DE102012103372A1 - Use of amino-functional polyorganosiloxanes as wood preservatives - Google Patents

Abstract

The present invention relates to functionalized polyorganosiloxanes for the treatment of lignocellulosic materials.

Description

The present invention relates to functionalized polyorganosiloxanes for the treatment of lignocellulosic materials, which are suitable to make wood and other substances based on cellulose and / or lignin preserved, and in particular to protect against weathering, microorganisms, insects and fungi. Furthermore, the water absorption of lignocellulosic materials, in particular wood, reduces the shrinkage behavior of lignocellulosic materials, in particular wood, by means of the polyorganosiloxanes used according to the invention. By using the polyorganosiloxanes according to the invention, moreover, an insecticidal composition is achieved which renders the use of conventional insecticides dispensable.

It is known to increase the resistance of wood to the weather by a coating of paints and colors. Dimensional changes of the wood, for example due to swelling and shrinkage due to water absorption, caused by external moisture fluctuations, however, lead to the flaking of such paints.

It is also known to protect the visual appearance and the resistance of wood against harmful microorganisms, such as fungal fungus or white rot, brown rot and soft rot by impregnation with a mixture of arsenic, ionic copper and chromium VI.

At this wood preservative is disadvantageous that at least chromium and arsenic are harmful to health and the environment. Also, copper complexes and boron compounds are now considered critical from the same aspects.

Furthermore, water-soluble wood preservatives are known which contain a quaternary ammonium compound, such as benzalkonium chloride. On these wood preservatives is disadvantageous that they are deposited due to their immediate binding to wood only in the upper layers of wood.

Other biocidal active ingredients are 3-iodo-2-propynyl-butylcarbamate (IPBC) or triazoles (propiconazole, tebuconazole).

The known organic wood preservatives are for use classes 1, 2 and 3 after DIN EN 351 used and do not lead to a hydrophobization of the wood, so that the tendency of the wood to absorb water and thus the dimensional stability remain unchanged.

In order to reduce the water absorption of wood, compounds based on oils, fats and waxes (paraffins, silicones such as polydimethylsiloxane oils) were mainly used.

Known wood preservatives which are used for hydrophobing and have a content of silicon compounds are also known. That's how it describes JP 2002-348567A Wood preservatives consisting of a mixture of different alkoxysilanes, including amino-containing alkoxysilanes and boric acid.

The US 6294608 discloses aqueous emulsions for treating mineral building materials and wood with a mixture of silanes provided with alkyl and alkoxy groups or aminoalkyl groups. Polysiloxane compounds are not disclosed.

The EP 0716127 discloses organopolysiloxanes and their aqueous mixtures, in particular for the hydrophobization of surfaces, eg. B. in the impregnation of leather and textiles from natural and / or artificial materials and in the field of organic and mineral building materials and building protection.

The EP 0716128 discloses aminoalkyl-alkoxysilanes which can be used inter alia for the hydrophobization of cellulose products or as additives for paints and coatings. Polyorganosiloxanes are not disclosed here.

The US 2002/0026881 describes a composition for the hydrophobization of surfaces which contains, inter alia, silicone.

The US 4757106 discloses the combination of aminosiloxanes with contents of basic nitrogen> 0.5% with siloxanes of molecular weight> 620 g / mol in largely solvent-free formulations for finishing mineral substrates.

DE 3447636 discloses the combination of aminosiloxanes with basic nitrogen contents> 0.5% with a second basic aminosiloxane with contents of 0 to 0.5% and optionally a siloxane with molecular weights <600 g / mol in the presence of solvents. EP 0621115 and DE 4241727 disclose the combination of aminosiloxanes with basic nitrogen contents> 0.5% with water-repellent active substances, eg siloxanes, if appropriate in the presence of a second compound with basic nitrogen with contents of 0 to 0.5% for the treatment of wood. The DE 10 2004 036918 suggests the use of aminosiloxanes in wood preservatives. The siloxanes should have a molecular weight of 500 to 500,000 g / mol and the degree of substitution of the siloxane units with amino groups should be up to 50%.

Disadvantage of all the above suggestions is that a lasting protection of wood in practice have so far been achieved only by a two-stage treatment of the wood. Thus, in the so-called Royal method, the wood is first soaked in a first step with an organic copper salt (Cu-HDO) or an inorganic copper salt, and then an impregnation in oil is carried out as a second step to prevent the leaching of the biocidal copper.

Siloxanes with hydrolyzable groups tend to condense after contact with water and acids or bases, with solubility, emulsifiability and reduced penetration of the wood. The impregnation with the in DE 10 2004 036918 siloxanes disclosed is not durable, since these siloxanes can be dissolved out after prolonged exposure to water.

It is therefore an object of the present invention, in a one-step, practical process to impregnate wood durable, thereby further reducing the tendency of the wood to absorb water, improve the dimensional stability of the change in moisture content of the environment and the degradation of the wood by fungi, bacteria and to effectively reduce insects such as wood destroying insects such as termites, domestic hive beetles, common weevils, sapwood beetles. At the same time, the yellowing and graying of the wood is to be suppressed by the effects of light and weather.

The present invention relates to polyorganosiloxanes for the treatment of lignocellulosic materials, such as in particular wood and other lignocellulosic materials to increase their resistance, for example, against microbial or caused by fungi degradation and / or weathering effects, such as sunlight (UV radiation), rain and others Dimensional variations of humidity. The polyorganosiloxanes used according to the invention serve for use as protective agents for lignocellulosic materials against the effects of the weather, fungi, microbes and insects. Furthermore, the use of the polyorganosiloxanes according to the invention for improving the properties such as shrinkage and swelling behavior of wood or lignocellulosic materials by treating the lignocellulosic materials with them. In a further aspect, the present invention relates to lignocellulosic materials, in particular wood, which have been treated with the polyorganosiloxanes used according to the invention.

The polyorganosiloxanes used according to the invention can be used in particular for the treatment of lignocellulosic materials such as wood and wood-based materials, chipboard, medium-density fiberboard, Oriented Strand boards (OSB), paper, cardboard, lignocellulose-based insulation boards, plywood, veneers and packaging material containing biodegradable compounds (hereafter collectively referred to as "lignocellulosic materials"). The polyorganosiloxanes used according to the invention furthermore have a high resistance to washing out after the impregnation. As a further advantage, the polyorganosiloxanes used in the invention allow the application, such. B. by impregnation, in a single process step. Surprisingly, the desired improvement is achieved with amino- and / or ammonium-functional radicals on very short-chain polyorganosiloxanes.

worin R¹ organische Reste darstellt, die gleich oder verschieden voneinander sein können, oder zwei Reste R¹ gemeinsam mit den Siliziumatomen, an die sie gebunden sind, einen verbrückenden Rest Si-R-Si bilden, mit der Maßgabe, dass mindestens einer der Reste R¹ und R ein Rest R^F ist, der mindestens eine funktionelle Gruppe F enthält, die ausgewählt wird aus Amino- und Ammonium-Gruppen, und worin der Rest R^F über ein Kohlenstoffatom mit einem Siliziumatom verbunden ist, und deren Salze.The present invention thus relates to polyorganosiloxanes for the treatment of lignocellulosic materials, characterized in that the polyorganosiloxanes are straight-chain, branched or cyclic polyorganosiloxanes, the number average of which are composed of 2 to 16 siloxy units selected from the group consisting of:

wherein R ^{1 represents} organic radicals which may be identical or different from one another, or two radicals R ¹ together with the silicon atoms to which they are bonded, a bridging radical Si-R-Si form, with the proviso that at least one of the radicals R is a radical R ^F is ¹ and R, which contains at least one functional group F is selected from amino and ammonium groups, and in which the radical R ^F on a carbon atom with a silicon atom, and their salts.

The radical R is preferably the radical Q ^F defined below.

The polyorganosiloxanes according to the invention are in particular characterized in that the radicals R ^{1 are} selected from the group of the radicals R ^F and R ^N , where the radicals R ^F are those radicals R ¹ which have the said functional groups F and at the radicals R ^N are radicals R ¹ which do not have the said functional groups F.

In a preferred embodiment of the invention, in the polyorganosiloxanes used according to the invention, the molar fraction of the radicals R ^F which contain at least one functional group F is from 10 to 100 mol%, based on the number of siloxy units. More preferably, this proportion is 15 to 100%, more preferably 20 to 100%, even more preferably 30 to 100%, and most preferably 50 to 100% by mole.

In the polyorganosiloxanes used in the invention, the molar fraction of branching radicals T and Q is suitably 0 to 50 mol%, preferably 0 to 20%, more preferably 0 to 10%, especially 0 to 5%, especially 0 mol%, based on the total number of siloxy units.

In the polyorganosiloxanes used in the present invention, the number average of the siloxy units (number of silicon atoms) is 2 to 16. The number average siloxy units in the polyorganosiloxanes used in the present invention is preferably determined by gel permeation chromatography (GPC) after appropriate calibration with polystyrene as the standard. The number average of the siloxy units is preferably from 6 to 14. It is within the scope of the invention to use mixtures of the polyorganosiloxanes used according to the invention. When mixtures of polyorganosiloxanes are used, bi-, tri- and higher modal distributions of the molecular weight are produced. In this case, binary mixtures with bimodal distribution are preferred. A further embodiment is the use of mixtures of the short-chain polyorganosiloxanes according to the invention with an average of 2 to 16 siloxy units and longer-chain polyorganosiloxanes having 17 to 50 siloxy units. The use of such mixtures has the advantage that in the lignocellulosic materials different sites of action are served. Thus, the longer-chain polyorganosiloxanes are preferably found in the intercellular spaces (lumens), whereas the shorter-chain polyorganosiloxanes accumulate more strongly in the cells or cell walls. As a result, a higher active ingredient permeation and concentration and thus an improved effect is achieved overall.

The functional groups F which carry the polyorganosiloxanes used according to the invention serve, on the one hand, to improve the solubility of the polyorganosiloxanes in the preferably aqueous dosage form, and, on the other hand, to anchor the polyorganosiloxanes in the lignocellulosic materials, in particular in the cells and cell walls of said materials, in particular to increase the dimensional stability the materials or the shrinkage behavior in the presence of swelling solvents, in particular moisture. From these points of view, functional groups F selected from amino and / or ammonium groups, in particular those selected from the group consisting of primary, secondary, tertiary amino or ammonium groups and proved to be particularly suitable in the polyorganosiloxanes according to the invention quaternary ammonium groups.

worin R² wie vorstehend definiert ist,

worin R² wie nachstehend definiert ist, und bevorzugt Wasserstoff, einen einwertigen, geradkettigen, cyclischen oder verzweigten, gesättigten, ungesättigten oder aromatischen Kohlenwasserstoffrest mit bis zu 30 Kohlenstoffatomen darstellt, der gegebenenfalls eine oder mehrere Gruppen ausgewählt aus -O-, -S-, -C(O)- und -C(S)- enthalten kann, und der gegebenenfalls durch eine oder mehrere Substituenten, ausgewählt aus der Gruppe, die besteht aus einer Hydroxylgruppe, einer gegebenenfalls substituierten, bevorzugt ein oder mehrere Stickstoffatome enthaltenden heterocyclischen Gruppe, Amino, Alkylamino, Dialkylamino, Ammonium, Polyetherresten und Polyetheresterresten substituiert sein kann, bevorzugt ein einwertiger, geradkettiger oder verzweigter, gesättigter Kohlenwasserstoffrest mit bis zu 30 Kohlenstoffatomen darstellt, wie Methyl, Ethyl, Propyl, Butyl, Pentyl, Hexyl und deren Isomere, wobei wenn mehrere Gruppen -NR² vorliegen, diese gleich oder verschieden sein können. Particularly preferably, the radicals R ^F contain amino or ammonium groups from the group consisting of:
-N (R ² ) ₂ , wherein R ^{2 is} as defined above,
-N ⁺ (R ² ) ₃ , wherein R ^{2 is} as defined above,

wherein R ^{2 is} as defined above,

wherein R ^{2 is} as defined below, and is preferably hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 30 carbon atoms, optionally containing one or more groups selected from -O-, -S-, -C (O) - and -C (S) -, and optionally by one or more substituents selected from the group consisting of a hydroxyl group, an optionally substituted, preferably one or more nitrogen atoms-containing heterocyclic group, amino , Alkylamino, dialkylamino, ammonium, polyether radicals and polyetherester radicals, preferably represents a monovalent, straight-chain or branched, saturated hydrocarbon radical having up to 30 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, wherein if several Group NR ² are present, these may be the same or different.

worin R² jeweils wie vorstehend oder nachstehend definiert ist, und R³ ein zweiwertiger, geradkettiger, verzweigter, cyclischer, aliphatischer, ungesättigter oder aromatischer Kohlenwasserstoffrest mit bis zu 30 Kohlenstoffatome ist, der eine oder mehrere Gruppen ausgewählt aus -O-, -NH-, -C(O)- und -C(S)-, bevorzugt ausgewählt aus -O-, -C(O)- und -C(S)- enthalten kann, und gegebenenfalls durch Hydroxy substituiert sein kann,
und wobei die Amino- oder Ammoniumgruppen gegebenenfalls auch protoniert vorliegen können.Particularly preferably, the radicals R ^F in the polyorganosiloxanes used according to the invention are selected from the group consisting of:
-CH ₂ CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ NH ₂
-R ³ -NHCH ₂ CH ₂ NH ₂
-R ³ -NHCH ₂ CH ₂ CH ₂ NH ₂
-R ³ -NHCH ₂ CH (CH ₃ ) NH ₂
-R ³ -NHCH (CH ₃ ) CH ₂ NH ₂
-CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂
-CH ₂ CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ NHCH ₂ CH ₂ NH ₂

wherein R ^{2 is in} each case defined as above or below, and R ^{3 is} a divalent, straight-chain, branched, cyclic, aliphatic, unsaturated or aromatic hydrocarbon radical having up to 30 carbon atoms and having one or more groups selected from -O-, -NH- , -C (O) - and -C (S) -, preferably selected from -O-, -C (O) - and -C (S) -, and may optionally be substituted by hydroxy,
and where appropriate the amino or ammonium groups may also be protonated.

worin R³ gleich oder verschieden sein können und wie oben oder nachstehend definiert sind, und b = 1 oder 2, bevorzugter 1 ist, und

ein gesättigter oder ungesättigter gegebenenfalls substituierter Stickstoff-haltiger 5- bis 6-gliedriger Heterocyclus ist, worin das Stickstoffatom gegebenenfalls positiv geladen ist, und wobei die genannten Amino- oder Ammoniumgruppen gegebenenfalls auch protoniert vorliegen können.The radicals Q ^F are preferably used in the polyorganosiloxanes of the formula (V) used according to the invention. ZQ ^F -Z (V) selected from divalent organic amino and / or ammonium functional groups, which in turn are preferably selected from:
-R ³ - [N (R ² ) -R ³ ] _a -
-R3- [N ⁺ (R ² ) ₂ -R ³ ] _a -
wherein each of R ² and R ^{3 may be the} same or different and are as defined above or below, and a = 1 to 10, more preferably 1 to 2, and

wherein R ^{3 may be the} same or different and are as defined above or below, and b = 1 or 2, more preferably 1, and

is a saturated or unsaturated optionally substituted nitrogen-containing 5- to 6-membered heterocycle, wherein the nitrogen atom is optionally positively charged, and wherein said amino or ammonium groups may optionally also be protonated.

The attachment of the radicals R ¹ , R ^N , R ^F and Q ^F to the polysiloxane is preferably carried out via a silicon-carbon atom bond.

More preferably, R ^{F is} a group of the formula: -CH ₂ CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ NHCH ₂ CH ₂ NH ₂ .

worin R¹ und R^F wie oben definiert sind, und n3 = 0 bis 6, bevorzugt 0 bis 5 ist,

worin R¹ wie oben definiert ist, und n4 = 0 bis 5, bevorzugt 0 bis 4 ist. The polysiloxane radicals Z in the polyorganosiloxanes of the formula (V) ZQ ^F -Z (V) are preferably selected from the group consisting of:

wherein R ¹ and R ^{F are} as defined above, and n 3 = 0 to 6, preferably 0 to 5,

wherein R ^{1 is} as defined above, and n4 = 0 to 5, preferably 0 to 4.

-C(O)- und
-C(S)- enthalten kann,
und wobei die genannten Kohlenwasserstoffreste durch einen oder mehrere Reste substituiert sein können, die ausgewählt sind aus der Gruppe, die besteht aus:

• – Hydroxy,
• – Amino (-NH₂),
• – Mercapto (-SH),
• – einem Polyetherrest mit bis zu 60 Kohlenstoffatomen, der gegebenenfalls noch eine oder mehrere Amino-, Mono- oder Dialkylamino, oder Arylamino-Gruppen tragen kann,
• – einem Saccharid-haltigem organischen Rest,

oder zwei Substituenten R¹ aus verschiedenen Siloxyeinheiten bilden gemeinsam einen geradkettigen, verzweigten oder cyclischen, gegebenenfalls durch -O-, -S-, -C(O)-, -NH- unterbrochenen und gegebenenfalls durch OH substituierten Alkandiylrest mit 2 bis 20 Kohlenstoffatomen zwischen zwei Siliziumatomen,
wobei die Anbindung an Silizium über ein Kohlenstoffatom und/oder ein Heteroatom, bevorzugt über ein Kohlenstoffatom erfolgen kann.In the polyorganosiloxanes used in the invention, the organic substituents R ^{1 are} suitably selected from the group consisting of:
straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 100 carbon atoms, optionally one or more groups selected from
-O-,
-S-,
-NR ² -, in which R ^{2 is} hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 60 carbon atoms and having one or more groups selected from -O-, -S-, -NH- , -C (O) - and -C (S) - and optionally substituted by one or more substituents selected from the group consisting of a hydroxyl group, an optionally substituted, preferably one or more nitrogen atoms-containing heterocyclic group, Amino, alkylamino, dialkylamino, ammonium, polyether radicals and polyether radicals may be substituted, wherein when several groups -NR ² are present, they may be the same or different,

-C (O) - and
-C (S) - may contain
and wherein said hydrocarbon radicals may be substituted by one or more radicals selected from the group consisting of:

• - hydroxy,
• Amino (-NH ₂ ),
• Mercapto (-SH),
• A polyether radical having up to 60 carbon atoms, which may optionally carry one or more amino, mono- or dialkylamino, or arylamino groups,
• A saccharide-containing organic radical,

or two substituents R ¹ of different siloxy units together form a straight-chain, branched or cyclic, optionally interrupted by -O-, -S-, -C (O) -, -NH- and optionally substituted by OH Alkandiylrest having 2 to 20 carbon atoms two silicon atoms,
wherein the attachment to silicon via a carbon atom and / or a heteroatom, preferably via a carbon atom can take place.

These radicals R ¹ are as mentioned above selected from the group of radicals R ^F and R ^N , wherein the radicals R ^F are those radicals R ¹ which have the said functional groups F and the radicals R ^N radicals R ¹ does not have the said functional groups F. As mentioned above, two radicals R ¹ together with the silicon atoms can form a bridging group of the formula Si-R-Si, where R is preferably the group Q ^F.

R ² is preferably hydrogen, saturated hydrocarbon radical having up to 24 carbon atoms, one or two groups selected from -O-, -S-, -NH-, -C (O) - and -C (S) -, preferably selected from -O-, -S-, -C (O) - and -C (S) -, and which may optionally be substituted by one or two hydroxyl group.

R ³ is preferably a divalent saturated aliphatic hydrocarbon radical having up to 20 carbon atoms, which may contain one or two groups -O-, and may optionally be substituted by hydroxy and attached to the silicon atom via carbon.

The radicals R ^N preferably include n-, iso- or tert-C ₁ -C ₂₂ -alkyl, C ₂ -C ₂₂ -alkoxyalkyl, C ₅ -C ₃₀ -cycloalkyl, C ₆ -C ₃₀ -aryl, C ₆ -C ₃₀ aryl (C ₁ -C ₆ ) alkyl, C ₆ -C ₃₀ alkylaryl, C ₂ -C ₂₂ alkenyl, C ₂ -C ₂₂ alkenyloxyalkyl, all of which are represented by one or more (such as to five) substituents, such as hydroxy halogen (in particular fluorine), which may have one or more ether groups, such as H ₃ C-, CH ₃ CH ₂ -, CH ₃ CH ₂ CH ₂ -, (CH ₃ ) ₂ CH- , C ₈ H ₁₇ - and C ₁₀ H ₂₁ -, H ₂ C = CH-O- (CH ₂ ) _1-6 , cycloaliphatic radicals such as cyclohexylethyl, limonyl, norbonenyl, phenyl, tolyl, xylyl, benzyl and 2-phenylethyl , Halo (C ₁ -C ₁₀ ) alkyl, such as C _f F _{fn + 1} CH ₂ CH ₂ - wherein f is 1 to 8, such as
CF ₃ CH ₂ CH ₂ -, C ₄ F ₉ CH ₂ CH ₂ -, C ₆ F ₁₃ CH ₂ CH ₂ -,
C ₂ F ₅ -O (CF ₂ -CF ₂ -O) _1-10 CF ₂ -,
F [CF (CF ₃ ) -CF ₂ -O] _1-5 - (CF ₂ ) _0-2 ,
C ₃ F ₇ -OCF (CF ₃ ) - and
C ₃ F ₇ -OCF (CF ₃ ) -CF ₂ -OCF (CF ₃ ) -.

Particularly preferred are methyl, vinyl, phenyl, 3,3,3-trifluoropropyl, most preferably R is ^N = methyl.

• – quaternäre Phosphoniumgruppen enthaltenden Resten, wie solchen der Formel: -R³–P⁺(R²)₃ worin R³ wie oben definiert ist, und die Anbindung an das Siliziumatom über Kohlenstoff erfolgt, die Reste R² gleich oder verschieden sein können und die Reste R² wie zuvor definiert ist, und bevorzugt mindestens einer der Reste R² nicht Wasserstoff ist, -R³–P(R²)₂ worin R³ wie oben definiert ist, und die Anbindung an das Siliziumatom über Kohlenstoff erfolgt, die Reste R² gleich oder verschieden sein können und die Reste R² wie zuvor definiert ist,
• – Urethangruppen enthaltenden Resten, wie solchen ausgewählt aus: -R³-OC(O)NH-R² worin R² und R³ wie vorstehend beschrieben sind,
• – Harnstoffgruppen enthaltenden Resten, wie solchen ausgewählt aus: -R³-NHC(O)NHR², worin R² und R³ wie vorstehend beschrieben sind,
• – Amid- bzw. Amidogruppen enthaltenden Resten, wie solchen ausgewählt aus: -R³-NHC(O)–R² oder -R³-C(O)NH-R², worin R² und R³ wie vorstehend beschrieben sind,
• – Enamingruppen-enthaltende Resten, wie solchen ausgewählt aus:
  
  worin R² gleich und verschieden sind und R² und R³ jeweils wie oben definiert sind, welche insbesondere erhältlich sind durch Umsetzung von aminofunktionellen Polyorganosiloxanen mit Ketonen, wie aliphatische oder aromatische Ketone mit bis zu 14 Kohlenstoffatomen, wie aliphatische C3-C14-Ketone, aromatische C8 bis C12 Ketone, des weiteren Enamine der Formel
  
  worin R² und R³ wie oben definiert sind, welche insbesondere erhältlich sind durch Umsetzung von aminofunktionellen Polyorganosiloxanen mit Monoaldehyden, wie aliphatische oder aromatische Aldehyde mit bis zu 14 Kohlenstoffatomen, wie aliphatische C1-C14-Aldehyde, beispielsweise Formaldehyd, Butyraldehyd, Furfural, Acrolein, Crotanaldehyd, Glykolaldehyd, Acetaldol, aromatische C7 bis C11 Aldehyde, beispielsweise Benzaldehyd, Anisaldehyd, Vanilin, Salizylaldehyd,
• – Aldehydgruppen-enthaltende Resten, wie solchen ausgewählt aus:
  
  worin R³ gleich oder verschieden und R² und R³ wie oben definiert sind, welche insbesondere erhältlich sind durch Umsetzung von aminofunktionellen Polyorganosiloxanen mit Dialdehyden, wie Glyoxal, Malonaldehyd, Succinaldehyd, Phthalaldehyd, Isophthalaldehyd, Terephthalaldehyd,
• – Zwitterionische Gruppen, wie Carbobetaingruppen enthaltenden Resten, ausgewählt aus:
  
  und Salze davon, worin R² und R³ gleich oder verschieden sind und wie oben definiert sind, Sulfobetaingruppen enthaltenden Resten, wie solchen ausgewählt aus:
  
  und deren Salze, worin R² und R³ gleich oder verschieden sind und wie oben definiert sind,
• – Carbonsäure-/Carboxylatgruppen enthaltenden Resten, wie solchen ausgewählt aus: -R³-COOR², -R³-COO^– worin R² und R³ jeweils wie oben definiert sind,
• – Sulfonsäure-/Sulfonatgruppen enthaltenden Resten, wie solchen ausgewählt aus: -R³-SO₃R², -R³-SO₃ worin R² und R³ jeweils wie oben definiert sind,
• – Schwefelsäurehalbester-/Sulfatgruppen enthaltenden Resten, wie solchen ausgewählt aus: -OSO₃R², -OSO₃ ^– worin R² wie oben definiert ist,
• – Phosphorsäureester-/Phosphatgruppen enthaltenden Resten, ausgewählt wie solchen aus:
  
  worin R² und R³ wie oben definiert sind, und Fluorphosphorsäureester, wie solchen ausgewählt aus:
  
  worin R² und R³ wie oben definiert sind,
• – Phosphonsäureester/Phosphonat-Gruppen enthaltenden Resten, wie solchen ausgewählt aus:
  
  bzw. die protonierten Formen davon, worin R² und R³ wie oben definiert sind (worin R³ über ein Kohlenstoffatom an das Phosphoratom gebunden ist), und worin R³ wie oben definiert ist,
• – Phosphorigsäureester/Phosphit-Gruppen enthaltenden Resten, wie solchen ausgewählt aus:
  
  worin R² und R³ wie oben definiert ist (und über Kohlenstoff an das Sauerstoffatom der Phosphorigsäureester/Phosphit-Gruppen gebunden sind),
• – Xanthogenat/Xanthogenatester-Gruppen enthaltende Reste, wie solchen ausgewählt aus
  
  worin R² und R³ jeweils wie oben definiert sind,
• – über N an Si gebundene Amino-Gruppen, wie solchen ausgewählt aus: -N(R²)₂, worin R² wie oben definiert ist, mit der Maßgabe, dass mindestens ein Rest R² nicht Wasserstoff ist,
• – über O an Si Alkoxy-Gruppen, wie solchen ausgewählt aus: -OR², worin R² wie oben definiert ist, und
• – Si-C-gebundene Polyether-Gruppen, wie solchen ausgewählt aus Polyethylenoxid- und/oder Polypropylenoxid-Gruppen.

The polyorganosiloxanes used according to the invention may optionally have, in addition to the radicals R ^F, further functionalized radicals R ^{1 which} have different functional groups from F. These different from R ^F functionalized radicals R ^1, hereinafter referred to briefly R ^FZ are preferably selected from the group consisting of:

• - quaternary phosphonium-containing radicals, such as those of the formula: -R ³ -P ⁺ (R ² ) ₃ wherein R ^{3 is} as defined above, and the attachment to the silicon atom is via carbon, the radicals R ^{2 may be} identical or different and the radicals R ^{2 is} as defined above, and preferably at least one of the radicals R ^{2 is} not hydrogen, -R ³ -P (R ² ) ₂ wherein R ^{3 is} as defined above, and the attachment to the silicon atom takes place via carbon, the radicals R ^{2 may be} identical or different and the radicals R ^{2 are} as defined above,
• Urethane group containing radicals such as those selected from: -R ³ -OC (O) NH-R ² wherein R ² and R ^{3 are} as described above,
• Urea group-containing radicals, such as those selected from: -R ³ -NHC (O) NHR ² , wherein R ² and R ^{3 are} as described above,
• Amide- or amido-containing radicals, such as those selected from: -R ³ -NHC (O) -R ² or -R ³ -C (O) NH-R ² , in which R ² and R ^{3 are} as described above,
• - Enamine group-containing residues, such as those selected from:
  
  wherein R ^{2 are the} same and different and R ² and R ^{3 are} each as defined above, which are particularly obtainable by reacting amino-functional polyorganosiloxanes with ketones, such as aliphatic or aromatic ketones having up to 14 carbon atoms, such as aliphatic C3-C14 ketones, aromatic C8 to C12 ketones, further enamine of the formula
  
  wherein R ² and R ^{3 are} as defined above, which are particularly obtainable by reacting amino-functional polyorganosiloxanes with monoaldehydes, such as aliphatic or aromatic aldehydes having up to 14 carbon atoms, such as aliphatic C 1 -C 14 aldehydes, for example formaldehyde, butyraldehyde, furfural, acrolein , Crotanaldehyde, glycolaldehyde, acetaldol, aromatic C7 to C11 aldehydes, for example benzaldehyde, anisaldehyde, vaniline, salicylaldehyde,
• Aldehyde group-containing radicals, such as those selected from:
  
  wherein R ^{3 are} identical or different and R ² and R ^{3 are} as defined above, which are obtainable in particular by reaction of amino-functional polyorganosiloxanes with dialdehydes, such as glyoxal, malonaldehyde, succinaldehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde,
• Zwitterionic groups, such as radicals containing carbobetaine groups, selected from:
  
  and salts thereof, wherein R ² and R ^{3 are the} same or different and are as defined above, sulfobetaine group-containing radicals such as those selected from:
  
  and their salts, wherein R ² and R ^{3 are the} same or different and are as defined above,
• - carboxylic acid / carboxylate group-containing radicals, such as those selected from: -R ³ -COOR ² , -R ³ -COO ^- wherein R ² and R ^{3 are} each as defined above,
• - sulfonic acid / sulfonate group-containing radicals, such as those selected from: -R ³ -SO ₃ R ² , -R ³ -SO ₃ wherein R ² and R ^{3 are} each as defined above,
• Sulfuric acid half ester / sulfate group-containing radicals, such as those selected from: -OSO ₃ R ² , -OSO ₃ ^- in which R ^{2 is} as defined above,
• Phosphoric acid ester / phosphate groups containing radicals selected from:
  
  wherein R ² and R ^{3 are} as defined above, and fluorophosphoric acid esters such as those selected from:
  
  wherein R ² and R ^{3 are} as defined above,
• Phosphoester / phosphonate group-containing radicals, such as those selected from:
  
  or the protonated forms thereof, wherein R ² and R ^{3 are} as defined above (wherein R ³ is bonded via a carbon atom to the phosphorus atom), and wherein R ^{3 is} as defined above,
• Phosphoric acid ester / phosphite group-containing radicals, such as those selected from:
  
  wherein R ² and R ^{3 are} as defined above (and bonded via carbon to the oxygen atom of the phosphorous acid ester / phosphite groups),
• - xanthogenate / xanthogenate ester-containing groups such as those selected from
  
  wherein R ² and R ^{3 are} each as defined above,
• Amino groups bonded to Si via N, such as those selected from: -N (R ² ) ₂ , in which R ^{2 is} as defined above, with the proviso that at least one R ^{2 is} not hydrogen,
• Via O to Si alkoxy groups, such as those selected from: -OR ² , wherein R ^{2 is} as defined above, and
• Si-C-bonded polyether groups, such as those selected from polyethylene oxide and / or polypropylene oxide groups.

Preference is given to polyorganosiloxanes according to the invention which only carry R ^F as functionalized radicals R ¹ .

In the polyorganosiloxanes of the invention optionally present positive or negative charges are preferably neutralized by cations which are selected from the group consisting of:
Ammonium cations (N ⁺ (R ² ) ₄ wherein R ^{2 is} as defined above), phosphonium cations (P ⁺ (R ² ) ₄ wherein R ^{2 is} as defined above), and mono- to trivalent metal cations such as Na ⁺ , K ⁺ , Fe ²⁺ , Fe ³⁺ , Al ³⁺ , Cu ²⁺ , Zn ²⁺ and Cr ³⁺ ,
and anions, which are selected from the group consisting of:
Halide, in particular chloride,
Hydroxide,
borate,
Sulfate,
Phosphate,
Nitrate and
Carboxylate, in particular formate, acetate, C8-C22 carboxylate, etc.

worin R¹ wie oben definiert, bevorzugt R^N, wie oben definiert ist, und R^F wie oben definiert ist.Polyorganosiloxanes which contain at least one radical of the formula M ^F are preferred according to the invention:

wherein R ^{1 is} as defined above, preferably R ^{N is} as defined above, and R ^{F is} as defined above.

worin n = 0 bis 14, bevorzugt n = 0 bis 10, und R¹ und R^F wie nachstehend definiert sind,

worin n1 + n2 = 1 bis 14, bevorzugt 1 bis 10, und n2 ≥ 1, und R¹ und R^F wie nachstehend definiert sind,

worin n1 + n2 = 1 bis 14, bevorzugt 2 bis 10, und n2 ≥ 1, und R¹ und R^F wie nachstehend definiert sind,

verwendet, worin n1 + n2 = 3 bis 7, und n2 ≥ 1, und R¹ und R^F wie zuvor definiert sind, und Polyorganosiloxane der Formel (V) Z-Q^F-Z (V) worin Z jeweils Polysiloxanreste darstellt, welche gleich oder verschieden sein können, welche zusammen bis zu 16 Siloxyeinheiten aufweisen, und die über ein Kohlenstoffatom an den Rest Q^F gebunden sind, und Q^F eine zweiwertige organische Gruppe darstellt, die mindestens eine funktionelle Gruppe F aufweist, und worin R¹ jeweils organische Reste darstellt, die gleich oder verschieden voneinander sein können, mit der Maßgabe, dass mindestens einer der Reste R¹ ein Rest R^F ist, der mindestens eine funktionelle Gruppe F enthält, die ausgewählt wird aus Amino- und Ammonium-Gruppen, und worin der Rest R^F über ein Kohlenstoffatom mit einem Siliziumatom verbunden ist, und deren Salze.According to the invention, particular preference is given to polyorganosiloxanes selected from the formulas (I) to (V):

wherein n = 0 to 14, preferably n = 0 to 10, and R ¹ and R ^{F are} as defined below,

wherein n1 + n2 = 1 to 14, preferably 1 to 10, and n2 ≥ 1, and R ¹ and R ^{F are} as defined below,

wherein n1 + n2 = 1 to 14, preferably 2 to 10, and n2 ≥ 1, and R ¹ and R ^{F are} as defined below,

in which n1 + n2 = 3 to 7, and n2 ≥ 1, and R ¹ and R ^{F are} as defined above, and polyorganosiloxanes of the formula (V) ZQ ^F -Z (V) wherein each Z represents polysiloxane residues, which may be the same or different, which together have up to 16 siloxy units and which are bonded via a carbon atom to the group Q ^F , and Q ^{F represents} a divalent organic group having at least one functional group F. and wherein each R ¹ represents organic radicals which may be the same or different from one another, with the proviso that at least one of R ^{1 is} a radical R ^F which contains at least one functional group F selected from amino and Ammonium groups, and wherein the radical R ^{F is} connected via a carbon atom to a silicon atom, and their salts.

The polyorganosiloxanes according to the invention are prepared, for example, by condensation and equilibration of amino- and / or ammonium-functional alkoxy- or chlorosilanes. Another method is the hydrogenation of cyano-functional polyorganosiloxanes. A third method consists in the reaction of SiH-functional polyorganosiloxanes with unsaturated optionally protected amino-functional organic compounds by means of the hydrosilylation reaction. A fourth method consists of reacting polysiloxane-containing alkylating agents with amines, wherein polysiloxane-containing alkylating agents are, for example, halogen-functional, epoxy-functional polyorganosiloxanes. The following polyorganosiloxanes can be mentioned by way of example:

For example, compounds according to WO 94/29324 A1 , as

The invention further relates to compositions containing at least one polysiloxane, as defined above, and at least one carrier medium, such as a solvent which is different from water, and / or water.

Such a composition may contain one or more biocidal agents known per se for the treatment of lignocellulosic materials.

The compositions according to the invention, preferably the water-containing compositions, preferably compositions present as aqueous emulsion, preferably have a content of the polyorganosiloxanes of more than 10% by weight, based on the total amount of the composition. More preferably, the content is more than 20% by weight, more preferably more than 30% by weight, and most preferably more than 35% by weight.

The compositions according to the invention containing at least one of the functionalized polyorganosiloxanes defined according to the invention may contain, for example, a solubilizer and / or an emulsifier which in particular leads to an increase in stability of the compositions according to the invention, for example an aqueous composition, eg. As an emulsion, or a solution or a dispersion in a solvent.

Suitable solubilizers or emulsifiers are, in particular, quaternary fatty amine alcoholates, in particular a quaternary fatty amine ethanolate.

As a solvent other than water depending on the application method in question: carbon dioxide, alcohol, ethane, ethylene, propane, butane, sulfur hexafluoride, nitrogen oxides, ionic liquids, chlorotrifluoromethane, monofluoromethane, methanol, ethanol, DMSO, isopropanol, acetone, THF, acetic acid, ethylene glycol , Polyethylene glycol, N, N-dimethylaniline, methane, pentane, hexane, cyclohexane, toluene, heptane, benzene, ammonia, propanol, etc. and mixtures, more preferably water, organic solvents such as polyhydric alcohols such as in particular propylene glycol, ethylene glycol or butyl diglycol, ethanol , Propanol, isopropanol, n-butanol, furfuryl alcohol, THF, DMSO, dioxane, acetic anhydride, aliphatic and / or chlorinated hydrocarbons etc. or mixtures thereof.

Examples of the biocidal active ingredients optionally contained in the compositions of the invention include, for example:
Boron compounds, such as, for example, borax, borate, boric acid, boric acid esters,
Copper compounds, such as water-soluble copper compounds, such as, for example, copper (II) salts (copper (II) oxide, copper (II) sulfate, copper (II) hydroxide carbonate, bis (N-cyclohexyldiazeniumdioxy) copper (II),
Mixtures of boron compounds and copper compounds,
organic biocidal compounds such as triazoles (such as azaconazole, cyproconazole, propiconazole, tebuconazole, TCMTB), phenylsulfamides (such as dichlorofluidide, tolylfluanid), carbamates (such as IPBC, carbendazim), aromatic fungicides (such as ortho-phenylphenol, chlorothalonil) and other fungicides ( such as bethoxazine, isothiazolone), synthetic pyrethroids (such as permethrin, cypermethrin, cyfluthrin, deltamethrin, silafluofen), insecticides (such as imidacloprid, flufenoxuron, chlorpyrifos, fenoxycarb).

The boron compounds are suitably used in an amount of 0.1 to 300 parts by weight per 100 parts by weight of the total amount of the polyorganosiloxanes.

The boron compounds stop microbial decomposition and allow defense against insects such as termites. Useful boron compounds include boric acid, borax, boron esters such as trialkyl borate, e.g. Trimethyl borate, triethyl borate, tripropyl borate and tributyl borate, borates such as Na ₂ B ₈ O ₁₃ .4H ₂ O or Timbor (R) available from US Borax Inc., borax and borates such as timbor (R) are preferred. An amount of the boron compounds of more than 300 parts by weight deteriorates the stability of the emulsions. When the boron compounds are used, they are preferably used in a concentration of at least 10% by weight based on the total amount of the polyorganosiloxanes.

Further auxiliaries which can be used in the compositions according to the invention include, for example: emulsifiers, as mentioned above, thickeners, pigments, dyes, antistatic agents, defoamers, flame retardants, etc.

Preferred compositions according to the invention contain:
10 to 100, more preferably 15 to 80, even more preferably 20 to 70 parts by weight of functionalized polysiloxane (s) as defined above
30 to 95, more preferably 40 to 80 parts by weight of carrier medium, such as those mentioned above, in particular water or carbon dioxide,
0 to 100, more preferably 0 to 80 parts by weight of further biocides, such as those mentioned above,
0 to 100, more preferably 1 to 80 parts by weight, parts by weight of other auxiliaries, such as those mentioned above, in particular emulsifiers.

The present application further relates to a method of treating lignocellulosic materials comprising treating the lignocellulosic material with at least one of the foregoing defined polyorganosiloxanes, or a composition as defined above, by surface treatment, dip treatment or vacuum or pressure impregnation.

In the process according to the invention, the lignocellulosic materials can be coated or impregnated with the composition according to the invention by any means known from the specialist literature for introducing aqueous solutions, such as, for example, by brushing, spraying, dipping, flooding, trough impregnation, vessel pressure impregnation, vacuum impregnation , Vacuum pressure impregnation, borehole impregnation or by the juice displacement method, cf. also "Holzlexikon of A-Z" (Volumes I and II), Ulf Lohmann, DRW-Verlag, Leinfeld-Echterdingen, 2003, see inter alia "Einbringverfahren", Volume I, pages 289-292 ,

In the process according to the invention, it is preferable to carry out a pressure impregnation of the vessel or a surface treatment process, such as brushing, spraying, dipping or flooding. With particular preference, a vacuum pressure impregnation is carried out in the process according to the invention. Thus, the substrate to be impregnated in a pressure-resistant impregnating reactor for 5 minutes to 8 hours, preferably 15 minutes to 2 hours, in particular about half to one hour, initially a pressure of 10 to 500 mbar abs., Preferably 50 to 200 mbar abs ., In particular about 100 mbar abs., maintain this pressure and then dip the substrate in the impregnant or cover with the impregnating agent, and the pressure for 0.5 to 4 hours abs to 1.5 to 20 bar, preferably for 1 to 3 hours to 5 to 15 bar abs., Especially for about 2 to 3 hours to 10 to 12 bar abs. Lift. Subsequently, the pressure can be lowered to ambient pressure. The substrate is removed from the impregnating solution, allowed to act after vacuum if necessary, or allowed to drip off and leads to the so vacuum vacuum impregnated substrate to the drying. Advantageously, a targeted drying process is carried out after the impregnation step. Thus, the impregnation step should be followed by a specific air drying and / or a specific technical drying process, for example microwave drying, IR drying, fresh / exhaust air drying, hot air drying, vacuum drying, freeze drying or a combination of methods such as, for example "Holzlexikon von A-Z" (Volumes I and II), Ulf Lohmann, DRW-Verlag, Leinfelden-Echterdingen, 2003, see inter alia "wood drying", Volume I, page 605 , are to be taken.

The combination of the polyorganosiloxanes used according to the invention with copper and / or boron compounds and / or organic biocidal protective agents can be used both in a preferred single-stage process and in a less preferred two-stage process. One-step processes are, for example, brushing, dipping or impregnating with formulations of the polyorganosiloxanes used in accordance with the invention in organic solvents or as an aqueous emulsion. In two-step processes, the copper and / or boron compounds and / or organic biocidal protective agents are preferably applied first, for example by brushing, dipping or impregnating, and then the polyorganosiloxanes used according to the invention.

In a preferred embodiment, the polyorganosiloxanes used according to the invention are present as an aqueous emulsion. An emulsifier may be added for the preparation and / or stabilization of such an aqueous emulsion, wherein the emulsifier may also be an amino-modified silicone other than the polyorganosiloxanes used according to the invention.

It is believed that the mechanism by which the polyorganosiloxanes used in the present invention render wood and other lignocellulosic materials more resistant to weathering and / or variations in moisture content is at least in part due to the surface, preferably the surface adjacent layers, extending to the surface entire volume of the wood or lignocellulosic material are hydrophobic. For wood, it is assumed that the polyorganosiloxanes used according to the invention lead to a reduced uptake of liquid water and to a reduced moisture absorption (gaseous water), which in turn leads to a smaller fluctuation in the dimensions in the case of rain or changing ambient humidity. Thus, the polyorganosiloxanes used in the invention therefore lead to a better dimensional stability of wood, because they penetrate into the cell wall of the wood and apparently remain there permanently due to their special functionalizations. As a result, even when dry, the wooden cell wall resembles a preswollen state and therefore absorbs less water than untreated wood. The penetration of the polyorganosiloxanes used in the invention is achieved especially with so-called aqueous microemulsions, for example with average particle sizes of 10 to 100 nm. Such microemulsions can penetrate into the pores of wood cell walls and also between cellulosic strands, so that the further uptake of water is permanently reduced. In this way, the dimensional change, such as the shrinkage during drying of wood is reduced when the Moisture content of the environment is reduced. In the case of macroemulsions, for example with a particle size of more than 150 nm, it is assumed that the polyorganosiloxanes used according to the invention at least partially coat the inner surfaces of wood cells and penetrate into the pores of the wood cell wall. On the one hand, the polyorganosiloxanes used according to the invention make possible a better association with the lignocellulosic material and, on the other hand, confer a growth-inhibiting effect on microorganisms. The treatment has an inhibitory effect on fungi in particular, so that lignocellulosic materials treated with the polyorganosiloxanes used according to the invention, such as wood, are less affected by discoloring, for example, fungi or mold, or destructive fungi (white rot, brown rot) and therefore have a greater resistance to microbial Have degradation. It is assumed that the impregnation with the polyorganosiloxanes used according to the invention suppresses the moisture content in the wood below the level required for the growth of the fungi. By means of the polyorganosiloxanes according to the invention, it is surprisingly possible to permanently impregnate wood in a one-step process, while further reducing the tendency of the wood to absorb water, to improve the dimensional stability when the moisture content of the environment changes and to reduce the degradation of the wood by fungi, bacteria and Insects, such as wood-destroying insects, such as termites, domestic goat beetle, common rodent beetle, sapwood beetle effectively reduce. At the same time the yellowing and graying of the wood is suppressed by light and weather.

In a further particularly preferred embodiment of the present invention, the functionalized polyorganosiloxanes are introduced into the lignocellulosic material as a carrier medium by means of a process using supercritical or liquid carbon dioxide or other preferably gaseous solvents (such as those mentioned above).

In the case of the particularly preferred use of carbon dioxide, this method comprises pressurizing, for example, about 10 to 200 bar at about 0 to 40 ° C. This method often requires special decompression methods so as not to damage the lignocellulosic material during decompression. During decompression, the generally gaseous carrier medium escapes, in particular carbon dioxide, and the polyorganosiloxanes used according to the invention remain behind in the lignocellulosic material, cell walls and intercellular spaces generally being filled with the polyorganosiloxanes used according to the invention. For more details on supercritical fluid treatments of wood-based materials can be referred to Morrell & Levien: "Development of New Wood Protection Treatment Process" Conference Report from "Wood Protection Conference in the 1990's and beyond", Savannah, Goergia, USA, September 26-28, 1994 ,

According to the invention, by the method of application or incorporation of the polyorganosiloxanes used according to the invention, contents of up to 7% by weight, preferably about 2 to 5% by weight, of the polyorganosiloxanes relative to the total mass of the treated dried lignocellulosic material are preferred.

By means of the polyorganosiloxanes used according to the invention, it is possible with a particularly low content to achieve the same maximum protective effect for the lignocellulosic material.

According to the invention, the content of the polyorganosiloxanes used according to the invention in the lignocellulosic materials can be increased by using particularly concentrated aqueous emulsions of the polyorganosiloxanes. Preferred concentrations of said aqueous emulsions are therefore at least about 10% by weight, more preferably at least about 15% by weight, even more preferably at least about 25% by weight, even more preferably at least about 35% by weight, based on the total amount the emulsion. Alternatively, solutions in solvents other than water of the polyorganosiloxanes can also be used, with the preferred concentrations corresponding to those of the emulsion. The use of the microemulsions (average droplet diameter of the polyorganosiloxanes smaller than 200 nm) is particularly preferred because the incorporation into the lignocellulosic material is particularly easy. According to the invention, it has been found that the penetration depth and thus the effectiveness of the functionalized polyorganosiloxanes according to the invention also depends on the molecular weight and the wettability of the lignocellulosic material with the said functionalized polyorganosiloxanes. It is found that especially the short-chain or low-molecular polyorganosiloxanes according to the invention which are used according to the invention are preferred here. The polyorganosiloxanes used according to the invention have, for example, number average molecular weights M _n of less than 2000 g / mol, more preferably less than 1500 g / mol, even more preferably less than 1000 g / mol (determined in each case by gel permeation chromatography on polystyrene as standard; , omega-functionalized (at the end groups functionalized) linear polyorganosiloxanes also the molecular weight determination by determination of the concentration of the functional groups, in particular by 1H or 29Si NMR method, applicable).

The invention is illustrated by the following examples.

EXAMPLES

example 1

Test specimens of size 25 × 25 × 10 mm ³ (radial × tangential × longitudinal) of the species pine pine (Pinus sylvestris L.) and beech (Fagus sylvatica L.) were dried at 103 ° C. for several hours to constant mass. Subsequently, a vacuum impregnation with a solution of water: isopropanol (1: 1) containing 5, 10, and 15 wt .-% of an analog DE 4318536 Example 22a Aminosiloxane of chain length D9 with the following structure, which was prepared by reaction of an epoxy-functional siloxane with ethylene diamine:

The resulting weight increases in dried after drying at 103 ° C to constant weight wood averaged about 9%, about 16% and about 24 wt .-% based on the initial weight of the samples. The associated permanent cell wall swellings (bulking, measured by the increase in the cross-sectional area) accordingly averaged about 1.2%, about 1.7% and about 2.4% relative to the starting cross-sectional area. The permanent cell wall swelling is a measure of the dimensional stabilization of the wood and therefore a desired effect. The more the cell wall swells permanently, the smaller the maximum dimensional changes become.

Comparative Example 1

Test specimens of size 25 × 25 × 10 mm ³ (radial × tangential × longitudinal) of the species pine pine (Pinus sylvestris L.) and beech (Fagus sylvatica L.) were dried at 103 ° C. for several hours to constant mass. Subsequently, a vacuum impregnation with a solution of water: isopropanol (1: 1) containing 5, 10, and 15 wt .-% of an analog DE 4319536 Example 22a Aminosiloxane of chain length D28 with the following structure, which was prepared by reaction of an epoxy-functional siloxane with ethylene diamine:

The resulting weight increases after drying at 103 ° C. to constant mass were on average about 8%, about 12% and about 22%, respectively, based on the respective starting weights, thus being comparable to those of example 1. The associated, permanent cell wall swelling ( measured by the increase in the cross-sectional area), however, only an average of about 0.4%, about 0.8% and about 1.2% based on the starting cross-sectional area. When comparing with Example 1, it becomes clear that a reduction in the chain length of the aminosiloxane used has a positive influence on the permanent cell wall swelling and thus dimensional stabilization.

The wood specimens prepared in Example 1 and Comparative Example 1 were examined with a scanning electron microscope (Leo Supra 35 SEM, Zeiss GmbH) using an X-ray microanalysis (Energy Dispersive X-ray, EDX, Thermo Fisher Scientific GmbH) ( ). FIG. 4 is an electron micrograph of a wood cross section for Example 1. FIG. shows the same specimen section, but this time as an EDX image, with silicon being detected primarily in the cell wall. This wood specimen was treated with the short-chain aminosiloxane (D9) of Example 1 according to the invention. is again a transmission electronic recording of a wood cross section and the corresponding EDX image for Comparative Example 1. Here, the wood was treated with the non-inventive long-chain siloxane (D28). Silicon is predominantly detected in the lumen of the cells. The enlargement photos of the show that the short-chain siloxanes with 9 dimethylsiloxy units (D9) have penetrated into the cell wall to a large extent, while the long-chain aminosiloxanes with 28 dimethylsiloxy units (D28) are predominantly found in the lumens of the cells. The analyzes thus provide information on the different site of action of the aminosiloxanes and allow conclusions to be drawn on the relationship between different degrees of cell wall penetration and swelling of long-chain and short-chain siloxanes from Example 1 and Comparative Example 1.

Example 2 and Comparative Example 2

Hardwood sapwood samples 5 × 40 × 40 mm ³ (radial × tangential longitudinal) were impregnated with 5% by weight and 15% by weight of the aminosiloxanes as in Example 1 and Comparative Example 1, analogous to Example 22a in FIG DE 4318536 were prepared by reaction of epoxy-functional siloxane with ethylenediamine and here have a chain length of D9 (Example 2) or D30 (Comparative Example 2) and had the following structures:

After interim drying as before, the test specimens were subjected to a leaching load according to EN 84 subjected. The samples were then conditioned in a climatic chamber at 20 ° C and 65% relative humidity and sterilized with the aid of gamma radiation (25 kGy, Isotron, Netherlands). Subsequently, the samples were immersed in a spore suspension of the blue-fungal fungi Aureobasidium pullulans (de Barry) and Sclerophoma pithyophila (Corda) and placed in a collection flask containing vermiculite incubated with 20 ml of the spore suspension. Two samples were used per collection bottle. The area colonized by the fungi was determined on the top and bottom of the samples and the infestation was divided into classes from 0 (no infestation) to 5 (more than 75% of the area infested). As Table 1 below shows, the two investigated aminosiloxanes of these examples, both in the low and in the high concentration, caused a marked reduction in the discoloration caused by blue fungi compared with the untreated control samples. In the case of the low concentration (5% by weight aminosiloxane solution), the wood samples treated with the short-chain D9 siloxane Example 2 showed a lower infestation of the blue fungi than the wood test specimens treated with the D30 siloxane from Comparative Example 2. Concentration / D chain length / Example Discolored area percentage (%) infestation class Front weight loss [%] Back of mass loss [%] Front weight loss [%] Back of mass loss [%] 5% D9 Ex. 2 13.6 ± 7.3 12.8 ± 5.7 2 2 5% D30 Comp. Ex. 2 16.6 ± 7.1 20.5 ± 10.3 2 2 15% D9 Ex. 2 5.5 ± 3.5 7.9 ± 3.1 1 1 15% D30 Comp. Ex. 2 5.9 ± 5.2 6.4 ± 4.9 1 1 Untreated control 74.3 ± 8.0 75.5 ± 6.5 5 5 Table 1: Area stained by blues fungi with standard deviation and the corresponding infestation class

It turns out that the wood treatment with the Aminopolyorganosiloxanen leads to a significant reduction of the bluish infestation over the untreated control, which increases with increasing concentration of the Aminopolysiloxan solution, the Aminopolyorganosiloxan solution according to the invention has a slightly higher efficiency at lower concentrations.

shows images of the pine samples after 8 weeks of incubation with a spore suspension of the blue fungus A. pullulans and S. pithyophila (surface with vermiculite contact). (A, B) control, (C, D) treated with 15% aminopolysiloxane solution (D9 of Example 2). It turns out that the wood treatment with aminosiloxanes leads to a significant reduction of the bluish inflow compared to the untreated control.

Example 3 and Comparative Example 3

Specimens of dimension 30 × 10 × 5 mm ³ , (radial × tangential × longitudinal) of the species pine pine (Pinus sylvestris L.) and beech (Fagus sylvatica L.) were mixed with 5 and 15% by weight as described in Example 2. % aqueous solutions of the amino-functional polyorganosiloxanes described in Example 2 and Comparative Example 2 with the chain lengths D9 and D30 treated and 14 days of a leaching in water according to EN 84 subjected. The resistance to fungal attack of the treated and untreated samples was based on the European standard EN 113 determined. The beech samples were incubated with Trametes versicolor (BAM Ebw. 15) and the pine samples with Coniophora puteana (CTB 863 A) for 12 weeks on 4% malt agar medium at a temperature of 22 ° C and a relative humidity of 70 %. After subsequent drying at 103 ° C to constant mass, the mass losses were determined. For each collection bottle, 3 untreated and 3 treated samples were used. A total of 15 samples per treatment were used in 5 collets. Table 2 shows the results. Table 2 Pine (C. puteana) Beech (T. versicolor) Treatment with siloxane concentration 5% 15% 5% 15% Mass loss [%] Example 3 (D9) 46.4 ± 8.6 1.6 ± 0.7 * 31.9 ± 4.6 * 11.8 ± 4.6 * Mass loss [%] Comp. Example 3 (D30) 48.8 ± 11.0 22.9 ± 6.9 * 43.3 ± 8.7 26.0 ± 6.3 * Mass loss [%] control 44.7 ± 11.8 44.7 ± 11.8 56.2 ± 9.5 56.2 ± 9.5

Table 2: Mass Losses and Standard Deviations of Amine Polyorganosiloxanes: Treated and Untreated Wood Samples After 12 Weeks of Incubation, in starred mass losses becomes a difference of more than 2 standard deviations between that with the siloxane of Example 3 of the present invention versus the Comparative Example 3 treated specimens found.

The results show that the treatment of the test specimens with a concentration of 15% by weight leads to a significantly lower loss in mass than in the untreated specimens. In the samples treated with 5% by weight solution, slight increased resistances can be observed only in the treated beech test specimens.

The short-chain aminopolyorganosiloxanes lead to a higher resistance (ie a lower mass loss) in the case of different types of wood or fungi than the long-chain aminopolyorganosiloxanes.

The examples make it clear that the novel aminopolyorganosiloxanes lower the water absorption in wood bodies. The reduced water absorption makes it possible to use the novel aminopolyorganosiloxanes as protective agents for wood and other lignocellulosic materials, wood u. Ä. Can be made more resistant to weather conditions such as changes in the moisture content of the environment. It has also been shown that wood which has been treated with aminopolyorganosiloxanes according to the invention as a protective agent is subject to significantly lower levels of attack by superficial mildew and blue fungi. As a further advantage, the aminopolyorganosiloxanes according to the invention as protection agents for lignocellulosic materials, for example wood, offer increased resistance to the attack of algae and harmful marine organisms, such as, for example, shells. As a further advantage, the novel aminopolyorganosiloxanes as protection agents for wood have an increased resistance to attack by algae. Furthermore, the novel aminopolyorganosiloxanes can increase the resistance of wood to wood-destroying insects, for example termites, domestic goat beetles, common barnacles, sapwood beetles. This is the case in particular if insecticides are introduced into the lignocellulosic material in addition to or simultaneously with the aminopolyorganosiloxanes according to the invention. Furthermore, the degradation experiments, ie the measured mass loss of beech and pine in contact with the white rot fungus Trametes versicolor or the brown rot fungus Coniophora puteana, show that the novel aminopolyorganosiloxanes make wood and other lignocellulosic materials more resistant to these wood-destroying fungi. Tests on the swelling and shrinkage behavior of beech and spruce wood samples show that the inventive aminopolyorganosiloxanes increased wood Give dimensional stability in contact with water or humidity variations of the environment. This is a desirable property since swelling and shrinkage are major drawbacks to the use of wood. For example, this increase in dimensional stability leads to a significantly reduced cracking, as could be shown in weathering experiments. The outdoor weathering experiments showed that wood samples treated with the aminopolyorganosiloxanes of the invention have increased color stability. This protection is due to the fact that in particular the lignin degradation in the upper cell wall layers of the wood takes place less quickly than in untreated wood. The leaching tests with boric acid as cobicidal for determining the fixation of hydrophilic substances by the novel aminopolyorganosiloxanes in lignocellulosic materials show that the aminopolyorganosiloxanes according to the invention achieve fixation or retention of hydrophilic substances in wood or lignocellulosic materials. The fixation or retention of lipophilic substances in lignocellulosic materials by the aminopolyorganosiloxanes according to the invention are due to the generally lipophilic properties of these silicone derivatives. Therefore, the novel aminopolyorganosiloxanes are suitable for fixing conventional wood treatment agents, such as flame retardants, fungicides, insecticides or dyes. This applies above all to those conventional compounds which are poorly retained in the matrix of the lignocellulosic material and easily washed out by water. To demonstrate a reduction in flammability, pinewood impregnated with an aminopolysiloxane according to the invention was examined by means of a thermo-balance (TGA). For this purpose, pine wood samples of size 5 × 10 × 30 mm ^{3 were} treated with aminopolyorganosiloxanes according to the invention and with a commercial wood flame retardant (Impralit F3 / 66, Rütgers Organics). The wood samples were then ground. By means of a thermo-balance (STA 409 PC, Netzsch), the wood flour was continuously heated under oxygen as a protective gas at a heating rate of 20 ° C / min from 0 ° C to 800 ° C and the changes in weight traced. The thermogravimetric analysis shows that the novel aminopolyorganosiloxanes lead to an increased flame resistance or fire resistance of the lignocellulosic materials treated therewith, as exemplified by wood. This is the case in particular when, in addition to the novel aminopolyorganosiloxanes, conventional flameproofing agents are applied to the lignocellulosic material, such as those from phosphorus compounds (phosphates, polyphosphates), magnesium compounds (magnesium hydroxide), aluminum compounds (aluminum hydroxide), bromine / chlorine compounds (hydrogen halides) and Flame retardant systems with inflating substances.

The novel aminopolyorganosiloxanes can also serve for the physical and / or chemical bonding of conventional treatment agents for wood or other materials based on cellulose and thus increase their stability. This relates in particular to the combination of novel aminopolyorganosiloxanes with flame retardants, insecticides or dyes, especially those compounds which are preferably stable or retained in a hydrophobic environment.

Moreover, woods treated with aminopolyorganosiloxanes according to the invention may have more resilient surfaces, i. H. For example, harder and / or more abrasion resistant surfaces.

Description of the pictures:

- : Scanning Electron Microscopic ( . ) and X-ray microanalytical recordings (EDX) ( . ) of polyorganosiloxanes of different chain length (Example 1 (D9): and and Comparative Example 1 (D28): and ) treated wood test specimens.

: Pictures of the pine samples after 8 weeks of incubation with a trace suspension of the blue fungus A. pullulens and S. pithyophila (surface with vermiculite contact). FIGS. A) and B) show the untreated test specimens of the control, FIGS. C) and D) show the specimens treated according to the invention with 15% aminosilicone (Example 2). Figures B) and D) show the samples of A) and C) after image evaluation to determine the affected areas with an Epson scanner (Expression 10000XL) using the GIMP software (GNU General Public Licenses).

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• JP 2002-348567 A [0009]
• US 6294608 [0010]
• EP 0716127 [0011]
• EP 0716128 [0012]
• US 2002/0026881 [0013]
• US 4757106 [0014]
• DE 3447636 [0015]
• EP 0621115 [0015]
• DE 4241727 [0015]
• DE 102004036918 [0015, 0017]
• WO 94/29324 A1 [0046]
• DE 4318536 [0070, 0075]
• DE 4319536 [0072]

Cited non-patent literature

• DIN EN 351 [0007]
• "Holzlexikon von A-Z" (Volumes I and II), Ulf Lohmann, DRW-Verlag, Leinfeld-Echterdingen, 2003, see inter alia "Einbringverfahren", Volume I, pages 289 to 292 [0059]
• "Holzlexikon von A-Z" (Volumes I and II), Ulf Lohmann, DRW-Verlag, Leinfelden-Echterdingen, 2003, see inter alia "Holztrocknung", Volume I, page 605 [0060]
• Morrell & Levien: "Development of New Wood Protection Treatment Process" Conference Report from "Wood Protection Conference in the 90's and Beyond", Savannah, Goergia, USA, September 26-28, 1994 [0065]
• EN 84 [0076]
• EN 84 [0079]
• European standard EN 113 [0079]

Claims (16)

Polyorganosiloxanes for the treatment of lignocellulosic materials, characterized in that the polyorganosiloxanes are straight-chained, branched or cyclic polyorganosiloxanes, the number average of which is composed of 2 to 16 siloxy units selected from the group consisting of:

wherein R ^{1 represents} organic radicals which may be identical or different from one another, or two radicals R ¹ together with the silicon atoms to which they are bonded, a bridging radical Si-R-Si form, with the proviso that at least one of the radicals R is a radical R ^F is ¹ and R, which contains at least one functional group F is selected from amino and ammonium groups, and in which the radical R ^F on a carbon atom with a silicon atom, and their salts. Polyorganosiloxanes according to claim 1, characterized in that the radicals R ^{1 are} selected from the group of radicals R ^F and R ^N , wherein the radicals R ^F are those radicals R ¹ which have the said functional groups F and at the radicals R ^N are radicals R ¹ which do not have the said functional groups F. Polyorganosiloxanes according to Claim 1 or 2, characterized in that the molar fraction of the radicals R ^F which contain at least one functional group F is 10 to 100 mol%, based on the number of siloxy units. Polyorganosiloxanes according to one of claims 1 to 3 for the treatment of lignocellulosic materials, characterized in that they are selected from the formulas (I) to (V):

wherein n = 0 to 14, and R ¹ and R ^{F are} as defined below,

wherein n1 + n2 = 1 to 14, and n2> 1, and R ¹ and R ^{F are} as defined below,

wherein n1 + n2 = 1 to 14, and n2> 1, and R ¹ and R ^{F are} as defined below,

in which n1 + n2 = 3 to 7, and n2> 1, and R ¹ and R ^{F are} as defined above, and polyorganosiloxanes of the formula (V) ZQ ^F -Z (V) wherein each Z represents polysiloxane residues, which may be the same or different, which together have up to 16 siloxy units and which are bonded via a carbon atom to the group Q ^F , and Q ^{F represents} a divalent organic group having at least one functional group F. in which R ^{1 represents} organic radicals which may be identical or different from one another, with the proviso that at least one of the radicals R ^{1 is} a radical R ^F which contains at least one functional group F which is selected from amino and ammonium Groups, and wherein the radical R ^{F is} connected via a carbon atom to a silicon atom, and their salts. Polyorganosiloxanes according to one of claims 1 to 4, characterized in that they contain at least one radical of the formula M ^F :

wherein R ¹ and R ^{F are} as defined above. Polyorganosiloxanes according to one of claims 1 to 5, characterized in that the number average number of siloxy units is 6 to 14. Polyorganosiloxanes according to any one of claims 1 to 6, characterized in that the substituents R ¹ are selected from the group consisting of straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 100 carbon atoms, optionally one or more Groups selected from -O-, -S-, -NR ² -, wherein R ^{2 is} hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 60 carbon atoms, one or more groups selected from -O-, -S-, -NH-, -C (O) - and -C (S) -, and optionally by one or more substituents selected from the group consisting of a hydroxyl group, a optionally substituted heterocyclic group containing preferably one or more nitrogen atoms, amino, alkylamino, dialkylamino, ammonium, polyether radicals and polyethers may be substituted, wherein when several groups -NR ² are present, they may be the same or different,

-C (O) - and -C (S) -, and may be substituted by one or more radicals selected from the group consisting of: - hydroxy, - amino (-NH ₂ ), - mercapto (-SH), - a polyether radical having up to 60 carbon atoms, which may optionally bear one or more amino, mono- or dialkylamino, or arylamino groups, - a saccharide-containing organic radical, or two substituents R ¹ of different siloxy units together form a straight-chain, branched or cyclic, optionally interrupted by -O-, -S-, -C (O) -, -NH- and optionally substituted by OH Alkandiylrest having 2 to 20 carbon atoms between two silicon atoms. Polyorganosiloxanes according to any one of claims 1 to 7, characterized in that the amino or ammonium groups are selected from the group consisting of primary, secondary, tertiary amino or ammonium groups and quaternary ammonium groups. Polyorganosiloxanes according to any one of claims 1 to 8, characterized in that the amino or ammonium groups are selected from the group consisting of: -N (R ² ) ₂ , wherein R ^{2 is} as defined above, -N ⁺ (R ² ) ₃ , wherein R ^{2 is} as defined above,

wherein R ^{2 is} as defined above, and

wherein R ^{2 is} as defined above. Polyorganosiloxanes according to any one of claims 1 to 9, characterized in that the radicals R ^F are selected from the group consisting of: -CH ₂ CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ NH ₂ -R ³ - NHCH ₂ CH ₂ NH ₂ -R ³ -NHCH ₂ CH ₂ CH ₂ NH ₂ -R ³ -NHCH ₂ CH (CH ₃ ) NH ₂ -R ³ -NHCH (CH ₃ ) CH ₂ NH ₂ -CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ -CH ₂ CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ NHCH ₂ CH ₂ NH ₂

wherein R ^{2 is in} each case as defined above, and R ^{3 is} a divalent, straight-chain, branched, cyclic, aliphatic, unsaturated or aromatic hydrocarbon radical having up to 30 carbon atoms and having one or more groups selected from -O-, -NH-, - C (O) - and -C (S) - and optionally substituted by hydroxy, and Q ^{F is} a divalent organic amino or ammonium functional group which is selected from: -R ³ - [N (R ² ) -R ³ ] a-, -R ³ - [N ⁺ (R ² ) ₂ -R ³ ] _a -, wherein each of R ² and R ^{3 may be the} same or different and are as defined above, and a = 1 to 10 is, and

wherein the radicals R ^{3 may be the} same or different and are as defined above, and b = 1 or 2, and

is a saturated or unsaturated optionally substituted nitrogen-containing 5- to 6-membered heterocycle, wherein the nitrogen atom is optionally positively charged, and wherein the amino or ammonium groups may optionally also be protonated. Polyorganosiloxanes according to any one of claims 1 to 10, wherein the polysiloxane radicals Z are selected from the group consisting of:

wherein R ¹ and R ^{F are} as defined above, and n 3 = 0 to 6,

wherein R ^{1 is} as defined above, and n4 = 0 to 5. Polyorganosiloxanes according to any one of claims 1 to 11, wherein the anions which neutralize the ammonium groups are selected from the group consisting of: Halide anions Hydroxide, Sulfate anions, Phosphate anions, Nitrate and Carboxylate anions. Compositions containing at least one polysiloxane as defined in any one of claims 1 to 12 and at least one carrier medium for the treatment of lignocellulosic materials. A composition according to claim 13, wherein the content of the polyorganosiloxanes is more than 10% by weight based on the total amount of the composition. A process for treating lignocellulosic materials, which comprises treating the lignocellulosic material with at least one polyorganosiloxane according to any one of claims 1 to 12 or a composition according to any one of claims 13 to 14 by surface treatment, dip treatment or vacuum or pressure impregnation. Use of at least one polysiloxane as defined in any one of claims 1 to 12 or a composition according to claims 13 to 14 for the defense against termites with or without additional insecticides for termite control.

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