DE10354865A1 - Solvent-free, continuous production of acrylate polymer-modified polyester resin, for use e.g. as binder in coatings, adhesives or inks, by polymerizing acrylate monomers in presence of polyester, e.g. in extruder - Google Patents

Abstract

Solvent-free, continuous production of polymer-modified resins (A), by reacting hydroxy- and/or carboxy-functional, (semi)crystalline and/or amorphous polyester(s) (I) and hydroxy- and/or carboxy-functional polyacrylate(s) (II), involves radical polymerization of the starting material(s) for (II) in the absence of organic solvents in presence of (I) in a brief reaction under thorough mixing in an extruder, intensive mixer, intensive kneader or static mixer, followed by isolation of (A) by cooling. An independent claim is included for the resins (A) obtained by the process.

Description

The The invention relates to a process for solvent-free and continuous Preparation of polymer-modified resins from hydroxy-functional, crystalline and / or semicrystalline and / or amorphous polyesters and at least one hydroxy-functional and / or carboxylic acid group-containing Polyacrylate in the absence of organic solvents.

Usually are different polymers not or difficult to mix with each other, there the Gibbs'sche Mixing enthalpy of polymers is generally positive. This is one reason why polyesters are often immiscible with polyacrylates and incompatible are. By the polymerization of acrylate monomers in a polyester matrix can However, stable mixtures are produced.

The EP 0 184 761 describes a low molecular weight, liquid reaction product of a hydroxyl-containing polyacrylate prepared in a polyester polyol. Disadvantage of such products is the low molecular weight, which z. B. mechanical properties, such as hardness and flexibility, and the adhesion to substrates are unsatisfactory. The use of higher molecular weight polyesters is difficult in solution, since then the solution viscosity is high. For the preparation of reaction products in the manner described a solvent is necessary.

The EP 0 206 072 describes a semi-continuous process for the preparation of the above-mentioned products at at least 150 ° C in the presence of a diluent having a molecular weight greater than 200. For the preparation of reaction products in the manner described, therefore, an organic solvent is required. The same applies to the EP 0 896 991 ,

In the EP 0 541 604 (WO 92/02590) discloses coating compositions based on hydroxyl-containing binder of polyesters and polyacrylates, wherein the polyacrylates are at least partially prepared in the polyester and isocyanates are contained as crosslinking agents. Again, organic solvents are used for the production.

DE 195 44 737 uses low molecular weight polyesters between 400 and 1100 g / mol. The same applies to EP 0 607 792 , where aqueous emulsions of the polyester-polyacrylates are produced there.

US Pat. No. 4,499,239 describes polyester-polyacrylate mixtures for powder coating applications wherein the polyester has an acid number of 20 to 200 mg KOH / g and the polyacrylate is glycidyl-containing. Again, organic solvents are used for the production.

In EP 0776 920 ( DE 195 44 737 ) special binders based on polyester acrylate are described. The products described are produced in organic solvents.

Polymer modified resins are also made DE 102 58 573 and DE 102 58 574 known.

In none of the documents becomes a process for continuous production of polymer modified resins of polyesters and polyacrylates in the absence of organic solvents described.

The object of the present invention was to develop a continuous, environmentally friendly process by means of which the production of polyester-polyacrylate compositions without the use of an organic solvent is possible during the entire production process. In addition, since the solubility of polyesters in organic solvents decreases with increasing crystallinity, it was an object of the present invention to develop a process by means of which the preparation of polyester-polyacrylate compositions of crystalline and / or semicrystalline and / or amorphous polyesters and polyacrylates is possible at all. In addition, since the viscosity of polymer solutions in organic solvents increases with increasing molecular weight, usually higher molecular weight polyester-polyacrylates can be prepared only in high dilution of an organic solvent. It was therefore an object of the present invention to find an economically advantageous, continuous process with high product throughput, the production of polyester-polyacrylate-together also higher molecular weight, crystalline and / or semicrystalline and / or amorphous polyesters and polyacrylates allowed.

such Products are suitable, for example, as binders in powder coatings or (melting) adhesives and support the idea of this environmentally friendly Systems by dispensing with organic solvents.

In addition, should Compositions are found as the main component, basic component or additional component in e.g. Coating materials are used can, whereby coatings are obtained which provide a high degree of flexibility at very good hardness properties have. At the same time, the adhesion of the coating should be on substrates be high. Not least, it was the object of the present invention by using the cheaper compared to polyester raw materials Acrylate raw materials to bring about a cheapening of the overall system.

It was surprising found that the method and the polymer-modified resins according to the invention meet the required criteria.

• I. mindestens einem hydroxyfunktionellen und/oder carboxyfunktionellen, kristallinen und/oder semikristallinen und/oder amorphen Polyester und
• II. mindestens einem hydroxyfunktionellen und/oder carbonsäuregruppenhaltigen Polyacrylat

durch radikalische Polymerisation der Ausgangskomponente(n) zur Herstellung von II. in Gegenwart des Polyesters I. und in Abwesenheit eines organischen Lösemittels in einem Extruder, Intensiv-Kneter, Intensiv-Mischer oder statischen Mischer durch intensive Durchmischung und kurzzeitige Reaktion und nachfolgender Isolierung des Endprodukts durch Abkühlung.The invention provides a process for the solvent-free and continuous preparation of polymer-modified resins obtained by reacting

• I. at least one hydroxy-functional and / or carboxy-functional, crystalline and / or semicrystalline and / or amorphous polyester and
• II. At least one hydroxy-functional and / or carboxylic acid group-containing polyacrylate

by radical polymerization of the starting component (s) for the preparation of II in the presence of the polyester I and in the absence of an organic solvent in an extruder, intensive kneader, intensive mixer or static mixer by intensive mixing and brief reaction and subsequent isolation of the final product by cooling.

• I. mindestens eines hydroxyfunktionellen und/oder carboxyfunktionellen, kristallinen und/oder semikristallinen und/oder amorphen Polyesters und
• II. mindestens eines hydroxyfunktionellen und/oder carbonsäuregruppenhaltigen Polyacrylats,

wobei diese erhalten werden durch radikalische Polymerisation der Ausgangskomponente(n) zur Herstellung von II. in Gegenwart des Polyesters I. und in Abwesenheit eines organischen Lösemittels in einem Extruder, Mehrwellenextruder, Planetwalzenextruder, Intensiv-Kneter, Intensiv-Mischer oder statischen Mischer durch intensive Durchmischung und kurzzeitige Reaktion bei Wärmezufuhr und nachfolgender Isolierung des Endproduktes durch Abkühlung.The invention also relates to polymer-modified resins obtained by a solvent-free and continuous process by reaction

• I. at least one hydroxy-functional and / or carboxy-functional, crystalline and / or semicrystalline and / or amorphous polyester and
• II. At least one hydroxyl-functional and / or carboxylic acid-containing polyacrylate,

which are obtained by radical polymerization of the starting component (s) for the preparation of II in the presence of the polyester I and in the absence of an organic solvent in an extruder, multi-screw extruder, planetary roller extruder, intensive kneader, intensive mixer or static mixer by intensive mixing and short-term reaction with heat and subsequent isolation of the final product by cooling.

The with the method according to the invention made resins can as the main component, base component or additive component in coating materials be used, whereby coatings are obtained, which high level flexibility with very good hardness properties have. At the same time, the adhesion of the coating to substrates very high. The use of cheaper compared to polyester raw materials Acrylic raw materials contributes to a cheapening of the whole system.

Of the (Semi-) crystalline and / or amorphous polyester is known Process produced by condensation. The used polyester consists of a di- and / or polycarboxylic and their derivatives and a di- and / or polyol mixture. It can too Proportions of the di- or polycarboxylic acid mixture partly by monocarboxylic acids be replaced.

in the Individuals can for the preparation of the polyester usual carboxylic acids and their esterifiable derivatives, such as. Phthalic acid, isophthalic acid, terephthalic acid, 1,2- and 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, Di- and tetrachlorophthalic, Endomethylenetetrahydrophthalic, glutaric, methylhexahydrophthalic, tetrahydrophthalic, dodecanedioic, adipic, azelaic, naphthalenedicarboxylic, pyromellitic and / or trimellitic and / or - as far as accessible - their Acid anhydrides and / or esterifiable derivatives, such. Methyl esters, alone or in mixtures, be used. It can also higher alkyl dicarboxylic acids, z. B. dodecanedioic acid and / or hexa- and / or octadecanedicarboxylic acid. Also is the use of monocarboxylic acids, such as Hexanoic acid, isononanoic and / or 2-ethylhexanoic acid, possible.

Especially are preferably used as the starting component for the polyester phthalic acid, isophthalic acid, terephthalic acid, 1,2-, 1,4-cyclohexanedicarboxylic acid, adipic acid, azelaic acid, Succinic acid, dodecanedioic and / or sebacic acid, Hexa- and / or Octadecandicarbonsäure, their acid anhydrides and / or esterifiable derivatives.

As the alcohol component z. Ethylene glycol, 1,2-, 1,3-propanediol, diethylene, dipropylene, triethylene, tetraethylene glycol, 1,2-, 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1 , 5-pentanediol, bis (1,4-hydroxymethyl) cyclohexane (cyclohexanedimethanol), glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, bisphenol A, B, C, F, norbornylene glycol, 1,4-benzyldimethanol, ethanol , 2,4-dimethyl-2-ethylhexane-1,3-diol, 1,4- and 2,3-butylene glycol, di-β-hydroxyethylbutanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8- Octanediol, decanediol, dodecanediol, neopentyl glycol, cyclohexanediol, 3 (4), 8 (9) -bis (hydroxymethyl) -tricyclo [5.2.1.0 ^2,6 ] decane (dicidol), 2,2-bis (4-hydroxycyclohexyl) propane, 2,2-bis- [4- (β-hydroxyethoxy) -phenyl] propane, 2-methyl-1,3-propanediol, 2-methylpentanediol-1,5, 2,2,4 (2,4,4 ) -Trimethylhexanediol-1,6, hexanediol-1,2,6, butanetriol-1,2,4, tris (β-hydroxyethyl) isocyanurate, mannitol, sorbitol, polypropylene glycols, polybutylene glycols, xylylene glycol or hydroxypivalic acid Reneopentylglykolester, used alone or in mixtures.

Especially preferred are 1,4-butanediol, 1,2-propanediol, cyclohexanedimethanol, Hexanediol, neopentylglycol, decanediol, dodecanediol, trimethylolpropane, Ethylene glycol.

Bevorzugte Ausführungsform 2:

Bevorzugte Ausführungsform 3:

Bevorzugte Ausführungsform 4 die folgende Zusammensetzung:

The (semi) crystalline polyester I contains in preferred embodiments 1 to 4 the following composition: Preferred embodiment 1:

Preferred embodiment 2:

Preferred embodiment 3:

Preferred Embodiment 4 The following composition:

Bevorzugte Ausführungsform 6:

Bevorzugte Ausführungsform 7:

Bevorzugte Ausführungsform 8:

The amorphous polyester I contains in further preferred embodiments 5 to 8 the following compositions: Preferred embodiment 5:

Preferred Embodiment 6:

Preferred embodiment 7:

Preferred embodiment 8:

there is the sum of the acid component and that of the alcohol component is in each case 100 mol% for all above standing embodiments.

Of the Polyester is made by esterification of the acid components with the alcohol components and subsequently Polycondensation produced. For this purpose, the ingredients are mixed and slowly heated (melted), which is then esterified with elimination of water. The preferred Reaction temperature is between 180 and 260 ° C. In the final phase becomes vacuum created, which then also split off diols and the molecular weight clearly increased becomes. In part you can Catalysts are used. The final parameters are acid number and OH number.

• – eine OH-Zahl von 0 bis 200 mg KOH/g, bevorzugt 2 bis 150 mg KOH/g, besonders bevorzugt 2 bis 70 mg KOH/g,
• – eine Säurezahl von 0 bis 200 mg KOH/g, bevorzugt 0 bis 50 mg KOH/g, besonders bevorzugt von 0 bis 20 mg KOH/g,
• – ggf. einen Schmelzbereich (Schmelzpeak, DSC, DIN 53765) Mp von –20 bis +150 °C, bevorzugt 0 bis 140 °C, besonders bevorzugt von 10 bis +140 °C,
• – ggf. eine Tg von –70 bis +70 °C, bevorzugt –40 bis +40 °C, besonders bevorzugt von –30 bis +30 °C
• – eine OH-Funktionalität (Verzweigung) von 1 bis 10, bevorzugt 2 bis 6, besonders bevorzugt von 2 bis 5.

The polyester mentioned under I. possesses

• An OH number of 0 to 200 mg KOH / g, preferably 2 to 150 mg KOH / g, more preferably 2 to 70 mg KOH / g,
• An acid number of 0 to 200 mg KOH / g, preferably 0 to 50 mg KOH / g, particularly preferably 0 to 20 mg KOH / g,
• Optionally a melting range (melting peak, DSC, DIN 53765) Mp of -20 to +150 ° C, preferably 0 to 140 ° C, particularly preferably from 10 to +140 ° C,
• - If necessary, a Tg of -70 to +70 ° C, preferably -40 to +40 ° C, particularly preferably from -30 to +30 ° C.
• - An OH functionality (branching) of 1 to 10, preferably 2 to 6, particularly preferably from 2 to 5.

The polyacrylate II contains hydroxyl groups and / or carboxylic acid groups and may be a copolymer of ethylenically unsaturated monomers, as in DE 199 63 586 be described.

Monomers which can be used are acrylic acid and / or methacrylic acid, C ₁ -C ₄₀ -alkyl esters and / or cycloalkyl esters of methacrylic acid and / or acrylic acid, hydroxyalkyl acrylates and / or hydroxyalkyl methacrylates, glycidyl methacrylate, glycidyl acrylate, 1,2-epoxybutyl acrylate, 1,2-epoxybutyl methacrylate, 2 , 3-Epoxycyclopentylacrylat, 2,3-Epoxycyclopentylmethacrylat and the analog amides, wherein also styrene and / or its derivatives may be present.

Preference is given to using butyl acrylate and / or butyl methacrylate, 2-hydroxyethyl acrylate and / or 2-hydroxyethyl methacrylate, methyl methacrylate, styrene, (meth) acrylic acid and further α, β-unsaturated monomers, where at least one hydroxyl-containing and / or carboxyl-containing monomer is used becomes.

• – eine OH-Zahl von 0 bis 300 mg KOH/g, bevorzugt 10 bis 150 mg KOH/g, besonders bevorzugt von 5 bis 120 mg KOH/g,
• – eine Säurezahl von 0 bis 300 mg KOH/g, bevorzugt 0 bis 150 mg KOH/g, besonders bevorzugt von 0 bis 120 mg KOH/g,
• – eine Tg von –40 bis +110 °C, bevorzugt –30 bis +100 °C, besonders bevorzugt von –20 bis +60 °C,
• – ein Mn von 1 000 bis 100 000 g/mol, bevorzugt 1 000 bis 50 000 g/mol, besonders bevorzugt von 1 000 bis 10 000 g/mol,
• – ein Mw von 2 000 bis 1 000 000 g/mol, bevorzugt 2 500 bis 500 000 g/mol, besonders bevorzugt von 5 000 bis 250 000 g/mol.

The polyacrylate II has

• An OH number of 0 to 300 mg KOH / g, preferably 10 to 150 mg KOH / g, more preferably of 5 to 120 mg KOH / g,
• An acid number of 0 to 300 mg KOH / g, preferably 0 to 150 mg KOH / g, more preferably from 0 to 120 mg KOH / g,
• A Tg of -40 to +110 ° C, preferably -30 to +100 ° C, more preferably -20 to +60 ° C,
• An Mn of from 1 000 to 100 000 g / mol, preferably from 1 000 to 50 000 g / mol, more preferably from 1 000 to 10 000 g / mol,
• An Mw of 2,000 to 1,000,000 g / mol, preferably 2,500 to 500,000 g / mol, particularly preferably 5,000 to 250,000 g / mol.

In a preferred embodiment, the polyacrylate II contains the following composition:

In a preferred embodiment, the polyacrylate II contains the following composition:

The Principle of the method is that the reaction of the reaction products continuously in an extruder (also multi-screw extruder as well Planetary roller extruder), intensive kneader, intensive mixer or static Mixer through intensive mixing and short-term reaction, in the range of a few seconds or minutes. Short term reaction means that the residence time of the starting materials in the above Aggregates usually 3 seconds to 15 minutes, preferably 3 seconds to 5 minutes, especially preferably 5 to 180 seconds. The reactants are thereby short term, preferably with heat, at temperatures of 10 to 325 ° C, preferably from 20 to 200 ° C, most preferably from 70 to 200 ° C, reacted.

It are generally temperatures of 10 to 325 ° C, preferably from 20 to 200 ° C, more preferably from 70 to 200 ° C, used in the process, the temperatures, as the examples show, depending on the product vary.

It succeeds, the resulting, homogeneous material continuously unsubscribe. Optionally, here can be a continuous reaction be followed, otherwise the hot product is cooled (z. On a cooling belt) and further compounded if necessary (eg ground).

As aggregates, extruders, such as single- or multi-screw extruders, in particular twin-screw extruders, planetary roller extruders or ring extruders, intensive kneaders, intensive mixers or static mixers are particularly suitable for the process according to the invention and are preferably used. Especially be preferred are the above-mentioned extruder.

Surprised it was that implementation, in the discontinuous process hardly possible is, in the aggregates mentioned completely expires. In addition, that falls Product in solid form, and can after cooling a further work-up (eg grinding or breaking) or else also directly to a storage (silo) or packaging (bagging) supplied become. Of a fundamental nature is the fact that short-term chemical reaction between the reactants in the presence of the polyester in interaction with the mixing effect of the aggregates and the temperature profile the aggregates is sufficient to complete the reactants or to implement as far as possible. The aggregates allow by suitable equipping the Mixing chambers or compilation of the screw geometries intensive rapid mixing with simultaneous intensive heat exchange. On the other hand, a uniform flow in longitudinal direction with as possible uniform residence time guaranteed. Furthermore is a different, independent Temperature control in the individual device housings or sections possible.

to Initiation of free radical polymerization find initiators from the group of peroxides, hydroperoxides, azo compounds and / or CC-cleaving compounds use. To be particularly suitable proved to be initiators that are not low molecular weight components (eg nitrogen from azo compounds) split off.

The Starting materials are usually separated into the aggregates reactant streams added. With more than two reactant streams, these can also be supplied bundled. The material flows can also be shared and so in different proportions of different Make the aggregates fed become. In this way, concentration gradients are targeted set what the completeness cause the reaction can. Furthermore is it possible specifically the production and the chemical structure of the polyacrylates to influence (influence of Copolymerisationsparametern). The entry point of the educt streams in the order can be handled variably and temporally offset become. As a rule, methods for solvent-free and continuous Preparation of polymer-modified resins used by are characterized in that the starting materials and / or initiators and / or catalysts and / or additives together or in separate product streams, in liquid or solid form, the extruder, intensive kneader, intensive mixer or static mixer supplied become.

to Pre-reaction and / or completion the reaction can several aggregates can also be combined.

The The rapid reaction downstream cooling can in the reaction part be integrated, in the form of a multi-housing embodiment as in extruders or Conterna machines. Can also be used: tube bundles, pipe coils, Chill rolls, air conveyor and conveyor belts made of metal.

The Assembly is depending on the viscosity of the aggregates or the Afterreaction zone leaving product first by further cooling by means corresponding aforementioned equipment brought to a suitable temperature. Then the pastillation takes place or a comminution into a desired particle size means Roll crusher, pin mill, Hammermill Classifier, Shingles or the like.

It results in a homogeneous resin mixture that is composed of 10 to 90 wt .-%, preferably 30 to 80 wt .-%, particularly preferably 60 to 80% by weight of polyester I and 90 to 10% by weight, preferably 70 to 20 wt .-%, particularly preferably 40 to 20 wt .-% polyacrylate II.

The polymer-modified according to the invention Resins are used as the main component, base component or additive component for applications in coating materials, adhesives, printing inks and inks, polishes, Glazes, pigment pastes, fillers and sealants and insulating materials used and preferably with amine-formaldehyde resins or polyisocyanates networked.

object The invention thus also relates to the use of the polymeric composition as main component, basic component or additional component for applications in coating materials, adhesives, printing inks and inks, polishes, glazes; Pigment pastes, fillers and sealants and insulating materials, preferably with polyisocyanates and / or melamine-formaldehyde resins as crosslinking agents, in particular with the crosslinkers described below.

As crosslinkers, for example, aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates and / or isocyanurates, such as. For example, cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate such as 1,6-diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), diisocyanatotoluene (TDI), 4,4'-methylenebis (phenylisocyanate) (MDI) , Nonanetriisocyanate, such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decandi and triisocyanate, undecanediisocyanate and triisocyanate, dodecandi- and triisocyanates, isophorone diisocyanate (IPDI), bis (isocyanatomethylcyclohexyl) methane (H ₁₂ MDI) , Isocyanatomethylmethylcyclohexylisocyanate, 2,5 (2,6) -bis (isocyanatomethyl) bicyclo [2.2.1] heptane (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ -XDI) or 1, 4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI), or d Isocyanurates as far as accessible, be used alone or in mixtures.

Example 1:

The Polyacrylate is made from a mixture consisting of 27.4% by weight of 2-hydroxyethyl methacrylate, 9.1 wt .-% butyl methacrylate and 63.5 wt .-% methyl methacrylate produced.

The Reaction takes place in the molten, crystalline polyester DYNACOLL 7390 (Degussa AG, hydroxyl number approx. 30 mg KOH / g, acid value <3 mg KOH / g, softening point about 118 ° C) instead of. The total formula is DYNACOLL 7390 69.3% by weight.

Of the Polyester is used as coarse powder in the first case of a corotating Twin-screw extruder fed in a quantity of 5.2 kg / h. The extruder has separately temperature-controlled housings (heatable and coolable). casing 1 is at 15 to 30 ° C, casing 2 to 80 to 120 ° C and the following cases at 120 to 160 ° C tempered. The acrylate mixture is at a feed temperature from 15 to 40 ° C in housing 2 metered with a throughput of 2.22 kg / h. At the same time in the same housing 4.0 wt .-% (based on acrylate) tert-butyl peroxy-2-ethylhexanoate to Initiation of the radical polymerization added.

The Exit temperature is between 100 and 135 ° C.

Of the Total throughput is 7.5 kg / h. Residence time: approx. 3 min.

The Extruder speed is 50 to 200 rpm.

The Product emerges as a viscous, transparent melt on one side cooling belt chilled and cured and being broken.

The Product is called colorless, cloudy Received chips.

Production of powder coatings:

When Comparison was a powder coating, the pure polyester DYNACOLL Contains 7390.

Application on untreated stole

• Curing conditions: 12 min, 200 ° C, layer thickness 60 to 80 μm
  

Example 2:

The Polyacrylate is made from a mixture consisting of 36.7% by weight of 2-hydroxyethyl methacrylate, 8.4 wt .-% butyl methacrylate and 54.9 wt .-% methyl methacrylate produced.

The Reaction takes place in molten, amorphous polyester CRYLCOAT 690 (UCB Chemicals). The total formula is the CRYLCOAT 690-part 69.3 wt .-%.

Of the Polyester is used as coarse powder in the first case of a corotating Twin-screw extruder fed in a quantity of 3.46 kg / h.

Of the Extruder has separately temperature-controlled housings (heatable and coolable). casing 1 is at 15 to 30 ° C, casing 2 to 80 to 120 ° C and the following cases at 110 to 160 ° C tempered.

The Acrylate monomer mixture is used at a feed temperature of 15 to 40 ° C in casing 2 metered with a throughput of 1.48 kg / h. At the same time in the same housing 4.0 wt .-% (based on acrylate) tert-butyl peroxy-2-ethylhexanoate to Initiation of free radical polymerization added.

The Exit temperature is between 120 and 140 ° C.

Of the Total throughput is 5.00 kg / h. Residence time: approx. 4 min.

The Extruder speed is 50 to 200 rpm.

The product exits as a viscous white melt which is cooled and cured on a chill roll mill.
T _g = 46 ° C (heating rate 10 ° C / min)
M _n = 5,900 g / mol; M _w = 29,700 g / mol (GPC, against polystyrene as standard)

Production of powder coatings:

When Comparison served a powder coating, the pure polyester Crylcoat 690 contains.

Application on untreated stole

• Curing conditions: 12 min, 200 ° C, layer thickness <65 μm
  

Claims (42)

Process for solvent-free and continuous Preparation of polymer-modified resins obtained by reaction from I. at least one hydroxy-functional and / or carboxy-functional, crystalline and / or semicrystalline and / or amorphous polyester and II. At least one hydroxyl-functional and / or carboxylic acid group-containing polyacrylate by radical polymerization of the starting component (s) for the preparation of II in the presence of the polyester I and in the absence an organic solvent in an extruder, intensive kneader, intensive mixer or static Mixer through intensive mixing and short-term reaction and subsequent isolation of the final product by cooling. Process for solvent-free and continuous preparation of polymer modified resins according to claim 1, characterized in that the polyester I. a OH number from 0 to 200 mg KOH / g, an acid number from 0 to 200 mg KOH / g, an OH functionality from 1 to 10, a Mp of -20 up to 150 ° C or a Tg of -70 up to 70 ° C having. Process for solvent-free and continuous preparation of polymer modified resins according to claim 1, characterized in that the polyester I. a OH number from 2 to 150 mg KOH / g, an acid number from 0 to 50 mg KOH / g and an OH functionality from 2 to 6, a Mp from 0 to 140 ° C or a Tg from -40 to 40 ° C has. Process for solvent-free and continuous preparation of polymer modified resins according to claim 1, characterized in that the polyester I. a OH number from 2 to 70 mg KOH / g, an acid number from 0 to 20 mg KOH / g and an OH functionality from 2 to 5, a Mp of 10 to 140 ° C or a Tg of -30 to 30 ° C. A process for the solvent-free and continuous preparation of polymer-modified resins according to at least one of the preceding claims, characterized in that as the alcohol component of the polyester I. compounds selected from ethylene glycol, 1,2-, 1,3-propanediol, diethylene, dipropylene, triethylene , Tetraethylene glycol, 1,2-, 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, Glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, bisphenol A, B, C, F, norbornylene glycol, 1,4-benzyldimethanol, ethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 1, 4- and 2,3-butylene glycol, di-β-hydroxyethylbutanediol; 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, decanediol, dodecanediol, neopentyl glycol, cyclohexanediol, 3 (4), 8 (9) -bis (hydroxymethyl) -tricyclo [5.2.1.0 ²⁶ ] decane ( Dicidol), bis (1,4-hydroxymethyl) cyclohexane (cyclohexanedimethanol), 2,2-bis (4-hydroxycyclohexyl) propane, 2,2-bis [4- (β-hydroxyethoxy) -phenyl] propane, 2 Methyl-1,3-propanediol, 2-methylpentanediol-1,5, 2,2,4 (2,4,4) -trimethylhexanediol-1,6, hexanetriol-1,2,6, butanetriol-1, 2,4, tris (β-hydroxyethyl) isocyanurate, mannitol, sorbitol, polypropylene glycols, polybutylene glycols, xylylene glycol, hydroxypivalate neopentyl glycol esters, used alone or in mixtures. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that as an acid component of the polyester I. Compounds selected from phthalic acid, isophthalic acid, terephthalic acid, 1,2-, 1,4-cyclohexanedicarboxylic acid, Succinic acid, sebacic, Methyltetra-, di- and tetrachlorophthal-, endomethylenetetrahydrophthal-, Glutaric, methylhexahydrophthalic, tetrahydrophthalic adipic acid, azelaic acid, Naphthalenedicarboxylic acid, pyromellitic acid, trimellitic acid, dodecanedioic acid, hexa, octadecanedicarboxylic, hexanoic, isononanoic acid, 2-ethylhexanoic and / or - as far as accessible - their anhydrides and / or lower alkyl esters, used alone or in mixtures become. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that as an acid component of the polyester I. Compounds selected from terephthalic acid, phthalic acid, isophthalic acid, 1,2-, 1,4-cyclohexanedicarboxylic acid, Succinic acid, sebacic, dodecanedioic, adipic acid, azelaic acid, Hexa- and / or octadecanedioic acid, their acid anhydrides and / or lower alkyl esters, alone or in mixtures. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the polyacrylate II. An OH number of 0 to 300 mg KOH / g, a acid number from 0 to 300 mg KOH / g, a Tg of -40 to 110 ° C, a Mn from 1,000 to 100,000 g / mol, Mw of 2,000 to 1,000,000 g / mol having. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the polyacrylate II. An OH number of 10 to 150 mg KOH / g, a acid number from 0 to 150 mg KOH / g, a Tg of -30 to 100 ° C, a Mn from 1,000 to 50,000 g / mol, an Mw of 2,500 to 500,000 g / mol. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the polyacrylate II. An OH number of 5 to 120 mg KOH / g, a acid number from 0 to 120 mg KOH / g, a Tg of -20 to 60 ° C, a Mn of 1,000 to 10,000 g / mol, an Mw of 5,000 to 250,000 g / mol. Process for the solvent-free and continuous preparation of polymer-modified resins according to at least one of the preceding claims, characterized in that the polyacrylate II. Is prepared from the monomers acrylic acid and / or methacrylic acid, C ₁ -C ₄₀ alkyl esters and / or cycloalkyl esters of methacrylic acid and / or acrylic acid, hydroxyalkyl acrylates and / or hydroxyalkyl methacrylates, glycidyl methacrylate, glycidyl acrylate, 1,2-epoxybutyl acrylate, 1,2-epoxybutyl methacrylate, 2,3-epoxycyclopentyl acrylate, 2,3-epoxycyclopentyl methacrylate, and the analogous amides, wherein also styrene and / or its derivatives may be present, wherein at least one hydroxyl-containing and / or carboxyl-containing monomer is used. Process for solvent-free and continuous preparation of polymer modified resins according to claim 11, characterized in that monomers selected from Butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Methyl methacrylate, styrene, acrylic acid and / or methacrylic acid used become. Process for the solvent-free and continuous preparation of polymer-modified resins according to at least one of the preceding claims, characterized in that the polymer-modified resin consists of I. 10 to 90 wt .-% of polyester and II. 90 to 10 wt .-% polyacrylate. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims 1 to 12, characterized that the polymer-modified resin I. 30 to 80 wt .-% polyester and II. 70 to 20 wt .-% polyacrylate consists. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims 1 to 12, characterized that the polymer-modified resin I. 60 to 80 wt .-% polyester and II. 40 to 20 wt .-% polyacrylate consists. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized the polymer-modified resin has an acrylate residual monomer content below 1% by weight. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized in that the polymer-modified resin has an acrylate residual monomer content below 0.5 wt .-%. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the reaction in an extruder, multi-shaft extruder, planetary roller extruder, Intensive kneader, intensive mixer or static mixer with several same or different housings, the independent can be thermally controlled from each other, takes place. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the reaction in the single-, two- or multi-screw extruder, ring extruder or planetary roller extruder takes place. Process for solvent-free and continuous preparation of polymer modified resins according to the previous claim, characterized in that the reaction in a twin-screw extruder or multi-screw extruder or planetary roller extruder he follows. Process for solvent-free and continuous preparation of polymer modified resins according to one of the preceding claims, characterized in that the reaction in an intensive mixer or intensive kneader takes place. Process for solvent-free and continuous preparation of polymer modified resins according to one of the preceding claims, characterized in that the reaction in a static mixer he follows. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the temperature in the extruder, multi-shaft extruder, planetary roller extruder, Intensive kneader, intensive mixer or static mixer 10 to 325 ° C preferred 20 to 200 ° C, more preferably 70 to 200 ° C, is. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the extruder, multi-screw extruder, planetary roller extruder or Intensive compounder by suitable equipment the mixing chambers and compilation of the screw geometry on the one hand to an intensive rapid mixing and fast reaction at the same time intensive heat exchange to lead and on the other hand, a uniform flow in longitudinal direction with as possible effect uniform residence time. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the reaction in the presence of initiators, catalysts and / or Aggregates takes place. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the starting materials and / or initiators, catalysts and / or Aggregates together or in separate product streams, in liquid or solid form, the extruder, intensive kneader, intensive mixer or supplied to static mixer become. Process for solvent-free and continuous preparation of polymer modified resins according to the preceding claim, characterized in that the aggregates combined with the feedstock to form a product stream become. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized in the case of more than two product streams, these are bundled. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that shared one or both product streams become. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the initiator and / or catalyst combined with one of the streams or in one of the streams solved is present. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the aggregates are combined with one of the material streams or in one of the streams solved available. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the entry point of the product streams in the order variable and staggered. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that added an after-reaction becomes. Process for solvent-free and continuous preparation of polymer modified resins according to the previous claim, characterized in that the post-reaction in continuously operated systems, such as tubular reactors, stirred or unstirred Verweilzeitbehältern, Pipes, tube bundles, he follows. Process for solvent-free and continuous preparation of polymer modified resins according to at least one of the preceding claims, characterized that the assembly according to the viscosity of the extruder, multi-screw extruder, Planetary roller extruder, intensive kneader, intensive mixer or static Mixer and / or leaving the post-reaction zone product by first further cooling on one for later filling mechanical comminution, such. As grinding and / or silage, sufficient temperature is initiated. Method according to at least one of the preceding claims, characterized characterized in that the residence time of the starting materials 3 seconds to 15 minutes, preferably 3 seconds to 5 minutes, more preferably 5 to 180 seconds. Polymer-modified resins obtained by a solvent-free and continuous process by reacting I. at least one hydroxy-functional and / or carboxy-functional, crystalline and / or semicrystalline and / or amorphous polyester and II. At least one hydroxy-functional and / or carboxylic acid-containing polyacrylate, which are obtained by free-radical Polymerization of the starting component (s) for the preparation of II in the presence of the polyester I and in the absence of an organic solvent in an extruder, multi-screw extruder, planetary roller extruder, intensive kneader, intensive mixer or static mixer intensive mixing and brief reaction and subsequent isolation of the final product by cooling. A polymeric composition according to claim 37, characterized characterized in that compounds and process parameters after at least one of the claims 2 to 36 are used. Use of the polymeric composition after at least one of the preceding claims as main component, basic component or additional component for applications in coating materials, adhesives, printing inks and inks, polishes, Glazes, pigment pastes, fillers and sealants and insulating materials. Use of the polymeric composition after at least one of the preceding claims as main component, basic component or additional component for applications in coating materials, adhesives, printing inks and inks, polishes, Glazes, pigment pastes, fillers and sealants and insulating materials with polyisocyanates and / or melamine-formaldehyde resins as crosslinkers. Use of the polymeric composition according to claim 40 as a binder with aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates and / or isocyanurates and / or modifications made therefrom as crosslinkers. Use according to claim 41 with cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, phenylene diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, such as 1,6-diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), nonanetriisocyanate such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane and triisocyanate, undecanediisocyanate and triisocyanate, dodecandi- and triisocyanate, isophorone diisocyanate (IPDI), diisocyanatotoluene (TDI), 4,4'-methylenebis (phenylisocyanate) (MDI), bis (isocyanatomethylcyclohexyl) methane (H ₁₂ MDI), Isocyanatomethylmethylcyclohexylisocyanate, 2,5 (2,6) -bis (isocyanatomethyl) bicyclo [2.2.1] heptane (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ -XDI) or 1,4- Bis (isocyanatomethyl) cyclohexane (1,4 -H ₆ -XDI), or their isocyanurates as far as accessible, alone or in mixtures as crosslinkers.