction mixture.
  • Two especially preferred solvents are TME and TEE.
  • the crude reaction solution is heated to drive off solvent.
  • the solvent is removed, the cyclic siloxane monomer is removed together with.
  • the solvent is completely removed from the polymer mixture and preferably the amount of solvent, in weight per reaction mixture weight, needed to bring the cyclic siloxanes under the 1000 ppm limit is between 0.25 % to 15 % by weight of solvent, preferably between 1 % to 10 % by weight of solvent.
  • linear and unfunctionalised polysiloxane oils are commercially purchased and analysed by GC to determine their initial contents in cyclic impurities.
  • linear and PEG or alkyl functionalised polysiloxane oils are commercially purchased and analysed by GC to determine their initial contents in cyclic impurities.
  • the amino functionalised oils are manufactured following the two examples S1 and S2 described herein-below and analyzed to determine their initial content in cyclic impurities.
  • a batch made following the invention uses a stirred reactor that contains a mixture of poylsiloxane polymeric material and starting material like cyclic siloxanes as residual impurities (introduced on purpose or present from the synthetical process).
  • a short distillation column as outlet is provided for removing volatilized solvent and impurities from the reactor.
  • the liquid polysiloxane/solvent mixture liquid is stirred using an agitator blade, and heated to the desired volatilization temperature. If desired, a slight vacuum is provided in the head space.
  • the solvent/impurities mixture is then distillate until completion (no distillate flow visible). The analysis if the cyclic siloxanes in the polysiloxane oil are performed at the end of the distillate and compared to the initial value.
  • the amino functionalised silanes are preferably copolymerized with cyclic siloxanes, for example hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
  • the copolymerization may be carried out in a manner known per se, principally by reaction of the reactants at moderate or elevated temperature, optionally under reduced pressure, in particular at temperatures in the range 15 to 180 °C, optionally in the presence of a catalyst and if desired with use of end-blocking groups, for example with hexamethyldisiloxane.
  • alkali metal or ammonium compounds for example alkali metal or ammonium silanolates (for example potassium silanolate or tetramethylammonium silanolate) or alkali metal hydroxides or ammonium hydroxides, which form the corresponding silanolates in situ with the respective silanes, or else alkali metal hydroxides, carbonates or bicarbonates (for example potassium hydroxide, sodium hydroxide or sodium bicarbonate) or further benzyltrimethylammonium hydroxide or tetrabutylammonium hydroxide.
  • acids in particular formic acid, acetic acid, sulphuric acid, acidic ion exchangers or trifluoromethanesulphonic acid
  • alkali metal or ammonium compounds for example alkali metal or ammonium silanolates (for example potassium silanolate or tetramethylammonium silanolate) or alkali metal hydroxides or ammonium hydroxides, which form the corresponding si
  • polydimethylsiloxane S(1) having an amine number of about 0.385 are obtained.
  • the functional groups may be randomly distributed or may be terminal or may be grouped as in block polymers or may also accumulate towards the extremities of the linear chains.
  • D x stands for the cyclic siloxane introduced and/or followed by analytical method.
  • the cyclic siloxanes may be present by incidence (product degradation) or have been introduced on purpose (monomer for the polymerization process).
  • [Dx] before stands for the concentration in (ppm) of the cyclic siloxane introduced and/or followed by analytical method before the treatment with stripping solvents.
  • [Dx] after stands for the concentration in (ppm) of the cyclic siloxane introduced and/or followed by analytical method after the treatment with stripping solvents.
  • [AZ] in mmol/g stands for the concentration in amine functionality evaluated by acidimetric dosage.
  • A is a typical polysiloxane oil terminated with OH groups and originally containing 40200 ppm of D4 (introduced on purpose). AZ number is zero mmol/g. This product is stripped with TME and after the treatment, the residual amount of D4 is 930 ppm. A' is the same polysiloxane oil containing D5 (introduced on purpose) and stripped this time by TEE. The residual amount of D5 is 780 ppm.
  • cyclic impurities are removed from the polysiloxane oils at temperatures below the boiling point of the cyclic impurities and at atmospheric pressure.
  • This process is easy to apply and doesn't require the use of aromatic and/or toxic solvents.
  • the acetals used for the stripping process have no influence on the groups present on the silicone backbone and don't change the final coloration of the purified oils.
  • the obtained products are found after analysis under the limit of 1000 ppm of D 4 impurity.
  • the stripping process described in this invention is preventing the future toxicological classification of the silicone oils by removing the most problematic cyclic impurities from the product.

Abstract

La présente invention porte sur un procédé pour l'élimination de monomères siloxanes cycliques résiduels d'une huile de polysiloxane préparée par polymérisation ou par polycondensation de tels monomères siloxanes cycliques, consistant à ajouter, dans une première étape, un solvant organique au mélange de polymérisation ou de polycondensation et dans une seconde étape enlever les monomères résiduels conjointement avec le solvant organique par distillation azéotropique.
PCT/EP2012/004154 2011-10-05 2012-10-04 Procédé d'extraction au solvant pour l'élimination de siloxanes cycliques (cyclométhicones) dans des produits à base de silicone WO2013050149A1 (fr)

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EP11008050.4 2011-10-05
EP11008050 2011-10-05

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2868672A1 (fr) * 2013-11-01 2015-05-06 Nissin Chemical Industry Co., Ltd. Poudre de résine de copolymère à base de silicone, son procédé de fabrication et produits cosmétiques
WO2019122230A1 (fr) 2017-12-22 2019-06-27 Friedrich-Schiller-Universität Jena Électrolyte acétalique
EP3744753A1 (fr) 2019-05-28 2020-12-02 Evonik Operations GmbH Procédé de purification d'acétoxysiloxanes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5045621A (en) * 1988-09-30 1991-09-03 Toray Silicone Company, Ltd. Method for manufacturing an organopolysiloxane in which a polymerizable functional group is present at one end
EP0652244A2 (fr) * 1993-11-10 1995-05-10 Shin-Etsu Chemical Co., Ltd. Polysiloxane à chaîne linéaire et procédé pour sa préparation
US5492647A (en) * 1995-05-08 1996-02-20 Dow Corning Corporation Octamethylcyclotetrasiloxane azeotropes
JPH11349684A (ja) * 1998-06-02 1999-12-21 Chisso Corp 高純度の片末端ラジカル重合性官能基含有オルガノポリシロキサンの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5045621A (en) * 1988-09-30 1991-09-03 Toray Silicone Company, Ltd. Method for manufacturing an organopolysiloxane in which a polymerizable functional group is present at one end
EP0652244A2 (fr) * 1993-11-10 1995-05-10 Shin-Etsu Chemical Co., Ltd. Polysiloxane à chaîne linéaire et procédé pour sa préparation
US5492647A (en) * 1995-05-08 1996-02-20 Dow Corning Corporation Octamethylcyclotetrasiloxane azeotropes
JPH11349684A (ja) * 1998-06-02 1999-12-21 Chisso Corp 高純度の片末端ラジカル重合性官能基含有オルガノポリシロキサンの製造方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2868672A1 (fr) * 2013-11-01 2015-05-06 Nissin Chemical Industry Co., Ltd. Poudre de résine de copolymère à base de silicone, son procédé de fabrication et produits cosmétiques
CN104606075A (zh) * 2013-11-01 2015-05-13 日信化学工业株式会社 基于有机硅的共聚物树脂粉末、制备方法和化妆品
EP3059262A1 (fr) * 2013-11-01 2016-08-24 Nissin Chemical Industry Co., Ltd. Poudre de résine de copolymère à base de silicone et procédé de fabrication
US9980885B2 (en) 2013-11-01 2018-05-29 Nissin Chemical Industry Co. Ltd. Silicone-based copolymer resin powder, making method, and cosmetics
CN104606075B (zh) * 2013-11-01 2019-04-09 日信化学工业株式会社 基于有机硅的共聚物树脂粉末、制备方法和化妆品
WO2019122230A1 (fr) 2017-12-22 2019-06-27 Friedrich-Schiller-Universität Jena Électrolyte acétalique
DE102017012021A1 (de) 2017-12-22 2019-06-27 Friedrich-Schiller-Universität Jena Acetalischer Elektrolyt
EP3744753A1 (fr) 2019-05-28 2020-12-02 Evonik Operations GmbH Procédé de purification d'acétoxysiloxanes
US11472822B2 (en) 2019-05-28 2022-10-18 Evonik Operations Gmbh Process for purifying acetoxysiloxanes

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