DE102010034701A1 - Composition containing hyperbranched polymers - Google Patents

Abstract

The present invention relates to compositions comprising a binder, a solvent, a solid lubricant and a hyperbranched polymer, in particular hyperbranched polyamides or polyesters, their use for increasing the abrasion resistance in tribological coatings, and to special hyperbranched polyamides and polyesters, the end groups of which are at least partially modified by blocked isocyanate groups are.

Description

The present invention relates to compositions comprising a binder, a solvent, a solid lubricant and a hyperbranched polymer, in particular a hyperbranched polyamide or a hyperbranched polyester, their use for increasing the abrasion resistance in tribological coatings, and special hyperbranched polyamides and polyesters whose end groups are at least partially blocked isocyanate groups are modified.

In order to reduce wear on tribologically highly stressed friction partners, polymeric coatings in the form of paints and plastic layers are used. Coating coatings are coatings which are applied to one of the two friction partners for permanent friction and wear reduction in friction contacts. The effect of the bonded coatings is that the paint layer is slowly removed, thereby releasing the solid lubricant contained therein. This forms a wear-reducing transfer film on the uncoated friction partner. The durability of the binder significantly determines the lifetime of the entire layer. If the binder layer acting as a solid lubricant depot is worn away, lubricant can no longer be replenished in the course of the further frictional load and the friction-reducing effect is lost.

Various possibilities are known in the prior art which contribute to increasing the resistance of the binder layer. One possibility is, for example, increasing the degree of crosslinking of the paint, for example by adding additional hardener. The disadvantage here is that the paint becomes more brittle with increasing crosslinking and thus the resistance is reduced again. Another possibility is, for example, the use of inorganic fillers, in particular nanoscale materials. Nanoparticles with reactive groups have proven to be particularly suitable, which react with the binder during curing and firmly integrate the particles into the paint matrix. Such particles are in WO 2009/129932 A1 described. In order to protect the inorganic particles from agglomeration, they are usually surface-modified by silanes.

In contrast, no agglomeration occurs when using soluble polymers. However, the use of low molecular weight crosslinkers or linear polymers with corresponding reactive groups does not lead to the same results as the use of reactively functionalized particles.

The object of the present invention was therefore to provide new additives for tribological formulations which reduce their abrasion and form no agglomerates in the formulations.

Surprisingly, it has been found that the addition of hyperbranched polymers increases the abrasion resistance and thus the service life of tribologically stressed layers.

The use of hyperbranched polymers in binder mixtures is known. WO 2008/068180 A1 discloses binder mixtures containing hyperbranched polymers which are used for the production of wood-based materials.

In DE 10 2006 021 855 A1 there are disclosed specific hyperbranched polyesters obtainable by the reaction of an anhydride of a tetracarboxylic acid with a triol. These polyesters may be used, inter alia, as an additive in compositions to improve their lubricity.

Furthermore, in Ishida et al. ( Ishida et al. 2000, Macromolecules 33: 2832-2838 ) describes the synthesis of hyperbranched polyamides starting from 3,5-diaminobenzoic acid as a monomer. The same monomer is reported by Yu et al. ( Yu et al. 2010, Polymer 51: 492-499 ) are used to produce hyperbranched aromatic polyamides, which surface-modify silicanoparticles.

None of these documents discloses the combination of such polymers with a solid lubricant or their use in tribological coatings.

A first subject of the present invention is therefore a composition comprising at least one binder, at least one solvent, at least one solid lubricant and at least one hyperbranched polymer.

The binders used according to the invention can be linear or branched polymers. According to the field of application and the type of possible application and lacquer curing (thermal treatment, Radiation curing, curing at room temperature), the person skilled in the art can select the suitable binder from commercially available lacquer binder systems. According to the invention, for example, the following binders can be used: polyamides, polyamide imides, polyurethanes, polyacrylates, polyacrylate polyols, polyester polyols, polyethers or epoxy resins.

Typical solvents which can be used according to the invention are, for example, alcohols, such as methanol or ethanol, ethers, such as diethyl ether, tetrahydrofuran and / or dioxane, esters, such as butyl acetate or hydrocarbons, such as toluene, petroleum ether, halogenated hydrocarbons, such as dichloromethane, or else commercially available products, such as solvent naphtha or Products based on Shellsol, a high-boiling hydrocarbon solvent such as Shellsol A, Shellsol T, Shellsol D40 or Shellsol D70. For certain coating systems, typical solvents are dimethylformamide (DMF) and / or alkylpyrrolidone, for example N-methylpyrrolidone (NMP) and N-ethylpyrrolidone (NEP).

According to the invention, a solid lubricant is understood to mean a solid substance which is in the form of powder or platelet-shaped and under tribological stress (pressure and shear) forms a layer which reduces the coefficient of friction of the friction partners. Typical solid lubricants are, for example, graphite, Teflon (PTFE) and molybdenum disulfide. The solid lubricant used is preferably graphite, teflon or molybdenum disulfide or a mixture of two or more of these solid lubricants.

In addition, the compositions of the invention may contain hardeners and other additives. In a specific embodiment, the hyperbranched polymer can also replace the binder completely, resulting in compositions of hyperbranched polymer, solid lubricant, solvent and optionally a curing agent and other additives.

For the purposes of this invention, the term hyperbranched polymer means compounds which can preferably be formed in a one-stage polymerization reaction using at least one type of monomer which has more than two reactive functional groups and thereby introduces branches into the polymer.

The stated monomers having more than two reactive functional groups preferably have a group a and at least two groups b (starting from _x monomer with x ≥ 2), where a and b react with one another. Both group a and group b may be reversibly blocked.

Furthermore, the monomers from _x with x ≥ 2 can also be formed in situ from other building blocks.

The hyperbranched polymers are irregularly branched and polydisperse, since they result from a polymerization reaction in which there is basically no complete and uniform reaction of all reactive groups present. Irregularly branched means in this context that in addition to branched sections in the polymer sequences are present in which no branches are present and are therefore linearly constructed.

Dendrimers are completely regularly branched, monodisperse compounds. They are thus not included in the above-defined concept of hyperbranched polymers.

General processes for the preparation of hyperbranched polymers are known to the person skilled in the art. An overview offers for example Voit et al. 2009, Chem. Rev 109: 5924-5973 , The preparation of hyperbranched polyamides is, for example, in US 2007/0191586 A1 disclosed.

The hyperbranched polymer is obtainable from a polymerization reaction of monomers. In a preferred embodiment, it is obtainable from a polymerization reaction of the same monomers.

• – 5 bis 50 Gew.-% hyperverzweigtes Polymer,
• – 5 bis 50 Gew.-% Bindemittel,
• – 20 bis 99 Gew.-% Lösemittel,
• – 5 bis 50 Gew.-% Festschmierstoff.

The composition according to the invention preferably contains, in each case based on the composition,

• From 5 to 50% by weight of hyperbranched polymer,
• From 5 to 50% by weight of binder,
• 20 to 99% by weight of solvent,
• - 5 to 50 wt .-% solid lubricant.

• – 5 bis 20 Gew.-% hyperverzweigtes Polymer,
• – 5 bis 20 Gew.-% Bindemittel,
• – 40 bis 95 Gew.-% Lösemittel,
• – 5 bis 20 Gew.-% Festschmierstoff.

Most preferably, the composition contains

• From 5 to 20% by weight of hyperbranched polymer,
• 5 to 20% by weight of binder,
• From 40 to 95% by weight of solvent,
• - 5 to 20 wt .-% solid lubricant.

The hyperbranched polymer is preferably a polyamide, a polyester, a polyurethane, a polyether or a poly (meth) acrylate.

Particular preference is given to using a hyperbranched polyamide or a hyperbranched polyester.

In particular, it is preferably a hyperbranched polyamide and / or a hyperbranched polyester, wherein the hyperbranched polyamide is obtainable by a polymerization reaction of monomers of the formula I. Z (NHR ¹ ) _n (X) _m I and wherein the hyperbranched polyester is obtainable by a polymerization reaction of monomers of formula II Z (OH) _n (X) _m II, wherein
Z represents a straight-chain, branched or cyclic alkyl group having 1 to 24 C atoms or an alkenyl or alkynyl group having 2 to 24 C atoms, each of which may be substituted by one or more R ² radicals, one or more non-adjacent CH ₂ groups by R ² C = CR ² , C≡C, Si (R ² ) ₂ , C = O, P (= O) (R ² ), SO ₂ , NR ² , O, S, COO or CONR ² and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic ring system having 5 to 24 C atoms, each by one or more radicals R ² may be substituted, or a combination of these groups,
R ¹ in each occurrence independently of one another represents H or a straight-chain, branched or cyclic alkyl group having 1 to 12 C atoms, an alkenyl or alkynyl group having 2 to 12 C atoms or an aromatic ring system having 5 to 12 C atoms,
R ² in each occurrence independently of one another is H, a straight-chain, branched or cyclic alkyl group having 1 to 12 C atoms, an alkenyl or alkynyl group having 2 to 12 C atoms, or an aromatic ring system having 5 to 12 C atoms .
X is a radical selected from the group consisting of carboxylic acid, carboxylic acid halide, carboxylic anhydride, carboxylic acid thioester, carboxylic acid ester, isocyanate, isothiocyanate, chloroformate, sulfonic acid halide, sulfinic acid halide, phosphoric acid halide, phosphonic acid halide and phosphinic acid halide,
n is a number from 1 to 5,
m is a number from 1 to 5, where n + m is 3 to 6.

Z is preferably a group containing aromatic groups.

The reactive functional groups as defined above are in the case of formula I (NHR ¹ ) and X, in the case of formula II (OH) and X.

For the purposes of the present invention is meant a straight-chain, branched or cyclic alkyl group having 1 to 12 carbon atoms, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, and also pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, 1-ethyl-pentyl, octyl, 1-ethyl-hexyl, nonyl, decyl, undecyl or dodecyl.

A straight-chain, branched or cyclic alkyl group having 1 to 24 C atoms may, in addition to the meanings given above, also be, for example, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl or tetracosyl. The cycloalkyl groups may be, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclopentenyl.

An alkenyl group having 2 to 24 carbon atoms, wherein several double bonds may also be present, is for example allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, iso-pentenyl, hexenyl, heptenyl, octenyl , -C ₉ H ₁₇ , -C ₁₀ H ₁₉ to -C ₂₄ H ₄₇ .

An alkynyl group having 2 to 24 carbon atoms, wherein a plurality of triple bonds may also be present, is, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, furthermore 4-pentynyl, 3-pentynyl, hexynyl, heptynyl, octynyl , -C ₉ H ₁₅ , -C ₁₀ H ₁₇ to -C ₂₄ H ₄₅ .

Examples of an aromatic ring system having 5 to 12 C atoms in the context of the present invention are benzyl, phenyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylbenzamidyl or naphthyl. An aromatic ring system having 5 to 24 carbon atoms includes, in addition to the meanings mentioned above, for example, also 1,3-diphenoxybenzyl.

In a further preferred embodiment of the invention, X is a radical selected from the group comprising a carboxylic acid, a carboxylic acid halide, carboxylic anhydride, carbonic acid thioester, carboxylic acid ester, isocyanate or isothiocyanate.

X is particularly preferably a carboxylic acid.

Preference according to the invention is given to monomers of the formula I or II where n is 2 and m is 1, or n is 1 and m is 2.

In formula I, the radical R ^{1 is} preferably H. The radical R ² is also preferably H.

According to the invention, the monomers of the formula I are particularly preferably selected from the compounds of the formulas Ia to Ih

Particular preference is given to compounds of the formula Ia (diaminobenzoic acid) and Ib (aminoisophthalic acid).

worin x für 1 bis 20 steht.The monomers of the formula II are particularly preferably selected from the compounds of the formula IIa to IIh

where x is 1 to 20.

In particular, it is preferably a compound of the formula IIa (dihydroxybenzoic acid) or IIb (hydroxyisophthalic acid).

In addition to the monomers described above, in a particular embodiment of the present invention, in addition to the polymerization, molecules having only one type of functional group may also be added during the polymerization. They correspond to the formulas I and II, in which case n = 2 - 6 and m = 0, if otherwise monomers with n> m are used. In the case of monomers with n <m, these can be used with monomers for n = 0 and m = 2-6. These then serve as "core molecules" and allow control of the molecular weight. Examples of such molecules are listed below:

In addition, the use of monomers of formula I or II, for which n = m = 1, together with the aforementioned monomers is possible. These serve as unbranched chain pieces.

In many application areas for bonded coatings in the field of mechanical engineering, especially in motors, the coatings are also thermally stressed in addition to the tribological stress. In the selection of suitable polymers, therefore, the thermal capacity is an important criterion. Aromatic hyperbranched polyamides and polyesters, in particular composed of diamino or Dihydroxybenzoic acid units of the formulas Ia and IIa are thermally particularly stable, and are therefore preferably used according to the invention.

In addition, compositions according to the invention which contain hyperbranched polymers which carry subsequently applied functional groups have proved to be particularly advantageous, in order to enable incorporation of the hyperbranched polymers into the lacquer matrix during the curing process of the lacquer. The interactions necessary for integration into the matrix can be achieved covalently or noncovalently (eg via hydrogen bonds). Due to the covalent incorporation, the abrasion-reducing effect of the hyperbranched polymers in tribologically stressed systems can be further enhanced.

Accordingly, compositions as defined above are also the subject of the present invention, characterized in that the end groups of the hyperbranched polymers are at least partially modified by one or more functional groups.

For the purposes of this application, the term end groups is understood to mean functional groups of the polymer which have not reacted with further monomer molecules. In the case of ₂ or more monomers, this refers to groups b. These are distributed throughout the polymer.

For example, the subsequent modification with functional groups which can react with the paint binder is advantageous. When used in binder and hardener 2-component systems, the hyperbranched polymers may be designed to either blend together with the binder and react with their functional groups with the hardener or, conversely, be added along with the hardener and functional groups with the binder Binder can react.

The integration into the paint matrix can also be non-covalent, for example via hydrogen bonds. For example, polyethers, preferably polyethylene oxide chains, are suitable for this purpose.

The subsequently introduced functional groups may optionally also be present in blocked form. According to the invention, a reversible blocking of the functional groups is preferred.

The reversible blocking increases the storage stability and the processing ability in the desired paint binders. The blocking is canceled according to the invention by an external influence, preferably heat or radiation, after application of the coating composition containing the reversibly blocked hyperbranched polymers. This allows the reaction of the polymers with the binder of the paint system, creating a network with covalent chemical bonds.

Suitable subsequently introduced functional groups may be selected from the group comprising isocyanate, amino, urea, thiourea, carbamate, thiocarbamate, hydroxyl, mercapto, epoxy, carbonate, ester, carboxyl, acid anhydride , Polyether groups, wherein the functional groups can optionally also be present in blocked form.

Preference is given to using subsequently introduced functional groups selected from polyethylene oxide radicals, epoxy groups and blocked isocyanate groups. Suitable protecting groups are known to those skilled in the art and, for example, in DE 2707659 A1 such as DE 2707660 A1 disclosed.

Examples of blocked isocyanate groups are toluene diisocyanate (TDI) or isophorone diisocyanate (IPDI), which are blocked with a group selected from caprolactam and oximes. Preference is given to using caprolactam-blocked isocyanate groups.

An isocyanate group reversibly blocked with caprolactam is stable at temperatures of 20 to 180 ° C. and can be reversibly deblocked from temperatures of 180 ° C. Depending on the application and curing conditions of the binder, the appropriate protecting groups can be readily selected by one skilled in the art.

In certain cases, it may be advantageous to attach the subsequently introduced functional groups over a longer chain to the hyperbranched polymer, wherein the functional group does not have to be at the end of the chain and several, even different, functional groups are possible in a chain.

Furthermore, the subsequently introduced functional groups can be applied as polymer chains (branched or linear) to the hyperbranched polymers.

For thermally less stressed systems, polyacrylates can be used as functionalization. The polyacrylates are synthesized starting from the hyperbranched polymer, which here acts as the core molecule, or separately synthesized and coupled to the core. This gives a polymeric, hyperbranched core of the polymer chains starting with functional groups. Polyacrylates have the advantage over the broad availability of monomers to adjust the properties of the polymers to a large extent. Thus, suitable functional monomers with epoxy functions and blocked isocyanates are available here for the frequently used binders.

Furthermore, it may be advantageous to provide the hyperbranched polymers subsequently with different functional groups. Thus, for example, after a partial functionalization with blocked isocyanate, a further functionalization with PEG chains can take place.

Another object of the present invention are compositions of the invention containing mixtures of the above-described hyperbranched polymers and inorganic fillers. These are preferably suitably functionalized nanoparticles. For incorporation into the coating matrix, the nanoparticles can carry the same functional groups as the hyperbranched polymers or compatible groups.

In addition, compositions are also subject matter of the present invention in which hyperbranched polymers are covalently bound to suitably functionalized nanoparticles. The synthesis of the hyperbranched polymers in this case typically takes place in the presence of the nanoparticles, the nanoparticles bearing functional groups with which the monomers of the hyperbranched polymers to be prepared can react. For example, hydroxy-functionalized nanoparticles can be used for the preparation of nanoparticles modified with a hyperbranched polyester from dihydroxybenzoic acid. In contrast, the production of nanoparticles modified with a hyperbranched polyamide from diaminobenzoic acid is made possible, for example, by amino-functionalized nanoparticles. The modification of silane nanoparticles with a hyperbranched aromatic polymer of 3,5-diaminobenzoic acid is disclosed in U.S. Pat Yu et al. (2010, Polymer 51: 492-499) described.

The hyperbranched polymers used in the compositions of the invention have a number of advantages:
Due to the high degree of branching and the approximately spherical shape, the hyperbranched polymers have a large number of reactive groups, which are also relatively concentrated. The polymers are relatively soluble even at high molecular weights and their solutions have a lower viscosity than the linear polymers.

The diameter of these spherical molecules in solution is generally between 2 and 20 nm and is therefore within the range of the silica particles hitherto used in the prior art.

Furthermore, the hyperbranched polymers are synthetically readily available (see, for example Voit et al. 2009, Chem. Re. 109, 5924-5973 ).

The compositions according to the invention have increased resistance and extended service life, which makes it possible to use them in areas in which hitherto more complex measures for reducing wear must be applied. Thus, in appropriate applications instead of run-in lubrication a lifetime lubrication is possible.

Therefore, the use of a composition as described above to increase the abrasion resistance in tribological coatings is also an object of the present invention.

According to the invention, the term "tribological coating" is understood to mean a coating which is applied to at least one of the two friction partners for permanent friction and wear reduction in frictional contacts. Such a coating can also be referred to as a bonded coating. The effect of such coatings is that by slowly ablating the layer, the solid lubricant contained therein is released, which forms a wear-reducing transfer film.

According to the invention, the abrasion resistance is after DIN 51834 determine: The coating is applied to a specimen made of bearing steel 100Cr6. The counterpart is a ball made of the same material with a diameter of 10 mm. The test is carried out in a translatory oscillation tester. Here, the ball is moved with a normal force of 10 N on the counter body oscillating with a frequency of 10 Hz. After a test period of 2 h, the wear on the test specimen wears off DIN 51834 certainly.

Compared to formulations which do not contain additives such as the hyperbranched polymers or nanoparticles, the compositions of the invention typically allow a reduction in wear to one-half, preferably one-third.

In particular, the compositions according to the invention are suitable for sliding pairs in which at least one sliding partner consists of metallic, polymeric and / or ceramic materials, preferably both sliding pairs, wherein at least one of the sliding partners has a coating with the composition according to the invention.

As sliding pairs for technical use, all known embodiments are conceivable. It is preferably plain bearings, roller bearings, ball bearings, link chains or gear wheels.

At least one of the surfaces is preferably metallic in the sliding pairs.

Another object of the present invention is a process for the preparation of a composition, characterized in that a hyperbranched polymer with at least one binder, at least one solvent and a solid lubricant is mixed.

A further subject of the present invention are hyperbranched polyamides and polyesters where the hyperbranched polyamides are obtainable by a polymerization reaction of monomers of the formula I. Z (NHR ¹ ) _n (X) _m I and wherein the hyperbranched polyesters are obtainable by a polymerization reaction of monomers of formula II Z (OH) _n (X) _m II, wherein
Z represents a straight-chain, branched or cyclic alkyl group having 1 to 24 C atoms or an alkenyl or alkynyl group having 2 to 24 C atoms, each of which may be substituted by one or more R ² radicals, one or more non-adjacent CH ₂ groups by R ² C = CR ² , C≡C, Si (R ² ) ₂ , C = O, P (= O) (R ² ), SO ₂ , NR ² , O, S, COO or CONR ² and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic ring system having 5 to 24 C atoms, each by one or more radicals R ² may be substituted, or a combination of these groups,
R ¹ in each occurrence independently of one another represents H or a straight-chain, branched or cyclic alkyl group having 1 to 12 C atoms, an alkenyl or alkynyl group having 2 to 12 C atoms or an aromatic ring system having 5 to 12 C atoms,
R ² in each occurrence independently of one another is H, a straight-chain, branched or cyclic alkyl group having 1 to 12 C atoms, an alkenyl or alkynyl group having 2 to 12 C atoms, or an aromatic ring system having 5 to 12 C atoms .
X is any group which combines with amino groups or hydroxy groups in a condensation or addition reaction,
n is a number from 1 to 5,
m is a number from 1 to 5, where n + m is 3 to 6,
characterized in that the end groups of the hyperbranched polyesters or polyamides are at least partially modified by one or more blocked isocyanate groups.

Preferred embodiments of the polyamides and polyesters are defined as previously described.

The monomers of the formulas I and II are particularly preferably selected from the compounds of the formulas Ia to Ih and IIa to IIh; in particular from the compounds of the formulas Ia, Ib, IIa and IIb.

Examples of the blocked isocyanate groups of the polyamides and polyesters of the invention and preferred embodiments of the blocked isocyanate groups are defined as previously described.

The following embodiments serve to illustrate and illustrate the invention without the subject matter of the invention being restricted to the content of the examples.

Examples:

Example 1:

Preparation of hyper-restricted poly-diaminobenzoic acid:

10 g of diaminobenzoic acid are heated with stirring for 30 min under argon 240 ° C. The result is a tough dark mass, which is dissolved after cooling under argon in NMP (N-methyl-2-pyrrolidone). The hyperbranched polymer is obtained as a pale colored powder by precipitation of methanol with 1% lithium chloride.

Example 2:

Preparation of hyperbranched poly-3,5-bis (4-aminophenoxy) benzoic acid:

8.4 g of 3,5-bis (4-aminophenoxy) benzoic acid (preparation according to Yang et al: Macromolecules 31, 5964 (1998) ) are dissolved in 50 ml NMP. Added to this are 12.5 ml of pyridine and 13 ml of triphenyl phosphite. The solution is heated to 100 ° C for 3 h. After cooling, the polymer is precipitated with methanol, washed and dried in vacuo at room temperature.

Example 3:

Preparation of hyperbranched poly-diacetoxybenzoic acid:

10 g of acetylated dihydroxybenzoic acid are dissolved in 100 ml of decalin and refluxed in a water separator for 8 h. After cooling, the polymer is dissolved in THF (tetrahydrofuran). The hyperbranched polymer is obtained as a pale colored powder by precipitation from hexane.

Example 4:

Preparation of hyperbranched poly-4,4-bis (4-hydroxyphenyl) pentanoic acid:

100 mmol of 4,4-bis (4-hydroxyphenyl) pentanoic acid are refluxed in 200 ml of diphenyl ether together with 10 mmol of dibutyltin diacetate for 5 h on a water separator. After cooling to room temperature, the polymer is precipitated with 11 methanol, washed with methanol and dried.

Example 5:

Preparation of hyperbranched poly-methyl 3,5-bis [(5'-hydroxy-3'-oxopentyl) oxylbenzoate:

500 mmol of methyl 3,5-bis [(5'-hydroxy-3'-oxopentyl) oxy] benzoate (preparation of the monomer according to J. Power Sources 81-82, 824-829 (1999) ) are heated together with 50 mmol of dibutyltin diacetate for 30 min at 160 ° C. After cooling, the polyester is dissolved in THF and precipitated with methanol.

The polymer can be used without further functionalization in the paint formulation.

Example 6:

Preparation of half-protected TDI (toluene-2,4-diisocyanate):

Production according to DE 27 07 660 113 parts of ε-caprolactam (CL), 174 parts of toluene-2,4-diisocyanate (TDI) and 420 parts of petroleum ether are dissolved at 50 ° C and heated to 60 ° C for 1 h. The solution increasingly separates into two phases, which are separated in a separating funnel. The bottom layer is 3 times washed with 50 ml of petroleum ether. The half-protected TDI is obtained after removal of the petroleum ether as a colorless solid.

Example 7:

Preparation of Polyesters Glycol Monomethyl Ether (PEG) Reversed Succinic Acid:

20 g of succinic anhydride are heated with 50 g of polyethylene glycol monomethyl ether (molecular weight 550 g / mol) in 500 ml of pyridine for 10 h at 50 ° C. The reaction solution is poured into an excess of dilute hydrochloric acid and the product is extracted by shaking with dichloromethane. After removal of the solvent, the PEG-functionalized acid is obtained.

Example 8:

Preparation of the Corresponding Acid Chloride from the Acid Derived in Example 7:

20 g of the acid from Example 7 are stirred with 2.7 ml of thionyl chloride for 3 h at 78 ° C. After stripping off the excess thionyl chloride in vacuo to obtain the acid chloride.

Example 9:

Functionalization of the hyperbranched aromatic polyamide from Example 1 with half-protected TDI:

10 g of the polymer from Example 1 and 2 g of half-protected TDI from Example 6 are heated to 80 ° C. in 88 g of NMP for 6 h. A solution of the functionalized polymer which can be used directly as a coating additive is obtained.

Example 10:

Functionalization of the hyperbranched aromatic polyamide of Example 1 with polyethylene oxide chains:

0.48 g of the acid from Example 7 are stirred in 10 ml NMP for 1 h at room temperature with 0.26 g DBOP (dibutyl o-phthalate) and 100 ul triethylamine and then to a solution of 10 g of polymer from Example 1 in Added 90 ml of NMP and stirred for a further 6 h at room temperature. The polymer is precipitated with methanol, washed and dried.

Example 11:

Functionalization of the hyperbranched aromatic polyamide of Example 2 with half-protected TDI:

The reaction is carried out analogously to Example 9.

Example 12:

Functionalization of the hyperbranched aromatic polyamide of Example 2 with polyethylene oxide chains:

The reaction is carried out analogously to Example 10.

Example 13:

Functionalization of the hyperbranched aromatic polyester of Example 3 with polyethylene oxide chains:

10 g of the polymer from Example 3 are dissolved in a mixture of 21 THF, 300 ml of methanol and 200 ml of water and refluxed together with 15 ml of hydrochloric acid, 25% for 16 h. Thereafter, the entire solvent is distilled off and the residue washed with water until neutral.

3 g of the residue are dissolved in 60 ml of THF and stirred with 140 mg of the acid chloride from Example 5 overnight at room temperature. Thereafter, the reaction mixture is added to ice-water, treated with 350 .mu.l of 25% hydrochloric acid and stirred. The polymer is filtered off with suction, washed with methanol and dried.

Example 14:

Functionalization of the hyperbranched aromatic polyester of Example 4 with polyethylene oxide chains:

The reaction is carried out analogously to Example 13.

Example 15:

Functionalization of the hyperbranched aromatic polyester of Example 3 with epoxy functions:

10 g of the polymer from Example 3 are dissolved in a mixture of 21 THF, 300 ml of methanol and 200 ml of water and refluxed together with 15 ml of 25% hydrochloric acid for 16 h. Thereafter, the entire solvent is distilled off and the residue washed with water until neutral. 3 g of the residue are dissolved in 60 ml of DMF (dimethylformamide) and stirred with 3.5 g of potassium carbonate and 2.95 g of epichlorohydrin for 10 h at 60 ° C. Thereafter, the solution is filtered and the solvent of the filtrate removed. The functionalized polymer is obtained in a slightly yellow color. For use as an additive, 1 g of the polymer is dissolved in 9 g of butyl acetate.

Example 16:

Functionalization of the hyperbranched aromatic polyester of Example 4 with epoxy functions:

The reaction is carried out analogously to Example 15.

Example 17:

Preparation of silica particles bearing blocked isocyanate functions (according to DE 10 2008 020 440):

Example 17a: Preparation of the amphiphilic silane:

Under an inert gas atmosphere, 4.00 ml of diethylene glycol mono-n-hexyl ether and 4.90 ml of 3-isocyanatopropyltriethoxysilane are combined in 6.00 ml of dried toluene and heated to 90 ° C. for 7 hours. The course of the reaction is monitored by IR spectroscopy. After completion of the reaction, the toluene is removed on a rotary evaporator.

Example 17b: Preparation of the Blocked Reactive Surface Modifier

Under an inert gas atmosphere, 28.29 g of epsilon-caprolactam and 61.84 g of 3-isocyanatopropyltriethoxysilane are combined in 113.00 ml of dried toluene and heated to 90 ° C. for 20 h. The course of the reaction is monitored by IR spectroscopy. After completion of the reaction, the toluene is removed on a rotary evaporator.

Example 17c: Preparation of Functionalized Particles

66.67 g of aqueous 30% SiO ₂ sol (particle diameter 20 nm) is diluted to 10% with 133.33 g of water. For this purpose, 5 g of the silane from Example 17b and 1 g of the silane from Example 17a are added. The mixture is stirred for 24 h at room temperature. Subsequently, 80.00 g of 1-methyl-2-pyrrolidone are added. At 30 ° C, the water is removed on a rotary evaporator.

The particles can be used together with functionalized polymers from Examples 1 to 5 and 9 to 16.

Example 18:

Preparation of silica particles with a hyperbranched polyamide:

A dispersion of 10 g silica particles (20 nm diameter) in 90 g NMP is stirred with 8 g Dynasilan AMMO (Evonik) for 4 h at 80 ° C. The reaction is carried out analogously to Example 13. Added to this are another 110 g of NMP, 30.4 g of diaminobenzoic acid, 50 ml of pyridine and 52 ml of triphenyl phosphite. The mixture is stirred for 3 h at 100 ° C. Addition of 1.5 L of methanol precipitates the product. For use as an additive, 10 g of the product are dissolved in 90 g of NMP.

Example 19:

Production of a Low Molecular Crosslinker:

50 g of MDI (diphenylmethane-4,4'-diisocyanate) and 46 g of epsilon-caprolactam are placed under nitrogen and melted in an oil bath at 80 ° C. The temperature is raised to 110 ° C for 90 minutes, during which the reaction mixture becomes solid. The crude product is dissolved after cooling in 500 ml of toluene at reflux and slowly cooled to room temperature. At 0 ° C precipitate colorless crystals, which are washed with cold toluene and dried at 50 ° C in a vacuum.

77 g of caprolactam-protected MDI are obtained.

Example 20:

Preparation of an Amide-Imide Bonded Coating with Hyperbranched Polyamide

To 100 g of Molykote (R) 7409 from Dow-Corning, the additives listed in the following table are dissolved or suspended in 10 g of NMP. The resulting mixture is sprayed onto phosphated steel bodies (100Cr6) and baked at 150 ° C for 120 minutes, then baked at 220 ° C for 30 minutes. paint mixture crosslinkers Particles from Ex. 17 hyperbranched polymer Hyperbranched polymer particles of Ex. 18 comment L1 Comparative example without additives L2 2 g Comparative Example with Low Molecular Crosslinker (Ex. 19) L3 2 g Comparative example only with particles L4 2 g from Ex. 5 L5 2 g from Ex. 9 L6 2 g from Ex. 10 L7 2 g from example 11 L8 2 g from Ex. 12 L9 4 g from Ex. 9 110 2 g 4 g from Ex. 9 L11 4 g

Example 21:

Comparison of abrasion resistance

The steel bodies of Example 19 become a wear test DIN 51834 The coating is applied to a sample of bearing steel 100Cr6. The counterpart is a ball made of the same material with a diameter of 10 mm. The test is carried out in a translatory oscillation tester. Here, the ball is moved with a normal force of 10 N on the counter body oscillating with a frequency of 10 Hz. After a test period of 2 h, the wear is reduced DIN 51834 certainly. exam paint mixture relative wear comment P1 L1 100% Comparative example without additives P2 L2 73-75% Comparative Example with Low Molecular Crosslinker (Ex. 19) P3 L3 36-39% Comparative example only with particles P4 L4 38-42% P5 L5 21-24% P6 L6 24-29% P7 L7 28-34% P8 L8 32-34% P9 L9 19-21% P10 L10 17-20% P11 L11 15-19%

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

• WO 2009/129932 A1 [0003]
• WO 2008/068180 A1 [0007]
• DE 102006021855 A1 [0008]
• US 2007/0191586 A1 [0021]
• DE 2707659 A1 [0054]
• DE 2707660 A1 [0054]
• DE 2707660 [0086]
• DE 102008020440 [0097]

Cited non-patent literature

• Ishida et al. 2000, Macromolecules 33: 2832-2838 [0009]
• Yu et al. 2010, Polymer 51: 492-499 [0009]
• Voit et al. 2009, Chem. Rev 109: 5924-5973 [0021]
• Yu et al. (2010, Polymer 51: 492-499) [0062]
• Voit et al. 2009, ChemRev 109, 5924-5973 [0065]
• DIN 51834 [0069]
• DIN 51834 [0069]
• Yang et al: Macromolecules 31, 5964 (1998) [0081]
• J. Power Sources 81-82, 824-829 (1999) [0084]
• DIN 51834 [0106]
• DIN 51834 [0106]

Claims (16)

Composition comprising at least one binder, at least one solvent, at least one solid lubricant and at least one hyperbranched polymer. Composition according to Claim 1, characterized in that the hyperbranched polymer is a polyamide, a polyester, a polyurethane, a polyether or a poly (meth) acrylate. A composition according to claim 1 or 2, characterized in that the hyperbranched polymer is a hyperbranched polyamide and / or a hyperbranched polyester, wherein the hyperbranched polyamide is obtainable by a polymerization reaction of monomers of the formula I. Z (NHR ¹ ) _n (X) _m I and wherein the hyperbranched polyester is obtainable by a polymerization reaction of monomers of formula II Z (OH) _n (X) _m II, wherein Z is a straight-chain, branched or cyclic alkyl group having 1 to 24 carbon atoms or an alkenyl or alkynyl group having 2 to 24 carbon atoms, each of which may be substituted by one or more R ² radicals, one or more not adjacent CH ₂ groups by R ² C = CR ² , C≡C, Si (R ² ) ₂ , C = O, P (= O) (R ² ), SO ₂ , NR ² , O, S, COO or CONR ² may be replaced and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic ring system having 5 to 24 carbon atoms, each by one or more radicals R ² may be substituted, or a combination of these groups, R ¹ at each occurrence is independently H or a straight, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl or alkynyl group having 2 to 12 C Atoms or an aromatic ring system having 5 to 12 C atoms, R ² in each occurrence independently of one another is H, a straight-chain, Verz a branched or cyclic alkyl group having 1 to 12 C atoms, an alkenyl or alkynyl group having 2 to 12 C atoms, or an aromatic ring system having 5 to 12 C atoms, X is a radical selected from the group comprising carboxylic acid, Carboxylic acid halide, carboxylic acid anhydride, carbonic acid thioester, carboxylic acid ester, isocyanate, isothiocyanate, chloroformate, sulfonic acid halide, sulfinic acid halide, phosphoric acid halide, phosphonic acid halide and phosphinic acid halide, n is a number from 1 to 5, m is a number from 1 to 5, where n + m 3 to 6 is. A composition according to claim 3, characterized in that in formula I and II n is 2 and m is 1, or that n is 1 and m is 2. A composition according to claim 3 or 4, characterized in that R ¹ in formula I is H. Composition according to one or more of claims 3 to 5, characterized in that R ² in formula I and II is H. Composition according to one or more of claims 3 to 6, characterized in that the monomers of the formula I used for a compound selected from the compounds of the formulas Ia to Ih

stand. Composition according to one or more of claims 3 to 4 and 6, characterized in that the monomers of the formula II used for a compound selected from the compounds of the formulas IIa to IIh

where x is 1 to 20. Composition according to Claim 7 or 8, characterized in that the monomers used are a compound of the formula Ia, Ib IIa or IIb. Composition according to one or more of claims 1 to 9, characterized in that the end groups of the hyperbranched polymers are at least partially modified by one or more functional groups. A composition according to claim 10, characterized in that the end groups having functional groups selected from the group comprising isocyanate, amino, urea, thiourea, carbamate, thiocarbamate, hydroxyl, mercapto, epoxy, carbonate, ester -, carboxyl, acid anhydride and polyether groups are modified, wherein the functional groups may optionally be present in a blocked form. Composition according to Claim 11, characterized in that the end groups are modified by functional groups selected from polyethylene oxide radicals, epoxy groups and blocked isocyanate groups. Use of a composition according to one or more of claims 1 to 12 for increasing the abrasion resistance in tribological coatings. Hyperbranched polyamides and polyesters, wherein the hyperbranched polyamides are obtainable by a polymerization reaction of monomers of the formula I. Z (NHR1) _n (X) _m I and wherein the hyperbranched polyesters are obtainable by a polymerization reaction of monomers of formula II Z (OH) _n (X) _m II, wherein Z is a straight-chain, branched or cyclic alkyl group having 1 to 24 carbon atoms or an alkenyl or alkynyl group having 2 to 24 carbon atoms, each of which may be substituted by one or more R ² radicals, one or more not adjacent CH ₂ groups by R ² C = CR ² , C≡C, Si (R ² ) ₂ , C = O, P (= O) (R ² ), SO ₂ , NR ² , O, S, COO or CONR ² may be replaced and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic ring system having 5 to 24 carbon atoms, each by one or more Radicals R ² may be substituted, or a combination of these groups, R ¹ in each occurrence independently of one another represents H or a straight-chain, branched or cyclic alkyl group having 1 to 12 C atoms, an alkenyl or alkynyl group having 2 to 12 C atoms Atoms or an aromatic ring system having 5 to 12 C atoms, R ² in each occurrence independently of one another is H, a straight-chain, Verz alkylene group having 1 to 12 C atoms, an alkenyl or alkynyl group having 2 to 12 C atoms, or an aromatic ring system having 5 to 12 C atoms, X is any group which reacts with amino groups or hydroxy groups in a condensation or addition reaction, n is a number from 1 to 5, m is a number from 1 to 5, where n + m is 3 to 6, characterized in that the end groups of the hyperbranched polyester or polyamides at least partially are modified by one or more blocked isocyanate groups. Hyperbranched polyamides and polyesters according to claim 14, characterized in that the monomers used are a compound of the formula Ia, Ib, IIa or IIb. Hyperbranched polyesters and polyamides according to claim 14 or 15, characterized in that the blocked isocyanate groups are toluene diisocyanate or isophorone diisocyanate blocked with a group selected from caprolactam and oximes.