DE10219734A1 - Production of (meth)acrylate-functional organosiloxanes, e.g. useful in coatings, comprises reacting a hydroxy-functional organosiloxane with a (meth)acrylate-functional silane - Google Patents

Abstract

Production of (meth)acrylate-functional organosiloxanes (I) comprises reacting a hydroxy-functional organosiloxane (II) with a (meth)acrylate-functional silane (III). Production of (meth)acrylate-functional organosiloxanes of formula (I) comprises reacting an organosiloxane of formula (II) with a silane of formula (III): (SiO4/2)k(R<1>SiO3/2)m(R<1>2SiO2/2)p(R<1>3SiO1/2)q(Ou/2(R<3>O)v-uR<1>(3-v)SiCR<2>2 -O-CO-CR<4>=CH2)s(O1/2H)t (I) (SiO4/2)k(R<1>SiO3/2)m(R<1>2SiO2/2)p(R<1>3SiO1/2)q(Ou/2H)r (II) (R<3>O)v-uR<1>(3-v)SiCR<2>2 -O-CO-CR<4>=CH2 (III) R<1> = H or a 1-20C hydrocarbyl or 1-15C hydrocarbyloxy group which is optionally substituted with CN, NCO, NR2, COOH, halo, epoxy, SH, OH or CONR2 and in which nonadjacent CH2 groups can be replaced by O, CO, COO, OCO, OCOO, S or NR2 and nonadjacent CH groups can be replaced by N, N=N or P; R = H or optionally CN- or halo-substituted 1-10C hydrocarbyl; R<2>, R<4> = H or optionally CN- or halo-substituted 1-20C hydrocarbyl; R<3> = optionally CN- or halo-substituted 1-15C hydrocarbyl; s, r = 1 or more; v, u = 1-3, provided that u <= v; s+t = r; k+m+p+q+r = 2 or more.

Description

The invention relates to a method for producing (meth) acrylic functional siloxanes using Alkoxysilanes.

(Meth) acrylic polysiloxanes are used in many areas useful, e.g. B. as photocrosslinkable coatings Production of adhesive layers, such as. B. from EP-A-624627 is known, and for the production of hard and soft Contact lenses. Other uses of these materials are Encapsulating, sealing, gluing or coating z. B. electronic components from WO 9602579 or US 4528081 known, the corresponding (meth) acrylic polysiloxanes still are partially functionalized with alkoxysilane functions a network can either run in two steps or also in regions inaccessible to light Enable networking. These materials are used for usually still with photoinitiators e.g. B. to increase the Networking speed equipped. Still coming Fillers (e.g. highly disperse silicas) or else Plasticizers (e.g. low molecular weight silicone oils) for variation the mechanical properties (e.g. tensile strength, modulus of elasticity, Shore hardness etc.) are used. The so equipped Materials can be used as adhesives and sealants or z. B. as coating materials e.g. B. in the Paper industry for the production of abhesive materials.

For the production of these (meth) acrylic functional silicone oils there are several ways. The addition of is known Allyl methacrylate on Si-H-containing compounds a hydrosilylation reaction, which is also the most common applied technical process is. Are problematic here which increased by the hydrosilylation reaction Reaction temperatures, which require the use of larger amounts Inhibitors required to be early Polymerize or gel the corresponding compounds suppress. In addition, in hydrosilylation as Side reaction is the addition of the Si-H component to the carbonyl Group observed. To suppress them have to be very expensive Precious metal catalysts (including rhodium) can be used. Since the corresponding acrylic functional compounds are far tend to polymerize more, they usually become by esterification of hydroxyalkyl-terminated siloxanes with z. E.g .: acrylic acid chloride using an acid scavenger manufactured. However, both methods have in common that both assume relatively expensive preliminary products (Si-H-terminated Siloxanes or hydroxypropyl-terminated siloxanes). The synthesis of (meth) acrylic functionalities can e.g. T. also from known equilibration reactions (meth) acrylic functional silanes or siloxanes with other siloxanes take place, which is catalyzed either by acids or bases become. The disadvantage here, however, is that there may be more By-products such as B. octamethylcyclotetrasiloxane arise, which z. T. must be removed from the product. Through this additional procedural step associated with that required heat can now the premature polymerization of the (meth) acrylic group, which leads to gelation of the all material.

The implementation of silanol-functional is also known Polydimethylsiloxanes with (meth) acrylalkoxysilanes such as. B. in EP-A-564253 described or the implementation of silanol functional polydimethylsiloxanes with (Meth) acrylic (meth) acryloxysilanes as described in US 5182315.

The implementation of silanol groups with acryloxysilanes (US 5182315) runs under mild conditions that are free carbonic acid with its strongly irritating and caustic Effect affects the smell of the resulting Silicon oil sustainable and can be used for. B. for Destruction of electronic components or more sensitive Surfaces such as B. lead marble. The carboxylic acid can at elevated temperatures from the reaction mixture remove, however, the (meth) acrylic functional Silicon oil exposed to a high temperature load, which leads to premature thermally initiated polymerization and thus to Gelling of the product can result.

The functionalization of silanol-terminated compounds is therefore preferably carried out with alkoxysilanes, which at appropriate reaction conditions using Catalysts also react. In the literature different catalysts such as amines, inorganic oxides, Potassium acetate, titanium compounds and others mentioned, the Disadvantages can be mentioned in EP-A-564253. The in EP-A-564253 Lithium compounds used are for functionalization of silanol-terminated compounds with alkoxysilanes, however well suited because they are odorless, the equilibration of the Siloxane chain not at slightly elevated temperatures equilibrate, easily neutralized by reaction with acid can, are non-toxic and also quite inexpensive got. Both organic lithium compounds can be used like butyllithium as described in EP-A-564253 but also inorganic lithium compounds such as lithium hydroxide, as in US 5079324 can be used. Key point of use of these lithium compounds, however, is the reaction conditions to be as mild as possible in the synthesis in order to to prevent premature polymerization of the reactive groups. In EP-A-564253 propane spaced (Meth) acrylpropyl-functionalized trialkoxysilanes used, but some Have disadvantages. So they are not suitable for the reaction to be carried out so carefully that premature polymerization can always be prevented. Furthermore, the corresponding ones (Meth) acrylic propyl functionalized dialkyl monoalkoxy silanes commercially very difficult to obtain and in their reactivity significantly weakened compared to silanol groups. You want to however, produce a (meth) acrylic functional siloxane, which no longer carries any additional alkoxy groups The use of monoalkoxy-functional silanes is absolutely necessary. On Another disadvantage of the silanes used in EP-A-564253 is that partly insufficient reactivity or Crosslinking rate of the alkoxysilane compound in the reaction with water, which leads to longer skin formation times. Skin formation times are particularly common in many industrial applications of great interest as it speeds up production be co-determined and it is therefore advantageous to be as short as possible To get skin formation times.

A process was sought which was based on one Side used inexpensive primary products, on the other However, the site is so flexible that it can be used in good yields acrylic and methacrylic functional siloxanes are produced can. The reaction must be as gentle as possible Conditions d. H. short response times and low Temperatures expire to premature polymerization of the To prevent (meth) acrylic groups. The manufactured Compounds should carry (meth) acrylic acid groups and optionally no or more alkoxysilane groups. Especially but the alkoxysilane groups should also be able to be sufficiently fast due to the influence of water network, d. H. the achievable skin formation times should be as short as possible.

The invention relates to a process for the preparation of (meth) acrylic-functional organosiloxane of the general formula I,

(SiO _4/2 ) _k (R ¹ SiO _3/2 ) _m (R ¹ ₂ SiO _2/2 ) _p (R ¹ ₃ SiO _1/2 ) _q [O _{u / 2} (R ³ O) _vu R ¹ _{( 3-v)} SiCR ² ₂ -O-CO-CR ⁴ = CH ₂ ] _s [O _1/2 H] _t (I),

with the organosiloxane general formula II

(SiO _4/2 ) _k (R ¹ SiO _3/2 ) _m (R ¹ ₂ SiO _2/2 ) _p (R ¹ ₃ SiO _1/2 ) _q [O _1/2 H] _r (II),

with silane of the general formula III

(R ³ O) _v R ¹ _3-v SiCR ² ₂ -O-CO-CR ⁴ = CH ₂ (III),

is implemented, whereby
R ^{1 is} a hydrogen atom or a monovalent C ₁ -C ₂₀ -substituted or substituted with -CN, -NCO, -NR ^x ₂ , -COOH, -halogen, -epoxy, -SH, -OH or -CONR ^x ₂ Hydrocarbon radical or C ₁ -C ₁₅ -hydrocarbonoxy radical in each of which one or more, not adjacent methylene units by groups -O-, -CO-, -COO-, -OCO-, or -OCOO-, -S-, or -NR ^x - can be replaced and in which one or more non-adjacent methine units can be replaced by groups, -N =, -N = N-, or -P =,
R ^{x is} hydrogen or a C ₁ -C ₁₀ hydrocarbon radical which is optionally substituted by -CN or halogen,
R ² and R ^{4 are} hydrogen or a C ₁ -C ₂₀ hydrocarbon radical which is optionally substituted by -CN or halogen,
R ^{3 is} an optionally cyano- or halogen-substituted C ₁ -C ₁₅ hydrocarbon radical,
s values of at least 1,
r values of at least 1,
v values of 1, 2 or 3,
u values of 1, 2 or 3,
where u must be less than or equal to v,
s + t the value of r and
k + m + p + q + r mean values of at least 2.

The process is simple and quick to perform and delivers hardly any by-products. When using (meth) acrylmethyl functionalized alkoxysilanes of the general formula I, are shortened compared to the propyl-spaced compounds Reaction times reached under the same reaction conditions, d. H. a product can either be manufactured faster or at low temperatures.

The silanes of the general formula III used can easily and in high yields, e.g. B. by Reaction of the corresponding (meth) acrylic acids with Chloromethylsilanes using an auxiliary base such as e.g. B. triethylamine.

The notation "meth (acrylic)" includes "methacrylic" and "acrylic", where the acrylic radical in the α-position can also carry other substituents R ^{4 in} addition to the methyl radical.

The C ₁ -C ₂₀ hydrocarbon radicals and C ₁ -C ₁₅ hydrocarbonoxy radicals R ¹ can be aliphatically saturated or unsaturated, aromatic, straight-chain or branched. R ¹ preferably has 1 to 12 atoms, in particular 1 to 6 atoms, preferably only carbon atoms, or an alkoxy oxygen atom and otherwise only carbon atoms. R ¹ is preferably a straight-chain or branched C ₁ -C ₆ alkyl or alkoxy radical. The radicals methyl, ethyl, phenyl, vinyl and trifluoropropyl are particularly preferred.

The compounds of the general formula I in which R ^{1 is} methyl, ethyl, phenyl, vinyl or trifluoropropyl are preferably prepared.

The radicals R ² and R ⁴ can, independently of one another, also be aliphatically saturated or unsaturated, aromatic, straight-chain or branched. R ² and R ⁴ are preferably each a C ₁ -C ₆ alkyl radical or hydrogen. R ⁴ is particularly preferably methyl or hydrogen.

The radicals R ³ can, independently of one another, also be aliphatic saturated or unsaturated, aromatic, straight-chain or branched. R ³ is preferably a C ₁ -C ₄ alkyl radical or hydrogen.

The (meth) acrylic functional organosiloxane of the general Formula III can be linear, cyclic or branched. The sum of k, m, p, q, s and t is preferably a number from 2 to 20000, especially 8 to 1000. To a reaction between the Organosiloxane of the general formula II and the silane To enable general formula III, r must be> 0, d. H. the Organosiloxane of the general formula I must have hydroxyl groups contain.

A preferred variant for a branched organosiloxane general formula I is an organosilicone resin. This can consist of several units, as in the general formula III is indicated, the mole percent of the contained Units denoted by the indices k, m, p, q, r, s and t become. A value of 0.1 to 20% of units r is preferred, based on the sum of k, m, p, q and r. At the same time but also be k + m> 0. The organosiloxane resin general formula I must be s> 0 and s + t must be r.

Resins are preferred in which 5% <k + m <90%, based on the sum of k, m, p, q, r, s and t, and preferably t is 0. In a particularly preferred case, R ¹ is a methyl radical.

If you want to produce resins here that only define one Have (meth) acrylic content, you choose the stoichiometric Ratios between resin and silane so that the desired (Meth) acrylic content is reached. Remaining Si-OH groups can if necessary, remain in the product.

Another preferred variant for a (meth) acrylic-functional organosiloxane of the general formula I is an organosiloxane of the general formula IV which is liquid at 25 ° C.

(R ¹ ₂ SiO _2/2 ) _p (R ¹ ₃ SiO _1/2 ) _q [O _{u / 2} (R ³ O) _vu R ¹ _(3-v) SiCR ² ₂ -O-CO-CR ⁴ = CH ₂ ] _s [O _1/2 H] _t (IV),

that from organosiloxane of the general formula V

(R ¹ ₂ SiO _2/2 ) _p (R ¹ ₃ SiO _1/2 ) _q [O _1/2 H] _r (V)

is prepared with (meth) acrylsilane of the general formula II, where
u the values 1 or 2,
v the values 1, 2 or 3 and
n is a number from 1 to 20,000.

U preferably has the value 1. p preferably has values of 1 to 20,000, especially 8 to 2,000.

If a mixture of starting compounds of the general Formula V is used, the value of p denotes the Average of the degrees of polymerization of the silanols present general formula V.

• 1. Viskosität (bzw. Molekulargewicht Mn)
• 2. Gehalt an (Meth)acrylgruppen
• 3. Gehalt an Alkoxysilan-Gruppen
• 4. Verzweigungsgrad.

The organosiloxanes of the general formula IV thus represented can essentially be characterized by 4 different sizes:

• 1. Viscosity (or molecular weight Mn)
• 2. Content of (meth) acrylic groups
• 3. Content of alkoxysilane groups
• 4. Degree of branching.

The viscosity of the siloxane is essentially through its molecular weight determined by the siloxane general formula V, the choice of silanes of formula II and underlying stoichiometry of the educt mixtures is influenced can be.

The content of (meth) acrylic groups is regulated by use of mono-, di- and trialkoxy (meth) acrylsilanes. In doing so the monoalkoxysilanes are incorporated as end groups in the polymer, the dialkoxy compounds are usually in the chain installed and the trialkoxysilanes are usually as Branch point built into a chain. However, are more Alkoxy groups in the reaction mixture as OH groups present, so can also di- or trialkoxy compounds End groups or as chain links can be installed. hereby remain in the siloxane chain or at the end of the siloxane chain remaining alkoxysilane groups, which if necessary under Exposure to OH groups (e.g. moisture) can be crosslinked can. In this way one obtains organofunctional ones Silicon compounds, which are e.g. B. by humidity can also be networked by the action of z. B. UV light let crosslink via the (meth) acrylic groups. One calls such systems are generally called "dual-cure" systems. The introduction of branches can be positive under certain circumstances Processing properties result in such. B. the Reduced fog formation during coating processes. in the in general, however, too high a proportion of branch points for gelatinizing the material, which is now more difficult process.

Particularly quickly and at low temperatures and therefore The implementation of compounds of the general formulas II and III for compounds of the formula I, if catalysts are chosen to accelerate the reaction which are either metal catalysts, basic or acidic catalysts are among those chosen However, reaction conditions hardly catalyze equilibration reactions. These are e.g. B. zinc salts, partially esterified phosphoric acids and Lithium bases, such as organolithium compounds, in particular Alkyl lithium compounds, lithium alkoxides or lithium hydroxide.

Basic catalysts are particularly preferred the reaction of the alcohol released with the Si-O-Si bonds also do not catalyze. This gives you the Possibility z. B. monofunctional (meth) acrylic compounds corresponding mono-hydroxy-functional silicone oils synthesize which are not under equilibration conditions are accessible. Are very particularly preferred Lithium compounds such as B. lithium silanolates, organic Alkyl lithium compounds, lithium alkoxides or lithium hydroxide.

These catalysts can optionally be dissolved in nonpolar Solvent, as a solid or also dissolved in polar Solvents are added. In the used Amounts of catalyst are naturally not maximum amounts specify. To a certain extent, however, the additional amounts of catalyst also side reactions and the catalyst may have to be removed. As The maximum amount of the catalysts used is therefore an amount of a maximum of 1% by weight based on the finished silicone oil or 1 mol equivalent based on the Si-OH groups, the silicone Educts completely sufficient. The minimum quantities used Catalysts are optionally 1 ppm based on that Total weight of the finished silicone oil or 0.001 mol Equivalents based on the Si-OH groups of the silicone educt. Amounts of 1 ppm to 5000 ppm are particularly preferred based on the total weight of the end product.

The compounds of general formula IV also have the The advantage is that if t> 0, either with yourself or condense with compounds of the general formula V. can, optionally with the support of a catalyst or other silanes, also compounds of general To produce Formula IV, which however is a higher one Have molecular weight, d. H. the numerical value of the number p increases. In In a particularly preferred case, p stands for a number of 8 to 50 before the condensation and 50 to 2000 after the Condensation.

To stabilize the compounds during the reaction or during storage may still Polymerization inhibitors such. B. phenothiazine or sterically hindered phenols are added in small amounts.

The process is preferred at 0 ° C to 140 ° C, especially preferably carried out at at least 10 ° C. to 80 ° C. The process can be carried out using both Solvents are carried out, or without Use of solvents in suitable reactors. there is optionally under vacuum or under pressure or at Normal pressure (0.1 Mpa) worked. The one in the reaction The resulting alcohol can either remain in the product or / and by applying a vacuum or increasing the temperature be removed from the reaction mixture. The catalysts can be added in solid form or in solution.

When using solvents are inert, especially aprotic solvents such as aliphatic hydrocarbons, such as B. heptane or decane and aromatic hydrocarbons such as B. toluene or xylene is preferred. Ether can also such as THF, diethyl ether or MTBE can be used. To the solution however, the catalysts can contain very small amounts protic compounds such as B. methanol or ethanol be used. The amount of solvent should be are sufficient to ensure sufficient homogenization of the Ensure reaction mixture. Solvent or Solvent mixtures with a boiling point or boiling range up to 120 ° C at 0.1 MPa are preferred.

Unreacted Si-OH groups in the compounds of the general Formula I remain in the product or z. B. with others Silanes according to the generally known prior art be implemented.

This second scheduling can also, if necessary refrain from doing so, however, it offers in terms of the stability of the Materials at elevated temperatures have clear advantages because Si-OH groups tend to condense at higher temperatures and so can increase the viscosity of the solutions obtained.

Those produced by the process according to the invention (meth) acrylic-functional organosiloxanes of the general formula I, have an increased reactivity of the alkoxysilane groups towards water on what to increase Networking speeds leads. The skin formation times are very short, especially when compared to propyl-spaced ones (meth) acrylic functional organosiloxanes. The according to the invention Process produced (meth) acrylic functional organosiloxanes General Formula I are used in the field radiation-curing coatings, technical coatings from Z. B. electronic components, paper or medical Articles such as B. contact lenses; in the field of technical Bonds z. B. of glass or transparent plastics and in the encapsulation of electronic components as well as Sealants and masses for moldings, such as. B. contact lenses.

All of the above symbols of the above formulas have theirs Meanings each independently.

In the following examples, unless otherwise different indicated, all quantities and percentages by weight related, all pressures 0.10 MPa (abs.) and all temperatures 20 ° C.

example 1

100 g bishydroxy-terminated polydimethylsiloxane with a Mn of 3000 g / mol (determined by 1H NMR spectroscopy, 33 mmol) were at 60 ° C with 12.5 g of methacrylmethyldimethylmethoxysilane (Mn = 188.3 g / mol, 66 mmol) and 500 ppm lithium methoxide (25% solution in methanol) implemented. The 1H-NMR and 29 Si-NMR showed that the reaction was complete after 3 hours and none There were more silanol groups. The resulting methanol was removed on a rotary evaporator under vacuum and that Lithium methoxide was made with tristrimethylsilyl phosphate neutralized. A silicone oil with a viscosity was obtained of 65 mPas, which at the chain ends with Methacrylmethyl groups was functionalized.

Example 2

120 g bishydroxy-terminated polydimethylsiloxane with a Mn of 3000 g / mol (determined by 1H NMR spectroscopy, 40 mmol) were at 60 ° C with 6.1 g Methacrylmethylmonomethyldimethoxysilane (Mn = 204.3 g / mol, 30 mmol) and 500 ppm lithium methoxide (25% solution in methanol) implemented. The 1H-NMR showed that the reaction was complete after 3 hours since there was no methoxysilane more could be demonstrated, the viscosity of the Silicon oil had risen to 310 mPas. The resulting methanol was removed on a rotary evaporator under vacuum and that Lithium methoxide was made with tristrimethylsilyl phosphate neutralized. A silicone oil with a viscosity was obtained of 65 mPas, which is in the chain with methacrylmethyl groups was functionalized.

Example 3

100 g bishydroxy-terminated polydimethylsiloxane with a Mn of 3000 g / mol (determined by 1H NMR spectroscopy, 33 mmol) were at 60 ° C with 11.5 g of Acrylmethyldimethylmethoxysilan (Mn = 174.3 g / mol, 66 mmol), 500 ppm lithium methoxide (25% Solution in methanol) and 20 mg phenothiazine as inhibitor implemented. The 1H-NMR and 29 Si-NMR showed that after 3 hours the The reaction was complete and there were no more silanol groups were. The resulting methanol was on a rotary evaporator removed under vacuum and the lithium methoxide was with Neutralized tristrimethylsilyl phosphate. You got one Silicone oil with a viscosity of 65 mPas, which on the Chain ends were functionalized with acrylic methyl groups.

Example 4

120 g bishydroxy-terminated polydimethylsiloxane with a Mn of 3000 g / mol (determined by 1H NMR spectroscopy, 40 mmol) were at 60 ° C with 12.5 g Methacrylmethylmonomethyldimethoxysilane (Mn = 190.3 g / mol, 66 mmol) 20 mg phenothiazine and 500 ppm Lithium methoxide (25% solution in methanol) implemented. The 1H NMR showed that the reaction was complete after 3 hours because no more methoxysilane could be detected, the Viscosity of the silicone oil had risen to 310 mPas. The The resulting methanol was on a rotary evaporator under vacuum deducted and the lithium methoxide became carbon dioxide neutralized. A silicone oil with a viscosity of 65 mPas, which is in the chain with methacrylmethyl groups was functionalized.

Example 5

104 g bishydroxy-terminated polydimethylsiloxane with a Mn of 940 g / mol (determined by 1H NMR spectroscopy, 110 mmol) were at 60 ° C with 41.4 g of methacrylmethyldimethylmethoxysilane (Mn = 188.3 g / mol, 220 mmol) and 500 ppm lithium methoxide (25% solution in methanol) implemented. The 1H-NMR and 29 Si-NMR showed that the reaction was complete after 3 hours and none There were more silanol groups. The resulting methanol was removed on a rotary evaporator under vacuum and that Lithium methoxide was made with tristrimethylsilyl phosphate neutralized. A silicone oil with a viscosity of 25 mPas, which at the chain ends with methacrylmethyl groups was functionalized.

Example 6

100 g bishydroxy-terminated polydimethylsiloxane with a Mn of 3000 g / mol (determined by 1H NMR spectroscopy, 33 mmol) were at 60 ° C with 14.5 g of methacrylmethyltrimethoxysilane (Mn = 220.3 g / mol, 66 mmol) and 500 ppm of lithium methoxide. The 1H-NMR and 29 Si-NMR showed that after 3 hours the The reaction was complete and there were no more silanol groups were. The methanol formed in the reaction was on Rotary evaporator removed under vacuum and that Lithium methoxide (25% solution in methanol) was with Neutralized tristrimethylsilyl phosphate. A silicone oil was also obtained a viscosity of 72 mPas, which at the chain ends with Methacrylmethyldimethoxysilan groups was functionalized.

Example 7

100 g monohydroxy-terminated polydimethylsiloxane with one Mn of 1000 g / mol (determined by 1H NMR spectroscopy, 100 mmol, made by anionic polymerization of D3-Cycles with sec.-BuLi as initiator and termination with acetic acid) at 60 ° C with 22.0 g methacrylmethyltrimethoxysilane (Mn = 220.3 g / mol, 100 mmol) and 500 ppm lithium methoxide (25% solution in Methanol) implemented. The 1H-NMR showed that after 3 hours the Implementation ended because there were no more silanol groups could be detected and 1/3 of the methoxy groups disappeared were, the viscosity of the silicone oil to 19 mPas had risen. The resulting methanol was on Rotary evaporator removed under vacuum and the lithium methoxide was neutralized with tristrimethylsilyl phosphate. You got one Silicone oil with a viscosity of 19 mPas, which on a Chain end with methacrylmethyldimethoxysilyl groups was functionalized.

Example 8

100 g monohydroxy-terminated polydimethylsiloxane with one Mn of 1000 g / mol (determined by 1H NMR spectroscopy, 100 mmol, made by anionic polymerization of D3-Cycles with sec.-BuLi as initiator and termination with acetic acid) at 60 ° C with 7.3 g methacrylmethyltrimethoxysilane (Mn = 220.3 g / mol, 100 mmol) and 500 ppm lithium methoxide (25% solution in Methanol) implemented. The 1H-NMR showed that after 3 hours the Implementation ended because there were no more silanol groups could be detected and all methoxy groups disappeared were, the viscosity of the silicone oil to 67 mPas had risen. The resulting methanol was on Rotary evaporator removed under vacuum and the lithium methoxide was neutralized with tristrimethylsilyl phosphate. You got one branched silicone oil, which with a Methacrylmethyl group was functionalized, but otherwise only still had three unreactive trialkylsilyl groups.

Example 9

120 g bishydroxy-terminated polydimethylsiloxane with a Mn of 3000 g / mol (determined by 1H NMR spectroscopy, 40 mmol) were at 60 ° C with 6.1 g Methacrylmethylmonomethyldimethoxysilane (Mn = 204.3 g / mol, 30 mmol) and 500 ppm lithium methoxide (25% solution in methanol) implemented. The 1H-NMR showed that the reaction was complete after 3 hours since there was no residual Methoxysilane could be detected more, the Viscosity of the silicone oil had risen to 310 mPas. Subsequently 4.4 g of methacrylmethyltrimethoxysilane (Mn = 220.3 g / mol, 20 mmol) The resulting methanol would on Rotary evaporator removed under vacuum and the lithium methoxide was neutralized with tristrimethylsilyl phosphate. You got one Silicone oil with a viscosity of 410 mPas, which in the Chain was functionalized with methacrylmethyl groups and on Chain end with methacrylmethyldimethoxysilane groups was functionalized.

Claims (6)

1. Process for the preparation of meth (acrylic) functional organosiloxane of the general formula I,

(SiO _4/2 ) _k (R ¹ SiO _3/2 ) _m (R ¹ ₂ SiO _2/2 ) _p (R ¹ ₃ SiO _1/2 ) _q [O _{u / 2} (R ³ O) _vu R ¹ _{( 3-v)} SiCR ² ₂ -O-CO-CR ⁴ = CH ₂ ] _s [O _1/2 H] _t (I)

with the organosiloxane general formula II

(SiO _4/2 ) _k (R ¹ SiO _3/2 ) _m (R ¹ ₂ SiO _2/2 ) _p (R ¹ ₃ SiO _1/2 ) _q [0 _1/2 H] _r (II),

with silane of the general formula III

(R ³ O) _v R ¹ _3-v SiCR ² ₂ -O-CO-CR ⁴ = CH ₂ (III),

is implemented, whereby
R ^{1 is} a hydrogen atom or a monovalent C ₁ -C ₂₀ -substituted or substituted with -CN, -NCO, -NR ^x ₂ , -COOH, -halogen, -epoxy, -SH, -OH or -CONR ^x ₂ Hydrocarbon radical or C ₁ -C ₁₅ -hydrocarbonoxy radical in each of which one or more, not adjacent methylene units by groups -O-, -CO-, -COO-, -OCO-, or -OCOO-, -S-, or -NR ^x - can be replaced and in which one or more non-adjacent methine units can be replaced by groups, -N =, -N = N-, or -P =,
R ^{x is} hydrogen or a C ₁ -C ₁₀ hydrocarbon radical which is optionally substituted by -CN or halogen,
R ² and R ^{4 are} hydrogen or a C ₁ -C ₂₀ hydrocarbon radical which is optionally substituted by -CN or halogen,
R ^{3 is} an optionally cyano- or halogen-substituted C ₁ -C ₁₅ hydrocarbon radical,
s values of at least 1,
r values of at least 1,
v values of 1, 2 or 3,
u values of 1, 2 or 3,
where u must be less than or equal to v,
s + t the value of r and
k + m + p + q + r mean values of at least 2. 2. The method according to claim 1, wherein a (meth) acrylic functional organosiloxane resin is produced, wherein r 0.1 to 20%, based on the sum of k, m, p, q and r is and k + m> 0. 3. The method according to claim 1 or 2, in which a (meth) acrylic functional organosiloxane of the general formula IV,

(R ¹ ₂ SiO _2/2 ) _p (R ¹ ₃ SiO _1/2 ) _q [O _{u / 2} (R ³ O) _vu R ¹ _(3-v) SiCR ² ₂ -O-CO-CR ⁴ = CH ₂ ] _s [O _1/2 H] _t (IV),

from organosiloxane of the general formula V

(R ¹ ₂ SiO _2/2 ) _p (R ¹ ₃ SiO _1/2 ) _q [O _1/2 H] _r (V)

is prepared with (meth) acrylsilane of the general formula II, where
u the values 1 or 2,
v the values 1, 2 or 3 and
n is a number from 1 to 20,000. 4. The method according to claim 1 to 3, in the catalyst added, which is selected from tin salts, partially esterified phosphoric acids and lithium bases. 5. The method according to claim 1 to 4, which at 0 ° C to 140 ° C is carried out. 6. The method according to claim 1 to 4, wherein the radicals R ² and R ⁴ each represent a C ₁ -C ₆ alkyl radical, or hydrogen.