Silicone peroxides

SUMMARY OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The invention relates to peroxide-functional organopolysilozanes.

[0003] 2. Background Art

[0004] JP 2001081187 A2 describes the reaction of siloxanes having silicon-bound acid chlorides with low molecular weight tertiary organic hydroperoxides to give the corresponding peroxyester siloxanes. In the process described therein, the organic molecule is initially peroxidized, not the silicone moiety. The low molecular weight hydroperoxides are very difficult to handle; for example, they must be transported only under extreme safety measures and tend to decompose.

SUMMARY OF THE INVENTION

[0005] The invention pertains to unique silicone peroxides prepared without the use of organic hydroperoxides, by reaction of a hydroxyalkyl- or alkenyl-functional organosilicon compound with hydrogen peroxide.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

[0006] The invention provides a peroxide-functional organopolysiloxane (P) which has at least one unit of the general formula (I)

YaRbSiO4-a-b/2 (I)

[0007] where

[0008] Y is a group of the general formula (II)

-A-CR″2—OO—R′″ (II),

[0009] R is a hydrogen atom, a C1- to C12-alkoxy, hydroxy or alkyl glycol radical or a monovalent, optionally cyano-, fluorine-, chlorine- or bromine-substituted C1- to C18-hydrocarbon radical which may be interrupted by divalent radicals bonded on both sides to carbon atoms, from the group of —O—, —COO—, —OOC—, —CONR1—, —NR1CO— and —CO—,

[0010] A is a chemical bond or a divalent, optionally cyano-, fluorine-, chlorine- or bromine-substituted C1- to C18-hydrocarbon radical,

[0011] R″ is an optionally cyano-, fluorine-, chlorine- or bromine-substituted C1- to C10-hydrocarbon radical,

[0012] R′″ is a hydrogen atom, a monovalent C1- to C18-hydrocarbon radical or C1- to C18-acyl radical which may be cyano-, fluorine-, chlorine-, bromine- or organopolysiloxane-substituted, and may be interrupted by divalent radicals bonded on both sides to carbon atoms, from the group of —O—, —COO—, —OOC—, —CONR′—, —NR1CO— and —CO—,

[0013] R1 is a hydrogen atom or an R″ radical,

[0014] a is 1, 2 or 3,

[0015] b is 0, 1 or 2 and

[0016] the sum of a+b is 1, 2 or 3.

[0017] The peroxide-functional organopolysiloxane (P) may decompose in a defined manner, for example thermally or by redox reaction, to generate a silicone macroinitiator.

[0018] The organopolysiloxane (P) can be used to modify organopolysiloxanes (M). For example, use of organopolysiloxanes allow silicone constituents to be directly polymerized into polymers, e.g. into free-radically crosslinkable silicone rubbers, via the organopolysiloxane (P). The silicone rubbers can then be free-radically crosslinked using organopolysiloxane (P), for example using vinyl groups bound to the silicone rubber, as when preparing HTV silicone rubber.

[0019] The organopolysiloxane (P) can also be used as a free radical initiator in the synthesis of silicone block and graft copolymers by polymerization with monomers.

[0020] On redox induced decomposition of organopolysiloxanes (P), in which R′″ is a hydrogen atom (hydroperoxide) a polymer radical is formed, but an OH anion is generated rather than a low molecular weight radical. The OH radical which would ordinarily be expected as an intermediate is apparently converted so rapidly to an OH anion that it can form no homopolymeric by-products in a free radical polymerization. The organopolysiloxane hydroperoxide (P) is therefore particularly suitable as an initiator for copolymerizations which are carried out at temperatures below the critical decomposition temperature of the organopolysiloxane hydroperoxide (P) (approximately 90° C.). The organopolysiloxane hydroperoxide (P) therefore copolymerizes in redox polymerization with monomers to give block or graft copolymers without troublesome formation of homopolymers of the monomer.

[0021] Organopolysiloxane (P) can be prepared by a simple, problem-free and direct route with the aid of starting materials which are easy to handle.

[0022] In the organopolysiloxane (P) the peroxide groups are less reactive than low molecular weight peroxides. The peroxide content in the organopolysiloxane (P) can be adjusted as desired and can be lowered by addition of further siloxane units such that no solvent is required for dilution.

[0023] Examples of unsubstituted R and R′″ radicals include alkyl radicals such as the methyl and ethyl radicals; cycloalkyl radicals such as the cyclohexyl radical; aryl radicals such as the phenyl, biphenylyl, naphthyl, anthryl and phenanthryl radicals; alkaryl radicals such as the o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals such as the benzyl radical and the alpha- and β-phenylethyl radicals.

[0024] Examples of substituted hydrocarbon radicals as R and R′″ radicals include halogenated hydrocarbon radicals; epoxyalkyl radicals; (meth)acryloxyalkyl radicals, cyanoalkyl radicals; aminoalkyl radicals; aminoaryl radicals; quaternary ammonium radicals; and hydroxyalkyl radicals. The alkoxy radicals R may be alkyl radicals such as those described above, bonded via an oxygen atom. The examples of alkyl radicals R also apply fully for the alkoxy radicals.

[0025] The R radical is preferably an unsubstituted or substituted C1- to C18-alkyl radical, hydrogen or the phenyl radical, in particular the methyl, ethyl, propyl, octyl, hexyl, dodecyl, octadecyl, phenyl, vinyl, allyl, methacryloxypropyl, 3-chloropropyl, 3-mercaptopropyl, 3-hydroxypropyl, 3-(2,3-dihydroxypropoxy)propyl, 3-aminopropyl and (2-aminoethyl)-3-aminopropyl radical, hydrogen, or a quaternary ammonium radical.

[0026] The R′″ radical is preferably hydrogen, an unsubstituted or substituted C1- to C18-alkyl radical, in particular a tert-butyl, isopropyl, octyl, hexyl, dodecyl or octadecyl radical.

[0027] The R″ radical is preferably an unsubstituted or substituted C1- to C6-alkyl radical, in particular the methyl, ethyl, or propyl radical.

[0028] Examples of divalent hydrocarbon radicals A include saturated alkylene radicals such as the methylene and ethylene radical, and also propylene, butylene, pentylene, hexylene, cyclohexylene and octadecylene radicals or unsaturated alkylene or arylene radicals such as the hexenylene radical and phenylene radicals, in particular linear C1- to C6-alkylene radicals, more preferably the ethylene radical.

[0029] In addition to the units of the general formula (I), the organopolysiloxane (P) may have further siloxane units, preferably those of the general formulae (III), (IV), (V) and (VI)

[R3SiO1/2] (III),

[R2SiO2/2] (IV),

[RSiO3/2] (V),

[SiO4/2] (VI),

[0030] where R is as defined above.

[0031] The organopolysiloxane (P) preferably comprises from 1 to 100.0 mol % of units of the general formula (I), from 0 to 50.0 mol % of units of the general formula (III), from 0 to 90.0 mol % of units of the general formula (IV), from 0 to 50.0 mol % of units of the general formula (V), and from 0 to 50.0 mol % of units of the general formula (VI).

[0032] In particular, the organopolysiloxane (P) comprises from 1 to 50.0 mol % of units of the general formula (I), from 0 to 40.0 mol % of units of the general formula (III), from 10 to 80.0 mol % of units of the general formula (IV), from 0 to 10.0 mol % of units of the general formula (V), from 0 to 10.0 mol % of units of the general formula (VI).

[0033] The organopolysiloxane (P) may be a linear or cyclic molecule, and the peroxy groups may be attached in a comb-like manner and/or to the chain end. The organopolysiloxane (P) may also be branched or crosslinked.

[0034] The organopolysiloxane (P) has a total of at least 2, in particular at least 3, units of the general formulae (I) and (III) to (VI). It may be liquid or solid at 25° C. The viscosity at 25° C. is preferably not more than 100 Pas, more preferably not more than 10 Pas, and in particular, not more than 2 Pas.

[0035] The peroxide-functional organopolysiloxane (P) which has at least one unit of the above general formula (I) may be prepared by reacting organopolysiloxane (A) which has at least one unit of the general formula (VII)

ZaRbSiO4-a-b/2 (VII)

[0036] where Z is a group of the general formula (VIII)

-A-CR″2—OH (VIII)

[0037] and/or where Z is a group of the general formula (IX)

-A-CR″═CH2 (IX)

[0038] where R, R″, a and b are each as defined above, with H2O2, resulting in an organopolysiloxane (P) where R′″ is a hydrogen atom.

[0039] The organopolysiloxane of the general formula (VII) which contains the radical of the general formula (VIII) may be prepared, for example, by transition metal-catalyzed reaction of unsaturated tertiary alcohols with polysiloxanes containing Si—H bonds (hydrosilylation), for example 2-methyl-3-buten-2-ol, 2-hydroxy-2,5-dimethyl-5-hexene or H2C═CMe-Ph-CMe2OH.

[0040] The organopolysiloxane of the general formula (VII) containing the radical of the general formula (IX) can be prepared, for example, by transition metal-catalyzed reaction of a sufficient excess of diunsaturated compounds containing 2-propenyl groups with polysiloxanes containing Si—H bonds (hydrosilylation), for example 2,5-dimethyl-1,5-hexadiene or H2C=CMe-Ph-CMe═CH2, so that on average only one of the double bonds is consumed in the reaction.

[0041] The organopolysiloxane of the general formula (VII) containing the radical of the general formula (IX) can likewise be prepared by Si—C coupling reactions using organometallic reagents, for example by reaction of polysiloxane containing Si—Cl groups with Grignard reagents of the formula H2C═CMe-MgCl or H2C═CMe-CH2MgCl or other organometallic coupling reagents.

[0042] To prepare the organopolysiloxanes (P) in which R′″ is a monovalent C1- to C18-hydrocarbon radical or C1- to C18-acyl radical which may be cyano-, fluorine-, chlorine-, bromine- or organopolysiloxane-substituted, and be interrupted by divalent radicals bonded on both sides to carbon atoms, and from the group of —O—, ‘COO—, —OOC—, —CONR—, —NR1CO— and —CO—, organopolysiloxane (P) in which R′″ is a hydrogen atom is reacted with the compound of the general formula (X)

XR′″ (X)

[0043] where

[0044] R′″ is a monovalent C1- to C18-hydrocarbon radical or C1- to C18 -acyl radical which may be cyano-, fluorine-, chlorine-, bromine- or organopolysiloxane-substituted, optionally interrupted by divalent radicals which are bonded on both sides to carbon atoms, and from the group of —O—, —COO—, —OOC—, —CONR1—, —NR1CO— and —CO— and

[0045] X is fluorine, chlorine, bromine, hydroxyl, hydrogen or an acid anhydride radical.

[0046] When X is hydrogen, the reaction may be effected, for example, together with CuCl. When X is fluorine, chlorine or bromine, the reaction may be effected, for example, together with dicyclohexylcarbodiimide. When R′″ is an acyl radical and X is an acid anhydride radical, the reaction may be effected, for example, together with CuCl.

[0047] The reaction of organopolysiloxane (A) with H2H2 preferably takes place under acid catalysis. Preference is given to strong acids, such as sulfuric acid.

[0048] The reaction of organopolysiloxane (A) with H2O2 preferably occurs in a solution or dispersion of the organopolysiloxane (A). Preference is given to using alcohols or similar polar solvents. The reaction of organopolysiloxane (A) with H2O2 preferably occurs at a temperature of from 20 to 100° C.

[0049] Organopolysiloxane (A) is known per se. It may be prepared, for example, by addition of aliphatically unsaturated tertiary alcohols to organopolysiloxanes having Si—H groups.

[0050] All of the above symbols of the above formulae are each defined independently of one another.

[0051] In the examples which follow, in each case unless otherwise stated, all amounts and percentages are based on weight, all pressures are 0.10 MPa (abs.) and all temperatures are 20° C.

EXAMPLE 1

[0052] In a stirred 2 liter three-neck flask equipped with a reflux condenser, 1000 grams of a polydimethylhydrosiloxane having terminal Si—H groups (active hydrogen content 0.055% by weight) were initially charged, and the flask was purged with nitrogen and heated to 90° C. 52.03 grams of 2-methyl-3-buten-2-ol which had been admixed beforehand with 0.5 gram of a 1.1% by weight platinum (IV)-containing catalyst solution (hexachloroplatinic acid in isopropanol, “Speier catalyst”) were subsequently metered in within 60 minutes via an attached dropping funnel. The metering was effected in such a way that the boiling point of the reaction mixture was not exceeded. After the end of the metered addition, another 0.2 g of the catalyst solution was added, and stirring was continued at 100° C. for 60 minutes. Excess methylbutenol was removed on a rotary evaporator at 100° C. and 5 mbar, and the product obtained was filtered through a pressure suction filter. The successful conversion to the corresponding hydrosilylation product is confirmed by 1H NMR.

EXAMPLE 2

[0053] In a stirred 2 liter three-neck flask equipped with a reflux condenser, 1000 grams of a polydimethylhydrosiloxane having pendant Si—H groups (active hydrogen content 0.32% by weight) were initially charged, and the flask was purged with nitrogen and heated to 90° C. 309 grams of 2-methyl-3-buten-2-ol which had been admixed beforehand with 0.6 gram of a 1.1% by weight platinum (IV)-containing catalyst solution (hexachloroplatinic acid in isopropanol, “Speier catalyst”) were subsequently metered in within 60 minutes via an attached dropping funnel. The metering was effected in such a way that the boiling point of the reaction mixture was not exceeded. After the end of the metered addition, another 0.2 g of the catalyst solution was added, and stirring was continued at 100° C. for 60 minutes. Excess methylbutenol was removed on a rotary evaporator at 100° C. and 5 mbar, and the product obtained was filtered through a pressure suction filter. The successful conversion to the corresponding hydrosilylation product is confirmed by 1H NMR. The hydrosilylation product has a chain length of 30-40, 8-10 tertiary OH side groups and 4.15% by weight of OH.

EXAMPLE 3

[0054] In a stirred 3 liter three-neck flask equipped with a reflux condenser, 500 grams of a tetramethyldisiloxane having pendant Si—H groups (active hydrogen content 1.5% by weight) were initially charged, and the flask was purged with nitrogen and heated to 90° C. 1370 grams of 2-methyl-3-buten-2-ol which had been admixed beforehand with 0.9 gram of a 1.1% by weight platinum (IV)-containing catalyst solution (hexachloroplatinic acid in isopropanol, “Speier catalyst”) were subsequently metered in within 120 minutes via an attached dropping funnel. The metering was effected in such a way that the boiling point of the reaction mixture was not exceeded. After the end of the metered addition, another 0.3 g of the catalyst solution was added, and stirring was continued at 100° C. for 60 minutes. Excess methylbutenol was removed on a rotary evaporator at 100° C. and 5 mbar, and the product obtained was filtered through a pressure suction filter. The successful conversion to the corresponding hydrosilylation product is confirmed by 1H NMR.

EXAMPLE 4

[0055] In a stirred 2 liter three-neck flask equipped with a reflux condenser, 1000 grams of a polydimethylhydrosiloxane having terminal Si—H groups (active hydrogen content 0.17% by weight) were initially charged, and the flask was purged with nitrogen and heated to 90° C. 156.1 grams of 2-methyl-3-buten-2-ol which had been admixed beforehand with 0.5 gram of a 1.1% by weight platinum (IV)-containing catalyst solution (hexachloroplatinic acid in isopropanol, “Speier catalyst”) were subsequently metered in within 60 minutes via an attached dropping funnel. The metering was effected in such a way that the boiling point of the reaction mixture was not exceeded. After the end of the metered addition, another 0.2 g of the catalyst solution was added, and stirring was continued at 100° C. for 60 minutes. Excess methylbutenol was removed on a rotary evaporator at 100° C. and 5 mbar, and the product obtained was filtered through a pressure suction filter. The successful conversion to the corresponding hydrosilylation product is confirmed by 1H NMR. The hydrosilylation product has a chain length of 15 to 20, terminal and tertiary OH groups, 2.75 % by weight of OH.

EXAMPLE 5

[0056] A polysiloxane hydroperoxide is prepared from the polysiloxane polyol prepared according to example 2 using alcoholic solvent:

1Raw materials:70% H2O2300 g72% H2SO4200 gTurpinal ® SL 5 ml (complexing agent based on phosphoricacid)Silicone copolyol500 g (approx. 1.22 mol of OH groups)according to example 2Ethanol125 g

[0057] Process:

[0058] H2O2, H2SO4 and Turpinal® are initially charged at approx. 25° C. The silicone copolyol/ethanol mixture is added dropwise at approx. 30° C. within about 30 minutes. The mixture is heated to 35° C. and stirred for 30 minutes, then heated to 50° C. and stirred for a further 45 minutes. After cooling to 25° C., 500 g of 5% (NH4)2SO4 solution are added, and the mixture is stirred for 5 minutes and then separated for 40 minutes. (712 g of a slightly cloudy, aqueous phase). The organic phase is washed four times more with 500 g each time of 10% (NH4)2SO4 solution, separating time in each case 45 minutes, aqueous phases clear. The organic phase is allowed to stand until the next day and the aqueous phase is again removed. Product: 520 g of viscous, cloudy liquid; active oxygen content: 3.01%, corresponding to 6.2% by weight of OOH groups, approximately 80% conversion of the OH groups.

EXAMPLE 6

[0059] A polysiloxane hydroperoxide is prepared from the polysiloxane polyol prepared according to example 4, without solvent:

2Raw materials:70% H2O2240 g72% H2SO4160 gTurpinal ® SL 2 mlSilicone copolyol370 g (approx. 0.6 mol of OH groups)

[0060] Process:

[0061] H2O2, H2SO4 and Turpinal® are initially charged at approx. 25° C. The silicone copolyol is added dropwise at approx. 30° C. within from 30 to 40 minutes. The mixture is then heated to 35° C. and stirred for 90 minutes, then heated to 50° C. and stirred for a further 30 minutes. After cooling to 25° C., the phases are separated for 30 minutes (375 g of clear, aqueous phase). The organic phase is washed three times with 300 ml each time of 5% (NH4)2SO4 solution (separating time in each case 30 minutes, aqueous phases clear, organic phase cloudy). Together with 30 g of anhydrous Na2SO4, the mixture is stirred for 30 minutes and filtered. Product: 358 g of clear, colorless, slightly viscous liquid; active oxygen content: 2.52% (corresponding to 5.2% by weight of OOH groups, approx. 100% conversion of the OH groups).

[0062] While embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention.

Silicone peroxides

Information

Publication Number

Date Filed

Date Published

Inventors

Original Assignees

CPC

US Classifications

International Classifications

Abstract

Description

Claims

Priority Claims (1)