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
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences

Definitions

• This invention relates to certain novel silicone polyethers, and both methods for making and uses for them. More particularly, the invention relates to silicone polyethers based on novel polyethers initiated by certain non-isomerizing alkenyl or alkynyl alcohols, methods for making these silicone polyethers by hydrosilation, and their uses in personal care and other products.
• Silicone polyethers are used in many applications, notably as surfactants and in the preparation of personal care products, polyurethanes and paint, ink and coating formulations. They may be produced by hydrosilation of a polyether initiated by an aliphatically unsaturated alcohol with a silicone having a SiH functionality.
• the polyether used may be produced from various initiators and epoxides under the influence of a variety of catalysts. Selection of the exact starting materials and routes utilized is important in determining the properties of the final polymer with even small changes producing very dramatic differences at times. The synthesis chosen for the polyether may be the most critical choice.
• Alkynyl alcohol initiated polyethers are difficult if not impossible to make using a basic catalyst as there tends to be decomposition of the product, and there is also the issue of migration of the triple bond.
• Use of Lewis acids solves these problems to some extent, but results in formation of large amounts of difficult to remove byproducts and cyclization of the polyethers.
• An example in the art showing use of a Lewis acid catalyst in this context is U.S. Pat. No. 3,644,535 to Batty et al., while U.S. Patent 5,066,756 to Raleigh et al. mentions use of acid and basic catalysts.
• the invention relates to a silicone based polyether comprising a monovalent group, R, with R having an average formula:
• Z is bonded to Si and —Z— is —CH2CH2— or —CH ⁇ CH—;
• R1 and R2 are independently alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever —Z— is —CH2CH2—, or
• R1 and R2 are independently H, halogen, NO2, NH2, an amine group, alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter mentioned groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever —Z— is —CH ⁇ CH—, and regardless of choice of —Z—,
• R1 and R2 may be independently aldehyde, keto or ester functional
• R3 is a divalent hydrocarbon group which may be substituted by one or more of halogen, NO2, NH2 or an amine group, or R3 is a nullity;
• R4 is —CH(R5)—CH2—, —CH2—CH(R5)— or a combination of these;
• R5 is H, methyl, ethyl, phenyl or may vary among these within the same molecule in any proportion or order, with the proviso that when —Z— is —CH2CH2—, R1 and R2 are free of halogen and nitrogen, and all R5 groups are solely some combination of H and methyl, then —CH2CH2— groups must make up on average at least 60 percent by weight of the total R4 groups per molecule;
• m 3 to 100 with the proviso that the range for m is expanded to 1 to 100 whenever —Z— is —CH2CH2— and the equivalent polydispersity of R is less than 1.4 or whenever R contains halogen, NO2, NH2, an amine group, or is aldehyde, keto or ester functional;
• R6 is H, an alkyl group or
• R7 is an alkyl group.
• the invention relates to a polymer of average formula:
• R, R1, R2 and R3 are independently alkyl groups having 30 carbons or less or phenyl;
• x is 0 to 500
• y is 1 to 100;
• R5 is an alkyl group
• R6 is H, an alkyl group or C(O)R7;
• R7 is an alkyl group
• R8 is H or an alkyl group
• R9 is CH(R10)CH2, CH2CH(R10) or a combination of these;
• R10 is H, methyl, ethyl or phenyl
• the equivalent polydispersity of R4 is less than 1.4.
• R, R1 and R2 are independently alkyl groups having 30 carbons or less or phenyl;
• x is 0 to 500
• m is 3 to 100
• R4 is an alkyl group
• R5 is H, alkyl or C(O)R6;
• R6 is an alkyl group
• R7 is H or an alkyl group
• R9 is CH(R10)CH2, CH2CH(R10) or a combination of these;
• R10 is H, methyl, ethyl or phenyl
• the equivalent polydispersity of R3 is less than 1.4.
• the invention relates to a method for making a silicone based polyether, the method comprising:
• Y— is CH2 ⁇ CH— or CH ⁇ C—;
• R1 and R2 are independently alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever Y— is CH2 ⁇ CH—, or
• R1and R2 are independently H, halogen, NO2, NH2, an amine group, alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter mentioned groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever Y— is —CH ⁇ —C—, and regardless of choice of —Y—,
• R1 and R2 may be independently aldehyde, keto or ester functional
• R3 is a divalent hydrocarbon group which may be substituted by one or more of halogen, NO2, NH2 or an amine group, or R3 is a nullity;
• R4 is —CH(R5)—CH2—, —CH2—CH(R5)— or a combination of these;
• R5 is H, methyl, ethyl, phenyl or may vary among these within the same molecule in any proportion or order, with the proviso that when Y— is CH2 ⁇ CH—, R1 and R2 are free of halogen and nitrogen, and all R5 groups are solely some combination of H and methyl, then —CH2CH2— groups must make up on average at least 60 percent by weight of the total R4 groups per molecule;
• m 3 to 100 with the proviso that the range for m is expanded to 1 to 100 whenever —Y— is —CH2CH2— and the equivalent polydispersity of U is less than 1.4 or whenever U contains halogen, NO2, NH2, an amine group, or is aldehyde, keto or ester functional;
• R6 is H, an alkyl group or
• R7 is an alkyl group.
• Another object of the present invention is to provide uses for subject silicone based polyethers.
• the invention further relates to methods for reducing surface tension.
• the present invention also relates to surfactants and paint, ink and coating formulations, personal care products for treating hair, skin and underarms, as well as polyurethane foams that contain the subject silicone based polyethers.
• compositions according to the present invention include silicone based polyethers comprising a monovalent group, R, with R having an average formula:
• Z is bonded to Si and —Z— is —CH2CH2— or —CH ⁇ CH—;
• R1 and R2 are independently alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever —Z— is —CH2CH2—, or
• R1 and R2 are independently H, halogen, NO2, NH2, an amine group, alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter mentioned groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever —Z— is —CH ⁇ CH—, and regardless of choice of —Z—,
• R1 and R2 may be independently aldehyde, keto or ester functional
• R3 is a divalent hydrocarbon group (such as aliphatic, including alkyl, alkenyl, alkynyl based whether linear or cyclic, aromatic or combinations thereof) which may be substituted by one or more of halogen, NO2, NH2 or an amine group, or R3 is a nullity;
• R4 is —CH(R5)—CH2—, —CH2—CH(R5)— or a combination of these;
• R5 is H, methyl, ethyl, phenyl or may vary among these within the same molecule in any proportion or order, with the proviso that when —Z— is —CH2CH2—, R1 and R2 are free of halogen and nitrogen, and all R5 groups are solely some combination of H and methyl, then —CH2CH2— groups must make up on average at least 60 percent by weight of the total R4 groups per molecule;
• m 3 to 100 with the proviso that the range for m is expanded to 1 to 100 whenever —Z— is —CH2CH2— and the equivalent polydispersity of R is less than 1.4 or whenever R contains halogen, NO2, NH2, an amine group, or is aldehyde, keto or ester functional;
• R6 is H, an alkyl group or
• R7 is an alkyl group.
• nullity as in “R3 is a nullity” should be taken to mean that group referred to is absent. For example, if R3 is a nullity in —CH2—R3—O—, then this structure is —CH2—O—.
• halogen should be taken to mean a member of the group consisting of fluorine, chlorine, bromine, iodine and others of this series with chlorine and bromine being preferred.
• amine group in this same context, should be taken to mean a monovalent group containing nitrogen bonded to at least one organic carbon such as —NHCH3 or —CH2—NH—CH3.
• Halogen and NO2 containing polymers according to this invention may be desirable for themselves or because they may be converted to NH2 containing polymers by methods such as simple exchange with ammonia or reduction, respectively.
• These functional groups along with aldehyde, keto and ester functionality can enhance the properties of the simpler polymers of this invention or provide reactive sites for various purposes. Even multifunctional polymers are possible and are often quite desirable in many applications.
• silicone based polyethers be fully liquid at “room temperature” (25 deg C. and 760 mm Hg pressure) as even partial solidification can result in products that are unsightly messes.
• room temperature 25 deg C. and 760 mm Hg pressure
• lower molecular weight polymers are preferred. In most cases, this translates to an weight average molecular weight for the overall polymer to be less than 10,000 and the equivalent, weight average molecular weight for the polyether/initiator portion to be less than 700.
• equivalent in this context is meant that this weight is based on the subject polymer side chains (polyether/initiator) as if they were separate molecules.
• the polydispersity of the overall polymers of the present invention not be very high. Practically speaking, this is usually determined by the polyether/initiator chains. Equivalent polydispersities of the these chains (determined as if these chains were separate molecules) should usually be less 1.6, preferably less than 1.4, more preferably less than 1.25 or less than 1.1 and most preferably less than 1.05 or lower (down to 1.0). These numerical ranges would apply to the polydispersity of the overall silicon based polyether as well.
• compositions according to the present invention that are of great interest include polymers of average formula:
• R, R1, R2 and R3 are independently alkyl groups having 30 carbons or less or phenyl, preferably methyl;
• x is0 to500
• y is 1 to 100;
• m is 3to 100
• R5 is an alkyl group, preferably methyl
• R6 is H, an alkyl group or C(O)R7;
• R7 is an alkyl group
• R8 is H or an alkyl group, preferably methyl
• R9 is CH(R10)CH2, CH2CH(R10) or a combination of these;
• R10 is H, methyl, ethyl or phenyl, preferably H.
• the equivalent polydispersity of R4 is less than 1.4.
• compositions according to the present invention that are of great interest include polymers of average formula:
• R, R1 and R2 are independently alkyl groups having 30 carbons or less or phenyl, preferably methyl;
• x is 0 to 500
• m is 3 to 100
• R4 is an alkyl group, preferably methyl
• R5 is H, alkyl or C(O)R6;
• R6 is an alkyl group
• R7 is H or an alkyl group, preferably methyl
• R9 is CH(R10)CH2, CH2CH(R10) or a combination of these;
• R10 is H, methyl, ethyl or phenyl, preferably H.
• the equivalent polydispersity of R3 is less than 1.4.
• the methods according to the present invention include those for making silicone based polyethers, such methods including those comprising: hydrosilating U with a silicone containing an SiH group, where
• Y— is CH2 ⁇ CH— or CH ⁇ C—;
• R1 and R2 are independently alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever Y— is CH2 ⁇ CH—, or
• R1 and R2 are independently H, halogen, NO2, NH2, an amine group, alkyl, phenyl, an alkyl substituted phenyl, a phenyl substituted alkyl, one of the four latter mentioned groups substituted or further substituted by one or more of halogen, NO2, NH2 or an amine group whenever Y— is —CH ⁇ —C—, and regardless of choice of —Y—,
• R1 and R2 may be independently aldehyde, keto or ester functional
• R3 is a divalent hydrocarbon group (which may be particularly groups as defined for the corresponding invented compositions above) which may be substituted by one or more of halogen, NO2, NH2 or an amine group, or R3 is a nullity;
• R4 is —CH(R5)—CH2—, —CH2—CH(R5)— or a combination of these;
• R5 is H, methyl, ethyl, phenyl or may vary among these within the same molecule in any proportion or order, with the proviso that when Y— is CH2 ⁇ CH—, R1 and R2 are free of halogen and nitrogen, and all R5 groups are solely some combination of H and methyl, then —CH2CH2— groups must make up on average at least 60 percent by weight of the total R4 groups per molecule;
• m 3 to 100 with the proviso that the range for m is expanded to 1 to 100 whenever —Y— is —CH2CH2— and the equivalent polydispersity of U is less than 1.4 or whenever U contains halogen, NO2, NH2, an amine group, or is aldehyde, keto or ester functional;
• R6 is H, an alkyl group or
• R7 is an alkyl group.
• the hydrosilation reaction is well known in the art. It is usually carried out in the presence of a catalyst such as one based on platinum which are also well known in the art, some examples of which are described below.
• U be of high purity for hydrosilation.
• U should be greater than 85 weight percent, preferably U should be greater than 92 weight percent and most preferably U should be greater than 96 weight percent of the material containing U added to the hydrosilation reaction mixture.
• the initiators for the polyethers used in making the polymers according to the present invention are, at least for the most part, nonisomerizing alcohols. This results in lower odor polymers as it is less likely that smelly products like propionaldehyde will form from them. It is also very efficient to use 1:1 stoichiometric ratios for polyether:silicone in the present hydrosilations in many cases, particularly when using polyethers at lower polydispersities.
• polyether precursors of the silicone based polyethers of the present invention are believed to be novel and methods for their synthesis (including catalysts used) may be as well. Both are described, at least in part, in co-pending applications assigned or to be assigned to the Dow Chemical Company (and at least in some cases having some common inventors with the present application) and these and those derived from them are incorporated by reference to the extent possible and such that they do not contradict the disclosures herein and may be referred to as necessary to make the present disclosure enabling and the present claims enabled. These applications are: PCTIUS00/18619, “Method for Fractionating Poly(ethylene oxide) Formed Using Metallic Cyanide Catalyst”, filed Jul. 7, 2000 and due to publish on or after Jan. 9, 2001.
• PCT/USOO/18621 “Polymerization of Alkylene Oxides Onto Functionalized Initiators”, filed Jul. 7, 2000 and due to publish on or after Jan. 9, 2001;
• Metal cyanide catalysts are suited for making the polyethers used to produce the silicone polyethers of the present invention as has been noted previously. This may be especially true when it is desired to have base sensitive groups in the polyether.
• DMC catalyst One form of these catalysts (referred to in this specification and the claims that follow as “DMC catalyst”) is:
• M is a metal ion that forms an insoluble precipitate with the M 1 (CN) r (X) t group and which has at least one water or organic solvent soluble salt;
• M 1 and M 2 are transition metal ions that may be the same or different; each X independently represents a group other than cyanide that coordinates with an M 1 or M 2 ion;
• L represents an organic complexing agent
• M 3 x A y represents a water or organic solvent soluble salt of metal ion M 3 and anion A
• M 3 is the same as or different than M
• b and c are positive numbers that together with d, reflect an electrostatically neutral complex
• d is zero or a positive number
• x and y are numbers that reflect an electrostatically neutral salt
• r is from 4 to 6
• z is zero or a positive number and n is a positive number indicating the relative quantities of the complexing agent L and of the metal salt, M 3 x ,A y , respectively.
• DMC catalysts of interest include:
• L is tertiary butanol, a polyether polyol, 1,2-dimethoxy ethane or combinations thereof.
• catalysts may be insoluble in nonpolar solvents like n-hexane, while the polyethers may be soluble, thus this can be useful in removing the catalyst from the polyether product.
• Other methods for catalyst removal has been previously described or noted.
• Another method according to the present invention is a method to reduce the surface tension of a system comprising adding a silicone based polyether of the present invention to the system or a component or components used to produce the system.
• compositions according to the present invention include those that are also manufactures that contain silicone based polyethers of the present invention.
• manufactures include surfactants (which could be made solely of a silicone based polyether), personal care products such as treatments for hair, skin or underarms and paint, ink or coating formulations that contain these silicone polyethers, as well as polyurethane foams containing such polyethers as a stabilizer or otherwise.
• a zinc hexacyanocobaltate/t-butanol/450 MW poly(propylene oxide) triol catalyst complex (6.0 g) and 271.87 g of 2-methyl-3-butyn-2-ol are charged to a 2 gallon (7.57 liter) reactor, taking care to transfer all of the catalyst complex into the reactor.
• the reactor is sealed and degassed/purged several times with nitrogen, with the pressure being maintained above atmospheric pressure at all times to prevent loss of initiator.
• the mixture is stirred and heated to 90° C.
• a portion of ethylene oxide (135 g) is added. After thirty minutes, an additional 50 g of ethylene oxide is added. After another 90 minutes, another 50 g of ethylene oxide is added.
• a zinc hexacyanocobaltate/t-butanol/450 MW poly(propylene oxide) triol catalyst complex (0.53 g) and 235.05 g of 2-methyl-3-buten-2-ol are homogenized and charged under nitrogen to a 2 gallon (7.57 liter) reactor, taking care to transfer all of the catalyst complex into the reactor.
• the reactor is sealed and degassed/purged several times with nitrogen, with the pressure being maintained above atmospheric pressure at all times to prevent loss of initiator.
• the mixture is stirred and heated to 90 0C.
• a portion of ethylene oxide (about 50-150 g) is added. When the pressure in the reactor drops, indicating the start of polymerization, a feed of ethylene oxide is begun.
• the feed rate is varied until a constant reactor pressure is obtained. A total of 2165 g of ethylene oxide is added. As the reaction progresses, a vigorous exotherm develops.
• the product has a M a of 940 via GPC and a polydispersity of approximately 1.1.
• a polyether may be prepared using the same general procedure as described in Example 1 with 1-chloro-2-methyl-3-butyn-2-ol as the initiator. (Corresponding substituted or functionalized polyethers such as NO2 and NH2 containing or keto functionalized can be made similarly from corresponding initiators and a similar procedure.)
• a silicone based polyether may be prepared using the general procedure of Example 4 with CH 2 ⁇ CHC(CH 2 Br) 2 (OCH 2 CH 2 ) 9 . 94 0H as the starting polyether.
• Corresponding substituted or functionalized silicone based polyethers such as NO2 and NH2 containing or keto functionalized can be made similarly from corresponding polyethers and a similar procedure.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Silicon Polymers (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Cosmetics (AREA)
• Polyethers (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Paints Or Removers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

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• 2001
  • 2001-01-08 US US09/756,440 patent/US20020091219A1/en not_active Abandoned
• 2002
  • 2002-01-07 JP JP2002555143A patent/JP2004525205A/ja active Pending
  • 2002-01-07 EP EP02701912.4A patent/EP1360223B1/en not_active Expired - Lifetime
  • 2002-01-07 CN CNB02803516XA patent/CN1283696C/zh not_active Expired - Fee Related
  • 2002-01-07 WO PCT/US2002/000393 patent/WO2002053625A2/en not_active Ceased
  • 2002-01-07 US US10/041,323 patent/US6987157B2/en not_active Expired - Lifetime
  • 2002-01-07 AU AU2002235312A patent/AU2002235312A1/en not_active Abandoned

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