Polymers containing silane
View Patent ↗Silane-containing polymers are prepared by the polymerization of one or more ethylenically unsaturated monomers in the presence of a silane-containing aldehyde, hemiacetal, or acetal as a regulator, optionally with further regulators as well. The silane-containing regulators produce polymers with superior properties and with improved polymerization parameters as compared to the conventional mercaptosilane regulators.
1. A silane-containing polymer prepared by free-radical addition polymerization of one or more ethylenically unsaturated monomers in the presence of silane-containing aldehydes, silane-containing hemiacetals, silane-containing acetals, or mixtures thereof, wherein the silane-containing aldehydes, hemiacetals, and acetals are selected from the group consisting of compounds of the structural formulae
R 3 Si—[OSiR 2 ] y —(CH 2 ) x —CH═O(aldehyde), I)
R 3 Si—[OSiR 2 ] y —(CH 2 ) x —CH(OR 1 ) 2 ((hemi)acetal), II)
R 3 Si—[OSiR 2 ] y —(CH 2 ) z —Ar—(CH 2 ) z —CH═O(aldehyde), III)
R 3 Si—[OSiR 2 ] y —(CH 2 ) z —Ar—(CH 2 ) z —CH(OR 1 ) 2 ((hemi)acetal), IV)
O═CH—(CH 2 ) x —Si(R) 2 —O—Si(R) 2 —(CH 2 ) x —CH═O(aldehyde dimers), V)
[SiO(R)—(CH 2 ) z —CH═O] 3-4 (cyclic trimers and tetramers), VI)
where R is identical or different at each occurrence and is halogen: an unbranched or branched, saturated or unsaturated, optionally substituted alkyl or alkoxy radical having 1 to 12 carbon atoms; an acyl radical having 2 to 12 carbon atoms; or an optionally substituted aryl or aryloxy radical having 3 to 20 carbon atoms, R optionally interrupted by one or more non-adjacent heteroatoms selected from the group consisting of N, O and S, and the aryl radical or the aryl group of the aryloxy radical optionally containing one or more heteroatoms selected from the group consisting of N, O and S, and
R 1 is H, an unbranched or branched, saturated or unsaturated, optionally substituted alkyl radical having 1 to 12 carbon atoms, the carbon atoms of which are optionally interrupted one or more non-adjacent heteroatoms selected from the group consisting of N, O and S,
Ar is an aromatic group, optionally containing one or more heteroatoms selected from the group consisting of N, O and S, and
x is a number from 2 to 40, y is a number from 0 to 100, and z is a number from 0 to 20,
wherein the silane-containing aldehyde, silane-containing hemiacetal, or silane-containing acetal is employed as a chain regulator in an amount of 0.0001 to 5.0% by weight based on the total weight of all monomers, and wherein the free radical polymerization is initiated by a non-redox free radical initiator, or when the initiator is a redox initiator, the oxidizing agent is selected from the group consisting of sodium, potassium, and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, t-butyl peroxide, potassium peroxodiphosphate, t-butyl peroxopivalate, cumene hydroperoxide, isopropylbenzene monohydroperoxide, azobisisobutyronitrile, dicetyl peroxydicarbonate, dicyclohexylperoxydicarbonate, dibenzoyl peroxide, t-butyl perneodecanoate, t-butyl per-2-ethylhexanoate, t-butylperipalate, and mixtures thereof.
2. The silane-containing polymer of claim 1 , wherein the ethylenically unsaturated monomers comprise one or more monomers selected from the group consisting of vinyl esters of unbranched and branched alkylcarboxylic acids having 1 to 18 carbon atoms; acrylic esters and methacrylic esters of branched and unbranched alcohols and diols having 1 to 18 carbon atoms; ethylenically unsaturated monocarboxylic and dicarboxylic acids, their amides, N-methylolamides and nitriles; ethylenically unsaturated sulfonic acids; ethylenically unsaturated heterocyclic compounds; alkyl vinyl ethers; dienes; olefins; vinylaromatics; and vinyl halides.
3. The silane-containing polymer of claim 1 , wherein ethylenically unsaturated, silane-containing monomers are copolymerized as one of said one or more ethylenically unsaturated monomers.
4. The silane-containing polymer of claim 1 , wherein ethylenically unsaturated, silane-containing monomers are copolymerized as one of said one or more ethylenically unsaturated monomers.
5. A process for preparing a silane-containing polymer of claim 1 , by free-radical addition polymerizing one or more ethylenically unsaturated monomers in the presence of at least one silane-containing aldehyde, silane-containing hemiacetal, silane-containing acetal, or mixture thereof.
6. The process of claim 5 , wherein polymerizing takes place in bulk, in solution, in suspension or in emulsion.
7. The process of claim 5 , wherein a portion of the silane-containing aldehydes, silane-containing hemiacetals and/or silane-containing acetals are included in the initial charge and the remainder is metered in.
8. The process of claim 5 , wherein silane-containing compounds other than silane-containing aldehydes, hemiacetals, or acetals, or aldehydes are also employed as further regulators.
9. In a release coating wherein a silane-containing polymer is employed as at least one component, the improvement comprising selecting as said silane-containing polymer, a silane-containing polymer of claim 1 .
10. In an architectural preservative composition wherein a silane-containing polymer is employed as at least one component, the improvement comprising selecting as a silane-containing polymer, a silane-containing polymer of claim 1 .
11. In a modifier or water repellent composition wherein a silane-containing polymer is employed as at least one component, the improvement comprising selecting as a silane-containing polymer, a silane-containing polymer of claim 1 .
12. In a binder in an adhesive, paint, printing ink or sealant composition wherein a silane-containing polymer is employed as at least one component, the improvement comprising selecting as a silane-containing polymer, a silane-containing polymer of claim 1 .
13. In a hydraulically setting construction product selected from the group consisting of construction adhesives, renders, filling compounds, trowel-applied flooring compounds, leveling compounds, non-shrink grouts, joining mortars and paints containing at least one hydraulically setting binder selected from the group consisting of cement, gypsum, and waterglass, wherein a polymer additive is employed, the improvement comprising selecting as at least one polymer additive, silane-containing polymer of claim 1 .
14. In a binder for coating materials and adhesives or as coating material or binder for textiles, fibers, wood or paper compositions wherein a silane-containing polymer is employed as at least one component, the improvement comprising selecting as a silane-containing polymer, a silane-containing polymer of claim 1 .
15. The silane-containing polymer of claim 1 , wherein the silane-containing aldehyde, silane-containing hemiacetal, or silane-containing acetal is employed in an amount of from 0.1 to 3.0 weight percent based on the weight of all monomers.
16. The silane-containing polymer of claim 1 , wherein the chain regulator consists of a silane-containing hemiacetal.
17. The silane-containing polymer of claim 1 , wherein the chain regulator consists of a silane-containing acetal.
18. The silane-containing polymer of claim 1 , wherein a silane-containing aldehyde, hemiacetal, or acetal is selected from the group consisting of 3,3-diethoxypropyltriethoxysilane, 3,3-dimethoxypropyltriethoxysilane, 3,3-diethoxypropyl-trimethoxysilane, 3,3-dimethoxypropyl-trimethoxysilane, 3,3-diethoxypropylmethyldiethoxy-silane, 3,3-dimethoxypropyldiisopropoxymethylsilane, 3,3-diethoxypropyldimethylethoxy-silane, 3,3-dimethoxypropyldiisopropoxymethylsilane, 3,3-dimethoxypropyltripropoxysilane, 3,3-dimethoxypropyltriisopropoxysilane, 3,3-dipropoxypropyltriethoxysilane, 3,3-diethoxypropylmethyldimethoxysilane, 3,3-diethoxypropyldimethylmethoxysilane, 3,3-dimethoxypropymethyldimethoxysilane, 3,3-dimethoxypropyldimethylmethoxysilane, 3,3-dimethoxyprolmethldimethoxysilane, 1,1′-diethylformyltetramethyldisiloxane, and mixtures thereof.