GB2215729A - Polyorganosiloxane emulsions - Google Patents
Polyorganosiloxane emulsions Download PDFInfo
- Publication number
- GB2215729A GB2215729A GB8828978A GB8828978A GB2215729A GB 2215729 A GB2215729 A GB 2215729A GB 8828978 A GB8828978 A GB 8828978A GB 8828978 A GB8828978 A GB 8828978A GB 2215729 A GB2215729 A GB 2215729A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polyorganosiloxane
- water
- ethoxylated
- group
- concentrate
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000000839 emulsion Substances 0.000 title claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000004094 surface-active agent Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000012141 concentrate Substances 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 20
- -1 alkyl phenols Chemical class 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000005372 silanol group Chemical group 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims 2
- 229910018540 Si C Inorganic materials 0.000 claims 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims 1
- 239000007764 o/w emulsion Substances 0.000 claims 1
- 239000004530 micro-emulsion Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical class CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical class CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical class CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- 241000316263 Asperoteuthis lui Species 0.000 description 1
- PJINIBMAHRTKNZ-UHFFFAOYSA-N CC(CCCCCCCCOCCCCCCCCC(C)(C)C)(C)C Chemical compound CC(CCCCCCCCOCCCCCCCCC(C)(C)C)(C)C PJINIBMAHRTKNZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000287118 Parus Species 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical class CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical class CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Colloid Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cosmetics (AREA)
Description
Z_ 1 "S 7 '2- 9 POLYORGANOSILOXANE EMULSIONS his inventici, relates to
aqueous emulsions oi poiyorganosiloxanes and is concerned in particular with a raethod f oi preparinL such emulsions whereli, thL. a% L-raz Lparticle size of the polyorganosiloxane in. the emulsified form is less than about 0.3 micron. The invention also relates to a concentrate comprising a polyorganosiloxane oil and a surfactant which is useful in the above-mentioned process.
Emulsions of polyorganosiloxanes have been known for many years and are widely employed in applications such as defoaming agents, the treatment of textiles to provide water repellency or soft handle, as mould release agents and in personal care products, for example hand lotions. Typically such emulsions have comprised a polyorganosil- oxane, water and one or more surface active aLents and heve possussed a milky, opaque appearar-ce which resul-cs from the particle size of the oil phase and the difference in refractive indices of the oil and aqueous phases. The relatively large particle size has also rendered the emulsions susceptible to separation of the oil and water phases during storage. It is possible to render the emulsion translucent and improve its-storage stability by cLiploying a large proportion of water relativc. to the oil phase. Such a technique, however, involves storing and transporting large volumes of water and is thus cornsn.ercially unattractive.
It has been disclosed in G.B. Patent Specification 1 441 4-04 that transparent emulsions (the so-called microemulsions) of organosilicon compounds can be prepared if there is employed a surface active agent which comprises in specified propcrtioi is (a) at least one n-alkyl Troncether of 2 a polyethylene glycol, (b) a sodium dialkylsulphosuccinate, (c) at least one acid selected fror-r. oleic, linoleic, 2& linolenic and r-.'Lcinoleic acids, and (d) at least one amine selected from triethanolanine and N-hydroxyethylmorpholine.
More recently, it has been proposed in European Patent Application 138 192 to prepare certain polyorganosi loxarie microemulsions by a process which, briefly stated, comprises mixing a polyor6anosiloxane and a surfactant, adding water to the mixture to form a translucent oil concentrate, and thereafter rapidly dispersing said trans lucent oil concentrate in water to provide an ctiulsion wherein the average particle size of the polyorganosiloxane - is less than about 0.3 micron.
Although the process of European Patent Application 138 192 can be employed successfully to prepare stable microemulsions it has been found that occasionally the 4 stabLlity of the emulsion is lcss than expected. VThile the precise reason for this phenomenon has not been estab"Llshed it is believed that it is the result of small batch-to batch variations in the nature or purity of the comr-er cially available raw materials e.g. the surface activc ac,ents employed in the manufacture of the emulsions. In C) such a case a possible remedy would lie in selecting the finished emulsions or the raw materials prior to acceptance and utilisation. however, such a procedure is wasteful of materials and involves a significant amount of time consuming testing.
We have now unexpectedly found that stable micro emulsions containing certain types of surfactants can be prepared by a modification of the procedure of E.P.
138 1922. The said modificatioi. has the advantage of belng easily implemented and avoids the disadvantages associated wi-L-fi the selection and testing plocedures referred to here inabove.
3 According to the present invention there is provided a process for preparing an oil-in-water er-u-Ision of a poly organosiloxane which comprises (A) forming a translucent or transparent oil concentrate by mixing (1) a polyorganosiloxane having at least one polar group attached to silicon through an -=SiC linkage and/cr at least one silanol group and being liquid at the temperature of mixing; (2) one or more surfactants selected from ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated fatty acids and ethoxylated fatty acid esters, at least one of said surfactants being insoluble in polyorganosiloxane (111 at the temperature of mixing; (3) an aliphatic monohydric alcohol having from 5 to 18 carbon atoms, and (4) water in an amount sufficient to produce a translucent or transparent oil concentrate; and (B) rapidly dispersing the translucent or transparent oil r (A) in water to form an oil-in-water concentrate of polyorganosiloxane emulsion wherein the average si.ze of the polyorganosiloxane particles in th& emuls.ion is less than 0.3 micron.
The polyorganosiloxanes (1) which can be emulsified according to the process of this invention contain at least one polar group attached to silicon via a silicon to carbon linkage. Examples of polar groups which may be present in the polyorganosiloxane are organic groups having substituted therein groups such as amine, aminc salt, amides, carboxylic, carboxylic acid salt, carbinol, phenolic, sulphonate salt and sulphate salt. Also operative are polyorganosiloxanes which contain one or more silanol 4 (SiOH) groups with or without the additional presence of the polar organic groups.
The polyorganosiloxanes (1) may be defined as those containing at least one unit of the general formula R a QSio 3-a (a) 2 in which each R represents a monovalent hydrocarbon group r or a non-polar monovalent substituted hydrocarbon group, Q represents a monovalent polar organic group attached to silicon through an SiC linkage, or a hydroxyl group and a has a value oil 'L or 2, any other units present in the polyorganosiloxane being those represented by the general formula R' b Sio 4-b (b) 1.
Z wherein each R' is as defined above for R ar- b is 1, 2 or 3. In the general lormulae (a) and (b) each R and each R' may be, for example, an alkyl group such as methyl, eth.,y!, butyl, cyclohexyl, n-octyl, trimethylphenyl, decyl and octadecyl, an alkenyl group such as vinyl, allyl, hexenyl and cyclohexenyl, an aryl, alkaryl or aralkyl group such as phenyl, naphthyl, tolyl, benzyl and 2-phenylethyl, or a substituted hydrocarbon group such as chloropropyl, 3,3,3trifluoropropyl, chlorophenyl and mercaptopropyl. For the majority of applicatioRs it is preferred that the R and R' groups are those having less than 8 carbon atoms. Most preferably, at least 50% of the total R and R' groups are methyl with any remaining such groups being vinyl and/or phenyl. When the group Q is a polar organic group it may be depicted as -CX in which W' represents a divalent S4 C orgaiii-c linking group attached to silicon via an L linkage and X represents a polar radical. The group W' may E.' carbon a.Lui.ib and hycli:cgen atoms o-.- of, be composed only of carbon, hydrogen and carbon chain interrupting or terminating heteroatoms, for example oxygen or sulphur. Examples of W' groups are -(Ch 2)3_ ' - (Ch 2)4-1 - CH 2 CH.CH 3 CH 2-' -OCH 2 CH 2_, -(CH 2) 3 OCH9- -(CH 2),C 6 H CH and 0 11 -(C11 2)3CSCH2 CH 2 When the polyorganosiloxane is amine-functional the polar radical X is preferablY, that represented by the general formula -NHR 2 wherein R 2 represents H, an alkyl group having from 'L to 4 carbon atoms, -CH 2 CH 2 NFI 21 (CH,)) N11, or -CH CH NHCH CH NH The radical X may also 2 4 2 2 2 2 2 2 represent a salt of the amine, for example the carboxylate or halide salt.
The substituent X may also represent other polar groups for example carbinol -O(C H 0) (C P 0) ri in which x 2 4 x 3 6 y and v may both be zero or an integer, carboxyl, -COO11-1 or carboxylic salt, for example -CO.ONa or COOK and phenol, e.g. C 6 H 4 OH, -6 6 F. 3 CH0H.
Particularly suited for emulsification according to the process of this invention are polyorganosiloxanes wherein the polar group comprises at least one amido substituent, that is wherein X is a radical such as 0 0 _C' 3 11 4 p3 -NE. CR or CNR 2 in which ' represents an alkyl group having fror, 1 to 6 C:, carbon atorrs and each R 4 represents hydrogen, an alkyl group having from 1 to 4 carbon atoms or the group 0 11 3 -CH 2 CH 2 MCR Specific examples of amide radicals X are 0 0 G h 01 p -N(CCH)CE CH NH(CCH and -1,1:l'C--i CH 1,1,H(CC13,. In the 3 2 2 3 '2 2 3 latter case the polar group W'X may be regarded either as containing both ar.,.ino arcj functionality or as an 6 amido functional polar group wherein the carbon chain of the linking group C is interrupted by a heteroatom (N).
Provided that they are liquid at the temperature o.L mixing with the surfactant the polyorganosiloxanes may be homopolymeric, that is composed only of units (a), or they may be copolymeric, that is consisting of both units (a) and units (b). Thus the polar (Q) groups may be attached to terminal or non terminal Si atoms in the molecule or they may be present on both. The polyorganosiloxanes may be liquid, branched homopolymers and copolymers but are preferably the so- called linear polydiorganosiloxanes, that is having a ratio of organic substituents to silicon atoms of approximately 2, generally from about 1. 9 to about 2.3. From economic considerations it is also preferred that the polyorganosiloxanes are copolymers wherein units (a) comprise no more than about 30%, preferably from 0.5' to 1% of the total units (a) and (b) in the copolymer. The preferred polydiorganosiloxanes may be represented by the general formula R 0-p)Qp Si(R' 2 Sio) q (RQSiO)r SiQ S R (3-s) in which R, R' and Q are as defined above and 2 and s are each 0 or 1. The values of _q and r may each vary from zero to 800 or more provided that the sum. of p + r + s is at least 1 and the resulting polyorgarlosiloxane is a liquid at the mixing temperature. For ease of dispersion of the oil concentrate in water it is preferred that _q + r has a value less than 600. It is also economically desirable that the proportion of polar substituents be kept to a minimum consistent with achieving the desired effect when using the emulsion. In general therefore the value of r preferably should not exceed 3C.1% of erablv. sl.'-c;u.ld _q + r and mc.-e pre' lie in the range from q+r to q+r.
400 lc 7 Polyorganosiloxanes which do not contain polar groups may be emulsified in the presence of polar group-containing polyorganosiloxanes by the process of this invention. Any such non polar polyorganosiloxanes should be incorporated 5 into the emulsion at the same time as the polar organosi- by weight loxane and preferably should not exceed about 30,, of the total polyorganosiloxane eraployed.
As the surfactant (2) there are employed one or more surfactarts selected fror- ethoxviated alcohols, ethoxylated alkyl phenols, ethoxylated fatty acids and ethoxylated fatty acid esters. At least one of the aforesaid surfactants must be insoluble in the polyorganosiloxane. The method of determining insolubility and of selecting appropriate surfactants for use with the polar polyorgano- siloxanes are taught in European Patent I.pplicatior 138 192. Examples of the operative surfactants are ethoxylated lauryl alcohol, ethoxylated tridecai)ol, ethoxylated stearyl alcohol, ethoxyj-ated C 12 to C15 secondary alcohols, trimethylnonyl ether of polyethylene glycol, ethoxylated nonylphenol, ethoxylated octylphenol, ethoxylated dodecylphenol, ethoxylated stearylphenol, ethoxylated stearic acid, ethoxylated lauric acid, ethoxylated sorbitan monolaurate and ethoxylated sorbitan monopalmitate. Such surfactants are well known materials and are generally commercially available under such trade narnes as Triton, Tergitol, Trycol and Dobanol. They can be obtained by the condensation of the appropriate alcohols, acids, alkyl phenols, or esters with ethylene oxide or polyethylene glycols and may contain varying amounts of ethylene oxide units, usually from about 2 to about 30. The proportion of surfactant(s) required to provide the desired erifalSiGri particle size and stability will vary depending on the nature of the polyorgarios-Lloxane and the 8UU'_LL__cnts 8 themselves. In general the smaller the particle size the greater the proportion of surfactant required. Usually the suriactant is employed in an amount of from 10 to 200 parts ferably 20 to 50 parts, per 100 parts by by weight, pro weight of polyorganosiloxane.
The aliphatic monohydric. alchols which are eriployed in the process of this invention are those having from 5 to 18 carbon atoms. Although the lower members e.g. pentanol and hexanol are effective to some extent in stabilizing the- micro-emulsions the best results have been obtained with the higher alcohols, particularly those having from 8 to 16 carbon atoms. The alcohols are effective in relatively small amounts and preferably are employed in proportions of from about 0.1 to 5% by weight based on the weight of the polyorganos4l-loxane. Amounts ir. excess of 5% may lic employed if desired but no advantage is be!-4eved to accrue fron, the use of such higher proportions.
The process of this invention is practised by il-rst forming the oil concentrate, that is by the poly- organosiloxane, one or more of the specified surfactants, the alcohol and sufficient water to render the nixture translucent or transparent. It is preferred to mix the polyorganosiloxane, surfactant and the alcohol first and thereaf-ter add sufficient water to obtain the desired translucency or transparency in the concentrate. Once the proportion of water required for a particular combination of polyorganosiloxane, surfactant and alcohol has been established the concentrate may easily be prepared by simply mixing the components. As a general indication the amount of water required to produce translucency or transparency will vary bctween about 4 and about 40 parts by weight per 100 parts by weight of polyorganosiloxane. Translucent or transparent oil concentrates comprising components (1), (2), (3) and (4) are included within the scope of this invention.
Step (B) of the process of this invention involves rapidly dispersing the oil concentrate in water. This 0 second step may be carried out immediately following Step (A). In many cases, however, it will be found that the concentrate is stable on storage for periods varying from several days to many months. In such cases the performance of Step (B) can be delayed as desired. For the preparatior_ of small amounts of the final microemulsion the required rapid dispersion may be achieved by shaking or other manual means. For large scale production, however, it is preferred to employ mechanical nLeans of dispersion, for example blenders, colloid mills and power driven stirrers, whereby L-) the emulsions may be prepared by a batch or a continuous process.
C.B. 1 441 424 referred to hereinabove discloses that the cloudiness which may form as the surfactant/organosilicon mixture is emulsified in water may be caused to 0 L disappear by the addition of successive portions of an alkanol as the emulsification proceeds. In the process of the present invention it is necessary that the alkanol be present in the concentrate prior to the final 'emuls.ification step if the desired emulsion stability is to be 25 obtaince.
The micro-emulsions of this invention can be employed in any of the applications known for the more conventional emulsions, for example as textile treatments, mould release agents and in personal care applications such as the 30 formulation of protective lotions and cosmetics.
The following Examples in. which the parus are expressed by weight illustrate the invention.
- 10 Example 1
Into a 100m1 glass container were introduced the following ingredients Amide-functional polyorganosilloxane 15 parts c 11-14 ethoxylated see. alcohol (7 ethoxy groups) 6 parts c 11-14 ethoxylated sec. alcohol (5 ethoxy groups) 3 parts 1-tridecanol 0.25 part The amide functional polyorganosiloxane was a trimethylsiloxy end-stopped polydimethylsilo.-Llane containing 2 mole percent of units of the formula (MeSiO) CH C11CH NCH CH NH 2 1 21 2 21 is CH 3 Cl=0 C=0 CH 3 h 3 and having a viscosity of 650 mPa.s at 25'C.
The ingredients were thoroughly mixed manually and to the resulting opaque mixture were then added, with stirring, 5.8 parts of water to give a viscous transparent (water white) composition. Further additions of 10.5 parts water and then 57.7 parts water were made, the mixture being stirred thoroughly after each addition. There was obtained a translucent microemulsion which was stable for longer than 3 months and which contained approximately 15Z by weight of polyorganosiloxane.
Two further compositions were similarly prepared employing the same ingredients in the same proportions except that in one case the tridecanol was omitted and in the other it was added after the formation of the final emulsion. A translucent microemulsion was obtained in each case but which had started to separate into oil and water phases after less than 24 hours.
Example 2 A microemulsion was prepared as described in Example 1 except that the tridecancl was replaced ijiz^n the quantity of n-pentanol. The emulsion was stable for about 2 days. This perioCt was longer than that obtained when the pentanol was omitted but was much less than that of the emulsi-lon obtained employing tridecanol. Example 3 The procedure of Example 1 was repeated except that the tridecanol was replaced with an equal amount of Dobanol 23 ( a C 12- 13 synthetic alcohol). A translucent emulsion was obtained which was stable for more than 3 months.
1
Claims (10)
1. A process for preparing an oil-in-water emulsion of a polyorganosiloxane which comprises (A) forming a translucent or transparent oil concentrate by mixing a polyorganosiloxar.e having at least one polar group attached to silicon through an =-SiC linkage and/or at least one silanol group and being liquid at the temperature of mixing; (2) one or more surfactants selected from ethoxylated alcohols, etho):ylated alkyl phenols, ethoxylated 9 fatty acids and ethoxylated fatty acid esters, at least one of said surfactants being insoluble in polyorganosilo::arLe (1) at the temperature of mixing; (3) an aliphatic monohydric alcohol having from 5 to 18 carbon atowis, and (4) water in an amount sufficient to produce a translucent or transparent oil concentrate; and (B) rapidly dispersing the translucent or transparent oil concentrate of (A) in water to form an oil-in-water polyorganosilo.-.arie emulsion wherein the average size of the polyorganosiloxane particles in the emulsion is less than 0.3 micron.
A process as claimed in Claim 1 wherein the aliphatic mono hydric alcohol (3) has from 8 to 16 carbon atoms.
3. A process as claimed in Claim 1 or Claim 2 wherein the aliphatic monohydric alcohol is employed ir. a proportion of fron. 0.1 to 5% based on the weight of the polyorganosiloxane.
4. A process as claimed in any one of the preceding claims wherein the polar group in the polyorganosiloxane comprises at ituent.
least one amido su',)st
5. A process as clainled in Claim, 4 wherein tht poLar g,,ciup ha,!:; the general formula -R"X in which R" represents a divalent organic group attached to silicon through a silicon-carbon 0 0 411 3 11 4 3 linkage and X represents -NR CR or -CNR 2 in which R represents an alkyl group having from 1 to
6 carbon atoms and each R 4 represents hydrogen, an alkyl group having from 1 to 4 0 11 3 carbon atoms or the group -CH2 CH 2NHCR 6. A process as claimed in any one o-f the preceding claims wherein the surfactant (2) is employed in an amount of from 20 to 50 parts by weight per 100 parts by weight of polyorganosiloxaric.
7. A process as claimed in Claim 1 substantially as described with reference to the Examples.
8. A translucent or transparent oil concentrate comprising (1) a liquid polyorgaricsi-loxane having at least one polar group attached to silicon through an -=Si-C linkage andlor at least one silanol group, (2) one or more surfactants selected from ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated fatty acids and ethoxylated fatty acid esters, at least one of said surfactants being insoluble in polyorganosiloxane (1), (3) an aliphatic monohydric alcohol having from. 5 to IS carbon atoms, and (4) water.
9. A concentrate as claimed in Claim 8 wherein the polar group in the polyorganosiloxane comprises at least one amido substituent.
10. A concentrate as claimed in Claim 8 or Claim 9 wherein the water component is present in an amount of from 4 to 40 parts by weight per 100 parts by weight of polyorganosiloxane.
l:
Published 1989 stThe Patent Office, State HouBe. 86 71 High Holborn, London WC1R 4TP. Further copies maybe obtalnedfrom The PatentOffice. Sales Branch, St Mary Cray, Orpington, Rent BR5 3RD- Printed by Multiplex techniques Rd, St Mary Cray, Kent, Con. 1/87
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB878729489A GB8729489D0 (en) | 1987-12-18 | 1987-12-18 | Polyorganosiloxane emulsions |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8828978D0 GB8828978D0 (en) | 1989-01-25 |
| GB2215729A true GB2215729A (en) | 1989-09-27 |
| GB2215729B GB2215729B (en) | 1991-09-25 |
Family
ID=10628658
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB878729489A Pending GB8729489D0 (en) | 1987-12-18 | 1987-12-18 | Polyorganosiloxane emulsions |
| GB8828978A Expired - Lifetime GB2215729B (en) | 1987-12-18 | 1988-12-12 | Polyorganosiloxane emulsions |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB878729489A Pending GB8729489D0 (en) | 1987-12-18 | 1987-12-18 | Polyorganosiloxane emulsions |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE3842471A1 (en) |
| FR (1) | FR2624867B1 (en) |
| GB (2) | GB8729489D0 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5071573A (en) * | 1990-07-23 | 1991-12-10 | The Procter & Gamble Company | Microemulsified silicones in liquid fabric care compositions containing dye |
| US5173201A (en) * | 1990-07-23 | 1992-12-22 | The Proctor & Gamble Company | Microemulsified amine functional silicone in liquid fabric softeners for reducing fiber-fiber and yarn-yarn friction in fabrics |
| DE4133358A1 (en) * | 1991-10-09 | 1993-04-15 | Pfersee Chem Fab | AQUEOUS COMPOSITIONS WITH NITROGEN POLYSILOXANES |
| US5302657A (en) * | 1990-02-16 | 1994-04-12 | Wacker-Chemie Gmbh | Highly dispersed organopolysiloxane emulsions |
| GB2289686A (en) * | 1994-05-27 | 1995-11-29 | Gen Electric | Method of preparing microemulsions of amino silicone fluids and MQ resin mixtures |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2658094A1 (en) * | 1990-02-14 | 1991-08-16 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF EMULSIONS, OF THE OIL IN WATER TYPE, MONODISPERSES. |
| DE4020036A1 (en) * | 1990-06-23 | 1992-01-02 | Klueber Chemie Kg | AQUEOUS RELEASE AGENT FOR PRODUCING POLYURETHANE MOLDED BODIES CONTAINING ETHOXYLATED ALCOHOL |
| RU2114881C1 (en) * | 1995-07-31 | 1998-07-10 | Товарищество с ограниченной ответственностью Научно-исследовательский центр "Поиск" | Aqueous emulsion composition on the base of polyorganosiloxane for treatment of fibrous materials |
| DE19539523A1 (en) * | 1995-10-24 | 1997-04-30 | Grace W R & Co | Release agents for rollers and processes for improving the release properties of rollers |
| US6071975A (en) * | 1999-01-11 | 2000-06-06 | Dow Corning Corporation | Method of preparing silicone oil-in-water microemulsions |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB915787A (en) * | 1959-11-13 | 1963-01-16 | Bayer Ag | Self-emulsifying organo-polysiloxane solutions |
| GB1220594A (en) * | 1967-06-14 | 1971-01-27 | Midland Silicones Ltd | Organopolysiloxane emulsions |
| GB2066659A (en) * | 1980-01-09 | 1981-07-15 | Kao Corp | Hair rinse compositions |
| EP0043985A2 (en) * | 1980-07-12 | 1982-01-20 | Bayer Ag | Organopolysiloxane emulsions with a stability in the cold |
| EP0138192A1 (en) * | 1983-10-17 | 1985-04-24 | Dow Corning Corporation | Method of preparing polyorganosiloxane emulsions having small particle size |
| EP0278846A1 (en) * | 1987-01-29 | 1988-08-17 | Laboratoire Lachartre Societe Anonyme: | Cosmetic composition in spray or aerosol form for the care, treatment and aesthetics of the hair |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4052331A (en) * | 1972-11-03 | 1977-10-04 | Rhone-Poulenc S.A. | Surface active composition |
| ZA823554B (en) * | 1981-06-19 | 1983-03-30 | Dow Corning Ltd | Siloxane compositions and process for treatment of materials |
-
1987
- 1987-12-18 GB GB878729489A patent/GB8729489D0/en active Pending
-
1988
- 1988-12-12 GB GB8828978A patent/GB2215729B/en not_active Expired - Lifetime
- 1988-12-15 FR FR8816537A patent/FR2624867B1/en not_active Expired - Fee Related
- 1988-12-16 DE DE3842471A patent/DE3842471A1/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB915787A (en) * | 1959-11-13 | 1963-01-16 | Bayer Ag | Self-emulsifying organo-polysiloxane solutions |
| GB1220594A (en) * | 1967-06-14 | 1971-01-27 | Midland Silicones Ltd | Organopolysiloxane emulsions |
| GB2066659A (en) * | 1980-01-09 | 1981-07-15 | Kao Corp | Hair rinse compositions |
| EP0043985A2 (en) * | 1980-07-12 | 1982-01-20 | Bayer Ag | Organopolysiloxane emulsions with a stability in the cold |
| EP0138192A1 (en) * | 1983-10-17 | 1985-04-24 | Dow Corning Corporation | Method of preparing polyorganosiloxane emulsions having small particle size |
| EP0278846A1 (en) * | 1987-01-29 | 1988-08-17 | Laboratoire Lachartre Societe Anonyme: | Cosmetic composition in spray or aerosol form for the care, treatment and aesthetics of the hair |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5302657A (en) * | 1990-02-16 | 1994-04-12 | Wacker-Chemie Gmbh | Highly dispersed organopolysiloxane emulsions |
| US5071573A (en) * | 1990-07-23 | 1991-12-10 | The Procter & Gamble Company | Microemulsified silicones in liquid fabric care compositions containing dye |
| US5173201A (en) * | 1990-07-23 | 1992-12-22 | The Proctor & Gamble Company | Microemulsified amine functional silicone in liquid fabric softeners for reducing fiber-fiber and yarn-yarn friction in fabrics |
| DE4133358A1 (en) * | 1991-10-09 | 1993-04-15 | Pfersee Chem Fab | AQUEOUS COMPOSITIONS WITH NITROGEN POLYSILOXANES |
| US5310783A (en) * | 1991-10-09 | 1994-05-10 | Ciba-Geigy Corporation | Aqueous compositions comprising nitrogen-containing polysiloxanes |
| GB2289686A (en) * | 1994-05-27 | 1995-11-29 | Gen Electric | Method of preparing microemulsions of amino silicone fluids and MQ resin mixtures |
| GB2289686B (en) * | 1994-05-27 | 1998-09-09 | Gen Electric | Method of preparing microemulsions of amino silicone fluids and MQ resin mixtures |
| US6180117B1 (en) | 1994-05-27 | 2001-01-30 | General Electric Company | Method of preparing microemulsions of amino silicone fluids and MQ resin mixtures |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8828978D0 (en) | 1989-01-25 |
| GB2215729B (en) | 1991-09-25 |
| GB8729489D0 (en) | 1988-02-03 |
| DE3842471A1 (en) | 1989-06-29 |
| FR2624867A1 (en) | 1989-06-23 |
| FR2624867B1 (en) | 1993-10-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19941212 |