EP1844094A1

EP1844094A1 - Impact-resistant compositions

Info

Publication number: EP1844094A1
Application number: EP06700275A
Authority: EP
Inventors: Jürgen Finter; Norman Blank
Original assignee: Sika Technology AG
Current assignee: Sika Technology AG
Priority date: 2005-01-11
Filing date: 2006-01-11
Publication date: 2007-10-17
Also published as: CN101128524A; CA2593606A1; EP1679341A1; KR20070110850A; CA2593606C; CN101128524B; JP2008527099A; WO2006075009A1

Abstract

The invention relates to compositions comprising at least one compound A, at least one linear or branched polyester B, and at least one toughening agent C, the linear or branched polyester B being produced from a macrocyclic poly(a,?- alkylene-terephthalate) or a macrocyclic poly(a,?-alkylene-2,6- naphtalene dicarboxylate) in the presence of an organotin catalyst or organotitanium catalyst). Also disclosed are a method for producing said compounds and the use thereof for producing composite members.

Description

MEASURES COMPOSITIONS

Technical area

The invention relates to the field of impact-resistant polyester compositions, in particular for use in fiber-reinforced composite bodies.

State of the art

Thermoplastic polyesters are known plastics and are widely used. For their use in fiber composites both good wetting of the fiber, ie low viscosity in the production of molded parts, as well as high molecular weight because of the required mechanical properties are desired. However, the viscosity of conventional polyesters is too high for this, especially when the polyesters are used for the production of moldings. No. 5,498,651 discloses a polymerization process of low-viscosity macrocyclic polyester oligomers in the presence of polymerization catalysts and epoxides and / or thioepoxides. 3,4-Epoxycyclohexyl-3,4-epoxycyclohexylcarboxylate is disclosed as particularly preferred epoxy for this purpose. No. 6,197,849 describes organophilic phyllosilicates which are used as an additive to thermosets (thermoset polymers), in particular to epoxy resins or polyurethanes. US 5,707,439 describes the preparation of cation-exchanged layered minerals. Furthermore, the polymerization of macrocyclic oligomers in these cation-exchanged layered minerals is shown. However, such polymer mixtures are extremely difficult to process and lead to poor mechanical properties, since the layer minerals can act as nucleating agents. Presentation of the invention

The object of the present invention is therefore to provide a composition which, on the one hand, is easy to process and, on the other hand, has increased impact strength.

This object is achieved by the composition according to claim 1.

MODES FOR CARRYING OUT THE INVENTION The present invention relates to compositions comprising at least one compound A and at least one linear or branched polyester B and at least one toughening agent C.

Compound A has at least two glycidyl ether groups and is preferably a diglycidyl ether of a bisphenol A or a bisphenol F or a bisphenol A / bisphenol F mixture or a liquid oligomer thereof. Particularly suitable compounds A have been diglycidyl ethers of bisphenol A (DGEBA), bisphenol F and bisphenol A / F (Die

Designation 'A / F' refers to a mixture of bisphenol A and bisphenol F, which is used as starting material in its preparation). Due to the manufacturing process of these resins, it is clear that in the

Liquid resins also contain higher molecular weight components. The structure of such diglycidyl ethers shows formula (I). For liquid resins is the

Degree of polymerization s in formula (I) typically between 0.05 and 0.20. Such liquid resins are commercially available, typical commercial products are for example Araldite® GY 250, Araldite® PY 304, Araldite® GY 282

(Huntsman) or D.E.R 331 (Dow).

R ^a is H or methyl. Furthermore, it is also possible that the compound A is a high molecular weight solid epoxy resin of formula (I) having a degree of polymerization s of typically a value between 2 and 12, is. It is understood that there is always a molecular weight distribution. Such solid epoxy resins are commercially available, for example from Dow or Huntsman or Resolution.

In one embodiment of the invention, a mixture of epoxy liquid resin and epoxy solid resin is used. The weight ratio of liquid resin to solid resin is preferably 9: 1 to 1: 1.

In particular, the polyester B is a linear polyester and preferably has a structural formula (II) or (III).

The indices n and n 'in this case each denote 1, 2, 3 or 4. In particular, n = 1 or 3 and n' = 1 or 3. Preferably, n = 3 and n '= 3. The indices m and m' are values from 50 to 2000, in particular from

50 to 800, preferably 100 to 600, particularly preferably from 100 to 600.

Preferred polyesters B are poly (1,2-ethylene terephthalate) (PET) poly (1,2-ethylene-2,6-naphthalene dicarboxylate) (PEN) and poly (1,4-butylene terephthalate) (PBT). The most preferred polyester B is poly (1,4-butylene terephthalate) (PBT). The macrocyclic poly (α, ω-alkylene terephthalate) or macrocyclic poly (α, ω-alkylene-2,6-naphthalene dicarboxylate) used for the preparation of the polyester B preferably has the structure of the formula (IV)

Here, R is an ethylene, propylene, butylene or pentylene group and R 'is a group of the formula

The dashed lines shown here are the connections with the

Alkylene group R and the index p is selected such that the

Molecular weight M _{n of} the macrocyclic poly (α, ω-alkylene terephthalate) or of the macrocyclic poly (α, ω-alkylene-2,6-naphthalene dicarboxylate) is between 300 and 2000 g / mol, in particular between 350 and 800 g / mol lies.

The preparation of the macrocyclic poly (α, ω-alkylene terephthalate) or the macrocyclic poly (α, ω-alkylene-2,6-naphthalene dicarboxylate) is carried out in a known manner, as described, for example, in US Pat. No. 5,039,783 ,

The organo-tin or organo-titanium catalyst present in the preparation of the linear or branched polyester B is any known to the person skilled in the art, for example from US Pat. No. 5,407,984.

The composition according to the invention preferably has an amount of linear or branched polyester B of 85-98% by weight, preferably 90-98% by weight of the composition.

Furthermore, the composition comprises at least one toughener C. A " toughener " In the following, an addition to a matrix is understood which causes a marked increase in toughness, in particular in the case of thermosets (thermosets) such as epoxy resins, at already low additions of 0.5-8% by weight and is thus capable of producing higher flexural, tensile, To absorb impact or impact stress before the matrix enters or breaks.

The toughener C is in particular an organic ion-exchanged layered mineral C1 or a reactive liquid rubber C2 or a block copolymer C3.

The ion-exchanged layer mineral C1 can be either a cation-exchanged layer mineral C1c or an anion-exchanged layer mineral.

The cation-exchanged layered mineral C1c is obtained from a layered mineral CV, in which at least part of the cations have been replaced by organic cations. Examples of such cation-exchanged layered minerals C1c are in particular those mentioned in US 5,707,439 or in US 6,197,849. Likewise, the process for producing these cation-exchanged layered minerals C1c is described there. Preferred as a layered mineral CV is a layered silicate. Particularly preferably, the layer mineral CV is a phyllosilicate, as described in US Pat. No. 6,197,849, column 2, line 38 to column 3, line 5, in particular a bentonite. Layer minerals CV such as kaolinite or a montmorillonite or a hectorite or an illite have proven particularly suitable.

At least some of the cations of the layered mineral CV are replaced by organic cations. Such organic cations are, in particular, organic cations which have the formulas (V), (VI), (VII), (VIII) or (IX).

The substituents R ¹ , R ¹ , R ¹ and R ¹ each independently represent H or a C ₁ -C 20 -alkyl or a substituted or unsubstituted aryl. Preferably, R ¹ , R ^{1 '} , R ¹ and R ^{1 are} not the same substituent. The substituent R ² is H or a C ₁ -C 20 -alkyl or a substituted or unsubstituted aryl.

R ⁷ NR ¹ (IX)

The substituents R ³ and R ⁴ are each H or a C ¹ -C ₂₀ -alkyl or a substituted or unsubstituted aryl or a substituent -N (R ² ) ₂ . The substituent R ⁵ is a substituent which together with the N ⁺ shown in formula (VII) forms an optionally substituted ring of 4 to 9 atoms and optionally has double bonds. The substituent R ⁶ represents a substituent which together with the N ⁺ shown in formula (VIII) forms an optionally substituted bicyclic ring of 6 to 12 atoms and optionally contains heteroatoms such as N, O, and S, or their cations. The substituent R ⁷ is a substituent which together with the N ⁺ shown in formula (IX) forms an optionally substituted heteroaromatic ring of the ring size of 5 to 7 atoms.

Specific examples of such organic cations of formula (V) are n-octylammonium (R ¹ = n-octyl, R ¹ = R ^{1 '=} R ¹ = H), Trimethyldodecylam- monium (R ¹ = C ₂ - alkyl, R ¹ = R ¹ = R ¹ = CH ₃ ), dimethyldodecylammonium (R ¹ = C ₁₂ - alkyl, R ^{1 '=} R ^1' = CH _3, R ^{1 "'=} H), or bis (hydroxyethyl) octadecylam- monium (R ¹ = C ₈ - alkyl, R ^1' = R ^{1 "} = CH ₂ CH ₂ OH, R ^{1 '"} = H) or similar derivatives of amines which can be obtained from natural fats and oils. Concrete examples of such organic cations of the formula (VI) are guanidinium cations or amidinium cations.

Concrete examples of such organic cations of the formula (VII) are N-substituted derivatives of pyrrolidine, piperidine, piperazine, morpholine, thiomorpholine. Concrete examples of such organic cations of the formula (VIII) are cations of 1,4-diazobicyclo [2.2.2] octane (DABCO) and 1-azobicyclo [2.2.2] octane.

Concrete examples of such organic cations of the formula (IX) are N-substituted derivatives of pyridine, pyrrole, imidazole, oxazole, pyrimidine, quinoline, isoquinoline, pyrazine, indole, benzimidazole, benzoxazole, thiazole phenazine and 2,2'-bipyridine. Also suitable are cyclic amidinium cations, in particular those disclosed in US Pat. No. 6,197,849 at column 3, line 6 to column 4, line 67.

Cyclic ammonium compounds are distinguished from linear ammonium compounds by an increased Thermostabi quality, since the thermal Hoffmann - degradation can not occur in them

Preferred cation-exchanged layered minerals C1c are known to the person skilled in the art under the term Organoclay or Nanoclay and are commercially available, for example, under the group names Tixogel® or Nanofil® (Southern Chemistry), Cloisite® (Southern Clay Products) or Nanomer® (Nanocor Inc.).

The anion-exchanged layer mineral C1a is in this case obtained from a layer mineral C1 "in which at least a part of the anions has been exchanged for organic anions An example of such an anion-exchanged layer mineral C1a is a hydrotalcite in which at least part of the carbonate Anions of the intermediate layers were replaced by organic anions. It is quite possible that the composition simultaneously contains a cation-exchanged layer mineral C1c and an anion-exchanged layer mineral C1a.

The reactive liquid rubber C2 has functional groups which can react at elevated temperature, typically at a temperature between 80 ° C and 200 ° C, especially between 100 ° C and 160 ° C, with itself or with other compounds in the composition. Particularly preferred such functional groups are epoxide groups. Particularly preferred are reactive liquid rubbers, as proposed for the toughening of Epoxydharzklebstoffen. Preferably, the reactive liquid rubber C2 is a glycidyl ether-terminated polyurethane prepolymer. Reactive liquid rubbers C2 of the formula (X) have proven to be particularly suitable.

In formula (X) Yi is a q-valent radical of an isocyanate group-terminated linear or branched polyurethane prepolymer after removal of the terminal isocyanate groups and Y _{2 is} a radical of a primary or secondary hydroxyl-containing aliphatic, cycloaliphatic, aromatic or araliphatic epoxide after removal of the hydroxide and epoxide groups. The index q in this case means a value of 2, 3 or 4 and the index r a value of 1, 2 or 3. In one embodiment, the formula (X) has at least one aromatic structural element which is incorporated into the polymer chain via urethane groups. As particularly advantageous liquid rubbers of the formula (XI) have been found.

In formula (XI), Y _{3 is} a (u + w) -value radical of an isocyanate group-terminated linear or branched polyurethane prepolymer after removal of the terminal isocyanate groups and Y _{2 is} a radical of a primary or secondary hydroxyl-containing aliphatic, cycloaliphatic , aromatic or araliphatic epoxide after removal of the hydroxide and epoxide groups. The index w here means a value of 1, 2 or 3 and the index u a value of 4-w and the index v a value of 1, 2 or 3. In formula (XI) X represents either an O or an NH or is an N-alkyl of 1 to 6 carbon atoms, and R "represents a branched or unbranched alkyl or alkenyl substituent of 6 to 24 carbons or a poly (dimethylsiloxane) radical of molecular weight 1000 to 10O00 g / mol. In one embodiment the formula (XI) has at least one aromatic structural element which is incorporated into the polymer chain via urethane groups.

The preparation of these reactive liquid rubbers takes place in a manner as described, for example, in EP 1 431 325 A1 on page 4, line 37 to page 6, line 55.

Liquid rubbers C2 of the formulas (X) and (XI) can be used individually or preferably in a mixture. When used in admixture, the weight ratio (X) / (XI) of the liquid rubbers of the formulas (X) and (XI) is advantageously from 100: 1 to 1: 1.

The block copolymer C3 is obtained from an anionic or controlled radical polymerization of methacrylic acid ester at least one further monomer having an olefinic double bond. A monomer having an olefinic double bond is, in particular, those in which the double bond is conjugated directly with a heteroatom or with at least one further double bond. In particular, monomers are suitable which are selected from the group comprising styrene, butadiene, acrylonitrile and vinyl acetate.

Particularly preferred block copolymers C3 are block copolymers of methyl methacrylate, styrene and butadiene. Such block copolymers are available, for example, as triblock copolymers under the group name SBM from Arkema.

In one embodiment, in the composition as toughening agent C, in addition to an ion-exchanged layered mineral C1, either a reactive liquid rubber C2 or a block copolymer C3 is additionally present. Particularly preferred is the simultaneous presence of ion-exchanged layered mineral C1 and reactive liquid rubber C2. As ion-exchanged layer mineral C1, a cation-exchanged layer mineral C1c is preferred here.

The amount of toughener C is preferably 10 to 85

Wt .-% based on the weight of the sum of A + C.

The composition may optionally have further constituents, in particular fillers, plasticizers, thixotropic agents, adhesion promoter substances, in particular alkoxysilanes and titanates, stabilizers, in particular heat stabilizers, such as those known to those skilled in the art under HALS (hindered amine light stabilizers), and UV stabilizers. Stabilizers such as those available under the trade name TINUVIN® from Ciba Specialty Chemicals or other additives and additives well known to those skilled in the formulation of adhesives, potting compounds or sealants. Preference is given to compositions which contain no solvents and / or plasticizers. The compositions are characterized on the one hand by high toughness, and on the other hand by good processing properties, such as low melt viscosity, and at the same time by a high melting temperature after polymerization.

The composition is preferably prepared by a process comprising the following steps:

- Forming a premix AC of toughener C and the compound A, which has at least two glycidyl ether groups.

- Addition of the mixing premix AC to the macrocyclic poly (α, ω-alkylene terephthalate) or macrocyclic poly (α, ω-alkylene-2,6-naphthalene dicarboxylate), which is mixed with the organo-tin or organo-titanium catalyst ,

The linear or polyester branched polyester B is preferably at a temperature of 160 ⁰ C to 220 ⁰ C, in particular between 160 ° C to 200 ⁰ C, in the presence of the master batch AC and an organo-tin or organo-titanium catalyst by ring-opening Polymerization of a macrocyclic poly (α, ω-alkylene terephthalate) or a macrocyclic poly (α, ω-alkylene-2,6-naphthalene dicarboxylate).

The preparation of the premix AC is preferably carried out by mixing the toughener C into the compound A. This premixing is preferably carried out at elevated temperature under high shear forces. If the compound is a solid resin, the premix AC can also be made by blending compound A in powder form, or by extrusion.

Preferably, a homogeneous premix of macrocyclic poly (.alpha.,. Omega.-alkylene terephthalate) or macrocyclic poly (.alpha., .Omega. Alkylene-2,6-naphthalene dicarboxylate) and organo-tin or organo-titanium catalyst at temperatures well below the polymerization temperature, for example produced in a twin-screw extruder and ground after cooling to a powder. Preferably, the premix AC is then added with stirring to a pulverulent premix of macrocyclic poly (α, ω-alkylene terephthalate) or macrocyclic poly (α, ω-alkylene-2,6-naphthalene carboxylate) and organo-tin or organo Titanium catalyst added at room temperature, and either in powder form or heated to the melting temperature of the macrocycle at 160-180 ⁰ C and then shaped as a liquid mixture. The ring-opening polymerization is then carried out at temperatures of more than 180 ⁰ C.

It is also possible, however, the mixture of AC pre-mix for example in an extruder at temperatures of less than 140 ⁰ C, grinding after cooling and storing, or cool, the mixture prepared in the melt, to crush and store.

Preferably, the composition is already used before the final degree of polymerization is achieved. Such a production has the advantage that the

Toughener C unexpectedly good and homogeneous can be incorporated, so that can be dispensed with the use of solvents or plasticizers or at least greatly reduced. This has particular effect on the fact that the melting temperature of the composition is not unnecessarily lowered.

In one embodiment of the present invention, the described composition is used for the production of composites, in particular nanocomposites. Such composites contain at least one previously described composition and fibers. The fibers are themselves fibers selected from the group comprising glass fibers, metal fibers, Carbon fibers, aramid fibers, mineral fibers, vegetable fibers and mixtures thereof. Preferred fibers are carbon fibers or metal fibers. Particularly preferred are steel fibers. Different types of fibers may also be present in the composite body simultaneously. The fibers can be present as short or long fibers and as individual fibers or as rovings. Furthermore, the fibers may be present as knitted fabric, scrim or fabric. The orientation of the fibers may be unidirectional or random. In a particularly preferred embodiment, the fibers are present as unidirectional fiber layers. There may also be multiple layers of such knits, mantles or fabrics in a composite body. The exact configuration of the fiber orientation and the fibers used is very dependent on the geometry of the composite and the mechanical stress requirement placed on the composite. The composite body preferably has a proportion of fibers of 30 to 65% by volume, based on the volume of the composite body.

Different methods can be used in the production of the composite body. Thus, for example, it is possible for endless profiles, in particular in the form of a lamellar form, to be produced by pulling the fibers through a heated mold by continuously unrolling rolls of a plurality of rovings or one or more fiber fabrics, plies or knits. in which the molten composition is added to the fibers and permeates the fibers. The mold, in one embodiment, has an exit through which the composite is continuously discharged during cooling. In another embodiment, this mold also has an outlet through which the composite body is discharged continuously, but in a further step is downstream compressed by pressing, preferably heated presses and possibly brought to the desired cross-sectional geometry by means of a mask. In a subsequent cooling zone, the composite body produced in this way is cooled to room temperature. The endless profile is finally rolled up or cut to length. Such endless profiles are particularly well suited as reinforcing profiles, in particular as reinforcing bars, as used for example for the static reinforcement of buildings. Such reinforcing profiles are advantageously glued non-positively by means of adhesive with the structure to be reinforced. Carbon fibers and glass fibers can be used as particularly preferred fibers for this purpose.

Furthermore, composite bodies can be filled with the composition by means of molds in which fibers are inserted. The final shape can be done by pressing and forming. The methods used for this purpose are well known to the person skilled in the art and include, in particular, also RIM, RTM methods.

Finally, especially if individual short fibers are used, the fibers can be homogeneously mixed with the molten composition, optionally in its manufacture, and cast or pressed into a mold to form a composite body.

The method used and the type of fiber reinforcement is highly dependent on the requirements placed on the composite body. The novel composite bodies can be widely used. In particular, they find application for static reinforcement of a building or a means of transport. On the one hand, they can be used together with other materials or alone. As an example, reinforcements of bridges or tunnels or houses are mentioned. Other exemplary examples include cabs, bodies, bumpers, mudguards, spare wheel wells, underbody and roof of automobiles, towing vehicles or buses or trucks. Other examples of applications of such composites can be found in sports and leisure articles such as tennis rackets, bicycles, pleasure boats. In particular, all applications are preferred in which the use of these inventive composite body leads to a weight saving compared to the use of conventional materials. Examples

Comparative Example 1 (Ref. 1):

20 g of macrocyclic polybutylene terephthalate (PBT) with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.) is melted under nitrogen and stirring at 160 ⁰ C. The melt is placed in a tempered to 195 ⁰ C metal mold and polymerized there for 30 minutes with exclusion of air. This gives a plate of dimension 2 ^* 40 ^* 120 mm, from which test rods are milled for subsequent mechanical measurements.

Comparative Examples 2 to 4 (ref 2, ref 3, ref 4):

19.0 g of macrocyclic polybutylene terephthalate (PBT) with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.) and 1.0 g of liquid epoxy resin (Araldite® GY 250, manufacturer Huntsman) are melted under nitrogen and stirring at 160 ⁰ C. The melt is placed in a tempered to 195 ⁰ C metal mold and polymerized there for 30 minutes with exclusion of air. This gives a plate of dimension 2 ^* 40 ^* 120 mm, from which test rods are milled for subsequent mechanical measurements (Ref.2).

In an analogous manner, the experiments for Ref.3 with 1.0 g of Araldite® MY 790 (distilled, pure bisphenol A diglycidyl ether, manufacturer Huntsman) and Ref.4 with 1.0 g of Araldite® CY 179 (3,4-epoxycyclohexyl-3 4-epoxycyclohexylcarboxylate, manufactured by Huntsman).

Comparative Example 5 (ref. 5): 19.6 g of macrocyclic polybutylene terephthalate (PBT) containing 1% of a

Titanate (PBT XB3 Cyclics Corp.) is melted under nitrogen and stirring at 175 ⁰ C and treated with 0.4 g Tixogel® VZ (cation-exchanged bentonite, manufacturer Südchemie) were added. The resulting solution is added to the polymerization in a heated to 195 ⁰ C metal mold and polymerized there for 30 minutes with exclusion of air. This gives a plate of dimension 2 ^* 40 ^* 120 mm, from which test rods are milled for subsequent mechanical measurements. Veraleich example 6 (Ref 6):

Comparative Example 6 (Ref. 6) is the same as Comparative Example 5 (Ref. 5) except that a double content of Tixogel® VZ was used, i. 0.8 g on 19.2 g PBT. However, I showed here that such a high concentration of cation-exchanged layered mineral could no longer be taken up homogeneously. Therefore, no mechanical values were determined.

Example 1 (1): 20 g of SBM AF-X M22 (triblock copolymer of styrene, butadiene,

Methyl methacrylate in the ratio 1: 1: 1, molecular weight 20'000 Dalton, manufacturer Arkema) ("SBM") are 80 g of technical bisphenol A diglycidyl ether (Araldite® GY 250, Huntsman) under nitrogen and stirring at 205 ⁰ C. After cooling to room temperature, a clear high-viscosity solution (AC) is obtained.

19.0 g of macrocyclic polybutylene terephthalate (PBT) with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.) are melted under nitrogen and stirring at 175 ⁰ C in an oil bath and treated with 1 g of the solution of SBM in liquid resin (AC). The resulting solution is added to the polymerization in a heated to 195 ° C metal mold and polymerized there for 30 minutes with exclusion of air. This gives a plate of dimension 2 ^* 40 ^* 120 mm, from which test rods are milled for subsequent mechanical measurements.

Example 2 (2): A reactive liquid rubber ("RLR") was prepared as follows:

200 g of PolyTHF® 2000 (OH number 57.5 mg / g KOH) were dried under vacuum at 100 ° C. for 30 minutes. Subsequently, 47.5 g of IPDI and 0.04 g of dibutyltin dilaurate were added. The reaction was conducted at 9O ⁰ h under vacuum C until a constant NCO content at 3:58%, after 2.5 (theoretical NCO content: 3.70%). Subsequently, 18.0 g of technical grade trimethylolpropane glycidyl ether (Araldite® DY-T, manufacturer Huntsman, OH content 1.85 equivalent / kg) were added. It was further stirred at 90 ° C. under reduced pressure until the NCO content remained below 0.1% after a further 3 h. sunken was. Thus, a clear product was obtained with an epoxide content of 2.50 eq / kg

25 g of the resulting reactive liquid rubber (RLR1) are diluted with 75 g of technical bisphenol A diglycidyl ether (Araldite® GY 250, Huntsman).

19.0 g of macrocyclic polybutylene terephthalate (PBT) with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.) are melted under nitrogen and stirring at 175 ⁰ C in an oil bath and treated with 1 g of the solution of RLR1 in liquid resin (AC). The resulting solution is added to the polymerization in a heated to 195 ° C metal mold and polymerized there for 30 minutes with exclusion of air.

Example 3 (3):

50 g of the reactive liquid rubber (RLR1) described in Example 2 are diluted with 50 g of technical bisphenol A diglycidyl ether (Araldite® GY 250, Huntsman). 19.0 g of macrocyclic polybutylene terephthalate (PBT) with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.) are melted under nitrogen and stirring at 175 ⁰ C in an oil bath and treated with 1 g of the solution RLR1 in liquid resin (AC). The resulting solution is added to the polymerization in a heated to 195 ° C metal mold and polymerized there for 30 minutes with exclusion of air.

Example 4 (4):

30 g (montmorillonite-exchanged cation, manufacturer Southern Clay Products) Cloisite® 93A are stirred at 90 ⁰ C with 70 g of technical-grade bisphenol A diglycidyl ether (Araldite GY 250, Huntsman). After one hour, a clear viscous mass is obtained.

19.0 g macrocyclic polybutylene terephthalate (PBT) with 1% of a titanate catalyst (PBT XB3 Cyclics Corp.) were melted under nitrogen and stirring at 160 ⁰ C in an oil bath and treated with 1 g of the swollen layered silicate in liquid resin (AC) was added. The resulting solution is added to the polymerization in a heated to 195 ° C metal mold and polymerized there for 30 minutes with exclusion of air. Example 5 (5):

A reactive liquid rubber ("RLR") was prepared as follows:

From 48.19 g (217 mmol) of isophorone diisocyanate (IPDI) and 200 g

(10 mmol) α, ω-dihydroxy-polybutylene oxide (PolyTHF® 2000, manufacturer BASF) is an isocyanate-terminated prepolymer with 25 mg of dibutyltin dilaurate as

Catalyst prepared at 90 ⁰ C. Thereafter, 1.1 g of monohydroxy-terminated poly (dimethylsiloxane) (Silaplan FM 041, molecular weight

1000 Dalton, manufacturer Itochu) and 109 g of a technical trimethylolpropane glycidyl ether (Araldite® DY-T, manufacturer Huntsman, OH content 1.85 equivalent / kg) are added after 60 minutes, the isocyanate concentration is less than 0.1% The resulting reactive liquid rubber (RLR2 ) is diluted with 100 g of liquid epoxy resin (Araldite® GY 250, manufacturer Huntsman).

150 g of this diluted with liquid epoxy reactive liquid rubber is at 90 ⁰ C with 50 g of Cloisite® 3OB (cation-exchanged montmorillonite, manufacturer Southern Clay Products) was added and swollen to a clear viscous paste. (AC)

19.0 g macrocyclic polybutylene terephthalate (PBT) with 1% of a titanate catalyst (PBT XB3 Cyclics Corp.) were melted under nitrogen and stirring at 175 ⁰ C in the oil bath, and with 1 of the RZ-fl above-described g ^ / NanocIay / liquid resin premix ( AC). The resulting solution is added to the polymerization in a heated to 195 ° C metal mold and polymerized there for 30 minutes with exclusion of air. This gives a plate of dimension 2 ^* 40 ^* 120 mm, from which test rods are milled for subsequent mechanical measurements.

Example 6 (6):

From 48.19 g (217 mmol) of isophorone diisocyanate (IPDI) and 200 g (l OOmmol) α, ω-dihydroxy-polybutylene oxide (PolyTHF® 2000, manufacturer BASF) is an isocyanate-terminated prepolymer with 25 mg of dibutyltin dilaurate as catalyst at 90 ⁰ C produced.

4.1 g (22.2 mmol) of n-dodecylamine and then 109 g of a technical trimethylolpropane glycidyl ether are then added, with stirring first (Araldite® DY-T, manufacturer Huntsman, OH content 1.85 equivalent / kg). After 60 minutes, the isocyanate concentration is less than 0.1%.

40 g of the thus obtained reactive liquid rubber (RLR3) are diluted with 40 g of technical Bisphenol A diglycidyl ether (Araldite GY 250, Huntsman) and heated with stirring to 90 ⁰ C. Then be

20 g of Cloisite® 93A (cation-exchanged montmorillonite, manufacturer Southern

Clay Products) and swollen to a clear viscous paste. (AC)

19.0 g macrocyclic polybutylene terephthalate (PBT) with 1% of a titanate catalyst (PBT XB3 Cyclics Corp.) were melted under nitrogen and stirring at 175 ⁰ C in the oil bath, and with 1 of the RZ-RS described above / NanocIay / g liquid resin premix (AC ). The resulting solution is added to the polymerization in a heated to 195 ° C metal mold and polymerized there for 30 minutes with exclusion of air.

Example 7 (7):

20 g RLR3 (as described in Example 6) diluted with 60 g of technical Bisphenol A diglycidyl ether (Araldite GY 250, Huntsman) and heated with stirring to 90 ⁰ C. Then, 20 grams of Cloisite® 93A (cation-exchanged montmorillonite, manufactured by Southern Clay Products) are added and swollen to a clear, viscous paste. (AC)

19.0 g macrocyclic polybutylene terephthalate (PBT) with 1% of a titanate catalyst (PBT XB3 Cyclics Corp.) were melted under nitrogen and stirring at 175 ⁰ C in an oil bath and treated with 1 of FTZ-ftS described above / NanocIay / g liquid resin premix (AC ). The resulting solution is added to the polymerization in a heated to 195 ⁰ C metal mold and polymerized there for 30 minutes with exclusion of air.

Comparative Example 7 (Ref. 7):

Comparative Example 7 (Ref.7) is the same as Example 1 (1), except that instead of Araldite® GY 250 an identical amount of Araldite® CY 179

(3,4-epoxycyclohexyl-3,4 epoxycyclohexylcarboxylate, manufacturer Huntsman) was used. The specimens prepared in this way were such brittle, that they shattered during milling and could not be measured.

Table 1: Composition of Examples.

^* based on the weight of the composition Test Methods

Flexural strength, flexural strain and flexural modulus were measured according to DIN EN ISO 178 rel (Determination of flexural properties) on an Instron testing machine Type 1 185-5500R with 2mm / min at 23 ⁰ C, 50%. Humidity measured.

Table 2: Mechanical properties of the examples. ^** nm = not measurable

Table 2 shows that technical grade epoxy liquid resin formulations (Araldite® GY 250) containing hydroxy-functional oligomers (s> 0 in formula (I)) exhibit better mechanical properties than those with hydroxyl-free bisphenol A diglycidyl ether (Araldite® MY 790) {Ref. 2 and Ref. 3). Furthermore, Table 2 shows that Araldite® GY 250 and Araldite® MY 790 compounds having two glycidyl ether groups have a marked improvement in mechanical properties as compared to Araldite® CY 179 (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Ref leads. Furthermore, the results of the compositions according to the invention show massively higher values in the mechanical properties. It is also noticeable that the compositions according to the invention have at the same time higher flexural strengths and bending elongations than the comparative examples.

Higher levels of tougheners than in the comparative examples can be realized in the compositions according to the invention. Thus, in Ref. 6, no homogeneously mixed compositions having a toughener content of 4% by weight are unavailable, while at 5 this is easily possible even with an even higher content.

Finally, it was found that the examples according to the invention have better toughness properties than the comparative examples.

Claims

claims

A composition comprising at least one compound A which has at least two glycidyl ether groups;

and a linear or branched polyester B which, in the presence of an organo-tin or an organotitanium catalyst, consists of a macrocyclic poly (α, ω-alkylene terephthalate) or of a macrocyclic poly (α, ω-alkylene terephthalate). 2,6-naphthalenedicarboxylate);

and at least one toughener C.

2. A composition according to claim 1, characterized in that the compound A, which has at least two glycidyl ether groups, is a diglycidyl ether of a bisphenol A or a bisphenol F or a bisphenol A / bisphenol F mixture or a liquid oligomer thereof is.

3. A composition according to claim 1 or 2, characterized in that the linear or branched polyester B is a linear polyester B.

4. A composition according to claim 3, characterized in that the polyester B has the structural formula (II)

with n = 1, 2, 3, 4, in particular n = 1 or 3, preferably n = 3; and with m = 50-2000, in particular 50-800, preferably 50-600, particularly preferably 100-600.

5. A composition according to claim 3, characterized in that the polyester B has the structural formula (III)

with n '= 1, 2, 3, 4, in particular n' = 1 or 3, preferably n '= 3; and with nϊ = 50-200, in particular 50-800, preferably 50-600, particularly preferred 100-600.

6. A composition according to any one of claims 1 to 5, characterized in that the macrocyclic poly (α, ω-alkylene terephthalate) or the macrocyclic poly (α, ω-alkylene-2,6-naphthalene dicarboxylate) has the structure of the formula (IV ) having

with R = ethylene, propylene, butylene, pentylene, especially ethylene or butylene, preferably butylene;

the dashed lines indicate the connections with R; and with p selected such that the molecular weight M _n of the macrocyclic poly (α, ω-alkylene terephthalate) or of the macrocyclic poly (α, ω-alkylene-2,6-naphthalene dicarboxylate) is between 300 and 2000 g / mol, in particular between 350 to 800 g / mol.

7. Composition according to one of the preceding claims, characterized in that the toughener C

is an ion-exchanged layer mineral C1;

or a reactive liquid rubber C2;

or a block copolymer C3 obtained from a radical polymerization of methacrylic acid ester having at least one other olefinic double bond

Monomers.

8. A composition according to claim 7, characterized in that the toughener C is an ion-exchanged layer mineral C1.

9. A composition according to claim 7, characterized in that in the composition as toughener C in addition to an ion-exchanged layered mineral C1 additionally either a reactive liquid rubber C2 or a block copolymer C3 is present.

10. A composition according to any one of claims 7 to 9, characterized in that the ion-exchanged layered mineral C1 is a cation-exchanged layered mineral C1c, which is obtained from a layered mineral CV, in which at least part of the cations have been replaced by organic cations ,

1 1. A composition according to any one of claims 7 to 10, characterized in that the layer mineral CV is a layered silicate.

12. A composition according to claim 11, characterized in that the layer mineral CV is a kaolinite, a montmorillonite, a hectorite or an illite.

13. A composition according to any one of claims 7 to 9, characterized in that ion-exchanged layer mineral C1 is an anion-exchanged layer mineral C1a, which is obtained from a layer mineral C1 ", in which at least part of the anions have been replaced by organic anions ,

14. The composition according to claim 13, characterized in that the layer mineral C1 "is a hydrotalcite.

15. A composition according to any one of claims 7 to 14, characterized in that the organic cations have the formulas (V), (VI), (VII), (VIII) or (IX)

ΓΛ

R ⁷ N ⁺ -R ¹ (IX)

^ J with X = N, O, P or S;

R ¹ , R ¹ , R ¹ and R ¹ independently of one another = H, C ₁ -C 20 -alkyl, substituted or unsubstituted aryl;

R ² = H, C ₁ -C 20 -alkyl, substituted or unsubstituted aryl;

R ³ = H, C "iC ₂ o-alkyl, substituted or unsubstituted aryl or N (R ² ) ₂ ; R ⁴ = H, C ₁ -C 20 -alkyl, substituted or unsubstituted aryl or N (R ² ) ₂ ; R ⁵ = substituent which together with the N ⁺ shown in formula (V) forms an optionally substituted ring of 4 to 9 atoms and optionally has double bonds; R ⁶ = substituent which together with that shown in formula (VIII)

N ⁺ forms an optionally substituted bicyclic ring of 6 to 12 atoms and optionally containing further heteroatoms or cations of heteroatoms;

R ⁷ = substituent which together with the N ⁺ shown in formula (IX) represents an optionally substituted heteroaromatic ring of

Ring size of 5 to 7 atoms forms.

16. A composition according to any one of claims 7 to 15, characterized in that the reactive liquid rubber C2 is a glycidyl ether-terminated polyurethane prepolymer.

17. A composition according to claim 16, characterized in that the reactive liquid rubber C2 has the formula (X)

wherein Yi is a q-valent radical of an isocyanate-terminated linear or branched polyurethane prepolymer after removal of the terminal isocyanate groups;

Y ₂ for a remainder of a primary or secondary

Hydroxyl group-containing aliphatic, cycloaliphatic, aromatic or araliphatic epoxide after removal of the hydroxide and epoxide groups; q = 2, 3 or 4; and r = 1, 2 or 3.

18. A composition according to any one of claims 7 to 17, characterized in that the at least one additional olefinically double bond-containing monomer used for the preparation of the block copolymer C3 is selected from the group comprising styrene, butadiene, acrylonitrile and vinyl acetate.

19. A composition according to claim 18, characterized in that the block copolymer C3 is a block copolymer of methyl methacrylate, styrene and butadiene.

20. A composition according to any one of the preceding claims, characterized in that the amount toughener C is 10 to 85 wt .-% based on the sum of the weight of A + C.

21. A composition according to any one of the preceding claims, characterized in that the amount of linear or branched polyester B 85-98 wt .-% of the composition.

22. A process for the preparation of a composition according to any one of claims 1 to 21, characterized in that it comprises the steps

Formation of a premix AC of toughener C and of compound A which has at least two glycidyl ether groups,

Addition of the mixing premix AC to the macrocyclic poly (α, ω-alkylene terephthalate) or macrocyclic poly (α, ω-alkylene)

2,6-naphthalene dicarboxylate) mixed with the organo-tin or organo-titanium catalyst.

23. The method according to claim 22, characterized in that the preparation of the linear or branched polyester B in a

Temperature of 16O ⁰ C to 220 ° in particular between 16O ⁰ C to 200 ° C in the presence of the premix AC occurs.

24. Use of a premix AC of toughener C and the compound A, which has at least two glycidyl ether groups in the preparation of the one linear or branched polyester B, as described in claims 1 to 21.

25. A composite comprising a composition according to any one of claims 1 to 21 and fibers, wherein the fibers are selected from the group comprising glass fibers, metal fibers, carbon fibers, aramid fibers, mineral fibers, vegetable fibers and mixtures thereof.

26. A composite according to claim 25, characterized in that the fibers are carbon fibers or metal fibers, in particular steel fibers.

27. A composite according to claim 25 or 26, characterized in that the proportion of fibers is 30 to 65 vol%, based on the volume of the composite body.

28. A composite according to any one of claims 25 to 27, characterized in that the composite body has a lamellenfömige shape.

29. A method for producing a composite body according to any one of claims 25 to 28, characterized in that the composition is in a molten state, is contacted with the fibers and in a mold by cooling to

Solidification is brought.

30. The method according to claim 29, characterized in that the mold has an outlet through which the composite body is discharged continuously during cooling.

31. Use of a composite body according to any one of claims 25 to 28 or a composite body, which was prepared by a process according to claim 29 or 30, for the structural reinforcement of a building or a means of transport.