EP2321242A1

EP2321242A1 - Use of 1,1-dimethylol cycloalkanes or 1,1-dimethylol cycloalkenes for the production of polymers

Info

Publication number: EP2321242A1
Application number: EP09781833A
Authority: EP
Inventors: Darijo Mijolovic; Sebastien Garnier; Qiang MIAO; Maria Guixa Guardia; Gerd-Dieter Tebben
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2008-08-26
Filing date: 2009-08-14
Publication date: 2011-05-18
Also published as: JP2012500874A; CN102131755A; US20110144259A1; WO2010026030A1; KR20110069026A

Abstract

Disclosed is a polymer obtained by polycondensing or forming addition polymers from monomer compounds, characterized in that 1,1-dimethylol cycloalkanes of formula (I) or 1,1-dimethylol cycloalkenes of formula (Ia) or the alkoxylated derivatives thereof are used as monomer compounds.

Description

Use of 1, 1-dimethylolcycloalkanes or 1, 1-dimethylolcycloalkenes for the preparation of polymers

description

The invention relates to a polymer which is obtainable by polycondensation or polyadduct formation of monomeric compounds, wherein as a monomeric compound

1, 1-dimethylolcycloalkanes of the formula I or 1, 1-dimethylolcycloalkenes of the formula Ia

or the alkoxylated derivatives of the compounds of the formula I and Ia is used.

Diols are used for the preparation of polymers, e.g. Polyesters or polyurethanes needed. In EP-A 562 578 z. For example, the use of various cyclohexanediols such as 1,4-cyclohexanedimethanol or 1,4-cyclohexanediethanol for the preparation of polyesters has been described. In Ullmann's Encyclopaedia of Industrial Chemistry "Alcohols, Polyhydric" by Peter Werle et al., Page 4-6, the use of neopentyl glycol is described instead of 1,4-cyclohexanedimethanol.

The use of 2-pentyl-2-propyl-1,3 propanediol for the production of polyesters is known from JP HEI 03-161452.

DE-A 922648 describes a process for the preparation of cycloalkane-1, 1-dicarboxylic acids, during which time the 1, 1-dimethylolcycloalkanes are also formed during the preparation. The use of these 1, 1-dimethylolcycloalkanes for the preparation of polymers is not disclosed.

DE-A 1468065 describes a process for preparing a mixture of cyclododecane derivatives containing mainly monoxymethylcyclododecane. The starting point is cyclododecatriene, which is subjected to hydroformylation by the addition of carbon monoxide and hydrogen. Subsequently, the resulting aldehyde is subjected to a further hydrogenation to the corresponding alcohol. According to this production method, however, only one methylol group is introduced per double bond. A preparation of a dimethylol derivative with both methylol groups on the same carbon atom is not described. 1, 1-Dimethylolcyclodecan and its use for the preparation of polymers is not described. US-A 2,993,912 describes the preparation of 2,2-bis (hydroxymethyl) furfural from formaldehyde and furfural, wherein the diol is prepared in the presence of a base such as NaOH. The use of such a 1, 1-diol for the preparation of polymers is not described.

Basically, it is desired to improve the performance properties of polymers in their different uses.

When using the polymers as binders in coating compositions, adhesives or sealants, in particular the viscosity is important, be it as melt viscosity (100% systems) or as solution viscosity (polymer solutions). The coatings produced are said to have good mechanical properties for coating applications, such as impact resistance and elasticity, high scratch and impact resistance, good resistance to water, solvents, grease and chemicals and environmental influences, and to have a high gloss. Furthermore, the polymers should have a high weather stability and a lower tendency to yellowing.

The object of the present invention was to provide such polymers.

This object is achieved by a polymer obtainable by polycondensation or polyadduct formation of monomeric compounds, characterized in that as a monomeric compound

1, 1-Dimethylolcycloalkane of the formula I or 1, 1, -Dimethylolcycloalkene of the formula Ia

or the alkoxylated derivatives of the compounds of the formula I and Ia are used, where n = 1, 2,4-9,

X = -CH ₂ - or -O- is and

R is hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms and for the compounds of the formula Ia, when n> 2, more than one double bond may be present düng represents.

The polymer according to the invention is advantageously characterized in that the monomeric compound or its alkoxylated derivatives of the formula I or of the formula Ia those are used, in which n = 2, 5 or 9, X = -CH ₂ - and R is selected from the group of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, iso-butyl and n-pentyl.

Advantageously, the polymer of the invention is characterized in that are used as monomeric compound or its alkoxylated derivatives of the formula I or formula Ia those in which n = 2, X = -CH ₂ - and R = hydrogen.

The polymer according to the invention is advantageously characterized in that the compounds of the formula I or of the formula Ia are obtained by reacting aldehydes of the formula II or of the formula IIa

wherein n, X and R are the same as above, are obtainable in a Cannizzaro reaction with formaldehyde.

Advantageously, the polymer according to the invention is characterized in that it is a polyester.

Advantageously, the polymer according to the invention is characterized in that it is a polycarbonate diol (obtainable by reaction of dialkyl carbonates or cyclic carbonates with diols with elimination of alcohol).

The polymer according to the invention is advantageously characterized in that it is a polyurethane.

Advantageously, the polymer according to the invention is characterized in that it is a polyadduct obtainable by ring-opening polymerization of lactones or lactams

Another object of the invention is the use of the polymer according to the invention for the preparation of a thermoplastic composition.

A further subject of the invention is a thermoplastic composition comprising a polymer according to the invention and / or repeat units of a polymer according to the invention. Another object of the invention is the use of the thermoplastic compositions according to the invention for the production of moldings.

Another object of the invention is the use of the polymer according to the invention for the preparation of coating compositions, sealants or adhesives.

Another object of the invention are coating compositions, sealants or adhesives containing repeating units of a polymer according to the invention.

Advantageously, the coating compositions, sealants or adhesives of the invention, characterized in that they are aqueous compositions.

Another object of the invention is the use of the polymer according to the invention for the preparation of powder coatings.

Another object of the invention are powder coating, containing repeating units of a polymer of the invention.

Another object of the invention is the use of the polymer according to the invention for the preparation of radiation-curable coating compositions.

Another object of the invention are radiation-curable coating compositions containing repeating units of a polymer of the invention.

Another object of the invention is 1, 1-dimethylolcyclododecane.

Another object of the invention is a process for the preparation of 1, 1-dimethylolcyclododecane, wherein cyclododecene is subjected to hydroformylation with hydrogen and carbon monoxide, the resulting aldehyde is reacted by means of formaldehyde to 1, 1 -dimethylolcyclododecane.

Another object of the invention is a mixture containing 1, 1-dimethylol-cyclooct-3-ene, 1, 1-dimethylolcyclooct-2-ene and 1, 1-dimethylolocycloct-4-ene.

The invention further provides a process for preparing the mixture comprising 1, 1-dimethylolcyclooct-3-ene, 1, 1-dimethylolcyclooct-2-ene and 1, 1-dimethylolcyclooct-4-ene, where 1, 5 Cyclooctadiene is subjected to a hydroformylation with hydrogen and carbon monoxide, the resulting aldehydes is reacted by means of formaldehyde to the mixture according to the invention. To prepare the polymers according to the invention, compounds of the formula I or of the formula Ia or the alkoxylated derivatives of the formula I or of the formula Ia are used in which n is a whole natural number selected from the group of 1, 2, 4 to 9. N is particularly preferably 2, 5 or 9, very particularly preferably n = 2. The radical R is selected from the group of hydrogen or a linear or branched alkyl group having 1 to 10 C atoms, particularly preferably R is selected from among Group of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl and n-pentyl, most preferably R is hydrogen. In the cycle of compounds of formula I or formula Ia, X is either a CH ₂ group or oxygen. Particularly preferably, X represents a CH ₂ group. Particular preference is given to compounds of the formula I or of the formula Ia in which n = 2, 5 or 9, R is hydrogen or methyl and X represents a CH ₂ group. Very particular preference is given to 1, 1-dimethylolcyclopentane as compounds of the formula I and dimethylolcyclopentene of the formula Ia.

The alkoxylated derivatives of the compound of the general formula I or of the formula Ia are products of the reaction with one or a mixture of alkylene oxides. Examples of alkylene oxides are ethylene, propylene, n-butylene, isobutylene, styrene or cyclohexene oxide. In particular, the above diols are ethoxylated and propoxylated. The alkoxylation products are obtainable in a known manner by reacting the above alcohols with alkylene oxides, in particular ethylene oxide or propylene oxide. Preferably, the degree of alkoxylation per hydroxyl group is 0 to 20, especially 0 to 10, i. 1 mol of hydroxyl group may preferably be alkoxylated with up to 20 mol, in particular 10 mol of alkylene oxides.

In a preferred embodiment, the compounds of the formula I or of the formula Ia are not alkoxylated.

The compounds of the formula I or of the formula Ia are obtained by a Cannizzaro reaction of the corresponding aldehydes of the formula II or of the formula IIa with formaldehyde. The process for the preparation of 1, 1-dimethylolcycloalkanes is already known and described in US 2993912 or DE 922648. Furthermore, compounds of the formal I or formal Ia can be obtained by aldol reaction of the corresponding aldehydes of the formula II or of the formula IIa with formaldehyde followed by hydrogenation. The aldol reaction is described, for example, in WO 01/51438, WO 97/17313 or WO 98/29374. The hydrogenation can be carried out analogously to the disclosure of EP-A 44412 or EP-A 44444. To the polymers

The polymers are obtainable by polycondensation or polyadduct formation of monomeric compounds with concomitant use of one or more compounds of formula I or formula Ia; the polymers may, if desired, be chemically modified by other or further reactions, e.g. functionalized or networked.

In a polycondensation of monomeric compounds, there is a cleavage of water or alcohol, with a polyadduct formation there is no cleavage.

Preferred polycondensates are polyesters, which are obtainable by reacting di- or polyols with di- or polycarboxylic acids, which can also be used in the form of reactive derivatives, such as anhydrides or esters.

The term polyester is to be understood below as meaning a polymer which contains more than 50% by weight, more preferably more than 70% by weight and in particular more than 90% by weight, of synthesis components selected from among diols, polyols , Dicarboxylic acids and polycarboxylic acids.

Also mentioned are polycarbonate diols which are obtainable by reacting dialkyl carbonates or cyclic carbonates with diols with elimination of alcohols.

Polyurethane in particular is called polyadduct. In particular, polyurethanes may also contain repeating units of polymers according to the invention.

Consider, for example, also polyadducts obtainable by ring-opening polymerization of lactones or lactams.

The term polyurethane is to be understood in the following to mean a polymer which contains more than 50% by weight, more preferably more than 70% by weight, in particular more than 90% by weight, of synthesis components selected from diisocyanates , Polyisocyanates, diols and polyols.

All these polymers have in common that they are composed essentially of diols and compounds reactive with these diols, such as di- or polycarboxylic acids (polyesters) or di- or polyisocyanates (polyurethanes).

Preferred polymers are polyesters and polyurethanes, particularly preferred are polyesters. The polymers according to the invention preferably have the following content of the monomer building blocks of the compounds of the formula I or of the formula Ia or its alkoxylated derivatives. The following weights for the content of the compounds of the formula I or of the formula Ia or its alkoxylated derivatives in the polymer refer to the units of the polymer which are derived from compounds of the formula I or the formula Ia or their alkoxylated compounds. In the case of polyadducts, the weight of these units corresponds unchanged to the compound of the formula I or of the formula Ia or their alkoxylated derivatives, in the case of polycondensates the weight of these units is reduced by the hydrogen atoms of the hydroxyl groups.

Preferred polymers are at least 0.5, particularly preferably at least 2, very preferably at least 5 and in particular at least 10% by weight and in a particular embodiment at least 20% by weight of compounds of the formula I or of the formula Ia or their alkoxylated derivatives. Since the concomitant use of other reactive with the diols compounds is mandatory, the polymers are generally not more than 90 wt .-%, in particular not more than 60 wt .-% or not more than 50 wt .-% of the compounds of the formula I or the formula Ia or their alkoxylated derivatives. In addition to the compounds of the formula I or of the formula Ia or their alkoxylated derivatives, the polymers may also contain other diols or polyols as synthesis components. In a preferred embodiment, it is at least 10 wt .-%, more preferably at least 25 wt .-% and most preferably at least 50 wt .-% of the diols and polyols, of which the polymers are made to the compounds of Formula I or Formula Ia or their alkoxylated derivatives.

In particular, at least 70% by weight or at least 90% by weight of the diols and polyols of which the polymers consist can be the compounds of the formula I or of the formula Ia or their alkoxylated derivatives.

In a particular embodiment, it may be at 100 wt .-% of all diols and polyols that make up the polymers to a single compound of formula I or formula Ia or a mixture of compounds of formula I or formula Ia or their alkoxylated derivatives.

To further components of the polyester

In addition to the compounds of the formula I or of the formula Ia or their alkoxylated derivatives, polyesters may contain further diols or polyols as synthesis components. Examples of further diols are ethylene glycol, propylene glycol and their more highly condensed representatives, for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc., 2-methyl-1,3-propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic acid Compounds, such as ethoxylated or propoxylated bisphenols, called cyclohexanedimethanol. Further suitable polyols are trifunctional and higher-functional alcohols, such as glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol.

Preferred mixtures of the compounds of formula I or formula Ia with a diol and a triol are mixtures of the unsubstituted and bearing as X CH ₂ group 5-, 8-, 10- and 12-rings with neopentyl glycol and trimethylolpropane.

The above diols or polyols may be alkoxylated, in particular ethoxy- and propoxylated. The alkoxylation products can be obtained in a known manner by reacting the above alcohols with alkylene oxides, in particular ethylene oxide or propylene oxide. Preferably, the degree of alkoxylation per hydroxyl group is 0 to 20, i. 1 mol of hydroxyl group may preferably be alkoxylated with up to 20 mol of alkylene oxides.

The polyesters also contain dicarboxylic acids or polycarboxylic acids as synthesis components. Dicarboxylic acids or polycarboxylic acids may also be used in the preparation of the polyesters in the form of their reactive derivatives, e.g. be used as anhydrides or esters. Suitable dicarboxylic acids are succinic acid, glutaric acid, adipic acid, sebacic acid, isophthalic acid, terephthalic acid, their isomers and hydrogenation products, such as tetrahydrophthalic acid. Also suitable are maleic acid and fumaric acid for unsaturated polyesters.

Polyesters may also contain monoalcohols or monocarboxylic acids as a constituent; By concomitant use of such compounds, the molecular weight can be adjusted or limited.

To achieve special properties, the polyesters may contain special functional groups. Water-soluble or water-dispersible polyesters contain the necessary amount of hydrophilic groups, for example carboxyl groups or carboxylate groups, in order to achieve water solubility or water dispersibility. Crosslinkable polyesters, for example for powder coatings, contain functional groups which undergo a crosslinking reaction with the crosslinking agent used. These may likewise be carboxylic acid groups if it is intended to crosslink with hydroxyl-containing compounds, for example hydroxyalkylamides. The functional groups may also be ethylenically unsaturated groups, for example by modification of the polyester with unsaturated dicarboxylic acids (maleic acid). or reaction with (meth) acrylic acid. Such polyesters are thermally or chemically crosslinkable or radiation-curable.

Unsaturated polyesters can be ₀ alkyl acrylates, Dialkylacrylaten, z with simple or multi-ethylenically un- saturated, free-radically polymerizable compounds such as styrene, C _r Ci. B. the diacrylate of ethanediol or butanediol are copolymerized. The unsaturated polyester may be used in admixture with the ethylenically unsaturated monomers, such as. As described in WO 00/23495 and EP 1 131372. The above ethylenically unsaturated compounds simultaneously serve as solvents (reactive diluents), so that the mixture is preferably present as a solution of the polyesters in these compounds. The mixture may, for. B. as a coating or impregnating agent, in particular for the production of laminates. The curing can be effected thermally or photochemically, in both cases optionally also with the addition of an initiator. Such compounds, which can be hardened chemically, thermally or by UV irradiation, are special thermoplastics, which are also called thermosets.

In particular, unsaturated compounds of the formula I or of the formula Ia are suitable for UPR (unsaturated polyester resins).

To further constituents of the polyurethanes

Polyurethanes contain diisocyanates or polyisocyanates as essential constituent components.

Particularly noteworthy are diisocyanates Y (NCO) 2, wherein Y is an aliphatic hydrocarbon radical having 4 to 15 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms or an arabiphatic hydrocarbon radical having 7 to 15 carbon atoms. Examples of such diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane , Trimethylhexane diisocyanate, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI ), the isomers of bis (4-isocyanatocyclohexyl) methane (HMDI) such as the trans / trans, the cis / cis and the cis / trans isomers, and mixtures consisting of these compounds.

Such diisocyanates are available commercially.

As mixtures of these isocyanates, especially the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanatodiphenylmethane are of importance, in particular the mixture of 80 mol% 2,4-diisocyanatotoluene and 20 mol% 2,6- Diisocyanatotoluol suitable. Furthermore, the mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI are particularly advantageous, the preferred mixing ratio of the aliphatic to aromatic isocyanates 4: 1 to 1: 4.

As diols or polyols which are reacted with the di- or polyisocyanates, according to the invention compounds of the general formula I or of the formula Ia are used as pure substances or as mixtures of compounds of the general formula I or of the formula Ia or mixed with other diols. or polyols used. In particular, it is also possible to use polymers of the invention as diols or polyols.

In the case of polyurethanes, polyester diols or polyols are preferably also used as diols or polyols. In the following commonly referred to as polyesterols. Such polyesterols are obtained beforehand by reacting di- or polyols with di- or polycarboxylic acids (see above description of the polyesters). The compounds of the general formula I or of the formula Ia or mixtures of compounds of the general formula I or of the formula Ia can be contained in the polyurethanes in the form of such polyesterols. As further diols, polyols, the above genierenden come into consideration, either as structural components which are reacted directly with the di- or polyisocyanates, either as part of the polyesterols. Suitable dicarboxylic acids or polycarboxylic acids for the polyesterols are also those mentioned above.

The polyurethanes may also contain monoalcohols or monoisocyanates as constituents; By concomitant use of such compounds, the molecular weight can be adjusted or limited.

In order to achieve special properties, the polyurethanes may contain special functional groups. Water-soluble or water-dispersible polyurethanes contain the necessary amount of hydrophilic groups, e.g. Carboxyl groups or carboxylate groups to achieve a water solubility or water dispersibility. As a suitable building component, e.g. Called dimethylolpropionic acid. Crosslinkable polyurethanes contain functional groups which undergo a crosslinking reaction with the crosslinking agent used. In addition to urethane groups, the polyurethanes may also contain other functional groups, e.g. Contain urea groups, which are formed by reaction of the di- or polyisocyanates with amino compounds.

If desired, the polymers may also be chemically modified, for example functionalized or crosslinked, at or in particular at a later time, for example during use, by other or further reactions. In particular, the polymers can contain crosslinking groups which, as soon as the necessary conditions are present, undergo a crosslinking reaction and thus act as a thermoset. The polymers can also be used in particular in admixture with crosslinkers which undergo a crosslinking reaction with the polymer at the desired time under the necessary conditions (in particular at elevated temperature).

Depending on the reactivity of the crosslinkers, a distinction is made between one-component (1 K) and two-component (2 K) systems. In 2K systems, the crosslinker is added just before the later use, in 1K systems, the crosslinker can be added to the system early (latent crosslinker), the crosslinking occurs only at the later set conditions, e.g. in the removal of solvent and / or temperature increase.

Typical crosslinkers are e.g. Isocyanates, epoxides, acid anhydrides or in the case of polymers having free-radically polymerizable ethylenically unsaturated groups, also ethylenically unsaturated monomers such as styrene.

For use of the polymers

The polymers are useful as a component of thermoplastic compositions. The polymers, e.g. Polyesters or polyurethanes preferably have a sufficiently high molecular weight to have thermoplastic properties.

Thermoplastic compositions are generally used to make molded articles using conventional methods such as injection molding, extrusion or blow molding.

In particular, the polymers are suitable as a constituent of coating compositions, sealants or adhesives.

The coating compositions, sealants or adhesives preferably contain the polymers according to the invention as binders. They may contain other binders and other additives, e.g. Antioxidants, stabilizers, dyes, pigments, flow control agents, thickeners or wetting aids.

The coating compositions, sealants or adhesives may be aqueous or solvent-containing compositions. Preference is given to aqueous compositions. Such compositions preferably contain the binders according to the invention in the form of solutions or dispersions in water or organic solvents or mixtures thereof. If necessary, the polymers contain additional functional groups. which cause solubility or dispersibility in water or organic solvents, preferably in water (see above).

The coating compositions, sealants or adhesives may also be masses which are substantially free of water or organic solvents (so-called 100% systems). Such compositions generally contain less than 10 parts by weight of water or other organic solvents (boiling point less than 150 ⁰ C, at 1 bar), per 100 parts by weight of the masses. More preferably, they contain less than 2 parts by weight, most preferably less than 1 part by weight, or less than 0.5 parts by weight of water or other organic solvents (boiling point less than 150 ⁰ C, at 1 bar), to 100 parts by weight of the masses.

These may be masses which are still free-flowing at room temperature or masses containing e.g. present as a powder and are processed only at elevated temperatures.

The compositions, in particular coating compositions, may be radiation-curable or used as radiation-curable compositions or coating compositions, which are referred to as thermosets. For this purpose, they preferably contain a radiation-curable polymer according to the invention, in particular a radiation-curable polyester (see above). Radiation curing can be performed with high energy radiation, e.g. Electron radiation or UV light; when using UV light, a photoinitiator may preferably be added to the polymers.

A preferred use in the context of the present invention is the use of the polymers according to the invention as or in powder coatings. Preferably, polyesters are used as powder coating, which are crosslinkable. In a preferred embodiment, the powder coating is prepared by mixing and melting the polyester, crosslinking agent and other additives, e.g. Pigments and dispersants produced at high temperatures. The mixture can be powdered by subsequent extrusion and processing of the extrudate.

The powder coating may be in the usual manner, e.g. also electrostatically, on the desired substrates; e.g. be coated with metal, plastic or wood surfaces.

The polymers according to the invention have a low viscosity, both a low melt viscosity (100% systems) or a low solution viscosity (polymer solutions). Furthermore, they have a high weathering stability and a very good hydrolysis resistance. The low viscosity allows easy handling, good coating properties and allows higher solids content in Lö- solutions or dispersions or lower binder contents in pigment-containing compositions. The polymers according to the invention are in particular also very resistant to hydrolysis.

When used in coating compositions, sealants and adhesives, the polymers according to the invention have good mechanical properties; in particular the coating compositions, e.g. Powder Coatings; have a high impact resistance, good elasticity and a good shine.

Examples

Abbreviations

ADS: adipic acid D: polydispersity index (Mw / Mn)

DPG: dipropylene glycol

DBZO: dibutyltin oxide

DMCD: 1,1-dimethylolcyclododecane (Formula I, n = 9, X = CH ₂ )

DMCO: 1,1-dimethylolcyclooctane (Formula I, n = 5, X = CH ₂ ) DMCP: 1, 1-dimethylolcyclopentane (Formula I, n = 2, X = CH ₂ )

DSC: differential scanning calorimetry

GPC: gel permeation chromatography

IPS: isophthalic acid

M _n : number average molecular weight in [g / mol] M _w : weight average molecular weight in [g / mol] nFA: non-volatile components

NPG: neopentyl glycol

OHZ: OH number

SZ: acid number T ₉ : glass transition temperature

TMP: trimethylolpropane

TMSA: trimellitic anhydride

TPS: terephthalic acid ηi: melt viscosity η ₂ : solution viscosity Polymer Characterization Methods

The molecular weight determinations are carried out with GPC. Stationary phase: highly cross-linked porous polystyrene-divinylbenzene, commercially available as PL-GEL from Polymer Laboratories. Eluent: THF. Flow: 0.3 ml / min. Calibration with polyethylene glycol 28700 to 194 Dalton from PSS.

The acid number of the polyester is determined according to the DIN standard method 53169. The determination of the melt viscosity ηi of the polyester is carried out with a cone and plate viscometer at 160 ⁰ C in the oscillatory mode and at an angular velocity of 0.1 rad / s. The determination of the solution viscosity r 2 of the polyesters is carried out with a cone-plate viscometer at room temperature in a rotary mode. The solutions consist of 70% polyester and 30% solvent (mixture SoIvesso 100 ™ / Solvenon PM ™ 5/1). The Tg of the polyester is determined by DSC according to ASTM D3418.

PREPARATION OF POWDER POLYESTER WITH COOH GROUPS

Polyester P1

Stage I - Preparation of the OH group-containing oligomer

98 g DMCP (0.75 mol), 261, 4 g NPG (2.51 mol), 14.6 g TMP (0.11 mol), 437.9 g TPS (2.64 mol), and 0.4 Catalyst DBZO are placed in a 2L four-necked flask equipped with thermometer, inert gas inlet, stirrer and reflux condenser. While passing a stream of nitrogen and under reflux, the Reaktantenmi- research is heated rapidly to 180 ⁰ C. Water is distilled off continuously. Subsequently, the reaction mixture is gradually heated to 230 ⁰ C within 3 to 5 h with stirring and nitrogen flow, and stirred at 230 ⁰ C until the oligomer has an SZ of 10 to 15 mg KOH / g. The SZ of the oligomer is 10 mg KOH / g.

Step II - Preparation of COOH Group-Containing Polymer P1 The oligomer synthesized above is cooled to 180 ° C before adding 187.7 g of IPS (1.13 mol). The temperature is raised to 230 ° C, and it is further condensed under these conditions until the polymer has an SZ of 50 ± 2 mg KOH / g. The water resulting from the polymerization can be drawn at the end of the reaction by a slight vacuum to reach the desired SZ. This gives a branched COOH-containing powder polyester P1 whose SZ is 49 mg KOH / g. P1 has a glass transition temperature T ₉ of 74 ° C and a melt viscosity ηi of 41, 9 Pa ^* s at 160 ⁰ C. The GPC analysis gives the following values: M _n = 2090 g / mol; D = 2.9 (see Table 1). Polyester P2 to P4

The procedure is as in the preparation of P1, with the compositions summarized in Table 1. This gives branched COOH-group-containing powder polyesters whose characteristics SZ, M _n , D, T ₉ and ηi are listed in Table 1.

P1 Example 1 P2 Example 2 P3 Example 3 P4 Comparative Example 4

Table 1

The polymers P2 and P3 according to the invention have a significantly higher glass transition temperature than the corresponding comparative polymer P4, which represents an advantage for powder coating.

PREPARATION OF AMORPHER POLYESTER WITH OH GROUPS

Polyester P5

153.7 g DMCP (1.18 mol), 195.1 g NPG (1.88 mol), 158.5 g TMP (1.18 mol), 458.1 g IPS (2.76 mol), 172, 7 g of ADS (1.18 mol) and 0.6 g of DBZO catalyst are placed in a 2L four-necked flask equipped with thermometer, inert gas inlet, stirrer and reflux condenser. By passing a stream of nitrogen under reflux, the reactant mixture is rapidly heated to 160 ^° C. Water is distilled off continuously. Subsequently, the reaction mixture is gradually to 230 ⁰ C. heated with stirring and nitrogen flow within 3 to 5 h, and further stirred at 230 ⁰ C until the polyester P5 has a SZ of 10 to 15 mg KOH / g. This gives a branched amorphous OH-containing polyester P5 whose SZ is 15 mg KOH / g. P5 has an OHN of 109 mg KOH / g and a glass transition temperature T ₉ of 23 ° C. The GPC analysis gives the following values: M _n = 1940 g / mol; D = 9.7. P5 has a melt viscosity ηi of 2.2 Pa ^* s at 160 ⁰ C. The solution viscosity n, 2 of the polyester P5 at room temperature (P3 solution with 70% nFA and a mixture Solvesso 100 ™ / Solvenon PM ™ 5/1 as solvent) is 16.3 Pa ^* s (see Table 2).

Polyester P6 and P7

The procedure is as for the preparation of P5, with the composition summarized in Table 2. The characteristics of the polyesters P6 and P7 are listed in Table 2.

P5 Example 5 P6 Example 6 P7 Comparative Example 7

Table 2

PREPARATION OF WATER-DILUTABLE POLYESTER

Polyester P8

Step I - Preparation of OH group-containing oligomer 181, 7 g DMCP (1.40 mol), 327.0 g NPG (3.14 mol), 435.0 g IPS (2.6 mol), and 0.6 Catalyst DBZO are placed in a 2L four-necked flask equipped with thermometer, inert gas inlet, stirrer and reflux condenser. By passing a nitrogen stream and under reflux, the reactant mixture is heated to 160 ⁰ C quickly. Water is distilled off continuously. Subsequently, the reaction mixture is gradually heated to 220 ⁰ C within 3 to 5 h with stirring and nitrogen flow, and stirred at 220 ⁰ C until the reaction mixture has an SZ of 10 to 15 mg KOH / g. The SZ of the oligomer is 11 mg KOH / g.

Stage II - Preparation of Polymer P8 The oligomer synthesized above is cooled to 160 ^° C before 167.7 g of TMSA

(0.87 mol) are added. The temperature is raised to 230 ⁰ C, and it is further condensed under these conditions until the polymer has an SZ of 42 to 48 mg KOH / g. The water resulting from the polymerization can be drawn by gentle vacuum at the end of the reaction to reach the desired SZ. A linear water-dilutable polyester P8 is obtained, the SZ of which is 42 mg KOH / g. P8 has a glass transition temperature T ₉ of 53 ° C and a melt viscosity ηi of 6.0 Pa ^* s at 160 ° C. The GPC analysis gives the following values: M _n = 1200 g / mol; D = 2.4 (see Table 3). Evaluation of Hydrolysis Resistance of P8 A 20% aqueous colloidal solution of P8 is prepared, brought to pH 8 with N, N-dimethylethanolamine and stored at 45 ° C. The time interval until the colloidal solution precipitates is taken as a measure of the hydrolysis resistance of the polyester (see Table 4).

Polyester P9

The procedure is as for the preparation of P8, with the composition summarized in Table 3. The characteristics of the polyester P9 are listed in Table 3.

Table 3

Table 4

The above table shows that the polyesters from DMCP are particularly high

Have hydrolysis resistance.

PREPARATION OF POWDER COAT

The reference binder (REF) used is the polyester resin Uralac® P-862 (T ₉ .70 ⁰ C, SZ 35 mg KOH / g) from DSM Resins BV. To prepare the powder coatings PL1, PL4 and PLR, 570.0 g of powder polyester P1, P4 or REF are each treated with 30.0 g of commercial primer Primid® XL-552 (hydroxylalkylamide from EMS), 300.0 g of Kronos® 2160 titanium dioxide pigment (Kronos Co.), 9.0 g of leveling agent Resiflow® PV5 (Worlee Chemie GmbH) and 2.5 g of benzoin are mixed in a laboratory universal mixer (MIT MIT Mischtechnik GmbH), melted and then dried in a twin-screw extruder ( MP 19, Fa. APV) at 80 - 100 ⁰ C extruded. The resulting extrudate is then roughly crushed, ground and sieved. The powder coatings PL1, PL4 and PLR thus obtained are subjected to the following tests:

Subsequently, the powder coatings are applied to Gradientenofenbleche and in a gradient oven (BYK-Gardner GmbH) 10 min. baked at 160 ⁰ C. The cured coatings are examined for their visual properties (yellowing). The yellow value is determined with the help of the colorimeter spectrocolor (from Hach Lange GmbH).

Subsequently, the powder coatings are applied electrostatically to steel test panels (Q-Panel R-36) and at 160 ⁰ C for 10 min. long burned. In this case, layer thicknesses of 60 microns to 80 microns are desired. The resulting coatings are subjected to the following tests:

The results of the paint tests are summarized in Table 5.

Table 5

^* 2 = orange peel, pinholes Thus, it can be conclusively shown that

The DMCP paint system has a very low tendency to yellowing, which is a great advantage compared to the reference (PLR) which contains phosphite additives against yellowing (PL1 not according to the invention).

• DMCP delivers excellent and significantly better mechanical properties than NPG.

Production of high-solids 1 component paints (1 K)

For the preparation of the high-solids 1K paints 1K-PL5, 1K-PL6 and 1K-PL7, 70% solutions of the polyesters P5, P6 and P7 are prepared in butyl acetate. 80 g of the 70% polyester solutions are each mixed with 14 g of commercial hardener Luwipal® 066 (melamine condensate from BASF), 4 g of n-butanol, and 2 g of catalyst p-toluenesulfonic acid. The resulting solutions (nFA 70%) are applied to glass plates and steel test plates with the aid of box doctor. In this case, layer thicknesses of 40 microns to 50 microns are desired. Following the coated test panels at 140 ⁰ C for 30 minutes are baked long.. The resulting coatings are subjected to the following tests:

The results of the paint tests are summarized in Table 6. 1 K-PL5 and 1 K-PL6 are according to the invention, 1 K-PL7 is considered as a comparative example.

Table 6

The high-solids paints 1K-PL5 and 1K-PL6 according to the invention have very good mechanical properties and high hydrolysis resistance.

Claims

claims

Polymer obtainable by polycondensation or polyadduct formation of monomeric compounds, characterized in that as a monomeric compound

or the alkoxylated derivatives of the formula I or of the formula Ia is used, where n = 1, 2,4- 9,

X = -CH ₂ - or -O- is and

R is hydrogen or a linear or branched alkyl group having 1 to 10 C

Atoms and for the compounds of formula Ia, when n> 2 is also more than one double bond may be present.

Polymer according to Claim 1, characterized in that the monomeric compound or its alkoxylated derivatives of the formula I or of the formula Ia used are those in which n = 2, 5 or 9, X is -CH ₂ - and R is selected from Group of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, iso-butyl and n-pentyl.

Polymer according to one of claims 1 to 2, characterized in that are used as the monomeric compound or its alkoxylated derivatives of the formula I or formula Ia those in which n = 2, X = -CH ₂ - and R = hydrogen.

4. Polymer according to any one of claims 1 to 3, characterized in that the compounds of the formula I or the formula Ia by reacting aldehydes of the formula II or the formula IIa

IIa where n, X and R are the same as above, are obtainable in a Cannizzaro reaction with formaldehyde.

5. Polymer according to one of claims 1 to 4, characterized in that it is a polyester.

6. Polymer according to one of claims 1 to 5, characterized in that it is a polycarbonate diol (obtainable by reaction of dialkyl carbonates or cyclic carbonates with diols with elimination of alcohol).

7. Polymer according to one of claims 1 to 6, characterized in that it is a polyurethane.

8. Polymer according to one of claims 1 to 7, characterized in that it is a polyadduct, which is obtainable by ring-opening polymerization of lactones or lactams

9. Use of the polymer according to any one of claims 1 to 8 for the preparation of a thermoplastic composition.

10. Thermoplastic compositions comprising a polymer and / or repeat units of a polymer according to any one of claims 1 to 8.

1 1. Use of the thermoplastic compositions according to claim 10 for the production of moldings.

12. Use of the polymer according to any one of claims 1 to 8 for the preparation of coating compositions, sealants or adhesives.

13. Coating compositions, sealants or adhesives containing repeating units of a polymer according to any one of claims 1 to 8.

14. Coating compositions, sealants or adhesives according to claim 13, characterized in that they are aqueous compositions.

15. Use of the polymer according to any one of claims 1 to 8 for the preparation of powder coatings.

16. Powder coating comprising repeating units of a polymer according to one of claims 1 to 8

17. Use of the polymer according to any one of claims 1 to 8 for the preparation of radiation-curable coating compositions.

18. Radiation-curable coating compositions comprising repeating units of a polymer according to one of claims 1 to 8.

19. 1, 1-dimethylolcyclododecane

20. A process for the preparation of 1, 1-dimethylolcyclododecane, wherein cyclododecene is subjected to hydroformylation with hydrogen and carbon monoxide, the resulting aldehyde is reacted by means of formaldehyde to 1, 1, dimethylolcyclododecane.

21. Mixture containing I J-dimethylolcyclooct-S-ene, 1, 1-dimethylolcyclooct-2-ene and 1, 1-dimethylolcycloct-4-ene.

22. A process for preparing the mixture of claim 21, wherein 1, 5-cyclooctadiene with hydrogen and carbon monoxide is subjected to a hydroformylation, the resulting aldehydes are reacted by means of formaldehyde to the mixture of claim 21