EP3538585A1

EP3538585A1 - Composite materials based on dual-curing isocyanurate polymers

Info

Publication number: EP3538585A1
Application number: EP17801426.2A
Authority: EP
Inventors: Paul Heinz; Richard MEISENHEIMER; Alisa KAYSER; Jörg TILLACK; Dirk Achten; Thomas Buesgen; Michael Ludewig; Christoph TOMCZYK; Roland Wagner
Original assignee: Covestro Deutschland AG
Current assignee: Covestro Deutschland AG
Priority date: 2016-11-14
Filing date: 2017-11-14
Publication date: 2019-09-18
Also published as: US20190367666A1; JP2019535554A; KR102388093B1; KR20190086447A; CN114874411A; US11613072B2; WO2018087395A1; CN109963890A; WO2018087382A1; US20190337224A1; CN109923143A; US10449714B2; EP3538584B1; CN109923142A; EP3538584A1; EP3538586A1; US20180133953A1; EP3538583A1; WO2018087396A1; JP7216644B2

Abstract

The present invention relates to polymerizable compositions which contain components that can be crosslinked both via isocyanurate bonds and by a radical reaction mechanism. The invention further relates to methods by way of which polymers can be produced from said compositions.

Description

Composite materials based on Isocvanuratpolvmeren dual cure

The present invention relates to polymerizable compositions containing components that can be crosslinked by isocyanurate bonds as well as by a free-radical reaction mechanism. It further relates to methods by which polymers can be made from these compositions.

WO 2015/155195 describes a composite material obtainable from a reinforcing material and a polyurethane composition consisting of at least one polyisocyanate (PIC), a PIC-reactive component consisting of at least one polyol and at least one methacrylate having OH groups, and a radical initiator. The addition reaction between PIC and OH groups occurs simultaneously with the free-radical initiated chain polymerization of the methacrylates. A disadvantage of the method used in addition to the short pot / gel times of the polyurethane compositions, the fact that in the production of polyurethanes, the mixing ratio of the components, in particular of the polyisocyanate and the polyol is limited by the need, the molar ratio of isocyanate and Keep isocyanate-reactive groups close to 1: 1.

WO 2016/087366 describes a free-radically polymerizable composition consisting of a polyurethane which contains double bonds and a reactive diluent based on various methacrylates.

The disadvantage here is the two-stage reaction procedure, since first a polyurethane starting from an isocyanate-containing component and a polyol prepared, and must be greatly diluted. Subsequent crosslinking takes place exclusively via a free radical polymerization in a separate step.

WO 2016/170057, WO 2016/170059 and WO 2016/170061 describe the preparation of polyisocyanurate plastics by polyaddition of oligomeric isocyanates. The use of oligomeric isocyanates instead of monomeric isocyanates results in less heat of reaction being produced during the polymerization and thus rapid polymerization is possible without the reaction mixture overheating. This is particularly important in the production of moldings, since here the heat generated in the interior of the molded body can be dissipated only limited over the surface.

The monomer-poor polyisocyanate compositions described in these applications as starting materials have the disadvantage of a high, relatively high viscosity, which may be a hindrance in some applications. This is especially true for the production of highly filled composites. The addition of monomeric polyisocyanates as reactive diluents is undesirable because of the above-described problem of heat of reaction. In addition, monomeric polyisocyanates are highly volatile and therefore should not be used for reasons of occupational safety. Alternatively, conventional organic solvents can be used to reduce the viscosity. However, these are disadvantageous for reasons of environmental protection, since they are released during or after the polymerization in the ambient air. In addition, the use of solvents in the production of moldings can lead to material defects, for example to the formation of voids, since the volume of the evaporating solvent is missing in the material.

The present invention was initially based on the object of providing a reaction system with a dual curing mechanism in which the mixing ratio of the reactants can be set in a significantly wider range than in the known polyurethane systems.

Furthermore, it has been desired to find a reaction system for the production of polyisocyanurate plastics in which the viscosity of the polyisocyanate can be lowered even without the use of high levels of monomeric polyisocyanates or organic solvents. Ideally, such additives should be completely dispensable.

These objects are achieved by the embodiments of the invention disclosed in the claims and in the description below.

In a first embodiment, the present invention relates to a polymerizable composition for producing a composite comprising a) a reactive resin having a ratio of isocyanate groups to isocyanate-reactive groups of at least 2.0 to 1.0 containing the components a) an isocyanate component A;

a2) at least one trimerization catalyst C; and

a3) at least one component selected from the group consisting of components B, D and E, wherein component B has at least one ethylenic double bond but no isocyanate-reactive group;

component D in a molecule has at least one isocyanate-reactive group and at least one ethylenic double bond; and

the component E in a molecule has both at least one isocyanate group and at least one ethylenic double bond; and b) at least one filler J.

A "reactive resin" is a mixture which can be cured by a combination of free-radical polymerization and crosslinking of the isocyanate groups of the isocyanate component with one another to form a solid material.The term "reaction mixture" is also used synonymously below. The reactive resin serves as a matrix material in which the filler J is embedded. The components A to I defined below are obligatory or optional components of the reactive resin.

The isocyanate component A allows the formation of a polymer formed by the addition of isocyanate groups. In particular, isocyanurate groups are formed. The crosslinking of the isocyanate groups contained in the isocyanate component A gives the polymer the majority of its mechanical and chemical stability. The crosslinking of the isocyanate groups is mediated by the trimerization catalyst C.

Components B, D and E are each characterized by the presence of an ethylenic double bond. This double bond is prerequisite for the fact that a second crosslinking mechanism is available in addition to the polyaddition of the isocyanate groups in the polymerizable composition. Here, the use of individual ones of these components or certain combinations of components has specific advantages:

Component B decreases the viscosity of the polymerizable composition. It can thus advantageously serve as a reactive diluent, i. it becomes part of the polymer after completion of the polymerization process. It can also serve the rapid build-up of viscosity, if initially, preferably by ionizing radiation, a radical polymerization of the ethylenic double bonds is initiated and only after the crosslinking of the isocyanate groups is performed.

If only one component B without components D or E is present in the polymerizable composition, two different polymer networks are formed by the two different crosslinking mechanisms. This can lead to turbidity in the finished product and possibly to poorer mechanical properties.

If this is to be avoided, the component B is used in combination with a component D or E. It can also be used in combination with both components. Components D and E mediate cross-linking of the radical B-forming network of component B with the polyaddition of the isocyanate-forming polymer of isocyanate component A. They thus ensure that no two separate polymer networks of components A and B, but a uniform polymer network.

In the absence of a component B, components D and F allow the construction of a polymer network by radical polymerization. In this way, the complete curing of the polymerizable composition according to the invention can take place separately in time in two different process steps. For example, in the polymerizable composition, first, the free-radical crosslinking of the viscosity which initially imparts a certain degree of dimensional stability to the resulting product in components D and E, but without further processing, e.g. by bending pressing or embossing impossible. Only subsequent cross-linking of the isocyanate groups with one another leads to complete curing, which gives the product its final stability. This results in a uniform polymer network, since the components B and D always react with the isocyanate groups of the isocyanate component A.

In a preferred embodiment of the present invention, the polymerizable composition contains at least one of the two components D and E, but no component B.

In another preferred embodiment, the composition according to the invention contains a component B and at least one of the two components D and E. Particularly preferred is the combination of B and D.

In a preferred embodiment, the polymerizable composition of the present invention preferably contains the isocyanate component A and component B in an amount that has the viscosity of the undiluted isocyanate component of at most 75%, more preferably at most 50%, even more preferably at most 33% of the viscosity of an undiluted isocyanate component A. lowers. The presence of at least one component D or E in this embodiment is preferred, but not mandatory.

In a preferred embodiment, the proportion of component A to the total amount of components B, D and E is such that the polymerizable composition has a viscosity of at most 100,000 mPas, more preferably at most 10,000 mPas, even more preferably at most 5,000 mPas and most preferably at most 2,000 mPas.

In a preferred embodiment, the proportion of component A to the total amount of components B, D and E is such that the polymerizable composition has a viscosity of at most 100,000 mPas, more preferably of highest 10,000 mPas, even more preferably at most 5,000 mPas, and most preferably at most 2,000 mPas.

The above conditions are particularly satisfied when the mass ratio of components A and B is in the range of 95 to 5 to 30 to 70, preferably 95 to 5 to 50 to 50, and more preferably 92.5 to 7.5 to 70 to 30.

The molar ratio of isocyanate groups and ethylenic double bonds is preferably in a range of 1 to 10 to 10 to 1, more preferably 1 to 5 to 8 to 1, and even more preferably 1 to 3 to 5 to 1). The molecular ratio of these functional groups can be determined by integrating the signals of a sample in the ¹³ C-NM spectrum.

The polymer obtainable by polymerization of the reactive resin according to the invention obtains its advantageous properties quite substantially by crosslinking the isocyanate groups with one another. Therefore, it is essential to the invention that the ratio of isocyanate groups to the total amount of isocyanate-reactive in the reactive resin is limited so that a clear molar excess of isocyanate groups is present. The molar ratio of isocyanate groups of the isocyanate component to isocyanate-reactive groups in the reactive resin is therefore at least 2.0 to 1.0, preferably at least 3.0 to 1.0, more preferably at least 4.0 to 1.0, and even more preferably at least 8.0 to 1.0. "For the purposes of the present application," isocyanate-reactive groups "are hydroxyl, thiol, carboxyl and amino groups, amides, urethanes, acid anhydrides and epoxides contained in the polymerizable composition Isocyanate groups are present in components A and, when present, E. The isocyanate-reactive groups may in principle be present in all other components except component B.

In comparison with the polyurethane resins known from WO 2015/155195 with additional radiation curing, the use of the reactive resin according to the invention allows greater flexibility in the selection of the proportions of the individual components. When a polyurethane or a polyurea is to be obtained, the molar ratio of isocyanate groups to isocyanate-reactive groups must be close to 1: 1 as far as possible. However, according to the present invention, there is a significant excess of isocyanate groups, which is therefore not only acceptable, but even desirable, because the resulting polymer owes its advantageous properties quite substantially to the reaction of isocyanate groups with other isocyanate groups. The resulting structures, in particular the isocyanurate groups, lead to polymers with particular hardness and particular resistance to chemicals. Also, isocyanurate groups already intrinsically flame-retardant, so that can be omitted for many applications of the otherwise necessary addition of flame retardants. Isocyanate component A

For the purposes of the invention, "isocyanate component A" refers to the isocyanate component in the reactive resin. In other words, it is the sum of all compounds in the reactive resin which have isocyanate groups with the exception of component E. The isocyanate component A is therefore used as educt If "isocyanate component A" is used here, in particular "preparation of isocyanate component A", then this means that isocyanate component A exists and is used as starting material The isocyanate component A preferably contains at least one polyisocyanate.

The term "polyisocyanate" as used herein is a collective term for compounds containing in the molecule two or more isocyanate groups (which is understood by those skilled in the art to include free isocyanate groups of general structure -N = C = O) These polyisocyanates are the diisocyanates which have the general structure O = C = NRN = C = O, where R usually stands for aliphatic, alicyclic and / or aromatic radicals.

Because of the multiple functionality (> 2 isocyanate groups), a multitude of polymers (eg polyurethanes, polyureas and polyisocyanurates) and low molecular weight compounds (eg those with uretdione, isocyanurate, allophanate, biuret, Iminooxadiazinedione and / or oxadiazinetrione structure).

In this application, the term "polyisocyanates" refers to monomeric and / or oligomeric polyisocyanates alike, but to understand many aspects of the invention it is important to distinguish between monomeric diisocyanates and oligomeric polyisocyanates. "Oligomeric polyisocyanates" are referred to in this application. then it means polyisocyanates which are composed of at least two monomeric diisocyanate molecules, ie they are compounds which are or contain a reaction product of at least two monomeric diisocyanate molecules.

The preparation of oligomeric polyisocyanates from monomeric diisocyanates is also referred to herein as modifying monomeric diisocyanates. This "modification" as used herein means the reaction of monomeric diisocyanates to oligomeric polyisocyanates having uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure.

For example, hexamethylene diisocyanate (HDI) is a "monomeric diisocyanate" because it contains two isocyanate groups and is not a reaction product of at least two polyisocyanate molecules:

HDI

Reaction products of at least two HDI molecules, which still have at least two isocyanate groups, are in contrast "oligomeric polyisocyanates" in the meaning of the invention .Parents of such "oligomeric polyisocyanates" are starting from the monomeric HDI, e.g. the HDI isocyanurate and the HDI biuret, each composed of three monomeric HDI building blocks:

(CH ₂ ) ₆ -NCO

(CH ₂ ) ₆ NCO

I I H l

OCN- (H ₂ C) ₆ "^ C" ^ (CH ₂ ) ₆ -NCO ΟΟΝ (ΟΗ ₂ ) ₆ ^{/ Ν} γ ΟΗ ₂ ) ₆ ΝΟΟ

O O

HDI isocyanurate HDI biuret (idealized structural formulas)

According to the invention, the weight fraction of isocyanate groups based on the total amount of isocyanate component A is at least 15% by weight.

In principle, monomeric and oligomeric polyisocyanates are equally suitable for use in the isocyanate component A according to the invention. Thus, the isocyanate component A may consist essentially of monomeric polyisocyanates or substantially of oligomeric polyisocyanates. But it can also contain oligomeric and monomeric polyisocyanates in any mixing ratios.

In a preferred embodiment of the invention, the isocyanate component A used as starting material in the trimerization is low in monomer (i.e., low in monomeric diisocyanates) and already contains oligomeric polyisocyanates. The terms "low in monomer" and "low in monomeric diisocyanates" are used interchangeably herein with respect to isocyanate component A.

Particularly practical results are obtained when the isocyanate component A is a proportion of monomeric diisocyanates in the isocyanate component A of at most 20 wt .-%, in particular at most 15 wt .-% or at most 10 wt .-%, each based on the weight of the isocyanate component A, has. The isocyanate component A preferably has a content monomeric diisocyanates of at most 5 wt .-%, preferably at most 2.0 wt .-%, particularly preferably at most 1.0 wt .-%, each based on the weight of the isocyanate component A, on. Particularly good results are obtained when the isocyanate component A is substantially free of monomeric diisocyanates. Substantially free means that the content of monomeric diisocyanates is at most 0.5% by weight, based on the weight of the isocyanate component A.

According to a particularly preferred embodiment of the invention, the isocyanate component A is completely or at least 80, 85, 90, 95, 98, 99 or 99.5 wt .-%, each based on the weight of the isocyanate component A, of oligomeric polyisocyanates. Here, a content of oligomeric polyisocyanates of at least 99 wt .-% is preferred. This content of oligomeric polyisocyanates refers to the isocyanate component A as provided. That the oligomeric polyisocyanates are not formed during the process according to the invention as an intermediate, but are already present at the beginning of the reaction in the isocyanate component used as starting material A.

Polyisocyanate compositions which are low in monomer or substantially free of monomeric isocyanates can be obtained by carrying out, after the actual modification reaction, in each case at least one further process step for separating off the unreacted excess monomeric diisocyanates. This monomer removal can be carried out in a particularly practical manner by processes known per se, preferably by thin-layer distillation under high vacuum or by extraction with suitable isocyanate-inert solvents, for example aliphatic or cycloaliphatic hydrocarbons, such as pentane, hexane, heptane, cyclopentane or cyclohexane.

According to a preferred embodiment of the invention, the novel isocyanate component A is obtained by modifying monomeric diisocyanates with subsequent removal of unreacted monomers.

According to a particular embodiment of the invention, however, a low-monomer isocyanate component A contains a monomeric foreign diisocyanate. Here, "monomeric foreign diisocyanate" means that it differs from the monomeric diisocyanates used to prepare the oligomeric polyisocyanates contained in the isocyanate component A.

An addition of monomeric foreign diisocyanate may be advantageous for achieving special technical effects, such as a particular hardness. Particularly practical results are obtained when the isocyanate component A is a proportion of monomeric foreign diisocyanate in the isocyanate component A of at most 20 wt .-%, in particular at most 15 wt .-% or at most 10 wt .-%, each based on the weight of the isocyanate component A, has. The isocyanate component A preferably has a monomeric foreign diisocyanate content of at most 5% by weight, preferably at most 2.0% by weight, particularly preferably at most 1.0% by weight, based in each case on the weight of the isocyanate component A.

According to a further particular embodiment of the process according to the invention, the isocyanate component A comprises monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two, i. with more than two isocyanate groups per molecule. The addition of monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two has been found to be advantageous for affecting the network density of the coating. Particularly practical results are obtained when the isocyanate component A is a proportion of monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two in the isocyanate component A of at most 20 wt .-%, in particular at most 15 wt .-% or at most 10 wt .-% , in each case based on the weight of the isocyanate component A. Preferably, the isocyanate component A has a content of monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two of at most 5 wt .-%, preferably at most 2.0 wt .-%, particularly preferably at most 1.0 wt .-%, each based on the weight of the isocyanate component A, on. Preferably, in the trimerization reaction according to the invention, no monomeric monoisocyanate or monomeric isocyanate with an isocyanate functionality greater than two is used.

According to the invention, the oligomeric polyisocyanates may in particular have uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures. According to one embodiment of the invention, the oligomeric polyisocyanates have at least one of the following oligomeric structural types or mixtures thereof:

Uretdione isocyanurate allophanate biuret iminooxadiazinedione oxadiazinetrione

According to a preferred embodiment of the invention, an isocyanate component A is used whose Isocyanuratstrukturanteil

According to a preferred embodiment of the invention, an isocyanate component A is used whose isocyanurate structure content is at least 50 mol%, preferably at least 60 mol%. %, more preferably at least 70 mole%, even more preferably at least 80 mole%, even more preferably at least 90 mole% and most preferably at least 95 mole% based on the sum of the oligomeric structures of the group consisting of uretdione , Isocyanurat-, allophanate, biuret, Iminooxadiazindion- and Oxadiazintrionstruktur in the isocyanate component A, is.

According to a further preferred embodiment of the invention, in the process according to the invention, an isocyanate component A which, in addition to the isocyanurate structure, contains at least one further oligomeric polyisocyanate with uretdione, biuret, allophanate, iminooxadiazinedione and oxadiazinetrione structure and mixtures thereof.

The proportions of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure in the isocyanate component A can be e.g. be determined by NM spectroscopy. The 13C-NMR spectroscopy, preferably proton-decoupled, may preferably be used in this case since the stated oligomeric structures give characteristic signals.

Irrespective of the underlying oligomeric structure (uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure), an oligomeric isocyanate component A to be used in the process according to the invention and / or the oligomeric polyisocyanates contained therein preferably has an (average) NCO Functionality of from 2.0 to 5.0, preferably from 2.3 to 4.5.

Particularly practical results are obtained when the isocyanate component A to be used according to the invention has a content of isocyanate groups of 8.0 to 28.0% by weight, preferably from 14.0 to 25.0% by weight, in each case based on the weight of the Isocyanate component A, has.

Preparation processes for the oligomeric polyisocyanates with uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure to be used according to the invention in the isocyanate component A are described, for example, in J. Prakt. Chem. 336 (1994) 185-200, in DE-A 1 670 666, DE-A 1 954 093, DE-A 2 414 413, DE-A 2 452 532, DE-A 2 641 380, DE-A 3 700 209, DE-A 3 900 053 and DE-A 3 928 503 or in EP-A 0 336 205, EP A 0 339 396 and EP-A 0 798 299.

According to an additional or alternative embodiment of the invention, the isocyanate component A according to the invention is defined by containing oligomeric polyisocyanates consisting of monomeric diisocyanates, regardless of the type of modification reaction used, while maintaining a degree of oligomerization of 5 to 45%, preferably 10 to 40% preferably 15 to 30% were obtained. By "degree of oligomerization" is the percentage of isocyanate groups originally present in the starting mixture which is consumed during the manufacturing process to form uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures.

Suitable polyisocyanates for the preparation of the isocyanate component A to be used in the process according to the invention and the monomeric and / or oligomeric polyisocyanates contained therein are any, in various ways, for example by phosgenation in the liquid or gas phase or on a phosgene-free route, such. by thermal urethane cleavage, accessible polyisocyanates. Particularly good results are obtained when the polyisocyanates are monomeric diisocyanates. Preferred monomeric diisocyanates are those which have a molecular weight in the range of 140 to 400 g / mol, with aliphatic, cycloaliphatic, araliphatic and / or aromatically bonded isocyanate groups, such as. B. 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-l, 5-diisocyanatopentane, l, 5-diisocyanato-2,2-dimethylpentane , 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,4-diisocyanato-3,3, 5-trimethylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), isocyanato -l-methyl-4 (3) isocyanatomethylcyclohexane, 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12MDI), 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, bis (isocyanatomethyl) norbornane (NBDI), 4,4'-diisocyanato-3,3'-dimethyldicyclohexylmethane, 4,4'-diisocyanato-3,3 ', 5,5'-tetramethyl-dicyclohexylmethane, 4,4'-diisocyanato-1' -bi (cyclohexyl), 4,4'-diisocyanato-3,3'-dimethyl-1, 1'-bi (cyclohexyl), 4,4'-diisocyanato-2,2 ', 5,5'-tetra-methyl -l, l'bi (cyclohexyl), 1,8-diisocyanato-p-menthane, 1,3-diisocyanato-adam Antan, l, 3-dimethyl-5,7-diisocyanatoadamantane, 1,3- and 1'-bis-fiso-cyanatomethylJbenzol (xyxlylene diisocyanate; XDI), 1,3- and 1,4-bis (1-isocyanato-1-methyl ethyl) benzene (TMXDI) and bis (4- (1-isocyanato-1-methylethyl) phenyl) carbonate, 2,4 and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 1,5-diisocyanatonaphthalene and any mixtures of such diisocyanates. Other likewise suitable diisocyanates can be found, for example, in Justus Liebigs Annalen der Chemie, Volume 562 (1949) pp. 75-136.

Suitable monomeric monoisocyanates which can optionally be used in the isocyanate component A are, for example, n-butyl isocyanate, n-amyl isocyanate, n-hexyl isocyanate, n-heptyl isocyanate, n-octyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, cetyl isocyanate, stearyl isocyanate, cyclopentyl isocyanate, cyclohexyl isocyanate, 3- or 4-methylcyclohexyl isocyanate or any mixtures of such monoisocyanates. As a monomeric isocyanate having an isocyanate functionality greater than two, which may optionally be added to the isocyanate component A, is exemplified by 4-isocyanatomethyl-l, 8-octane diisocyanate (triisocyanatononane, TIN). According to one embodiment of the invention, the isocyanate component A contains at most 30% by weight, in particular at most 20% by weight, at most 15% by weight, at most 10% by weight, at most 5% by weight or at most 1% by weight. %, in each case based on the weight of the isocyanate component A, of aromatic polyisocyanates. As used herein, "aromatic polyisocyanate" means a polyisocyanate having at least one aromatic-bonded isocyanate group.

By aromatically bound isocyanate groups is meant isocyanate groups which are bonded to an aromatic hydrocarbon radical.

According to a preferred embodiment of the process according to the invention, an isocyanate component A is used which has exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups.

By aliphatic or cycloaliphatic bound isocyanate groups is meant isocyanate groups which are bonded to an aliphatic or cycloaliphatic hydrocarbon radical. According to another preferred embodiment of the process according to the invention, an isocyanate component A is used which consists of or contains one or more oligomeric polyisocyanates, the one or more oligomeric polyisocyanates having exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups.

According to a further embodiment of the invention, the isocyanate component A is at least 70, 80, 85, 90, 95, 98 or 99 wt .-%, each based on the weight of the isocyanate component A, of polyisocyanates exclusively aliphatic and / or cycloaliphatic bound Having isocyanate groups. Practical experiments have shown that particularly good results can be achieved with isocyanate components A in which the oligomeric polyisocyanates contained therein have exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups.

According to a particularly preferred embodiment of the method according to the invention, a polyisocyanate A composition is used which consists of or contains one or more oligomeric polyisocyanates, wherein the one or more oligomeric polyisocyanates based on 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), isophorone diisocyanate (IPDI) or 4,4'-diisocyanatodicyclohexylmethane (H 12MDI) or mixtures thereof.

According to a further embodiment of the invention, in the process according to the invention, isocyanate components A having a viscosity of greater than 500 mPas and less than 200,000 mPas, preferably greater than 1,000 mPas and less than 100,000 mPas, more preferably greater than 1,000 mPas and less than 50,000 mPas and even more preferably greater than 1,000 mPas and less than 25,000 mPas, measured in accordance with DIN EN ISO 3219 at 21 ° C.

Component B

As component B, all compounds are suitable which contain at least one ethylenic double bond. This ethylenic double bond is crosslinkable by a radical reaction mechanism with other ethylenic double bonds. This condition preferably fulfills activated double bonds located between the - and the β-carbon atom adjacent to an activating group. The activating group is preferably a carboxyl or carbonyl group. Most preferably, component B is an acrylate, a methacrylate, the ester of an acrylate or the esters of a methacrylate. Component B preferably contains no isocyanate-reactive groups as defined above in this application.

Preferred components B are components B1 with one, components B2 with two and components B3 with three of the ethylenic double bonds described above. Particularly preferred are Bl and / or B2.

In a preferred embodiment, component B used is a mixture of at least one component B1 and at least one component B2.

In a further preferred embodiment, a mixture of at least one component Bl and at least one component B3 is used as component B.

In still another preferred embodiment, component B is a mixture of at least one component B2 and at least one component B3.

In still another preferred embodiment, as component B, a mixture of at least one component Bl, at least component B2 and at least one component B3 is used. Preferably, a mixture of at least one component Bl with at least one component B2 is used. Here, the mass ratio of the components Bl and B2 is preferably between 30: 1 and 1: 30, more preferably between 20: 1 and 1:20, even more preferably between 1:10 and 10: 1, and most preferably between 2: 1 and 1: 2.

Preferred components Bl are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, iso-propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, iso-octyl (meth) acrylate, decyl (meth) acrylate, benzyl ( meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, octadecyl (meth) acrylate, dodecyl (meth) acrylate,

Tetradecyl (meth) acrylate, oleyl (meth) acrylate, 4-methylphenyl (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate, cetyl (meth) acrylate, 2-phenylethyl (meth) acrylate, isobornyl (meth) acrylate, neopentyl (meth) acrylate, methacrylamide and n-isopropylmethacrylamide.

Preferred components B2 are vinyl (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylates, 1,6-hexanediol di (meth) acrylate, neopentyl glycol propoxylate di (meth) acrylate, tripropylene glycol di (meth) acrylate, bisphenol A ethoxylated di (meth ) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate and 4,4'-bis (2- (meth) acryloyloxyethoxy) diphenylpropane ,

Preferred components B3 are ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane ethoxytri (meth (acrylate, trimethylolpropane tri (meth) acrylate, alkoxylated tria (meth) crylate and tris (2- (meth) acryloylethyl) isocyanurate.

Trimerization catalyst C

The trimerization catalyst C may be mixed from one or more types of catalyst but contains at least one catalyst which effects the trimerization of isocyanate groups to isocyanurates or iminooxadiazinediones.

Suitable catalysts for the process according to the invention are, for example, simple tertiary amines, such as e.g. Triethylamine, tributylamine, Ν, Ν-dimethylaniline, N ethylpiperidine or N, N'-dimethylpiperazine. Suitable catalysts are also the tertiary hydroxyalkylamines described in GB 2 221 465, e.g. Triethanolamine, N-methyldiethanolamine, dimethylethanolamine, N-isopropyldiethanolamine and 1- (2-hydroxyethyl) pyrrolidine, or those known from GB 2 222 161, from mixtures of tertiary bicyclic amines, e.g. DBU, with simple low molecular weight aliphatic alcohols existing catalyst systems.

Also suitable as trimerization catalysts for the process according to the invention is a multiplicity of different metal compounds. Suitable examples are described in DE-A 3,240,613 as catalysts octoates and naphthenates of manganese, iron, cobalt, nickel, copper, zinc, zirconium, cerium or lead or mixtures thereof with acetates of lithium, sodium, potassium, Calciu m or barium, the known from DE-A 3 219 608 sodium and potassium salts of linear or branched alkanecarboxylic acids having up to 10 carbon atoms, such as propionic, butyric, valeric, caproic, heptanoic, caprylic, pelargonic, capric and Undecylic acid, the known from EP-A 0 100 129 alkali or alkaline earth metal salts of aliphatic, cycloaliphatic or aromatic mono- and polycarboxylic acids having 2 to 20 C atoms, such as, for example, sodium or potassium benzoate, the alkali phenolates known from GB-PS 1 391 066 and British Patent 1 386 399, such as, for example, sodium or potassium phenolate, the alkali and alkaline earth oxides, hydroxides, carbonates, alcoholates and phenolates known from GB 809 809, alkali metal salts of enolisable compounds and metal salts of weak aliphatic or cycloaliphatic carboxylic acids, such as sodium methoxide, sodium acetate, potassium acetate, sodium acetoacetic ester, lead 2 ethylhexanoate and lead naphthenate, the basic alkali metal compounds known from EP-A 0 056 158 and EP-A 0 056 159 complexed with crown ethers or polyether alcohols, for example complexed sodium or potassium carboxylates, the pyrrolidinone known from EP-A 0 033 581 Potassium salt, the mono- or polynuclear complex compound of titanium, zirconium and / or hafnium known from the application EP 13196508.9 such as zirconium tetra-n-butylate, zirconium tetra-2-ethylhexanoate and zirconium tetra-2-ethylhexylate, as well as tin compounds of the type described in European Polymer Journal, Vol. 16, 147-148 (1979), such as dibutyltin dichloride, diphenyltin dichloride, triphenylstannanol, Tributyltin acetate, tributyltin oxide, tin dioctoate, dibutyl (dimethoxy) stannane and tributyltin imidazolate.

Further suitable trimerization catalysts for the process according to the invention are, for example, the quaternary ammonium hydroxides known from DE-A 1 667 309, EP-A 0 013 880 and EP-A 0 047 452, such as, for example, US Pat. tetraethylammonium,

Trimethylbenzylammonium hydroxide, N, N-dimethyl-N-dodecyl-N- (2-hydroxyethyl) ammonium hydroxide, N- (2-hydroxyethyl) -N, N-dimethylN- (2,2'-dihydroxymethylbutyl) -ammonium hydroxide and (2-hydroxyethyl) -l, 4-diazabicyclo [2.2.2] octane hydroxide (monoadduct of ethylene oxide and water on 1,4-diazabicyclo [2.2.2] octane) obtained from EP-A 37 65 or EP -A 10 589 known quaternary hydroxyalkylammonium hydroxides, such as N, N, N-trimethyl-N- (2-hydroxyethyl) -ammonium hydroxide, the trialkylhydroxyalkylammonium carboxylates known from DE-A 2631733, EP-A 0 671 426, EP-A 1 599 526 and US 4,789,705, such as e.g. N, N, N-trimethyl-N-2-hydroxypropylammonium p-tert-butylbenzoate and N, N, N-trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate, those known from EP-A 1 229 016 quaternary Benzylammonium carboxylates, such as N-benzyl-N, N-dimethyl-N-ethylammonium pivalate, N-benzyl-N, N-dimethyl-N-ethylammonium 2-ethylhexanoate, N-benzyl-N, N, N-tributylammonium 2-ethylhexanoate, N, N-dimethyl-N-ethyl-N- (4-methoxybenzyl) ammonium 2-ethylhexanoate or N, N, N-tributyl-N- (4-methoxybenzyl) ammonium pivalate, which are known from WO 2005/087828 tetrasubstituted ammonium a-hydroxycarboxylates, such as Tetramethylammonium lactate, the quaternary ammonium or phosphonium fluorides known from EP-A 0 339 396, EP-A 0 379 914 and EP-A 0 443 167, e.g. N-methyl-N, N, N-trialkylammonium fluorides with C 8 -C 10 -alkyl radicals, N, N, N, N-tetra-n-butylammonium fluoride, Ν, Ν, Ν-trimethyl-N-benzylammonium fluoride, tetramethyl phosphonium fluoride .

Tetraethylphosphonium fluoride or tetra-n-butylphosphonium fluoride, the known from EP-A 0 798 299, EP-A 0 896 009 and EP-A 0 962 455 known quaternary ammonium and Phosphoniumpolyfluoride, such as benzyl-trimethylammoniumhydrogenpolyfluorid, from EP-A 0 668 271 known tetraalkylammonium alkyl carbonates, which are obtainable by reaction of tertiary amines with dialkyl, or betaine structurized quaternary Ammonioalkylcarbonate known from WO 1999/023128 known quaternary ammonium bicarbonates, such as choline bicarbonate, known from EP 0,102,482, from tertiary Amines and alkylating esters of acids of phosphorus available quaternary ammonium salts, such as reaction products of triethylamine, DABCO or N-methylmorpholine with Methanphosphonsäuredimethylester, or known from WO 2013/167404 tetrasubstituted ammonium salts of lactams, such as Trioctylammoniumcaprolactamat or Dodecyltrimethylammoniumcaprolactamat.

Further suitable trimerization catalysts C according to the invention can be found, for example, in J.H. Saunders and K.C. Frisch, Polyurethanes Chemistry and Technology, p. 94 ff (1962) and the literature cited therein.

Particular preference is given to carboxylates and phenolates with metal or ammonium ions as the counterion. Suitable carboxylates are the anions of all aliphatic or cycloaliphatic carboxylic acids, preferably those with mono- or polycarboxylic acids having 1 to 20 C atoms. Suitable metal ions are derived from alkali or alkaline earth metals, manganese, iron, cobalt, nickel, copper, zinc, zirconium, cerium, tin, titanium, hafnium or lead. Preferred alkali metals are lithium, sodium and potassium, more preferably sodium and potassium. Preferred alkaline earth metals are magnesium, calcium, strontium and barium.

Very particular preference is given to the octoates and naphthenates described in DE-A 3 240 613 as catalysts of manganese, iron, cobalt, nickel, copper, zinc, zirconium, cerium or lead or mixtures thereof with acetates of lithium, sodium, potassium, calcium or barium.

Also very particularly preferred are sodium or potassium benzoate, the alkali phenolates known from GB-PS 1 391 066 and GB-PS 1 386 399, such as. As sodium or potassium phenolate, and known from GB 809 809 alkali and alkaline earth oxides, hydroxides, carbonates, alkoxides and - phenolates.

The trimerization catalyst C preferably contains a polyether. This is especially preferred when the catalyst contains metal ions. Preferred polyethers are selected from the group consisting of crown ether, diethylene glycol, polyethylene and polypropylene glycols. In the process according to the invention, it has proven to be particularly practical to use a trimerization catalyst B which contains as polyether a polyethylene glycol or a crown ether, more preferably 18-crown-6 or 15-crown-5. Preferably, the Trimiersierungskatalysator B contains a polyethylene glycol having a number average molecular weight of 100 to 1000 g / mol, preferably 300 g / mol to 500 g / mol and in particular 350 g / mol to 450 g / mol. Very particularly preferred is the combination of the above-described carboxylates and phenolates of alkali or alkaline earth metals with a polyether.

Component D

Component D is a compound which defines in a molecule at least one isocyanate-reactive group as defined earlier in this application and has at least one ethylenic double bond. The isocyanate-reactive group of component D may also be a uretdione group. Ethylenic double bonds are preferably those which are crosslinkable by a radical reaction mechanism with other ethylenic double bonds. Corresponding activated double bonds are defined in more detail for component B above in this application.

Preferred components D are alkoxyalkyl (meth) acrylates having 2 to 12 carbon atoms in the hydroxyalkyl radical. Particular preference is given to 2-hydroxyethyl acrylate, the isomer mixture or 4-hydroxybutyl acrylate formed in the addition of propylene oxide onto acrylic acid.

Component E

Component E is a compound which has both at least one isocyanate group and at least one ethylenic double bond in one molecule. It can advantageously be obtained by crosslinking a component D described in the preceding section with a monomeric or oligomeric polyisocyanate as described above in this application. This crosslinking is effected by reaction of the isocyanate-reactive groups, in this case in particular a hydroxyl, amino or thiol group, and an isocyanate group of the polyisocyanate. This is preferably catalyzed by a component G as described later in this application. But it is also any other suitable and known in the art catalyst conceivable. Also can be completely dispensed with a catalyst.

Particularly preferred are combinations in which an oligomeric polyisocyanate based on hexamethylene diisocyanate or pentamethylene diisocyanate is combined with a component D selected from the group consisting of 2-hydroxyethyl acrylate, the mixture of isomers resulting from the addition of propylene oxide to acrylic acid and 4-hydroxybutyl acrylate.

Further preferred components E are 2-isocyanatoethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanate tri (meth) acrylate, vinyl isocyanate, allyl isocyanate and 3-isopropenyl, - dimethylbenzyl isocyanate

Component F In principle, the free-radical polymerization of the ethylenically unsaturated compounds present in the reaction mixture can be effected by actinic radiation with sufficient energy content. This is in particular UV-VIS radiation in the wave range between 200 and 500 nm. In this case, the polymerizable composition according to the invention need not contain any component F.

However, if it is desired to dispense with the use of appropriate radiation, then the presence of at least one component F is necessary, which is suitable as an initiator of a radical polymerization of the ethylenic double bonds present in the polymerizable composition according to the invention. Initiators of this type have the effect, under suitable conditions, in particular on heating or the action of suitable radiation, of forming radicals which react with the ethylenic double bonds to give vinyl radicals, which in turn react in a chain reaction with further ethylenic double bonds. The component F contains at least one radiation-activated initiator F1 or at least one temperature-activated initiator F2. However, it may also contain a mixture of at least one radiation-activated initiator F1 and at least one temperature-activated initiator F2.

Preferred radiation-activated initiators Fl are compounds of the unimolecular type (I) and of the bimolecular type (II). Suitable type (I) systems are aromatic ketone compounds, such as. As benzophenones in combination with tertiary amines, alkylbenzophenones, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), anthrone and halogenated benzophenones or mixtures of the types mentioned. Also suitable are type (II) initiators such as benzoin and its derivatives, benzil ketals, acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacylphosphine oxides, phenylglyoxylic acid esters, camphorquinone, α-aminoalkylphenones, dialkoxyacetophenones and hydroxyalkylphenones. Specific examples are lrgacur ^® (phenyl ketone, a mixture of benzophenone and (l-hydroxycyclohexyl), Messrs. Ciba, Lampertheim, DE) 500, Irgacure ^® 819 DW (Phenylbis- (2, 4, 6-trimethylbenzoyl) phosphine oxide, Fa. Ciba, Lampertheim, DE) or Esacure ^® KIP EM (oligo- [2-hydroxy-2-methyl-l- [4- (l-methylvinyl) phenyl] -propanone], Fa. Lamberti, Aldizzate, Italy) and bis ( 4-methoxybenzoyl) diethylgerman. It is also possible to use mixtures of these compounds.

Care should be taken with the photoinitiators to have sufficient reactivity with the source of radiation used. There are a variety of photoinitiators known in the market. Commercially available photoinitiators cover the wavelength range in the entire UV-VIS spectrum.

Preferred temperature-activated initiators F2 are organic azo compounds, organic peroxides and CC-cleaving initiators, such as benzpinacol silyl ethers, N, N-diacyl-hydroxylamines, alkylated N, N-diacyl-hydroxylamines or O-acylated N, N-diacyl-hydroxylamines. Also suitable are inorganic peroxides such as peroxodisulfates. Other suitable thermal free radical initiators are azobisisobutyronitrile (AIBN), dibenzoyl peroxide (DBPO), di-tert-butyl peroxide, dicumyl peroxide (DCP) and peroxybenzoic acid ieri-butyl ester. However, the person skilled in the art can also use all other thermal initiators known to him.

Component G

Component G is a catalyst which catalyzes the crosslinking of an isocyanate group with an isocyanate-reactive group. This is preferably a urethane group, a Thiourethangruppe or a urea group.

The polymerizable composition preferably contains a component G when a component D with at least one isocyanate-reactive group is present. However, the use of a component G also in this case is not mandatory, since the crosslinking of isocyanate groups with isocyanate-reactive groups, the trimerization catalysts used C can be accelerated and runs well without catalysis sufficiently fast, if the reaction temperature is high enough. The addition of a component G can be dispensed with in particular if the crosslinking of the isocyanate groups present in the isocyanate component A is carried out at temperatures of at least 60 ° C., preferably at least 120 ° C.

Preferred components G are the typical urethanization catalysts, as indicated, for example, in Becker / Braun, Kunststoffhandbuch Volume 7, Polyurethanes, Chapter 3.4. The catalyst used may in particular be a compound selected from the group of tertiary amines, tertiary amine salts, metal salts and organometallic compounds, preferably from the group of tin salts, tin organyls and bismuth organyls.

Component H

The viscosity of the polymerizable composition according to the invention is preferably adjusted by the use of a component B in a suitable concentration. These act as reactive diluents and fundamentally make it possible to dispense with the use of additional solvents for lowering the viscosity of the isocyanate component A.

In particular embodiments, however, it may be desirable to additionally add a solvent suitable for isocyanates to the polymerizable composition according to the invention. This may be desirable, for example, if the proportion of component B in the polymerizable composition is to be limited and a viscosity reduction is sought, which with this limited proportion of component B is not achievable. In this case, the polymerizable composition according to the invention may contain all solvents known to those skilled in the art for the dilution of isocyanates. These are preferably hexane, toluene, xylene, chlorobenzene, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl or ethyl ether acetate, diethylene glycol ethyl and butyl ether acetate, propylene glycol monomethyl ether acetate, 1-methoxypropyl 2-acetate, 3-methoxy-n-butyl acetate , Propylene glycol diacetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, lactones such as β-propiolactone, γ-butyrolactone, ε-caprolactone and ε-methylcaprolactone, but also solvents such as N-methylpyrrolidone and N-methylcaprolactam, 1,2-propylene carbonate, methylene chloride, Dimethyl sulfoxide, triethyl phosphate or any mixtures of such solvents.

Component I

In a preferred embodiment, the polymerizable composition according to the invention additionally comprises at least one additive I selected from the group consisting of UV stabilizers, antioxidants, mold release agents, water scavengers, slip additives, defoamers, leveling agents, rheology additives, flame retardants and pigments. These auxiliaries and additives are usually present in an amount of at most 10% by weight, preferably at most 5% by weight and more preferably at most 3% by weight, based on the polymerizable composition of the invention.

Component J

In a particularly preferred embodiment of the present invention, the polymerizable composition comprises at least one organic filler J1 and / or at least one inorganic filler J2. Said fillers can be present in any shape and size known to those skilled in the art. These are in particular particulate fillers having a particle size distribution of a polydispersity of at most 50, preferably at most 30 and very particularly preferably at most 10 lO with an average grain diameter of at most 0.1 mm and preferably at most 0.05 mm.

In a further particularly preferred embodiment, fillers having an aspect ratio of at least 1000 are used.

In a further particularly preferred embodiment, particulate fillers and fillers having an aspect ratio of at least 1000 in a weight ratio of 1: 100 to 100: 1 are preferably used 1:80 to 50: 1 and more preferably 1:50 and 20: 1.

In a preferred embodiment, the fillers are predominantly inorganic in nature, preferably based on (semi) metal salts and (semi) metal oxides. Preferred organic fillers J1 are wood, cellulose, paper, cardboard, tissue chips, cork, wheat chaff, polydextrose, cellulose, aramids, polyethylene, carbon, carbon nanotubes, polyesters, nylon, plexiglas, flax, hemp and sisal.

Preferred inorganic fillers J ₂ are AlOH ₃ , CaCO ₃ , silicon dioxide, magnesium carbonate, TiO ₂ , ZnS, minerals containing silicates, sulfates, carbonates and the like, such as magnesite, barite, mica, dolomite, kaolin, talc, clay minerals, and carbon black, graphite, boron nitride , Glass, basalt, boron, ceramics and silicic acid.

The polymerizable composition according to the invention is preferably suitable for producing a highly filled composite material. "Highly filled" means that filler contents of up to 50% by volume to 80% by volume, preferably 60% to 80% by volume, can be achieved.

In a particularly preferred embodiment, the filler is a fibrous filler J3. The fibrous filler J3 may be made of any of the inorganic fibers, organic fibers, natural fibers or mixtures thereof known to those skilled in the art. The fact that a fibrous filler is made of one or a mixture of different materials does not exclude that it contains other substances, e.g. serve as sizing.

Preferred inorganic fibers are glass fibers, basalt fibers, boron fibers, ceramic fibers, whiskers, silica fibers and metallic reinforcing fibers. Preferred organic fibers are aramid fibers, carbon fibers, carbon nanorhorm, polyester fibers, nylon fibers and Plexiglas fibers. Preferred natural fibers are flax fibers, hemp fibers, wood fibers, cellulose fibers and sisal fibers.

According to the invention, fibrous fillers J3 are all fibers whose aspect ratio is greater than 1000, preferably greater than 5000, more preferably greater than 10,000, and most preferably greater than 50,000. The aspect ratio is defined as the length of the fiber divided by the diameter.

If the aspect ratio defined above is adhered to, the fibrous fillers J3 preferably have a minimum length of 1 m, more preferably 50 m and most preferably 100 m.

According to a preferred embodiment of the invention, the fibrous filler J3 is selected from the group consisting of glass fibers, basalt fibers, carbon fibers and mixtures thereof. The fibers can be present individually, but they can also be woven or knitted into mats or tiles in any shape known to those skilled in the art. Preferably, less than 50% by weight, more preferably less than 35% by weight, is even more preferred less than 20% by weight, most preferably less than 10% by weight, of the fibers used in the form of mats or tiles.

The individual fibers preferably have a diameter of less than 0.1 mm, more preferably less than 0.05 mm, and even more preferably less than 0.03 mm.

According to a preferred embodiment of the invention, there is a size on the surface of the fibers. The sizing agent is a thin polymeric film which often contains reactive groups and improves wetting with the resin or interfacial bonding between the matrix and the fiber.

According to a further embodiment of the invention, the fibers used have a low water content. For example, water may be absorbed on the surface of the fibers and later undergo undesirable side reactions with the isocyanate groups. It has therefore proved to be advantageous if the water content of the fibers is less than 5% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, in particular less than 1% by weight and most preferably less than zero , 5 wt .-% based on the total weight of fibers. At best, the fibers have no moisture content. This can optionally be achieved by drying the fibers. The moisture content of the fibers can be determined by gravimetric measurement before and after drying, preferably at 120 ° C for 2 hours.

In a preferred embodiment of the present invention, at least 50%, more preferably at least 70%, even more preferably at least 80% and most preferably at least 90% of the fibers are oriented parallel to one another. Fibers are oriented parallel to each other when the angle between them is less than 15 degrees, preferably less than 10 degrees and even more preferably less than 5 degrees, over a length of 0.5 m, preferably 1 m, and more preferably 2 m. Most preferably, the angle between at least 90% of the fibers over a length of 2 m is at most 10 degrees and even more preferably at most 5 degrees. The person skilled in the art is aware that the above-mentioned information makes sense only when using individual fibers. As far as the fibers used are in the form of mats or nonwovens, it follows from the arrangement of the fibers in these materials that these conditions can not be met.

The ratio between the reactive resin, the fibrous filler J3 and all other constituents of the composite is preferably chosen such that the fiber content is at least 30% by volume, preferably 45% by volume, more preferably at least 50% by volume, even more preferably at least 60% by volume and most preferably at least 65% by volume of the cured composite material. use

In a further embodiment, the present invention relates to the use of at least one component selected from the group consisting of components B, D and E for the preparation of a polymerizable composition having a ratio of isocyanate groups to isocyanate-reactive groups of at least 2.0 to 1.0 which contains an isocyanate component A and a filler J and is polymerizable both by free-radical polymerization and by crosslinking of isocyanate groups with one another.

Preferably, additionally at least one component B is used as defined above in this application.

All of the definitions given for the polymerizable composition A above in this application are also applicable to this embodiment. This applies in particular to the proportions of components A, B, D and E and the ratio of isocyanate groups to the total amount of isocyanate-reactive groups in the polymerizable composition.

method

In a further embodiment, the present invention relates to a process for the preparation of a polymer comprising the steps of a) providing the reactive resin described above in this application; b) providing at least one filler J described above in this application; c) wetting the filler J with the reactive resin mixture;

d) crosslinking of the ethylenic double bonds contained in said polymerizable composition; and

e) crosslinking of the isocyanate groups contained in said polymerizable composition; wherein the method steps d) and e) are carried out simultaneously or in any order and the method step c) before the method steps d) and e) is performed.

In a preferred embodiment of the present invention, viscosity is first built up by method step d) before the final curing of the polymer takes place in method step e). In this case, the two process steps do not have to follow one another directly in time. It is particularly preferred that between the two process steps, a further step takes place, in which the product of process step d) is transformed. All definitions given above for the polymerizable composition according to the invention also apply to the process according to the invention, unless otherwise stated below.

If the process steps d) and e) are not to be carried out simultaneously, it is preferred that the polymerizable composition according to the invention does not contain a temperature-activated initiator F2. Conversely, it is advantageous that a temperature-activated initiator F2 is used in a simultaneous implementation of process steps d) and e), since in this case the temperature increase required for the crosslinking of the isocyanate groups in process step e) also cross-links the ethylenic double bonds in process step d). causes.

When the polymerizable composition contains at least one component D, it is preferred that the method according to the invention comprises a further process step f) in which the isocyanate-reactive group of component D is crosslinked with an isocyanate group of isocyanate component A or a reaction product of isocyanate component A. Said process step f) can be carried out before process step d), it can be carried out between process steps d) and e), it can be carried out in parallel to process step d) or e) or else after process steps d) and e). In any case, it will be carried out after process step c).

Since the crosslinking of an isocyanate group of the component A and an isocyanate-reactive group of the component D also takes place by the trimerization catalyst C alone or completely without the assistance of a catalyst, the process step f) is preferably carried out in parallel to the process step e), since there is already an increase in temperature, which also causes the reaction of components A and D.

Wetting the filler with the reactive resin mixture

To produce the anisotropic composite materials according to the invention, the filler J in process step c) J is wetted with the reactive resin mixture from process step a). Good wetting is necessary to ensure transfer of force between the filler and the matrix in the finished part and include inclusions, e.g. Air, avoid.

The wetting step can be carried out both continuously and discontinuously; preferred is a continuous process.

According to one embodiment of the invention, all known methods are suitable which allow a good wetting of the filler with the resin matrix. Called here without claim to Completeness Doctor blade, dip, injection box, spray method, resin injection method, resin infusion method with vacuum or pressure, applicator roll and hand lamination method.

If it is a fibrous filler J3, the dipping bath is used according to a particularly preferred embodiment of the invention. The dry fibers are drawn through an open resin bath, with the deflection of the fibers via guide diaphragms in and out of the resin bath (bath process). Alternatively, the fibers can also be drawn straight through the impregnating device without deflection (pull-through method).

According to a further particularly preferred embodiment of the invention, the injection box is used in the case of a fibrous filler J. In the injection box, the fibers are drawn without deflection in the impregnating unit, which already has the shape of the later profile. By pressure, the reactive resin mixture is pumped into the box, preferably transversely to the fiber direction.

It has proved to be advantageous if the fibers of a fibrous filler J3, which are present in the form of fiber bundles, so-called rovings, are spread before the impregnation step in order to achieve a better impregnation of the individual fibers. This can be achieved, for example, by deflecting pulleys or guide plates.

When fibrous fillers J3 are processed, the process according to the invention is preferably a pultrusion process in which the process step c) is carried out in a dipping bath or in an injection box as described above and the process step e) is carried out without further intermediary process steps such that the wetted fibers of the Filler pulled by a heated tool whose profile corresponds to the profile of the workpiece to be produced. In this embodiment, temperature-activated initiators are preferably used. The viscosity of the reactive resin is preferably adjusted to be between 10 mPas and 10,000 mPas, preferably between 10 and 5,000 mPas and even more preferably between 10 and 2,000 mPas.

Crosslinking of the ethylenic double bonds

The crosslinking of the ethylenic double bonds contained in the polymerizable composition according to the invention is carried out by a free-radical polymerization. This polymerization reaction, when a radiation-activated initiator Fl is present, according to the invention by the use of radiation, which is suitable for its activation, initiated. When a temperature-activated initiator F2 is present in the polymerizable composition used, crosslinking of the ethylenic double bonds is initiated by heating the polymerizable composition to the required temperature. In principle, however, the use of sufficiently high-energy radiation, as defined above in this application, is sufficient for initiation of the free-radical polymerization in process step d), irrespective of the presence of initiators F1 or F1.

Crosslinking of isocyanate groups

The "crosslinking" of the isocyanate component A in process step e) is a process in which the isocyanate groups contained therein together with or forming at least one structure selected from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structures In this case, the isocyanate groups originally present in the isocyanate component A are consumed by forming the abovementioned groups, and the monomeric and oligomeric polyisocyanates contained in the isocyanate component A are combined to form a polymer network.

Since a marked molar excess of isocyanate groups over isocyanate-reactive groups is present in the polymerizable composition according to the invention, the crosslinking reaction results in at most 20%, preferably at most 10%, particularly preferably at most 5%, very particularly preferably at most 2% and in particular at most 1 % of the total nitrogen content of the isocyanate component A in urethane and / or allophanate groups.

In a particularly preferred embodiment of the invention, however, the cured isocyanate component A is not completely free of urethane and allophanate groups. It therefore preferably contains at least 0.1% of urethane and / or allophanate groups, based on the total nitrogen content, taking into account the upper limits defined in the preceding paragraph.

It is preferred that the crosslinking of the isocyanate groups present in the polymerizable composition according to the invention predominantly by cyclotrimerization of at least 50%, preferably at least 60%, more preferably at least 70%, especially at least 80% and most preferably 90% of present in the isocyanate component A. free isocyanate groups to Isocyanuratstruktureinheiten takes place. Thus, in the finished material, corresponding proportions of the nitrogen originally contained in the isocyanate component A are bound in isocyanurate structures. Side reactions, in particular those to uretdione, allophanate, and / or iminooxadiazinedione structures, however, usually occur and can even be used selectively in order to influence, for example, the glass transition temperature (Tg) of the obtained polyisocyanurate plastic advantageous. However, the above-defined content of urethane and / or allophanate groups is preferably also present in this embodiment. The crosslinking of the isocyanate groups is preferably carried out at temperatures between 50 ° C and 220 ° C, more preferably between 80 ° C and 200 ° C and even more preferably between 100 ° C and 200 ° C.

The abovementioned temperatures are maintained in process step c) until at least 50%, preferably at least 75% and even more preferably at least 90% of the free isocyanate groups present in the isocyanate component A at the beginning of process step b) are consumed. The percentage of isocyanate groups still present can be determined by comparing the content of isocyanate groups in% by weight in the isocyanate component A present at the beginning of process step b with the content of isocyanate groups in% by weight in the reaction product, for example be determined by the aforementioned comparison of the intensity of the isocyanate at about 2270 cm-1 by means of I spectroscopy.

The exact duration of process step e) of course depends on the geometry of the workpiece to be produced, in particular the ratio of surface area and volume, since in the core of the resulting workpiece, the required temperature for the required minimum period must be achieved. The person skilled in the art can determine these parameters by simple preliminary tests.

In principle, crosslinking of the abovementioned proportions of free isocyanate groups is achieved if the abovementioned temperatures are kept for 1 minute to 4 hours. Particularly preferred is a period between 1 minute and 15 minutes at temperatures between 180 ° C and 220 ° C or a period of 5 minutes to 120 minutes at a temperature of 120 ° C.

If the process is a pultrusion process, then process step e) is preferably carried out in a mold heated to the above temperatures and having a recess in the shape of the profile to be produced, through which the fibrous filler J3 wetted with the reactive resin passes becomes.

Composite material

In yet another embodiment, the present invention relates to a composite obtainable by the method described above.

The composite is preferably present as a shaped body.

The molded article may preferably be obtained by casting using suitable molds. In particularly preferred embodiments, the composite material is present as an open or closed hollow body.

A "molded article" is defined as having an edge length of at least 0.5 mm, preferably at least 1 mm in at least one of the three dimensions and a dimension of at least 2 cm, preferably at least 5 cm, in at least one of the other two dimensions. It preferably has an edge length of at least 2 cm in all three dimensions.

More preferably, the composite of the present invention is the product of a pultrusion process, i. it contains a fibrous filler J and has a profile. A "profile" as understood in the present application is a body that has substantially the same cross-section over its entire length The "profile" is preferably at least 2 meters, more preferably at least 10 meters, and even more preferably at least 50 meters long , It is expressly intended that the profile can be divided into several segments after the curing of the reactive resin. The previously given lengths then refer to a hypothetical undivided product, as it emerges from the process and without any further division.

Even if this cross-section is not always reached at all times due to production, a profile has "the same cross-section over its entire length, even if these sections are short in relation to the overall length of the profile differing cross-section are short if their total length is less than 10%, preferably less than 5%, and most preferably less than 1% of the total length of the hypothetical undivided profile deviates from the desired value.

The following examples serve only to illustrate the invention. They are not intended to limit the scope of the claims in any way.

Examples

General Information:

Unless otherwise specified, all percentages are by weight (% by weight).

The prevailing ambient temperature of 23 ° C. at the time of the experiment is referred to as RT (room temperature).

The methods listed below for determining the corresponding parameters were used for carrying out or evaluating the examples and are also the methods for determining the parameters relevant to the invention in general.

Determination of phase transitions by DSC

The phase transitions were determined by means of DSC (Differential Scanning Calorimetry) using a Mettler DSC 12E (Mettler Toledo GmbH, Giessen, Germany) in accordance with DIN EN 61006. Calibration was performed by the temperature of the indium-lead melted on-set. 10 mg of substance were weighed into normal capsules. The measurement was carried out by three heats from -50 ° C to +200 ° C at a heating rate of 20 K / min with subsequent cooling at a cooling rate of 320 K / min. The cooling was carried out by liquid nitrogen. Nitrogen was used as purge gas. The given values are based on the evaluation of the 2nd heating curve. The glass transition temperature T _g was obtained from the temperature at half the height of a glass transition stage.

Determination of infrared spectra

The infrared spectra were measured on a Bruker FT-IR spectrometer equipped with an ATR unit.

starting compounds

Polyisocyanate AI: HDI trimer (NCO functionality> 3) with an NCO content of 23.0 wt .-% of the company. Covestro AG. The viscosity is about 1200 mPa-s at 23 ° C (DIN EN ISO 3219 / A.3).

Polyisocyanate A2: PDI trimer (NCO functionality> 3) with an NCO content of 21.5% by weight from Covestro AG. The viscosity is about 9500 mPa-s at 23 ° C (DIN EN ISO 3219 / A.3).

Hexanediol diacrylate (HDDA) was obtained with a purity of <= 100% by weight from Sigma-Aldrich. Hydroxypropyl methacrylate (HPMA) was obtained with a purity of 98 wt .-% of the Fa. GmbH GmbH.

Isobornyl methacrylate (IBOMA) was obtained with a purity of <= 100 wt .-% of the company. Sigma Aldrich.

Initiator: Trigonox "C (peroxybenzoic acid, iperi-butyl ester) was purchased at 98% purity by Akzo Nobel.

Potassium acetate was obtained with a purity of> 99 wt .-% of the company. ACROS.

Polyethylene glycol (PEG) 400 was obtained with a purity of> 99 wt .-% of the company. ACROS.

The mold release agent INT-1940 RTM was manufactured by Axel Plastics Research Laboratories, INC. and is, according to the data sheet, a mixture of organic fatty acids and esters.

The 910A-10P short glass fiber was supplied by Owens Corning and was present in about 4.5 mm long bundles. The diameter of the individual fibers was 0.01 mm.

The continuous glass fiber was a standard size glass fiber bundle for UP, VE and epoxy resin type 4800 Tex Advantex 399 'from 3B-fiberglass. The continuous glass fibers have a diameter of 24 microns according to the data sheet, are boron-free and consist of E-CR glass. The tensile modulus is 81-83 GPa, the tensile strength is 2200-2400 MPa and the density is 2.62 g / cm ³ .

All raw materials with the exception of the catalyst were degassed before use in a vacuum, the polyethylene glycol additionally dried.

Preparation of Catalyst K:

Potassium acetate (5.0 g) was stirred in the PEG 400 (95.0 g) at r.t. until everything was dissolved. There was thus obtained a 5 wt .-% solution of potassium acetate in PEG 400 and used without further treatment as a catalyst.

Preparation of the reaction mixtures

Unless stated otherwise, the isocyanate composition was first prepared by mixing the corresponding isocyanate components (AI or A2) with a corresponding amount of catalyst K, initiator and acrylate at 23 ° C. in a Speedmixer DAC 150.1 FVZ from Hauschild for 60-300 ° to prepare the polyisocyanurate composites Seconds at 2750 min-1. Subsequently, the isocyanate composition was first one tenth of the amount of short glass fiber added. The entire mass was mixed in a Speedmixer DAC 150.1 FVZ from Hauschild for 60 to 300 seconds at 2750 min-1, whereby the short-glass fiber bundles exfoliate and all forms a pulpy mass. Now add the remaining amount of short glass fiber and mix the mass again for about 60 seconds at 2750 min-1 in the Speedmixer.

The mixture was then placed in a mold (metal lid, about 6 cm in diameter and about 1 cm high) and cured in the oven.

Embodiment 1

As described above, polyisocyanate AI (16.13 g) was treated with initiator I (0.064 g), Catalyst K (0.595 g) and HPMA (1.60 g) according to the above mentioned. Method of preparation for reaction mixtures treated and filled the mass without the addition of glass fibers in the mold. The mixture after production had a viscosity of 929 mPas.

After curing for 3 minutes at 200 ° C, a material with a T _G of 58 ° C was obtained. After a stepwise hardening of 100 ° C. for 3 minutes and 200 ° C. for 3 minutes, a material with a T _G of 87 ° C. was obtained.

Embodiment 2

As described above, polyisocyanate AI (16.13 g) was treated with initiator I (0.064 g), Catalyst K (0.595 g) and HPMA (1.60 g) according to the above mentioned. Prepared for reaction mixtures prepared, the short glass fiber (4.0 g) incorporated and filled the mass into the mold.

After curing for 3 minutes at 200 ° C, a material having a T _G of 87 ° C was obtained. After curing for 2 minutes at 100 ° C. and 2 minutes at 200 ° C., a material having a T _g of 91 ° C. was obtained.

Embodiment 3

As described above, polyisocyanate AI (32.2 g) was treated with initiator I (0.12 g), Catalyst K (12.3 g), HPMA (0.29 g), HDDA (3.08 g), IBOMA (3 , 08 g) according to the above-mentioned preparation instructions for reaction mixtures. The mixture had a viscosity of 611 mPas after preparation. After curing for 5 minutes at 220 ° C, a material having a T _G of 102 ° C was obtained.

Embodiment 4

As described above, polyisocyanate A2 (29.7 g) was treated with initiator I (0.16 g), Catalyst K (1.23 g), HPMA (0.41 g), HDDA (4.21 g), IBOMA (4 , 21 g) according to the above-mentioned preparation instructions for reaction mixtures. The mixture after production had a viscosity of 1560 mPas. After curing for 10 minutes at 200 ° C, a material having a T _G of 126 ° C was obtained. Preparation of the resin mixture for pultrusion

The isocyanate was placed in an open container at room temperature and stirred using a Dispermat ^® and dissolver disc at 100 revolutions per minute (rpm). Subsequently, first the acrylate, and then the mold release agent was added and the stirring speed increased to 300 rpm and stirred for a further 5 min, so that a homogeneous mixture was formed. Now, the catalyst solution and the initiator were metered in and the resin mixture was stirred for a further 5 minutes at 300 rpm. This reactive resin mixture was used without further treatment for pultrusion.

Embodiment 5

As described above, polyisocyanate AI (3.22 kg) was treated with initiator I (12 g), Catalyst K (123 g), HPMA (29 g), HDDA (308 g), IBOMA (308 g), and INT-1940 RTM mold release (103 g) according to the above Preparation procedure for resin mixture for pultrusion treated. The mixture had a viscosity of 611 mPas after preparation.

The glass fiber bundles (126 rovings) were oriented and passed through an injection box, which was firmly connected to the tool and was filled with the resin mixture via a window opening at the top of the box. The glass fibers so impregnated with resin were drawn directly into the heated tool. The temperature zones were Hl = 180 ° C, H2 = 220 ° C, H3 = 200 ° C and H4 = 180 ° C. The pulling speed was 0.3 m / min and 0.5 m / min. The deduction forces were approx. 0.7 t. In each case 5 m profile were produced at both speeds. The surface of the profile was homogeneous and dull, and the glass content was 80 mass%.

Embodiment 6

As described above, polyisocyanate A2 (2.97 kg) was treated with initiator I (16 g), catalyst K (123 g), HPMA (41 g), HDDA (421 g), IBOMA (421 g) and mold release agent INT-1940 RTM (102 g) according to the above Preparation procedure for resin mixture for pultrusion treated.

The glass fiber bundles (126 rovings) were oriented and passed through an injection box, which was firmly connected to the tool and was filled with the resin mixture via a window opening at the top of the box. The glass fibers so impregnated with resin were drawn directly into the heated tool. The temperature zones were Hl = 180 ° C, H2 = 220 ° C, H3 = 200 ° C and H4 = 180 ° C. The pulling speed was 0.3 m / min and 0.5 m / min. The deduction forces were approx. 0.7 t. In each case 5 m profile were produced at both speeds. The surface of the profile was homogeneous and dull, and the glass content was 80 mass%. Comparative Example 7

As described above, polyisocyanate AI (93.5 g) and Catalyst K (4.0 g) according to the above-mentioned. Preparation procedure for reaction mixtures treated and the mass filled into the mold. The mixture after production had a viscosity of 2180 mPas.

After curing for 3 minutes at 220 ° C, a material having a T _G of 98 ° C was obtained. Comparative Example 8

As described above, polyisocyanate A2 (93.5 g) and catalyst K (4.0 g) were used according to the above mentioned. Preparation procedure for reaction mixtures treated and the mass filled into the mold. The mixture had a viscosity of more than 10,000 mPas after preparation.

After curing for 3 minutes at 220 ° C, a material with a T _G of 128 ° C was obtained.

Comparative Example 9

As described above, polyisocyanate A2 (4.39 kg) was treated with catalyst K (188 g), and mold release agent INT-1940 RTM (117 g) according to the above-mentioned preparation for resin mixture for pultrusion. The mixture after production had a comparatively high viscosity of more than 10,000 mPas. After curing for 3 minutes at 220 ° C, a material having a T _G of 126 ° C was obtained.

The glass fiber bundles (126 rovings) were oriented and passed through an injection box, which was firmly connected to the tool and was filled with the resin mixture via a window opening at the top of the box. The treated glass fibers were drawn directly into the heated tool. The temperature zones were H l = 180 ° C, H 2 = 220 ° C, H 3 = 200 ° C and H 4 = 180 ° C. The pulling speed was 0.2 m / min and 0.3 m / min. The deduction forces were between approx. 0.4 and 0.9 t. The glass fibers came out of the tool almost unchanged because the resin could not penetrate the fibers due to the high viscosity.

discussion

Exemplary embodiments 1, 3 and 4 show that addition of double bond-containing (acrylate-based) monomers to polyisocyanate-based reaction mixtures leads to significantly reduced starting viscosities in comparison with pure polyisocyanate-based reaction mixtures (compare Comparative Examples 7 and 8). Such reduced initial viscosities often aid in the use of such formulations as resins for (composite) fiber composites, as they facilitate the wetting of (fibrous) fillers (see below). The working examples 1, 3 and 4 furthermore show that a combination of the addition reaction of isocyanate groups with the radical polymerization of double bond-containing monomers leads in principle to cured plastics having high glass transition temperatures.

Moreover, Embodiment 2 shows that such blends are well suited to embed (fibrous) fillers without sacrificing material properties (e.g., Tg). Finally, embodiments 5 and 6 show that such mixtures are well suited to continuously produce fiber composite materials with very high filler contents (> 80% by mass) by means of pultrusion. Whereas Comparative Example 9 demonstrates that too high starting viscosities of polymer resins prevent the continuous production of fiber composites.

Claims

claims

A polymerizable composition for producing a composite comprising a) a reactive resin having a ratio of isocyanate groups to isocyanate-reactive groups of at least 2.0 to 1.0 containing the components a) an isocyanate component A;

a2) at least one trimerization catalyst C; and

The polymerizable composition of claim 1, wherein the reactive resin a) contains at least one component B.

The polymerizable composition according to claim 1 or 2, wherein the reactive resin a) contains at least one component D or E.

4. The polymerizable composition according to claim 2 or 3, wherein the amount ratio of the component A to the total amount of the components B, D and E is such that the reactive resin has a viscosity of at most 10,000 mPas.

The polymerizable composition according to any one of claims 1 to 4, wherein the molar ratio of isocyanate groups to isocyanate-reactive groups in the reactive resin is at least 4.0 to 1.0.

The polymerizable composition according to any one of claims 1 to 5, wherein the reactive resin additionally contains a component F which is suitable as an initiator of radical polymerization of the ethylenic double bonds contained in the polymerizable composition of the present invention.

7. Use of at least one component selected from the group consisting of components B, D and E for the preparation of a polymerizable composition having a ratio of isocyanate groups to isocyanate-reactive groups of at least 2.0 to 1.0, which is an isocyanate component A and a Contains filler J and is polymerizable both by radical polymerization and by crosslinking of isocyanate groups with one another.

8. A process for producing a polymer comprising the steps of a) providing a reactive resin as defined in claims 1 to 6;

b) providing at least one filler J;

c) wetting the filler J with the reactive resin mixture;

9. The method of claim 8, wherein the reactive resin contains a temperature-activated initiator F2, the polymerizable composition contains at least one fibrous filler J3 and the process steps d) and e) are carried out in parallel.

10. The process according to claim 8 or 9, wherein the polymerizable composition contains at least one component E and the process comprises a further process step d), in which the isocyanate-reactive group of the component E with an isocyanate group of the isocyanate component A or a reaction product of the isocyanate component A is networked.

11. The method according to any one of claims 8 to 10, wherein in step b) at least 50% of the free isocyanate groups present in the isocyanate A are converted to Isocyanuratstruktureinheiten.

12. Composite material, obtainable by the method according to one of claims 8 to 11.

13. The composite material according to claim 12, present as a profile.

14. The composite material according to claim 12, in the present case as a hollow body.

15. The composite material according to claim 12, present as a shaped body and produced by a casting process.