EP2217660A1

EP2217660A1 - Radically cross-linkable polymer compositions containing epoxy-functional copolymers

Info

Publication number: EP2217660A1
Application number: EP08858142A
Authority: EP
Inventors: Thomas Köhler; René GRÄWE
Original assignee: Wacker Chemie AG
Current assignee: Wacker Chemie AG
Priority date: 2007-12-03
Filing date: 2008-12-01
Publication date: 2010-08-18
Also published as: DE102007055692A1; CN101883823A; CA2704889C; CA2704889A1; US20100256287A1; WO2009071508A1

Abstract

The invention relates to radically cross-linkable polymer compositions containing one or more radically cross-linkable polymers, one or more ethylenically unsaturated monomers (reactive monomers), optionally initiators, optionally filling material, and optionally other additives. The invention is characterised in that additionally one or more vinyl halogenid-free, epoxy- functional vinylester-copolymers (epoxy-functional copolymers) are contained in said compositions.

Description

Radically crosslinkable polymer compositions containing epoxy-functional copolymers

The invention relates to free-radically crosslinkable polymer compositions containing epoxy-functional copolymers,

Process for their preparation and the composite components obtainable by curing said polymer compositions and the use of the epoxy-functional copolymers as low-profile additives.

Radical cross-linkable polymer compositions based on, for example, unsaturated polyester resins (UP resins) are frequently used for the production of composite components. Unsaturated polyester resins are obtainable by polycondensation of dicarboxylic acids or dicarboxylic acid anhydrides with polyols. The free-radically crosslinkable polymer compositions further comprise monomers having ethylenically unsaturated groups, generally styrene. For example, styrene is added to the radically crosslinkable polymer composition to dissolve the crosslinkable polymer and to ensure that the radically crosslinkable polymer composition is a flowable mass. As further constituents, the radically crosslinkable polymer compositions often also contain fiber materials such as glass fibers, carbon fibers or corresponding fiber mats

(Fiber Reinforced Plastic Composites = FPR composites), which lead to an amplification of the composites components obtainable by curing the free-radically crosslinkable polymer compositions.

A problem in the processing of such radically crosslinkable polymer compositions to composite components is the volume shrinkage during the curing of the polymer composition. To reduce the shrinkage during curing, so-called low-profile additives (LPA) are added to the free-radically crosslinkable polymer compositions. Low-profile additives reduce shrinkage during curing, reduce residual stresses, reduce microcracking tion, and facilitate compliance with manufacturing tolerances. The low-profile additives are usually thermoplastics such as polystyrene, polymethyl methacrylate and in particular polyvinyl acetate, which frequently also contain carboxyl-functional comonomer units. For example, in US 3718714 or DE-A 102006019686 copolymers based on vinyl acetate and ethylenically unsaturated carboxylic acids are recommended as LPA for the production of composite components based on unsaturated polyester resins.

EP-A 0075765 recommends free-radically crosslinkable polymer compositions for the production of composite components, which contain, as LPA polymers based on vinyl acetate or alkyl acrylates and additionally ethylenically unsaturated fatty acid esters, through which the formation of composite components with as smooth as possible less corrugated surfaces is favored. For the production of composite components, US Pat. No. 4,525,498 discloses radically crosslinkable polymer compositions comprising unsaturated polyester resin, vinyl acetate-based or alkyl acrylate-based LPA and saturated, epoxy group-bearing, low molecular weight compounds by which the shrinkage-reducing effect of the LPA during curing increased the composition and the surface properties of the composite components can be improved. A significant increase in the mechanical properties of the composite components did not cause the addition of epoxide group-bearing, low molecular weight compounds. In addition, low molecular weight compounds tend to migrate and are easily released from the composite components.

For the production of composite components, US Pat. No. 4,284,736 recommends free-radically crosslinkable polymer compositions which contain as LPA terpolymers based on vinyl esters, glycidyl esters of unsaturated monocarboxylic acids and at least 45% by weight of vinyl halides, based on the total weight of the respective terpolymer. The compositions described therein are by good compatibility with organic and inorganic pigments and, after curing, by characterized a uniform pigmentation of the composite components. However, the use of vinyl halide polymer-containing polymers is frowned upon for environmental reasons, since they tend, for example, to dehydrochlorination and release large amounts of hydrochloric acid on disposal.

Copolymers based on vinyl esters and ethylenically unsaturated, epoxy-functional monomers are used in various fields of application. Thus, for example, EP-A 0897376 describes corresponding copolymers as sizing agents for reinforcing glass fibers. The sizing agents are aqueous compositions of saturated, thermoplastic polyurethanes, vinyl acetate-glycidyl methacrylate copolymers and silane coupling agents, which are applied to the fibers in thin layers as they are used.

Against this background, the object was to add free-radically crosslinkable polymer compositions such vinyl halide-free additives that counteract the volume shrinkage in the curing of the radically crosslinkable polymer compositions and at the same time to composite components with an improved mechanical property profile, such as an improved flexural strength, lead and beyond the other disadvantages mentioned above do not have.

The object has surprisingly been achieved with free-radically crosslinkable polymer compositions which contain vinyl halide-free, epoxy-functional vinyl ester copolymers.

The invention relates to radically crosslinkable polymer compositions containing one or more radically crosslinkable polymers, one or more ethylenically unsaturated monomers (reactive monomers), optionally initiators, optionally fillers and optionally further additives, characterized in that additionally one or more vinyl halide-free, epoxy-functional vinyl ester copolymers (epoxy-functional copolymers) are contained.

The epoxy-functional copolymers are obtainable by free-radically initiated polymerization of a) one or more vinyl esters and b) one or more ethylenically unsaturated, epoxy-functional monomers and optionally one or more further ethylenically unsaturated monomers other than vinyl halides.

Preferred vinyl esters are vinyl esters of unbranched or branched carboxylic acids having 1 to 18 carbon atoms. Particularly preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate and vinyl esters of C-C-branched monocarboxylic acids having 5 to 13 C atoms, for example vinyl pivalate, VeoVa9 ^R or VeoValO ^R (trade names of Hexion) or mixtures of the vinyl ester monomers mentioned. Most preferred is vinyl acetate.

Preferably Vinylester a) 15 to 99.9 weight .-% ^¬ is set, particularly preferably 20 to 99 wt .-%, each based on the total weight of the monomers to prepare the epoxy functional copolymers.

The ethylenically unsaturated, epoxy-functional monomers b) preferably have 1 to 20 C atoms, more preferably 1 to 10 C atoms, which may be linear or branched, open-chain or cyclic.

Examples of preferred ethylenically unsaturated, epoxy-functional monomers b) are glycidyl acrylate, glycidyl methacrylate (GMA) or allyl glycidyl ether; particularly preferred are glycidyl acrylate and glycidyl methacrylate; most preferred is glycidyl methacrylate. Preferably, 0.1 to 20 wt .-%, particularly preferably 0.2 to 15 wt .-% ethylenically unsaturated, epoxy-functional monomers b) are used, each based on the total weight of the monomers for the preparation of the epoxy-functional Copolyme- re ,

As further ethylenically unsaturated monomers for the production of the epoxy-functional copolymers one or more monomers can be used selected from the group consisting of acrylates and methacrylates of unbranched or branched alcohols having 1 to 20 C atoms, vinyl aromatics, olefins and dienes (monomers c)) ,

Preferred monomers c) from the group of the esters of acrylic acid or methacrylic acid are esters of unbranched or branched alcohols having 1 to 15 C atoms. Particularly preferred acrylic acid esters or methacrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-, iso- or t-butyl acrylate, n-, iso- and t-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate, isobornyl acrylate, stearyl acrylate. Most preferred acrylic acid esters or methacrylic acid esters are methyl acrylate, ethyl acrylate, methyl methacrylate, n-, iso- and t-butyl acrylate, 2-ethylhexyl acrylate and isobornyl acrylate.

Preferred dienes are 1,3-butadiene and isoprene. Examples of copolymerizable olefins are ethene and propene. As vinyl aromatic styrene and vinyl toluene can be copolymerized.

Preference is given to using from 0 to 70% by weight, particularly preferably from 0 to 50% by weight, of ethylenically unsaturated monomers c), based in each case on the total weight of the monomers for preparing the epoxy-functional copolymers.

As further ethylenically unsaturated monomers for the preparation of the epoxy-functional copolymers it is also possible to use one or more monomers selected from the group comprising ethylenically unsaturated carboxylic acids, ethylenically unsaturated saturated alcohols, ethylenically unsaturated sulfonic acids and ethylenically unsaturated phosphonic acids (monomers d)). Preference is given to ethylenically unsaturated mono- and dicarboxylic acids having 3 to 20 C atoms, ethylenically unsaturated alcohols having 3 to 20 C atoms, vinyl sulfonate and vinyl phosphonate. Particular preference is given to acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate.

The proportion of monomers d) in the epoxy-functional copolymers is preferably 0 to 15% by weight, more preferably 0 to 10% by weight, based in each case on the total weight of the epoxy-functional copolymers.

Preference is given to epoxy-functional copolymers obtainable by free-radically initiated polymerization of one or more vinyl esters a) selected from the group comprising vinyl acetate, vinyl pivalate, vinyl laurate, VeoVa9 ^R and VeoVal0 ^R , and one or more ethylenically unsaturated, epoxy-functional monomers b) selected from the group comprising glycidyl acrylate, glycidyl methacrylate (GMA) and allyl glycidyl ether, and optionally one or more monomers c) selected from the group of (meth) acrylic esters, in particular methyl acrylate, methyl methacrylate, ethyl acrylate, n-, iso or t-butyl acrylate , 2-ethylhexyl acrylate, isobornyl acrylate or stearyl acrylate, from the group of dienes, in particular isoprene or 1,3-butadiene, from the group of olefins, in particular ethene, propene or styrene, and optionally one or more monomers d) selected from A group comprising acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.

Particular preference is given to epoxy-functional copolymers based on vinyl acetate and one or more monomers b), such as in particular glycidyl methacrylate, and optionally vinyl laurate, acrylic acid or crotonic acid in the abovementioned amounts.

The epoxy-functional copolymers preferably contain ≥ 1, more preferably 1 to 200 and most preferably 10 to 150 epoxy-functional monomer units per 1000 monomer units.

The epoxy-functional copolymers have molecular weights Mw of preferably ≥6,500 g / mol, more preferably from 6,500 to 1,500,000 g / mol, very preferably from 6,500 to 1,000,000 g / mol and most preferably from 10,000 to 800,000 g / mol.

The epoxy-functional copolymers preferably contain the epoxy-functional monomer units in random distribution, i. the epoxy-functional copolymers are preferably not grafted with epoxy-functional monomers or compounds.

The preparation of the epoxy-functional copolymers is carried out by free-radical substance, suspension, emulsion or Lösungspolymerisationsverfahren the monomers a) and b) and optionally the monomers c) to d) in the presence of free-radical initiators - such as in EP-A 1812478 or DE-A 10309857 described.

Suitable reactive monomers are the monomers which are suitable, preferably or particularly preferred, which are also suitable, preferred or particularly preferred for the polymerization for the preparation of the epoxy-functional copolymers. Very particularly preferred reactive monomers are styrene, methyl methacrylate, methyl acrylate and butyl acrylate. The most preferred reactive monomer is styrene.

Preferred free-radically crosslinkable polymers are unsaturated polyester resins or vinyl ester resins. The unsaturated polyester resins are reaction products of one or more dicarboxylic acids or one or more dicarboxylic acid anhydrides with one or more polyols. The preparation of the unsaturated polyester resins is known to the person skilled in the art.

The dicarboxylic acids or the dicarboxylic acid anhydrides preferably have 2 to 20, particularly preferably 4 to 20 and most preferably 4 to 10 carbon atoms. The unsaturated polyester resins contain at least one ethylenically unsaturated dicarboxylic acid or at least one ethylenically unsaturated dicarboxylic anhydride. Preferred ethylenically unsaturated dicarboxylic acids or dicarboxylic acid anhydrides are maleic acid, maleic anhydride, fumaric acid, methylmaleic acid and itaconic acid. Particularly preferred are maleic acid, maleic anhydride and fumaric acid.

In addition to the ethylenically unsaturated dicarboxylic acids or dicarboxylic acid anhydrides, saturated dicarboxylic acids or anhydrides can be used. Suitable saturated acids or dicarboxylic acid anhydrides are, for example, orthophthalic acid, isophthalic acid, phthalic anhydride, terephthalic acid, hexahydrophthalic acid, adipic acid, succinic acid and isophthalic acid.

Suitable polyols preferably have 2 to 20 and more preferably 2 to 10 carbon atoms. Polyols preferably carry 2 to 3, more preferably 2 alcohol groups. Examples of suitable polyols are ethylene glycol, diethylene glycol,

Propylene glycol, dipropylene glycol, butylene glycol, Neopentylgly- kol, glycerol and 1, 1, 1-trimethylolpropane.

The unsaturated polyester resins have molecular weights Mw of preferably 500 to 10,000 g / mol, more preferably 500 to 6,000 g / mol, and most preferably 1,000 to 6,000 g / mol. Vinyl ester resins are reaction products which are formed by polyadditions or esterification reactions of phenol derivatives and ethylenically unsaturated mono- or dicarboxylic acids or dicarboxylic anhydrides having 3 to 20 carbon atoms, such as, for example, acrylic acids or methacrylic acids. Preferred phenol derivatives are bisphenol A and phenol novolac. The preparation of the vinyl ester resins is known to the person skilled in the art.

Suitable initiators are, for example, t-butyl perbenzoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, dibenzoyl peroxide, t-amyl peroxypivalate, di (2-ethylhexyl) peroxydicarbonate, 1,1-bis (t-butyl peroxy ) -3, 3, 5-trimethylcyclohexane, di (4-t-butylcyclohexyl) peroxydicarbonate, azobisisobutyronitrile.

Suitable fillers are, for example, talc, aluminum hydroxide, kaolin, calcium carbonate, dolomite, glass beads or glass fibers, quartz, aluminum oxide or barium sulfate.

The radically crosslinkable polymer compositions preferably contain from 30 to 60 parts by weight of radically crosslinkable polymers, from 5 to 40 parts by weight of epoxy-functional copolymers, from 30 to 160 parts by weight of reactive monomers, optionally from 0.5 to 2% by weight. Parts initiator, optionally fillers such as 25 to 100 parts by weight of glass fiber or 50 to 200 parts by weight of calcium carbonate, optionally further additives such as 0.5 to 3 parts by weight of mold release agents, for example zinc stearate, and optionally other additives, for example Pigments, thickeners, flame-retardant additives.

Furthermore, the free-radically crosslinkable polymer compositions may comprise further polymers, for example polymers known to act as low-profile additive, such as polyvinyl acetate, carboxyl-functional polyvinyl acetate or polymethyl methacrylate. The proportion of the further polymers is 0 to 100 wt .-%, preferably 0 to 50 wt .-%, each based on the amount by weight of epoxy functional copolymers in the respective radically crosslinkable polymer composition.

Another object of the invention are methods for preparing the radically crosslinkable polymer compositions by mixing one or more radically crosslinkable polymers, one or more ethylenically unsaturated monomers (reactive monomers) and optionally of initiators, optionally of fillers and, where appropriate, of further additives, characterized in that in addition one or more vinyl halide-free, epoxy-functional vinyl ester copolymers (epoxy-functional copolymers) admixed.

The epoxy-functional copolymers and the radically crosslinkable polymers are dissolved separately or together, optionally in combination with other polymers, generally in reactive monomers and optionally mixed with further additives such as fillers, thickeners, initiators and processing aids. If the epoxy-functional copolymers or the radically crosslinkable polymers are dissolved in reactive monomers, the radically crosslinkable polymers are preferably used as 50 to 70% solution in reactive monomers and the epoxy-functional copolymers preferably as 30 to 50% solution in used reactive monomers.

The mixing of the components for the preparation of the radically crosslinkable polymer compositions can be carried out using the customary devices known to the person skilled in the art, such as, for example, reactors, stirred vessels or mixers, and stirrers, such as, for example, blade, armature or blade stirrers.

Another object of the invention are composite components obtainable by curing the radically crosslinkable polymer compositions. The curing of the radical-crosslinkable polymer compositions preferably takes place at temperatures of ≥ 20 ⁰ C, particularly preferably from 20 to 200 ⁰ C and most preferably 20-165 ⁰ C. Preferably, the curing in the opposite waiting of one or more initiators by radical-initiated polymerization. Optionally, the free-radically crosslinkable polymer compositions are compacted on curing at the particular temperature using pressures of ≥1 mbar, more preferably from 1 to 200,000 mbar, and most preferably from 1,000 to 200,000 mbar.

The composite components can be obtained from the free-radically crosslinkable polymer compositions by all common production methods, for example by means of sheet molding compound technology (SMC), bulk molding compound technology (BMC), resin transfer molding (RTM) or resine injection Molding (RIM).

Preferably, the composite components by means of BMC technology (BuIk Molding Compound) or SMC technology (Sheet Molding Compound) are produced.

In the BMC process, the solutions of the radically crosslinkable polymers in reactive monomer and the epoxy-functional copolymers and optionally the further components such as the initiator, filler, mold release agent or other polymers, low-profile additives or additives are mixed to form a pasty mass, Thereafter, if appropriate, glass fiber is admixed, and then the resulting free-radically crosslinkable polymer compositions are cured using pressure and temperature to form the composite component. For example, reflectors for car headlights are produced with this technology.

In the SMC process is analogous to the BMC process, a radically crosslinkable polymer composition in the form of a pasty mass of a solution of free-radically crosslinkable polymers in reactive monomer and the epoxy-functional Copolymer and optionally the other components such as initiator, filler, mold release agents, other polymers, low-profile additives or additives produced and applied to a polyamide film. Then, if appropriate, glass fiber is sprinkled onto this layer, then optionally a further layer of the pasty mass is applied and finally covered with a further polyamide film. This sheet sandwich is then peeled from the film, cut into pieces and pressed using compression and temperature to composite components. Composite components made by this technique are used, for example, as tailgates of automobiles.

The composite components according to the invention have advantageous performance properties, such as improved mechanical strength, in particular high bending strength. The mechanical strength can be increased by using epoxy-functional copolymers having a larger number of epoxy-functional monomer units and / or a higher molecular weight M w. In addition, the epoxy-functional copolymers act as low-profile additives in the production of the composite components.

Another object of the invention is the use of the epoxy-functional copolymers as low-profile additives (LPA).

The following examples serve to further illustrate the invention without limiting it in any way.

Preparation of Epoxy-Functional Copolymers:

Example 1 :

307.0 g of ethyl acetate, 50.0 g of vinyl acetate, 0.5 g of glycidyl methacrylate and 1.6 g of PPV (t-butylperpivalate, 75% strength solution in aliphatics) were mixed in a 21-glass stirred vessel with anchor stirrer, reflux condenser and metering devices. submitted. Subsequently, the template was heated to 70 ⁰ C under nitrogen at a stirrer speed of 200 rpm. After reaching the internal temperature of 70 ⁰ C (14.8 g PPV) added 1150.0 g of vinyl acetate, 12.0 g of glycidyl methacrylate and an initiator solution. The monomer solution was added within 240 minutes and the initiator solution within 300 minutes. After the end of the initiator feeds for 2 hours at 80 ⁰ C nachpolyme- was rised. A clear polymer solution having a solids content of 79% by weight was obtained. Under vacuum and elevated temperature, the ethyl acetate was distilled off. The dried film of ethyl acetate solution (layer thickness 70 microns) was clear. The copolymer had a content of glycidyl methacrylate of 1 wt .-%, based on the total mass of the monomers used.

Example 2:

Analogously to the procedure of Example 1, a copolymer was prepared which was obtained from 97% by weight of vinyl acetate and 3% by weight of glycidyl methacrylate. The polymer properties are listed in Table 1.

Example 3 Analogously to the procedure of Example 1, a copolymer was prepared which was obtained from 97% by weight of vinyl acetate and 3% by weight of glycidyl methacrylate. Unlike Example 1 but instead of ethyl acetate 247 g of isopropanol were used. The polymer properties are listed in Table 1.

Example 4:

Analogously to the procedure of Example 1, a copolymer was prepared which consisted of 95% by weight of vinyl acetate and 5% by weight. Glycidyl methacrylate was obtained. The polymer properties are listed in Table 1.

Example 5 Analogously to the procedure of Example 1, a copolymer was prepared which was obtained from 94% by weight of vinyl acetate and 6% by weight of glycidyl methacrylate. The polymer properties are listed in Table 1.

Example 6:

Analogously to the procedure of Example 1, a copolymer was prepared, which was obtained from 90 wt .-% vinyl acetate and 10 wt .-% glycidyl methacrylate. The polymer properties are listed in Table 1.

Example 7:

Analogously to the procedure of Example 1, a copolymer was prepared, which was obtained from 88 wt .-% vinyl acetate and 12 wt .-% glycidyl methacrylate. The polymer properties are listed in Table 1.

Table 1: Compositions and properties of the epoxy-functional copolymers

a) VAc: vinyl acetate; GMA: glycidyl methacrylate b) the percentage by weight refers to the total weight of the monomers. c) Hoppler: Hoppler viscosity according to DIN 53015 (10% in ethyl acetate, 2O ⁰ C) d) K-value: determined according to DIN EN ISO 1628-2 (1 wt .-% in acetone). e) Mw: Mw (weight average) determined by SEC

"Size exclusion chromatography", polystyrene standard, THF, 6O ⁰ C. f) Polydispersity (Mw / Mn). Production of composite components:

A mixture of 100 parts by weight of an unsaturated polyester resin (orthophthalic acid-maleic anhydride resin, 65% dissolved in styrene) with 1 part by weight of a cobalt accelerator (NL 49-P from Akzo Nobel), 1.5 parts by weight of an initiator (Butanox M 50 by Akzo Nobel) and optionally 2 parts by weight of polymer additive (Table 2) intimately mixed and poured into a mold. After curing for 24 hours at room temperature, 24 hours at 65 ° C and 2 h at 100 ⁰ C, the test specimen (length / width / height = 100mm / 15mm / 2mm) were obtained. The corresponding test specimens are characterized in greater detail by the data in Table 2.

Testing the mechanical properties of the composite components:

Table 2: Introduction of Epoxy Functional Copolymers on the Mechanical Properties of Composites

a) GMA: glycidyl methacrylate; the indication in Gew. -% refers to the total weight of the copolymer. b) Mw: molecular weight M w (weight average) determined by means of SEC "Si ze exclusion chromatography", polystyrene standard, THF; 6O ⁰ C. c) BF: flexural strength: determined according to DIN EN I SO 14125. The flexural strength of the composite components was determined on the basis of the test specimens according to EN ISO 14125. The test results for the various specimens are listed in Table 2.

From the comparative examples, it can be seen that the test body V9 modified with a vinyl acetate homopolymer has a considerably poorer flexural strength than the unmodified test body V8. In contrast, the addition of the epoxy-functional copolymer of Example 3 led to an increase in the flexural strength of specimens in Example 10. Examples 10 to 13 show that by further increasing the number of epoxy-functional monomer units or the molecular weight Mw of the epoxy Functional copolymers, the flexural strengths of the specimens can be significantly increased.

Testing the Effect of the Epoxy-Functional Copolymers as LPA:

Table 3: Formulation for composite components

As low-profile additives were used:

LPAl (comparison):

Copolymer of vinyl acetate and 1 wt .-% crotonic acid (molecular weight Mw = 175 kg / mol).

LPA2:

Epoxy-functional copolymer of Example 4.

From the raw materials listed in Table 3, a paste was kneaded. Shortly before processing, Luvatol MK 35, a thickener, was stirred in. Thereafter, a hand laminate was made with the paste and the glass fibers and processed into an SMC. The product was stored for 3 days at 20 ^° C. and 50% room humidity. Then it was pressed at 160 ⁰ C in a common SMC press to a composite component.

The shrinkage was determined after the press had cooled and the volume change in percent was determined (Table 4). Minus values indicate that the composite component was larger than the original shape.

Table 4: Dimensions of the composite components

From Table 4 it can be seen that the epoxy-functional copolymers and conventional, carboxyl-functional polyvinyl acetates are comparable in a comparable manner as LPA. Both effect in the formulation an expansion during compression. In addition, the addition of the epoxy-functional copolymers of the invention results in an improvement of the mechanical properties of the present invention. see properties of composite components, as shown in Table 2. The molecular weight and the fixation of the epoxy-functional copolymers via the epoxy groups on the composite components also ensures that the epoxy-functional copolymers can not migrate to the surface of the composite components. This reduces problems with the coating of the composite components, such as the detection of defects or surface defects in the paint.

Claims

Claims:

1. Radically crosslinkable polymer compositions corresponds holding one or more radically crosslinkable polymers, one or more ethylenically unsaturated monomers (reactive monomers), optionally initiators gegebe ^¬ appropriate, fillers, and optionally further additives, characterized in that additionally one or more vinylhalogenidfreie , Epoxy-functional vinyl ester copolymers (epoxy-functional copolymers) are contained.

2. Radically crosslinkable polymer compositions according to claim 1, characterized in that the epoxy-functional copolymers are obtainable by free-radically initiated polymerization of a) one or more vinyl esters and b) one or more ethylenically unsaturated, epoxy-functional monomers and optionally one or several other ethylenically unsaturated monomers other than vinyl halides.

3. Radically crosslinkable polymer compositions according to claim 2, characterized in that the ethylenically unsaturated, epoxy-functional monomers b) have 1 to 20 carbon atoms, which may be arranged linear or branched, open-chain or cyclic.

4. Radically crosslinkable polymer compositions according to claim 2 or 3, characterized in that it is the ethylenically unsaturated, epoxy-functional monomers b) glycidyl acrylate, glycidyl methacrylate (GMA) or allyl glycidyl ether.

5. The radically crosslinkable polymer compositions according to claim 2 to 4, characterized in that the ethylenically ^¬ cally unsaturated, epoxy-functional monomers b) in a proportion of 0.1 to 20 wt .-%, based on the total weight of the monomers for the preparation of the epoxy-functional copolymers.

6. Radically crosslinkable polymer compositions according to claim 1 to 5, characterized in that the epoxy-functional copolymers have a molecular weight Mw of ≥ 6,500 g / mol.

7. Radically crosslinkable polymer compositions according to claim 1 to 6, characterized in that the radically crosslinkable polymers are unsaturated polyester resins or vinyl ester resins.

8. Radically crosslinkable polymer compositions according to claim 1 to 7, characterized in that the reactive monomers are selected from the group consisting of vinyl esters, acrylic esters and methacrylic esters, vinyl nylaromaten, olefins, dienes and vinyl halides.

9. A process for preparing the free-radically crosslinkable polymer compositions by mixing one or more radically crosslinkable polymers, one or more ethylenically unsaturated monomers (reactive monomers) and optionally initiators, optionally fillers and optionally further additives, characterized in addition, one or more vinyl halide-free, epoxy-functional vinyl ester copolymers (epoxy-functional copolymers) are mixed in.

10. Composite components obtainable by curing the radically crosslinkable polymer compositions according to claim 1 to 8.

11. Use of the epoxy-functional copolymers of claim 2 to 6 as low-profile additives (LPA).