VERFAHREN ZUR HERSTELLUNG KOMPAKTER POLYURETHANE MIT VERBESSERTER HYDROLYSESTABILITÄT

A process for the production of compact polyurethanes having improved hydrolytic stability

The present invention relates to a method for preparing a polyurethane, comprising reacting a composition (Z1) comprising at least a ten towards isocyanates reactive compound (P1), and a composition (Z2), comprising at least one polyisocyanate, wherein the compound (P1) obtainable or obtained at least a polyepoxide with a connection (V1) is selected from the group consisting of polyether amines and polyether polyols by the reaction. Further, the present invention polyurethanes obtainable relates to or obtained by such a method and the use of a polyurethane according to the invention for the coating of pipelines, as "field joint" or of underwater equipment (subsea equipment), such as "christmas tree" for off-shore area as well as glass syntactic polyurethane.

Polyurethanes are used in different areas. Polyurethanes are tailored to their properties so that this optimal in processing or application properties provide for these different areas. So Polyurethanes are used, for example, coatings of moldings, also for the coating of pipelines.

When extracting oil from the sea oil reserves are promoted from great depths increased. The petroleum production sites of such has a temperature of greater than 100 ° C (150 ° C). This oil is pumped towards the mainland by means of pipelines from the offshore production site. To reduce heat loss of the oil, and thereby to avoid the precipitation of guards from the oil at a delivery stop, the pipeline is usually provided with a coating of polyurethane. Due to the ever deeper drilling and thereby resulting higher temperature of the oil pipeline Coatings an increasingly higher heat load to be suspended. This heat load under water requires improved hydrolytic stability of the coating.

WO 2005/056629 describes a method for producing a glass-filled hollow spheres polyurethane in order to reduce the heat loss of an oil pipeline. In this case, in WO 2005/056629 preferred aromatic isocyanates are used. Disadvantage of such Polyetherpo- lyurethane based on aromatic isocyanates is that the urethane bond at higher temperatures may also hydrolyze. To overcome this disadvantage, disclose eg WO 2007/04241 1, WO 99/03922 and WO 2010/003788 coatings based on polyisocyanurates. These have the advantage of better temperature stability. The hydrolytic stability at high temperatures, however, is only partially better than normal polyurethanes. In addition, the systems have to react very quickly the disadvantage, Sieren so that a filling of large volumes difficult to realized is. Likewise, polyisocyanurates relatively brittle due to the large cross-linking by the isocyanurate ratring.

WO 201 1/161047 discloses a method in which a higher functional, high molecular weight polyol is used in combination with an epoxy resin. The disadvantage of this method is that the relatively high functionality, high molecular weight polyols have high viscosities and are difficult to manufacture. Further, the materials described in WO 201 1/161047 can not provide a sufficient long-term hydrolytic stability at the required temperatures. US 4,647,624 discloses reaction of a polyether polyol with a polyepoxide, wherein further starting materials are used for the preparation of a polymer polyol. The polymer obtained are, in turn, reacted with isocyanates, wherein the production of polyurethane foams is disclosed. As evidenced by Example 2 of US 4,647,624 is an epoxy adduct to form. However, calculations show that, among those referred to in Example 2 of US 4,647,624 conditions, no reaction of the components may have taken place, the starting materials used are merely mixed.

In WO 2012/030339 a method is described to avoid the general poor long-term hydrolytic stability of polyurethane elastomers. Here WO revealed

2012/030339 an epoxy material with good mechanical properties, which has a hydrolysis resistance of 160 ° C. The raw materials used and reaction products for the production of such elastomeric epoxy resins are known in the art and are described for example in EP 0,510,265. The person skilled in the disadvantages of WO

2012/030339 disclosed method can be seen. The processing of these epoxy materials is difficult because these materials must be processed at higher temperatures and hardened. usually because the processing in the field or on the high seas takes place, this is difficult to accomplish. Furthermore, the materials have long demold times, which proves to be in the application as not very economical. One of the problem underlying the present invention was to provide materials having improved hydrolytic stability at high temperatures. A further object of the present invention is based was to provide materials having improved hydrolytic stability at high temperatures and at the same time meet the high mechanical demands in the oil and gas industry. Another object of the invention was to provide coatings made from these materials.

According to the invention this object is achieved by a method for preparing a polyurethane comprising reacting at least the following components: (i) composition (Z1) comprising at least one isocyanate-reactive compound (P1), and

(Ii) composition (Z2), comprising at least one polyisocyanate, wherein the compound (P1) is obtainable or obtained by reacting at least one polyepoxide with a connection (V1) is selected from the group consisting of mineral Polyethera- and polyetherols. The inventive method comprises reacting at least one composition (Z1) and a composition (Z2). The composition (Z1) in this case comprises at least one isocyanate-reactive compound (P1) which is obtainable or obtained by reacting at least one polyepoxide with a connection (V1) is selected from the group consisting of polyether amines and polyetherols. Composition (Z2) comprises min- least one polyisocyanate.

According to the invention, further components, such as further isocyanate-reactive compounds such as polyols, chain extenders or additives can be used. According to a further embodiment, the present invention therefore relates to a process for preparing a polyurethane as described above, wherein in the reaction in addition to components (i) and (ii) at least one of the following components is used:

(Iii) a further isocyanate-reactive compound,

(Iv) a chain extender,

(V) further additives.

In the inventive process one isocyanate-reactive compound (P1) is used which is obtainable or is obtained by reacting at least one polyvinyl lyepoxids with a compound (C1) selected from the group consisting of polyether amines and polyetherols. The compound (P1) is thus obtainable or obtained by reacting at least one polyepoxide with a polyether amine or by reacting at least one polyepoxide with a polyether polyol. According to the invention, the compound (P1) as the reaction product of at least one polyepoxide with a polyether amine or a reaction product is obtained at least a polyepoxide with a polyether polyol. According to the invention, it is possible that the compound (P1) is isolated before being used in the composition (Z1).

It was surprisingly found, that can be realized through the use of a reaction product based on a polyether amine or polyether polyol with a polyepoxide as a polyol component in the polyurethane formulation similar hydrolytic stabilities as described in WO 2012/030339 disclosed pure Epoxyelastomeren, but the processing technical advantages of polyurethane can still be used ,

The reaction products of polyepoxides and polyether amine or polyether polyol preferably have a theoretically calculated OH number of 0.5 mg KOH / g to 75 mg KOH / g is calculated according to the following formula: With:

ΟΗ: theoretically calculated ΟΗ number of the reaction product according to the invention in mg KOH / g

MA: mass of added polyetheramine polyol or mixtures in g

M _B: mass of added epoxy resin or epoxy mixture in g

EW: OH amino equivalent weight or equivalent weight of the polyether used, or polyol or polyol mixture Polyetheraminmischung or in g / eq

Particularly preferred reaction products according to the invention have a theoretically calculated OH number of 5 mg KOH / g to 65 mg KOH / g, more preferably from 10 mg KOH / g to 55 mg KOH / g, and most preferably from 15 mg KOH / g to 50 mg KOH / g.

Here, any existing OH groups of the epoxy resin are not considered in this calculation and definition.

According to a further embodiment, the present invention relates to a method for preparing a polyurethane as described above, wherein the compound (P1) has a theoretically calculated OH number in the range of 0.5 mg KOH / g to 75 mg KOH / g.

The reaction products (P1) of the invention have an epoxy equivalent weight in the range of 180 to 5000 g / eq calculated according to the following formula:

EEWP = ^{(Ma + Mb)}

(M _B M

EEW EW

EEWP: theoretically calculated epoxy equivalent weight of the reaction product according to the invention g / eq

MA: mass of added polyetheramine polyol or mixtures in g

MB: Mass of added epoxy resin or epoxy mixture in g

EW: OH amino equivalent weight or equivalent weight of the polyether used,

Polyol or mixtures in g / eq

EEW: epoxy equivalent weight of the epoxy resin used or epoxy mixture in g / eq

According to a further embodiment, the present invention accordingly relates to a process for preparing a polyurethane as described above, wherein the compound (P1) has a theoretically calculated epoxy equivalent weight in the range of 180 to 5000 g / eq. As stated, the compound of the invention (P1) is obtainable by reacting at least one polyepoxide with a polyether amine or by reacting at least one polyepoxide with a polyether polyol. According to the invention the ratio of the NH or OH groups to epoxide groups is preferably in the range of 1: 1, 5 to 1: 75, preferably in the range of 1: 2 to 1: 50, more preferably in the range of 1: 2.5 to 1: 25 and most preferably in the range of 1: 3 to 1: 15 °.

Suitable polyepoxides, polyether amines and polyether polyols are the skilled worker known per se. The preparation of the reaction products of polyether or polyether polyols with polyepoxides may run as known in the art. In this case, polyepoxide or polyvinyl be lyepoxidmischungen with a polyetheramine polyol or mixtures of polyether amines and / or polyols are mixed and optionally adding a catalyst. The reaction can be carried out with the use of polyetheramines at room temperature and without a catalyst. When using polyetherols a corresponding catalyst is required for the reaction. the reaction at 50 ° C to 180 ° C is carried out, particularly preferably between 80 ° C to 150 ° C and most preferably between 90 ° C and 130 ° C.

The polyepoxides used in the present invention may be any connects fertilize. The polyepoxides containing on average more than one epoxy, preferably two or more epoxy groups. Suitable polyepoxides the expert from the literature such as Handbook of Epoxy Resins (H. Lee, K. Neville, McGraw-Hill Book Company) are known. In the present invention, the epoxide compounds used can thereby be rocyclisch and also contain hydroxyl groups both saturated and unsaturated and aliphatic, cycloaliphatic, aromatic or hetero-. You can continue such Substituents included that do not cause troublesome secondary reactions under the mixing and reaction conditions, for example alkyl or aryl substituents, ether groups and the like. Preferably, these epoxy compounds are polyglycidyl ethers based on polyhydric, preferably dihydric alcohols, phenols, hydrogenation products of these phenols and / or novolaks (reaction products of mono- or polyhydric phenols with aldehydes, particularly formaldehyde, in the presence of acidic catalysts). The epoxy equivalent weights (EEW) of these epoxy compounds are vorzugswei- se between 100 and 2000, particularly between 170 and 250. The epoxy equivalent weight of a substance is defined as that amount of substance (in grams) which contains 1 mol of oxirane rings.

Preferred polyhydric phenols include the following compounds: resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), isomer mixtures of dihydro- xydiphenylmethans (bisphenol F), tetrabromobisphenol A, 4,4 ' dihydroxy-diphenylcyclohexane, 4,4-dihydroxy-3,3-dimethyldiphenylpropane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy benzophenone, bis (4-hydroxyphenyl) -1, 1 -ethane, bis (4-hydroxyphenyl) -1, 1-isobutane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) -sulfone etc. and the chlorination and bromination the compounds mentioned above; Bisphenol A is most particularly preferred. The polyglycidyl ethers of polyhydric alcohols useful in the present invention. Examples of such polyhydric alcohols include ethylene glycol, diethyl englykol, triethylene glycol, 1, 2-propylene glycol, polyoxypropylene glycols (n = 1 - 20), 1, 3- propylene glycol, 1, 4-butylene, 1, 5-pentanediol, 1, 6 hexanediol, 1, 2,6-hexanetriol, glycerol, trimethylolpropane, Pentaaerythrit, isosorbide and bis (4-hydroxycyclohexyl) -2,2-propane called. It can also be used polyglycidyl ethers of alkoxylated polyhydric alcohols.

Next polyglycidyl esters of polycarboxylic acids by the reaction of epichlorohydrin or similar epoxy compounds with an aliphatic, Cyc loaliphatischen or aromatic polycarboxylic acid such as oxalic acid, succinic acid, adipic acid, glutaric acid, phthalic acid, terephthalic acid, hexahydrophthalic acid, 2,6-

Naphthalene dicarboxylic acid and dimerized linolenic acid, are obtained. Examples are adipic pinsäurediglycidylester, phthalic acid and hexahydrophthalic.

Such products are marketed by various manufacturers under the trade names Araldite © WHO ©, Epilox © or © Baxxores. Particularly preferred are bisphenol A epoxides and bisphenol F epoxides and derivatives thereof, in particular glycidyl ethers such as diglycidyl ether bisphenol A, and mixtures with the above aliphatic di- or triepoxides. According to the invention, mixtures of different polyepoxides can be used, for example mixtures of two or three polyepoxides.

According to the invention, the polyepoxide can containing the polyepoxide and at least one diluent be used in pure form or in the form of a composition. Suitable diluents are known in the art, for example inreaktive solvent such as ethyl acetate, hydrocarbons, reactive diluents such as linear, low-viscosity di- or triepoxides, plasticizers such as phthalates or Zitronensäureester. Further are to be understood as a diluent in the context of this invention low-viscosity reactive diluents such as Monoglycidether or diglycidyl ethers based on short-chain diols or triols such as 1, 4-butanediol, 1, 6-hexanediol, trimethylolpropane, 1, 4 cyclohexanedimethanol, or polyoxypropylene glycol.

Also polyether amines and methods for their preparation are known in the art per se. Preferably polyether amines are used which have a molecular weight in the range of 500 to 30,000 g / mol. Such materials are commercially available from various manufacturers. Examples are Jeffamin® D-2000; Jeffamin®-D4000

Jeffamin®-T3000, T5000-Jeffamin®; Polyetheramine D 2000; Polyetheramine T 5000; Poly A 27- 2000; Poly A 37-5000. According to a further embodiment, the present invention relates to a method for preparing a polyurethane as described above, wherein the compound (V1) is a polyvinyl lyetheramin having a molecular weight in the range of 500 to 30,000 g / mol. Particularly preferred are the polyether amines have a molecular weight in the range from 1,000 to 15,000 g / mol, and most preferably a molecular weight in the range from 1500 to 10,000 g / mol.

In addition to the molecular weight and the amino equivalent weight (AEW), which is known in the art, be used as a description of the polyether amines can. This can be calculated by titration or the like. The polyetheramines employed preferably have an amino equivalent weight in the range from 80 to 7500 g / eq, particularly preferably in the range of 150 to 3750g / eq, and most preferably an amino equivalent weight in the range of 250 to 2500 g / eq.

According to the invention, at least one polyetherol may be employed.

Preferably, the polyether polyols have a number average molecular weight in the range of 500 to 30,000 g / mol, particularly preferably greater than 500 g / mol to less than 12,000 g / mol and in particular from 600 g / mol to 8,000 g / mol.

In addition to the molecular weight, the OH value, which is known in the art, can be used for the description of polyether polyols. This can be calculated by titration or the like. The polyether polyols used preferably have an OH number in the range of 5 to 650 mg KOH / g, more preferably in the range of 10 to 600 mg KOH / g, and most preferably in the range of 15 to 500 mg KOH / g.

The determination of the molecular weight may be based on gel permeation chromatography or by determination of the OH number (or the amino equivalent weight) of the polyol (or polyvinyl lyetheramins) take place and subsequent conversion. Corresponding methods are DIN 16945 described under.

According to a further embodiment, the present invention relates to a method for preparing a polyurethane as described above, wherein the compound (V1) is a polyvinyl mol lyetherol having a molecular weight in the range of 500 to 30,000 g /.

Polyetherols are prepared by known methods, for example by anionic polymerization using alkali metal hydroxides or alkali metal alcoholates as catalysts and with addition of at least one initiator molecule containing 2 to 8 reactive hydrogen atoms in bound form or by cationic polymerization with Lewis acids such as antimony pentachloride or Borfluo- rid etherate or bases such as potassium hydroxide of one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical. Suitable alkylene oxides 3- propylene oxide, 1, 2- or 2,3-butylene oxide and preferably ethylene oxide and 1, 2-propylene oxide are, for example, 1,. Furthermore tetrahydrofuran monomer may be used. Further, as catalysts and multimetal, known as DMC catalysts, are used. The alkylene oxides may be used individually, alternately in succession or as mixtures. wherein said ethylene oxide is used in quantities of 1 to 50%, and is more preferably used as the ethylene oxide end block ( "EO cap") so that are preferably 1, 2-propylene oxide and mixtures of 1, 2-propylene oxide and ethylene oxide, the polyols formed have over 70% primary OH terminal groups.

In a particularly preferred embodiment, mixtures of starter molecules metadata used so that the average number is due to the reactive hydrogen atoms of from 2 to starter molecules. 6

As the initiator molecule preferably water or 2- to 8-valent alcohols such as ethyl englykol, 1, 2- and 1, 3-propanediol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, glycerol or trimethylolpropane, pentaerythritol, sugar alcohols such as sorbitol or come sugars such as Saachero- se, amine compounds such as ethylenediamine, diethanolamine or toluene or mixtures of the starter molecules contemplated.

The most preferred polyether polyols, preferably polyoxypropylene-polyoxyethylene polyols or polyoxypropylene-polyols preferably have a functionality of 1, from 5 to 5.8, preferably a functionality of 1, 7 to 5, and most preferably has a functionality of 1, 85-4 , 5, and number average molecular weights of 1,000 g / mol to 12,000 g / mol (or an OH number of 7 to 325 mg KOH / g), preferably from 1,500 g / mol to 8,000 g / mol (or an OH number 12-190 mg KOH / g), particularly of 2,000 g / mol to 6,000 g / mol (or an OH number of 17 to 125 mg / KOH).

Suitable polyisocyanates include aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates may be used. Specifically, the following aromatic isocyanates may be mentioned include: 2,4-tolylene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, 4,4'-, 2,4'- and / or 2,2 'diphenylmethane-diisocyanate (MDI), mixtures of 2,4'- and

4,4'-diphenylmethane-diisocyanate, urethane, carbodiimide or uretonim-modified liquid 4,4'-and / or 2, 4-diphenylmethane diisocyanate, 4,4'-diisocyanato-diphenylethane, the mixtures of monomeric and Methandiphenyldiisocyanaten higher-nuclear homologues of Methandiphenyldiisocyanats (polymeric MDI), (1, 2) and 1, 5-naphthylene diisocyanate or Prepo- mers are used from these isocyanates and polyols or isocyanates and isocyanate-reactive components.

As the aliphatic diisocyanates conventional aliphatic and / or cycloaliphatic diisocyanates, such as tri-, tetra-, penta-, hexa-, hepta- and / or Oktamethylendiiso- diisocyanate, 2-methyl-pentamethylene diisocyanate, 1, 5, 2-ethyl butylene-diisocyanate-1, 4, 1-lsocyanato- 3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3- bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohexane-diisocyanate, 1-methyl-2, -2,6-diisocyanate, 4- and / or, 4,4'-, 2,4'- and / or 2, 2 ' -Dicyclohexylmethan-diisocyanate, or prepolymers of these isocyanates.

aromatic polyisocyanates or prepolymers are preferably used according to the invention from aroma tables polyisocyanates. According to a further embodiment, the present invention therefore relates to a process for preparing a polyurethane as described above, wherein the polyisocyanate is an aromatic polyisocyanate.

Polyisocyanate prepolymers are obtainable by reacting polyisocyanates in excess, for example at temperatures from 30 to 150 ° C, preferably at temperatures of 50 to 120 ° C and most preferably at about 80 ° C, are reacted with polyols to give the prepolymer described above. Preferably, for the preparation of the prepolymers according to the invention and commercially available polyisocyanates polyols based on polyesters, for example derived from adipic acid, or polyethers, for example, starting from ethylene oxide and / or propylene oxide is used. Polyether polyols are particularly preferred.

Polyols are known in the art and described for example in "Plastics Manual, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. The polymeric compounds described above with respect to isocyanates reactive hydrogen atoms are preferably used as polyols. Particularly preferred polyols polyether polyols used.

Optionally, the polyols mentioned in the preparation of the isocyanate prepolymers usual chain extenders or crosslinking agents are added. Such substances are known funda- additionally from the prior art. 4-butanediol, dipropylene glycol and / or tripropylene glycol is particularly preferred as the chain 1, is used. The ratio of organic polyisocyanates to polyols and chain preferably is selected so that the isocyanate prepolymer has an NCO content of 2 to 33.5%, preferably 10 to 32%, more preferably from 12 to 30%, and most preferably an NCO having content of 15 to 28%.

According to a particularly preferred embodiment of the invention, the isocyanate containing component or the isocyanate prepolymer a proportion of carbodiimide-modified 4,4'-MDI of at least 2.5 wt .-%, preferably of at least 7.5 wt .-% and most vorzugt loading of at least 12.5 wt .-% and less than 30 wt .-%. The fraction is obtained from carbodiimide-modified 4,4'-MDI component to the isocyanate used in the Isocyanatkompo- or isocyanate prepolymers.

According to a further embodiment, the present invention relates to a method for preparing a polyurethane as described above, wherein the polyisocyanate having an NCO content of 2 to 33.5%. According to the invention the polyisocyanate may be used in pure form or in form of a composition such as an isocyanate prepolymer. In a further embodiment, a mixture containing polyisocyanate and at least one solvent may be used. Suitable solvents are known in the art.

According to the invention it is also possible that, besides the compound (P1) further towards isocyanates reactive compounds, such as other polyols, are used.

For example, further polyether polyols or polyester polyols can be used. Suitable polyetherols are in particular those mentioned above.

Suitable polyester polyols are known to the skilled worker. Polyester polyols can, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms and polyhydric alcohols, preferably diols, having 2 to 12 carbon atoms, preferably be prepared from 2 to 6 carbon atoms. Suitable dicarboxylic acids are, for example: succinic acid, adipic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, maleic acid, fumaric acid, phthalic acid and terephthalic acid. The dicarboxylic acids can be used either individually or in a mixture with each other. Instead of the free dicarboxylic acids, the corresponding dicarboxylic acid derivatives such as dicarboxylic esters of alcohols having 1 to 4 carbon atoms or dicarboxylic anhydrides. Dicarboxylic acid mixtures of succinic, glutaric and adipic acid in ratios of, for example, 20 to 35: 35 to 50: 20 to 32 parts by weight, and in particular adipic acid. Examples of dihydric and polyhydric alcoholate le, in particular diols, are: ethanediol, diethylene glycol, 1, 2- or 1, 3-propanediol, dipropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol , 1, 10-decanediol, glycerol and trimethyl olpropan. Preference is given to using ethanediol, diethylene glycol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol. also possible to use polyester polyols from lactones NEN, eg ε-caprolactone or hydroxycarboxylic acids, eg ω-hydroxycaproic acid.

To prepare the polyester polyols, the organic, for example aromatic and preferably aliphatic polycarboxylic acids and / or derivatives and polyhydric alcohols can be a catalyst or preferably in the presence of esterification catalysts, expediently in an atmosphere of inert gas such as nitrogen, carbon monoxide, helium, argon, etc., in the melt at temperatures of 150 to 250 ° C, preferably, optionally polycondensed under reduced pressure until the desired acid number, which is preferably less than 10, more preferably less than 2 180 to 220 ° C. According to a preferred embodiment, the esterification mixture at the abovementioned temperatures to an acid number of 80 to 30, preferably 40 to 30, under atmospheric pressure and then polycondensed under a pressure of less than 500 mbar, preferably 50 to 150 mbar. The esterification catalysts are, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts. However, the polycondensation can in waiting counter of diluents and / or entrainers such as benzene, toluene, xylene or chlorobenzene to azeotropically distill off the water of condensation also in the liquid phase. To prepare the polyester polyols, the organic polycarboxylic acids and / or derivatives and polyhydric alcohols are advantageously in a molar ratio of 1: 1 to 1, 8, preferably 1: 1 polycondensed 05-1; 2.

The polyester polyols preferably have a functionality of 2 to 4, especially from 2 to 3, and for example a number average molecular weight of from 480 to 3000 g / mol, preferably 1000 to 3000 g / mol.

Only polyether polyols are particularly preferred in the present invention as a further polyol component used.

According to the invention, other components can be used, such as chain extenders, crosslinking agents, auxiliaries and additives, or additives such as surfactants, dyes, pigments, antioxidants, UV-protection agents, water scavengers, catalysts, latent heat storage and Mikroholkugeln, defoamers, hydrolysis. Suitable auxiliaries and additives can for example be taken from the Kunststoffhandbuch, Volume VII, published by Vieweg and Hochtlen, Carl Hanser Verlag, Munich, 1966 (p 103-1 13).

As a chain extender and / or crosslinking agents are substances having a molecular weight of preferably less than 450 g / mol, particularly preferably from 60 to 400 g / mol, chain extender two atoms which are reactive hydrogen isocyanate reactive hydrogen atoms and crosslinker 3 isocyanate. These may preferably be used singly or in the form of mixtures. Preferably diols and / or triols having molecular weights of less than 400 g / mol, particularly preferably from 60 to 300 g / mol and in particular 60 to 150 g / mol. Come into consideration, for example, aliphatic, cycloaliphatic and / or araliphatic diols having 2 to 14, pre- preferably 2 to 10 carbon atoms, such as ethylene glycol, 1, 3-propanediol, 1, 10-decanediol, 1, 2-, 1, 3-, 1, 4-dihydroxycyclohexane, diethylene glycol, dipropylene glycol and 1, 4-butanediol, 1, 6- hexanediol, and bis (2-hydroxyethyl) hydroquinone, triols, like 1, 2,4-, 1, 3,5-trihydroxy- cyclohexane, glycerol and trimethylolpropane, and low molecular weight hydroxyl-containing polyvinyl lyalkylenoxide based on ethylene oxide and / or 1, 2-propylene oxide and the abovementioned diols and / or triols as starter molecules. Further, also aromatic amines such as diethyltoluenediamine, 3,3 ^{'dichloro-4,4'-diaminodiphenylmethane,} 3,5-diamino-4 can chlorisobutylbenzoat as a chain extender, 4-methyl-2,6-bis (methylthio) -1, 3-diaminobenzene, trimethylene glycol di-p-aminobenzoate are used. Such aromatic amine chain extenders are available from various manufacturers and the skilled person usually tions under various abbreviations such as MOCA, MOCA, MCDEA, DETA known. 4-butanediol, Diethylengylcol, glycerol, trimethylolpropane or mixtures are particularly preferred as chain monoethylene glycol, 1, thereof. According to the invention the process is conducted such that mainly takes place in the use of amine chain extending a reaction of the chain extender with the isocyanate and a reaction of the chain extender with the compound (P1) is carried out only to a small extent or not at all. Such methods are known in the art, for example, the addition of the amine chain extender can only take place in the mixing chamber. Such methods are of course also possible with other chain extenders.

In a preferred embodiment of the invention, the proportion of chain extender in the composition (Z1) in the range of 0 to 35 wt .-%, preferably in the range of 5 and 30 wt .-% and most preferably in the range of 7.5 and 25 wt .-%.

Optionally auxiliaries and additives may be added. Here following are examples of roholkugeln surfactants, dyes, pigments, hydrolysis stabilizers, oxidation onsschutzmittel, UV stabilizers, water scavengers, catalysts, latent heat storage and micro-.

Are used as additives Mikroholkugeln, the resulting polyurethane is also referred to as glass-syntactic polyurethane.

As catalysts for the preparation of the polyurethane molding compounds are preferably used which accelerate the reaction of the hydroxyl group-containing compounds of component Z1 with the organic, modified or unmodified polyisocyanates (Z2) thick. Examples which may be mentioned are amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl-, N-cyclohexylmorpholine, Ν, Ν, Ν ', Ν'-tetramethylethylenediamine, Ν, Ν, Ν', Ν'- tetramethyl-butanediamine, Ν, Ν, Ν ', Ν'-tetramethyl-hexanediamine, pentamethyl-diethylenetriamine, tetramethyl-diaminoethyl ether, bis (dimethylaminopropyl) - urea, dimethylpiperazine, 1, 2- dimethylimidazole, 1-aza-bicyclo- (3,3,0) -octane, and preferably 1, 4-diaza-bicyclo (2,2,2) octane and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyl-diethanolamine, and dimethylethanolamine.

Likewise, organic metal compounds can be considered. organic metal compounds based on tin, zinc, bismuth, titanium, zirconium, manganese, iron, cobalt, copper, aluminum are preferably used. For example, mentioned are organic tin compounds such as tin (II) salts of organic carboxylic acids, for example tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the dialkyltin (IV) salts of organic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, and also bismuth carboxylates such as bismuth (III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate, titanium compounds such as titanium-IV- (triethanolamito) isopropxide or titanium-IV-bis (triethanolamito) diisopropxide or mixtures of various metal compounds. The organic metal compounds can be used alone or in combination with strongly basic amines. exclusively organic metal compounds are preferably used as catalysts for the reaction of Z1 and Z2. In a preferred embodiment of the invention, the proportion of catalyst in the composition (Z1) in the range of from 0.00001 wt .-% to 5 wt .-%, preferably in the range of from 0.0001 wt% to 2 wt .-% and most preferably in the range of 0.0005 wt% and 1 wt .-%.

The term hollow microspheres of this invention are understood to be organic and mineral hollow spheres in the frame. As the organic hollow spheres, for example hollow plastic spheres, for example of polyethylene, polypropylene, polyurethane, polystyrene or a mixture thereof can be used. The mineral hollow spheres may contain, for example, clay, aluminum silicate, glass or mixtures thereof.

The hollow spheres may have inside a vacuum or partial vacuum or with air, inert gases such as nitrogen, helium or argon, or reactive gases such as oxygen, to be filled.

Usually, the organic or mineral hollow spheres have a diameter of 1 to 1000 μηη, preferably from 5 to 200 μηη on. Usually, the organic or mineral hollow spheres have a bulk density of 0.1 to 0.5 g / cm ^3. They have in general mean a thermal conductivity of 0.03 to 0.12 W / mK.

are preferred as the hollow microspheres hollow glass microspheres used. In a particularly preferred embodiment, the hollow glass microspheres have a hydrostatic pressure resistance of at least 20 bar. For example, as hollow glass microspheres 3M - used Scotchlite Glass Bubbles ^®.

As a latent heat accumulator, encapsulated and non-encapsulated lipophilic substances can be used with a solid / liquid transition above 20 ° C, mostly waxes. These may be encapsulated in a polymer. For current crude oil production, the latent heat storage take up heat from the hot crude oil and melt. In a short-term production stops the insulation from the outside cools slowly, also the lipophilic filling of the latent heat storage is cooled, solidified, and thereby the heat received write back to the crude oil. Similar solutions are described in DE 10256550, WO 2004/003424, US

6,000,438, WO 2002/016733 or CN described 101545565th

Further, it is possible to add as auxiliaries and additives of the prior art known blowing agents such as water, pentane, cyclopentane, etc.. It is preferred, however, that no blowing agent is used, in particular, that no water is added. Further, it is particularly preferred if the residual water content of the starting materials is reduced by the addition of water scavengers. Water scavengers such as zeolites are suitable. The water scavenger, for example in an amount of 0.1 to 10 wt .-%, based on the total weight of the polyol used. For the preparation of the polyurethane reaction mixture of the invention, the composition (Z1) and the composition (Z2) in such amounts are reacted, that the equivalence ratio of NCO groups of the isocyanate groups is the sum of the reaction ven hydrogen atoms in a particular area. The expert used the term "index" or "index". This reflects the molar ratio of the NCO groups to the reactive hydrogen atoms again. An index of 100 corresponds here a ratio of 1: 1. When an index of greater than 100, a molar excess of isocyanate is present, has an index of less than 100, an excess of reactive hydrogen atoms before. Preferably, the index 50-2500, particularly preferably 60-350, most preferably 85-130, and in particular 90-1 15th

According to the above definition, the epoxide groups present the compound (V1) according to the invention are not included in the calculation of the index or measure with.

The starting components are usually mixed at a temperature of 5 ° C to 120 ° C, preferably 10 ° C to 80 ° C, more preferably mixed for 20 ° C to 60 ° C and reacted. According to a further aspect, the present invention also relates to the use of a compound (P1) obtainable or obtained by reacting at least one polyepoxide with a connection (V1) is selected from the group consisting of polyether and polyether polyols for making polyurethanes. As stated, are obtained with the inventive method polyurethanes which have particularly good hydrolytic stability, in particular good resistance to hydrolysis at high temperatures.

According to a further embodiment, the present invention relates to a polyurethane as described above, wherein the polyurethane is a casting elastomer. These can be used in various technical fields, for example as mine screens, wheels and pulleys, roller coatings etc ..

According to a further aspect, the present invention relates to a polyurethane obtainable or obtained by a process for preparing a polyurethane as described previously.

According to a further embodiment, the present invention relates to a polyurethane as described above, wherein the polyurethane is a compact polyurethane. The polyurethanes are particularly suitable for the coating of pipelines, field joint and for Underwater Technology (subsea equipment). Insofar as described above, no blowing agents are used, obtained as the product of the invention, compact polyurethanes and polyurethane foams no. Suitable reaction conditions and production method for producing the polyurethanes or coatings are known in the art per se

The mixing of the components can be carried out with the usual processing machines. In a preferred embodiment, the mixing by low pressure machine or a high pressure machine is carried out. The parts to be coated may be prepared via cast molding or either by a rotary method. However, the molding is preferably used. The reaction mixture is poured into a mold, which, for example, containing the element to be coated, the pipe. After curing the polyurethane, the mold is removed. The material can be used directly. In a particular embodiment of the invention, the coated member to a heat treatment is subjected.

During rotational molding, the application of the reaction mixture is carried out by pouring on the rotating member, such as the pipeline pipe. In this case, the reaction mixture by means of conventional mixing devices, such as low-pressure mixing head was obtained. In a particular embodiment, the discharge takes place via a slot die. The feed of the mixing head or the tube is generally set so that at a constant discharge the desired thickness of polyurethane coating is achieved. For this purpose, the reaction mixture may preferably contain thixotropic additives, whereby dripping of the reaction mixture is prevented from the rotating member. Alternatively, the coating may be indirect. For this, the reaction mixture of components is poured into a mold and then removed from the mold. The molding thus prepared is then applied to the pipe to be coated element, for example by gluing or screwing. The thickness of the polyurethane layer is preferably 5 to 200 mm, particularly preferably 10 to 150 mm and in particular 20 to 100 mm. If necessary, can be applied to the polyurethane layer, one or more additional layers, including an insulating layer and / or a covering layer of a thermoplastic. Preferably, no further layers are applied to the polyurethane layer.

The polyurethane coating of the invention is characterized by excellent mechanical properties such as elongation and tensile strength as well as excellent hydrolysis stability. A to be coated element such as a pipe element, for example a tube may be an uncoated duct element made of steel, but it can also be used line elements that already have one or more layers of coating. Preferably, in the present invention, the line element is directly coated with the ER inventive polyurethane reaction mixture. Alternatively, the polyurethane reaction mixture according to the invention coated pipe element may for example also be applied to a powder with fusion bonded epoxy or sprayed with polypropylene (or polyethylene). Optionally, the line element can also be already coated with a first layer of polyurethane, for example, containing latent heat storage. Thereafter, the polyurethane reaction mixture is cured to form a polyurethane layer, optionally with heat treatment, for example by irradiation or in an oven. When coated with polyurethane line elements in the sense of the present invention are not only classic coated pipe coatings, but also polyurethane-coated welding areas of pipes, so-called "field joints", and coated with polyurethane objects connected with pipelines in connection, such as sleeves, Borlochanschlüsse , Christmas trees, pipe collector, pumps and buoys to be understood. also, line elements are coated with polyurethane cable preferably comprise off-shore cable. further, a polyurethane coated pipe element includes in the sense of the present invention also includes tubes, the casings for reinforcement, such as Bend have stiffener or bend restrictors, wherein the bend stiffener and the bend restrictors of polyvinyl correspond lyurethanbeschichtung. Preferably, under the invention with polyvinyl lyurethan coated conductive element is a line element an offshore pipeline or a to understand offshore cable. Here, "off-shore", that these items come into contact when in normal use with sea water. Particularly preferred is according to the invention, coated with polyurethane conduit member coated with polyurethane pipe of an offshore pipeline, a field joint of an off-shore pipeline or igneous cross (also called X-mas tree) of an off-shore pipeline, in particular an off-shore pipeline to the production of crude oil.

The coating of the parts can be carried out as stated, directly or indirectly, wherein the polyurethane is prepared separately in an indirect coating and then through for example screw connections is applied to the element to be coated. Polyurethane is preferably cast directly onto the surface of the material to be coated or sprayed. In general, the surfaces to be coated of metals such as steel, iron, copper or aluminum, or of plastics such as polypropylene or epoxy resins exist. For better adhesion optionally typical coupling agents, such as internal coupling agent which are added to the polyurethane components, external bonding agents, which are applied directly to the surface to be coated and / or physical adhesion promoter can still be used. Also may be pretreated surface to be coated, for example by flame treatment or plasma treatment. Accordingly, the present invention relates in another aspect to the use of a polyurethane obtainable or obtained by a process for preparing a polyurethane as described above, or a polyurethane for loading stratification of pipes, as a pipeline coating, field joint or christmas tree as previously described for the off-shore sector.

According to a further aspect, the present invention relates to the use of a polyurethane obtainable or obtained by a process for preparing a polyurethane as described above, or a polyurethane as described previously as a glass-syntactic polyurethane.

Further embodiments of the present invention are disclosed in the claims and the Beispie- len. It will be appreciated that the hereinbefore identified and the hereinafter described features of the object / process / uses of the invention are useful not only in the respectively specified combination but also in other combinations without departing from the scope of the invention. So z. As well as the combination of a preferred feature with a particular feature, or a not-characterized feature with a particularly preferred feature etc. includes implicitly even if this combination is not explicitly mentioned.

Hereinafter, exemplary embodiments of the present invention are listed, these do not limit the present invention. In particular, the de vorliegen- invention also includes those embodiments which result from the indicated below rear covers and combinations thereof.

1. A process for preparing a polyurethane comprising reacting at least the following components:

(I) composition (Z1) comprising at least one isocyanate-reactive compound (P1), and

(Ii) composition (Z2), comprising at least one polyisocyanate, wherein the compound (P1) is obtainable or obtained by reacting at least one polyepoxide with a connection (V1) is selected from the group consisting of polyether amines and polyetherols.

2. A process for producing a polyurethane according to embodiment 1, wherein in addition to the components in the reaction (i) and (ii) at least one of the following components is used:

(Iii) a further isocyanate-reactive compound,

(Iv) a chain extender,

(V) further additives. 3. A process for producing a polyurethane according to Embodiment 1 or 2, wherein the compound (P1) has a theoretically calculated OH number in the range of 0.5 mg KOH / g to 75 mg KOH / g. 4. A process for producing a polyurethane according to any of embodiments 1 to 3, wherein the compound (P1) has a theoretically calculated epoxy equivalent weight in the range of 180 to 5000 g / eq.

5. A process for producing a polyurethane according to any of embodiments 1 to 4, wherein the compound (V1) is a polyetheramine having a molecular weight in the range of 500 to 30,000 g / mol.

6. A process for producing a polyurethane according to any of embodiments 1 to

5, wherein the compound (V1) is a polyether polyol having a molecular weight in the range of 500 to 30,000 g / mol.

7. A process for producing a polyurethane according to any of embodiments 1 to

6, wherein the polyisocyanate is an aromatic polyisocyanate. 8. A process for producing a polyurethane according to any of embodiments 1 to

7, wherein the polyisocyanate has an NCO content of 2 to 33.5%.

9. A process for producing a polyurethane according to any of claims 1 to 8, wherein a catalyst is used.

10. A process for producing a polyurethane according to any of claims 1 to 9, wherein the proportion of catalysts in the composition (Z1) in the range from 0.00001 wt% to 5 wt .-% is. 1 1. polyurethane obtainable or obtained by a process according to any one of claims 1 to 10 degrees.

12. The polyurethane of claim 1 1, wherein the polyurethane is a compact polyurethane. 13. The polyurethane of claim 1 1 or 12, wherein the polyurethane is a casting elastomer.

14. Use of a compound (P1) obtainable or obtained by reacting at least one polyepoxide with a connection (V1) is selected from the group consisting of polyether and polyether polyols for making polyurethanes.

15. The use of a polyurethane obtainable or obtained by a process according to any one of claims 1 to 10, or a polyurethane according to any of claims 1 1 to 13 for the coating of pipelines, as field joint or for underwater equipment (subsea equipment) for the off- Shore area.

6. The use of a polyurethane obtainable or obtained by a process according to any one of claims 1 to 10, or a polyurethane according to any of claims 1 1 to 13 as a glass-syntactic polyurethane.

7. The use of a polyurethane obtainable or obtained by a process according to any one of claims 1 to 10, or a polyurethane according to any of claims 1 1 to 13 in technical or industrial applications.

In the following the invention will be explained in more detail by way of examples without restricting the subject matter of the invention.

Examples:

1. Input materials

Poly 1: Jeffamine® T-403 polyetheramine having a molecular weight of about 440 g / mol, an AHEW of 81 g / eq Huntsman

Poly 2: Jeffamine® T-3000 polyether amine having a molecular weight of about 3000 g / mol and an AHEW of 530 g / eq Huntsman

Poly 3: Jeffamine® T-5000 polyether amine having a molecular weight of about 5000 g / mol and an AHEW of 952 g / eq Huntsman

Poly 4: polyetheramine D-2000 by BASF having a molecular weight of about 2000 g / mol and an AHEW of 500 g / eq Huntsman

Poly 5: Jeffamine® D-4000 polyetheramine having a molecular weight of about 4000 g / mol and an AHEW of 1000 g / eq Huntsman

Poly 6: Lupranol 2090 from BASF Polyurethanes GmbH, a trifunctional polyvinyl lyol having an OH number of 28 mg KOH / g

Poly 7: polyetherol based on sorbitol, propylene oxide and ethylene oxide with a

Ethylene oxide content of 10 wt .-% and an OH number of 43 mg KOH / g poly 8: 1005/1 Lupranol of the BASF Polyurethanes GmbH; Polyproylenglycol having an average molecular weight of 4000 g / mol and an OH number of 28 mg KOH / g

Poly 9: polyetherol based on trimethylolpropane and propylene oxide with an OH number of 860 mg KOH / g

Poly 10 Lupranol 1200 from BASF Polyurethanes GmbH company Polyproylenglycol having an average molecular weight of 450 g / mol and an OH number of 248 mg KOH / g of poly 1 1 Lupranol 2010/1 BASF Polyurethanes GmbH, having an OH number of 45 mg KOH / g

Epoxy 1: EPON ™ Resin 828 from Momentive, a 2 functional epoxy resin

Based on bisphenol-A and epichlorohydrin having an EEW of 185 g / eq

Epoxy 2: Araldite® GY 250 from Huntsman, an epoxy resin based on bisphenol-A and epichlorohydrin having an EEW of 185 g / eq

Epoxy 3: 13-21 Epilox® Leuna resins, an epoxy reactive diluent based on 1, 4-butanediol and epichlorohydrin having an EEW of 132 g / eq

Epoxy 4: 13-31 Epilox® Leuna resins, an epoxy reactive diluent based on trimethylolpropane and epichlorohydrin and an EEW of 136 g / eq

Epoxide 5: Epilox® M 985 Leuna resins, a diglycidyl ether based on polyvinyl lyoxyproplyen having an EEW of 460 g / eq

Epoxide 6: IPOX® RD 19 of the company ipox chemicals, Polyoxypropylendiglycidether having an EEW of 315 g / eq

Epoxide 7: IPOX® RD 21 of the company ipox chemicals, poly (tetramethylene oxide) - diglycidyl ether having an EEW of 420 g / eq

Epoxide 8: 19-03 Epilox® A Leuna resins having an epoxy equivalent weight

190 g / eq

DL: propylene

DF: defoamers

ZP: zeolite paste 50% in polyol having an OH number of 80 mg KOH / g

KV1: 1, 4-butanediol

AV1: 2-amino-1-propanol obtained from the Aldrich

Cat 1: Lupragen N 201 from BASF Polyurethanes GmbH

Cat 2: Fomrez UL 28 from Momentive

Cat 3: 2,4,6-tris (dimethylaminomethyl) phenol obtained from the Aldrich Cat 4: K-Kat XK 604 from King Industries

Cat 5: Anchor® 1040 from Air Products

Cat 6: Tyzor TE company Dorf Ketal

IS01: Lupranat® MP 102 BASF Polyurethanes GmbH company having an NCO content of 23%

IS02: Lupranat M 20 BASF Polyurethanes GmbH company having an NCO content of 31, 5%

IS03: Lupranat® MM 103 from BASF Polyurethanes GmbH, a carbodiimide modified 4,4'-diisocyanate having an NCO content of 29.5%

IS04: ISO 134/7 Company GmbH Polyurethanes having an NCO content of 26.2% IS05: mixture of 30% ISO and 70% ISO 1 2 with an NCO content of 28.9% IS06: mixture of 50% ISO 1 and 50% ISO 3 having an NCO content of 26.2% IS07: mixture of 70% ISO and 30% ISO 1 2 with an NCO content of 25.5% General method for preparing the reaction products of polyetheramines and polyepoxides

For the preparation of reaction products of polyetheramines and polyepoxides the appropriate amount of epoxy resin or epoxy mixture will be in a 4-necked flask equipped with stirrer, nitrogen inlet and cooler initially charged and then supplied to the appropriate amount of polyether or Polyetheraminmischungen. The reaction mixture is slowly heated to a temperature of 125 ° C and held at this temperature for a period of at least 3 h. Thereafter, the material is heated to about 60 ° C - 80 ° C cooled and bottled. In Table 1a and 1b are examples of inventive reaction products are listed.

Table 1a

B1 B2 B3 B4 B5 B6 B7 B8

Momentive Resin 828 88.1 78.7 78.7 64.9 64.9 48.1 52.6 35.7

Polyetheramine D 2000 1 1 9 21 3 35.1 47.4

Jeffamine D-4000 21 35.1 3 51 64.3 9

EEWP (calculated) 221 247 261 317 356 481 528 777

OH value (calculated) 13.4 1 1 9 23.9 19.7 39.4 29.1 53.2 36.1

Viscosity at 50 ° C

1 82 1 89 3.21 2.90 8.36 5.36 34.9 13.21 [Pas]

Table 1 b

B9 B10 B11 B12 B13 B14 B15 B16

Araldite GY 250 64.36 48.68 63.02 91, 77 47.46

Epoxide 3 35.92

Epoxide 4 41 68

7 epoxide 78,95

Polyetheramine D 2000 35.64

Jeffamine D-4000 52.54

Jeffamine T-5000 51 32 64.08 58.32 21 05

Jeffamine T-3000 36.98

Jeffamine T-403 8.23

EEWP (calculated) 359 478 369 253 490 488 408 603

OH value (calculated) 39 30 39 57 29 38 34 12

Attempts to wet stability at storage of epoxides The use of bisphenol-A and epichlorohydrin for offshore applications is explicitly in WO 201 1/161047 and WO 201 1/003529 described as an optional additive. However, in these systems, only small amounts of epoxy resins can be used, because the epoxy resin is not incorporated in the matrix. Further, the high use of epoxy resins in a reduction in elongation at immersion in water or steam and high temperatures leads. A normal polyurethane elastomer is little stable at warm and humid conditions at elevated temperatures. This will be illustrated by the following examples.

For this purpose, initially the components of the polyol component were (polyols, chain extenders rer, zeolite paste, defoamer reaction products according to the invention from Polyethe- raminen or polyols and polyepoxides, etc.) by means of a SpeedmixerTM the company Haunschild for 20 seconds at 800 RPM and mixed for 40 seconds at 2000 RPM and degassed, following in vacuo. To the mixture the appropriate amount of isocyanate was then added to degassed and mixed for 40 sec at 2,000 RPM in SpeedmixerTM. The reactive mixture was then placed in a heated to 70 ° C mold to prepare test plates with a thickness of 2 mm. After 2 hours at 70 ° C the test panels were removed from the mold and after a 7-day storage under standard climate tensile bars were punched out from these test sheets and the tensile strength and elongation according to DIN 53504 is determined. Another part of these tensile bars were then stored in water vapor, and then determines the tensile strength and elongation according to DIN 53504 for 5, 10 or 15 hours at 130 ° C.

Table 2 below shows the composition of the formulations and the results of tests again.

table 2

V1 V2 B17 B18 B19 V3

Poly 6 85.32

Epoxide 1 80.498 86.500

Material B 9 80.498 86.500

Material from B 10 86,500

KV 13.00 17.000 17.000 1 1, 000 1 1 000 1 1 000

ZP 1 50 2.000 2.000 2.500 2.500 2.500

DL 5,000 5,000

DF 0,500 0,500

kat1 0.18

Kat2 0.002 0.002 0.0005 0.0005 0.0005

ISO 4 XXXX

ISO 5 XX Index 103 103 103 103 103 103

Oh 130 ° C / water vapor

Tensile strength [MPa] 16 20 28 21 18 nM

Elongation [%] 490 90 80140120 nM

5h 130 ° C / steam

Tensile strength [MPa] 10 52 33 28 22 nM

Elongation [%] 390 5 50150130 nM

10h 130 ° C / steam

Tensile strength [MPa] 24 36 6 28 22 nM

Elongation [%] 220 120 130 nm 2 40

15h 130 ° C / steam

Tensile strength [MPa] 23 37 4 27 25 nM

Elongation [%] 1 10 1 40130150 impossible NMNM measurement because Matetrial is too soft and does not let demold

As can be seen from the comparative examples and examples, a normal polyurethane elastomer exhibits no particular resistance in humid conditions and high temperatures. The use of high concentrations of epoxides in the sample V2 shows that the materials lose very much of expansion. Furthermore, in Example V3 no material could be obtained, which could be used for testing. The material from V3 was too soft and could not be removed from the mold even after 24 hours curing at 70 ° C. This illustrates that high concentrations of epoxy resins can not be used in a polyurethane system easily. The inventive examples B17 - B 19 show that the materials have excellent properties under hot and humid conditions include without that the elongation drops below a critical level. Further, apparent from the examples that by appropriate modification of the isocyanate prepolymers can still improve systems of the invention may be realized and materials which are not possible with the pure epoxy resins.

Attempts - storage under humid conditions

Those disclosed in WO 201 1/161047 systems having a concentration of epoxy resins 2-15 wt .-%, based on the polyol, also exhibit at long-term storage in artificial seawater (ASTM D1 141-98 "Standard Practice for the Preparation of Substitute Ocean Water) at elevated temperatures is also poor hydrolytic stability. To avoid the negative impact of high concentrations of epoxy resins in the formulations, the practitioner could suggest to use epoxy resins based on polyether polyols and epichlorohydrin. However, these materials have negative characteristics, which will be illustrated in the following examples.

For this purpose, initially the components of the polyol component were (polyols, chain extenders rer, zeolite paste, defoamer reaction products according to the invention from Polyethe- raminen or polyols and epoxides, etc.) by means of a SpeedmixerTM the company Haun- shield for 20 seconds at 800 RPM and 40 sec at 2000 RPM mixed and degassed, following in a vacuum. The mixture was then degassed at the corresponding amount of cyanate iso- added and mixed for 40 sec at 2,000 RPM in SpeedmixerTM. The reactive mixture was then placed in a heated to 70 ° C mold to prepare test plates with a thickness of 2 mm. After 2 hours at 70 ° C the test panels were removed from the mold and after a 7-day storage under standard climate tensile bars were punched out from these test sheets and the tensile strength and elongation according to DIN 53504 is determined. Another part of these tensile bars was then stored in artificial sea water in a pressure vessel at 120 ° C and at specified intervals were

Tensile bars taken and the tensile strength and elongation in the freshly extracted state. Further, also the tensile strength of the materials in the dried state was determined. For this purpose, the tensile bars were dried after removal from the artificial sea-water for at least 16 hours at 40 ° C and then conditioned for an additional 2 hours under standard climatic conditions.

The following Tables 4a and 4b provide information about the results. The composition results from Tables 3a and 3b. As is clear from the experiments V6 - seen V 8, the high concentrations of epoxy resins based on epichlorohydrin and polyetherols show a poor compatibility with the polyurethane system. The epoxy resin to migrate out of the polyurethane out during the 7 days of storage. Partly this effect was also found after removal from the mold. B23, however, shows that can be introduced by the use of the inventive materials, a large amount of these incompatible epoxides in a polyurethane system. The Versu che V4 and V5 show that disclosed in the prior art combinations of

lead epoxy resins in polyol no sufficient hydrolytic stability at high temperatures. The inventive materials in B20 to 22 have a very good hydrolytic stability at higher temperatures.

table 3a

V4 V5 V6 V7 V8 V9 V10

Poly 6 82.498

Poly 7 73,000 65,000

Epoxy 2 15.000 15.000 82.498

Epoxide 5 82.498

6 Epoxy 82.498

Epoxy material 7 82.498

from B 10

material

from B 14

material

from B 15

material

from B 16

KV 10.000 18.000 15.000 15.000 15.000 15.000 15.000

ZP 1, 500 1, 500 2.500 2.500 2.500 2.500 2.500

DL

DF 0,500 0,500

kat1

Kat2 0.005 0.005 0.002 0.002 0.002 0.002 0.002

ISO 2 XXXXX

ISO 6 XX

Index 103 103 103 103 103 103 103

table 3b

B20 B21 B22 B23

poly 6

poly 7

epoxide 2

epoxide 5

epoxide 6

epoxide 7

material

82.498

from B 10

material

82.498

from B 14

material

82.498

from B 15

material

82.498

from B 16

KV 15.000 15.000 15.000 15.000

ZP 2.500 2.500 2.500 2.500

DL DF

kat1

Kat2 0.002 0.002 0.002 0.002

ISO 2 XXXX

ISO 6

Index 103 103 103 103

table 4a

V4 V5 V6 V7 V8 V9 V10

Comments CCABAC c

Mech. Properties

Hardness [Shore A] 85 94 91 n B n B 97 90

Hardness [Shore D] 49 nB nB nB 31 59 38

Tensile strength [MPa] 12 23 22 13 nB 12 nB

Break [%] 170 170 n B n B 90 90 80

7 days hydrolysis (120 ° C)

12 22 4 48 4

Tensile strength [MPa] nbnb

(NB) (NB) (6) (NB) (8)

150 160 120 3170

Break [%] nbnb

(NB) (NB) (130) (NB) (180)

14 days hydrolysis (120 ° C)

9 18 2

Tensile strength [MPa] nBnBnB F

(NB) (NB) (3)

170170100

Break [%] nBnBnB F

(NB) (NB) (120)

28 days hydrolysis (120 ° C)

5 10

Tensile strength [MPa] nB nbnb F F

(NB) (NB)

150 100

Break [%] n B F F nbnb

(NB) (NB)

56 days hydrolysis (120 ° C)

Tensile strength [MPa] nB FF F F nbnb

Elongation [%] nB FF F F nbnb Table 4b

Comments on the table:

A: epoxy resin not compatible with polyurethane system resin migrated (sweat) from the test plate strong, no determination of the mechanical properties possible

B: Epoxy resin is not well compatible with polyurethane system resin migrated (sweat) from the test panel easy, determining the mechanical properties possible

C: Homogeneous look full mech. testing possible

D: homogeneous appearance, no migration of the reaction product of IPOX RD 21 and Jeffamine T-5000 from the PU material

F: the material is destroyed by the hydrolysis - no measurement of Mech. Properties longer possible (): the value in brackets describes the value of the mechanical property after drying at 40 ° C for min. 16 hours

nB property has not been determined

Processability of the polyurethanes

Furthermore, the inventive materials have significant processing advantages over epoxy elastomers, as described for example in WO 2012/030339. Those described in WO 2012/030339 materials are processed at higher temperatures and also require high mold temperatures. As materials for the oil & gas industry are often applied in the field (eg as field joint) this is very difficult to implement. Furthermore, the materials have a long demolding time, which makes the systems very economical. The advantages of the materials of the invention will be further illustrated in the following examples.

The materials according to the invention was prepared as follows: First, the components of the polyol component were (polyols, chain extenders, zeolite paste, defoamer reaction products according to the invention from polyetheramines or polyols and epoxides, etc.) by means of a SpeedmixerTM the company Haunschild for 20 seconds at 800 RPM and 40 sec mixed at 2000 RPM, and degassed, following in vacuo. The Polyolmi- research of Example B25 was then heated to a temperature of 50 ° C. In Example B24 was carried out at room temperature. To the mixture the appropriate amount of degassed isocyanate component at a temperature of 25 ° C (B24 and B25) was then added and mixed for 40 sec at 2,000 RPM in SpeedmixerTM. The material was then placed in a stored form at room temperature with dimensions 5x5x1 cm and stored at room temperature. After 5 minutes at room temperature was checked every minute whether the material already had a sufficient hardness, which was determined using a commercially available Shore A dial gauge. At the time a measurable Shore A hardness of the material was removed from the mold and then documents the development of hardness over time.

The preparation of the epoxy-based elastomers was prepared analogously to the method which is described in WO 2012/030339. For this purpose the Epoxidprepolymere were heated to a temperature of 50 ° C and degassed. Following the amine crosslinker and the catalyst is 2,4, 6-tris (dimethylaminomethyl) phenol was added in the appropriate amount and for 30 seconds at 800 RPM and then mixed for 60 seconds at 2300 RPM by means of a Speed ​​Mixer Company Haunschild and in a 100 ° C preheated mold cast 5x5x1 cm with the dimension and stored at 100 ° C in an oven. After 10 minutes at 100 ° C was tested every minute, if the material already had a sufficient hardness, which was determined using a commercially available Shore A dial gauge. At the time a measurable Shore A hardness of the material was removed from the mold and then documents the development of hardness over time. Table 5 below provides information on the composition of the systems and the development of hardness over time.

table 5

B24 B25 1 V1 V12

Material B 9 80,500 100

Material from B 10 85.493 100

KV 17,000 12,000

ZP 2,000 2,000

DL 5,000

DF 0,500 0,500

kat2 0.002

AV1 10.5 7.9

Kat3 2.0 3.2

Kat4 0.007

ISO 6100

ISO 7100

Index 103-103 -

Time [min] hardness [Shore A]

5 48

7 40 54

9 48 60

1 1 52 65

13 54 35 73 20

15 56 38 78 28

16 40 33

17 61 84

18 42 40

19 67 89

20 46 92 47

21 73

22 52 51

24 84

25 55 59

30 94 67 69 The examples clearly show that the inventive materials to build much faster hardness, which thus leads to faster mold removal and higher productivity. Furthermore, the inventive materials can also cure at low mold temperatures. This is advantageous in that are not easy to implement in the processing in the field, high mold temperatures and proves to be technologically difficult.

Attempts to hydrolysis

In addition to the shorter demolding the inventive materials show a similar resistance to hydrolysis, such as those known in the literature elastomeric epoxy resins. This will be illustrated in the following examples.

For this purpose, initially the components of the polyol component were (polyols, chain extenders rer, zeolite paste, defoamer reaction products according to the invention from Polyethe- raminen or polyols and polyepoxides, etc.) by means of a SpeedmixerTM the company Haunschild for 20 seconds at 800 RPM and mixed for 40 seconds at 2000 RPM and degassed, following in vacuo. To the mixture the appropriate amount of isocyanate was then added to degassed and mixed for 40 sec at 2,000 RPM in SpeedmixerTM. The reactive mixture was then placed in a heated to 70 ° C mold to prepare test plates with a thickness of 2 mm. After 2 hours at 70 ° C the test panels were removed from the mold and after a 7-day storage under standard climate tensile bars were punched out from these test sheets and the tensile strength and elongation according to DIN 53504 is determined. Another part of these tensile bars was then stored in artificial seawater in a pressure vessel at 150 ° C and at specified intervals tensile bars were removed and determines the tensile strength and elongation in the freshly extracted state.

The preparation of the epoxy-based elastomers was prepared analogously to the method which is described in WO 2012/030339. For this purpose the Epoxidprepolymere were heated to a temperature of 50 ° C and degassed. Following the amine crosslinker and the catalyst is 2,4, 6-tris (dimethylaminomethyl) phenol was added in the appropriate amount and for 30 seconds at 800 RPM and then mixed for 60 seconds at 2300 RPM using a speed mixer of the company Haunschild. The reactive mixture was then placed in a heated to 100 ° C mold to prepare test plates with a thickness of 2 mm. After 2 hours at 100 ° C the test panels were removed from the mold and after a 7-day storage under standard climate tensile bars were punched out from these test sheets and the tensile strength and elongation according to DIN 53504 is determined. Another part of these tensile bars was then stored in artificial seawater in a pressure vessel at 150 ° C and at specified intervals tensile bars were removed and determines the tensile strength and elongation in the freshly extracted state. Table 6 below provides information on the results. As seen from the examples shown, showing the inventive materials in addition to the excellent stability under damp heat conditions, a significantly better tensile strength than the elastomers described in the prior art based on epoxy resins, a comparable stability under damp heat conditions.

table 6

B26 V13

Material from B 10 76.665 100

KV 16.190

ZP 1, 905

DL 4.762

DF 0,476

kat2 0.002

AV1 7.9

Kat3 1, 6

ISO 2100 -

Index 103 -

mechanical properties

Tensile strength [MPa] 25 8

Break [%] 90 90

7 days hydrolysis (150 ° C)

Tensile strength [MPa] 9 2

Elongation [%] 150 100

14 days hydrolysis (150 ° C)

Tensile strength [MPa] 7 2

Elongation [%] 220 90

28 days hydrolysis (150 ° C)

Tensile strength [MPa] 7 2

Elongation [%] 220 90

56 days hydrolysis (150 ° C)

Tensile strength [MPa] 7 2

Elongation [%] 220 90

98 days hydrolysis (150 ° C)

Tensile strength [MPa] 7 2

Elongation [%] 200 1 10 PREPARATION

In addition to the reaction products of polyether amines and epoxides, reaction products of polyols and epoxides can be used. This will be explained in the following examples: Example B27:

In a 11 four-necked flask equipped with stirrer, thermocouple, reflux condenser, and oil bath heating stopper 80g epoxide 8 (Epilox A 19-03, Leuna resins, Epoxyaquivalentgewicht EEW = 190) and 410,2g Poly 8 (Lupranol 1005/1) were weighed. The mixture was heated homogenized and N2 purge and stirring, to 1 10 ° C. On reaching the temperature, 2.0 g of cat 5 were added as the catalyst, a sample was taken for the determination EEW- and the reaction mixture heated cautiously to 130 ° C. It was determined of 1013 g / eq an EEW. After one hour at reaction temperature (130-135 ° C) was an EEW of 2304 g / eq measured (2270g / eq calculated). The reaction mixture was cooled and bottled at about 70 ° C in a glass bottle. There was a slightly cloudy, slightly yellow viscous liquid having the following characteristics obtained EEW: 2606 g / eq (measured)

OH number: 24 mg KOH / g (calculated)

Viscosity: 18.5 Pas (at 22 ° C) Example B28:

In a 11 four-necked flask equipped with stirrer, thermocouple, reflux condenser, stopper and oil bath heating 200g epoxide 8 (Epilox A 19-03, Leuna resins, epoxy equivalent weight = EEW 190) and 410,2g Poly 8 (Lupranol 1005/1) were weighed , The mixture was heated homogenized and N2 purge and stirring, to 1 10 ° C. On reaching the temperature 2.4 g of Cat 5 were added as the catalyst, a sample was taken for the EEW determination, and the reaction mixture heated cautiously to 130 ° C. It was determined by an EEW 580. After one hour at reaction temperature (130-135 ° C) having an EEW of 773 was measured (calculated 720 g / eq). The reaction mixture was cooled and bottled at about 70 ° C in a glass bottle. This gave a clear, pale yellow and slightly viscous liquid with the following characteristics:

EEW: 825 g / eq (measured)

OH number: 19 mg KOH / g (calculated)

Viscosity: 3.7 Pas (at 22 ° C) Example B29

with 3 increments MIG-stirrer, thermocouple, reflux condenser, oil heating in a 3 l laboratory reactor were 1600,5g bisphenol A diglycidyl ether (Epilox A 19-03, Leu- na resins, epoxy equivalent weight EEW = 190) and 381, 2g polyI O (Lupranol 1200, BASF, OH value 248) were weighed. The mixture was heated homogenized and N2 purge and stirring, to 1 10 ° C. On reaching the temperature (Air Products-Anchor 1040) were 6.0 g BF3 amine complex added as a catalyst, a sample was taken for the EEW determination, and the reaction mixture heated cautiously to 130 ° C. It was determined by 218.9 (7.31% EpO) an EEW. The ensuing exotherm was intercepted by lowering the oil heating and maintaining the reaction temperature of between 130 and 135 ° C. After one hour at reaction temperature having an EEW of 287.4 was measured (5.58% EpO). After another hour, the EEW 295.5 Con t (5.41% EpO) The reaction mixture was cooled and filled at about 70 ° C. There was obtained a clear, slightly yellow and viscous liquid having the following characteristics: EEW: 296 g / eq (measured)

OH number: 67.3 mg KOH / g

Viscosity: 36 Pas (at 22 ° C) Example B30

In a 3 liter laboratory reactor equipped with 3-stage MIG-stirrer, thermocouple, reflux condenser, oil heating were 872,0g bisphenol A diglycidyl ether (Epilox A 19-03, Leuna resins, epoxy equivalent weight EEW = 190) and 1 143,0g 1 poly 1 (Lupranol 2010/1, BASF, OH number 45) was weighed. The mixture was heated homogenized and N2 purge and stirring, to 1 10 ° C. On reaching the temperature (Air Products-Anchor 1040) were 6,16g BF3 amine complex added as a catalyst, a sample was taken for the EEW determination, and the reaction mixture heated cautiously to 130 ° C. It was determined by 428.6 (3.37% EpO) an EEW. The ensuing exotherm was intercepted by lowering the oil heating and maintaining the reaction temperature of between 130 and 135 ° C. After one hour at reaction temperature having an EEW of 466.6 was measured (3.43% EpO). After two more hours, the EEW 546.2 Con t (2.93% EpO) The reaction mixture was cooled and filled at about 70 ° C. This gave a clear, slightly reddish yellow and slightly viscous liquid with the following characteristics:

EEW: 548 g / eq (measured)

Viscosity: 17.7 Pas (at 22 ° C)

OH number: 36.6 mg KOH / g Example B 31

In a 3 liter laboratory reactor equipped with 3-stage MIG-stirrer, thermocouple, reflux condenser, oil heating were 670,4g bisphenol A diglycidyl ether (Epilox A 19-03, Leuna resins, epoxy equivalent weight EEW = 190) and 1410,3g Poly6 (Lupranol 2090, BASF, OH number 28) was weighed. The mixture was heated homogenized and N2 purge and stirring, to 1 10 ° C. Amine complex (Anchor 1040, Air Products) was added as a catalyst, a sample was taken for the EEW determination, and the reaction mixture heated cautiously to 130 ° C - on reaching the temperature, 6.3 g BF. ₃ It was determined on 573 (2.79% EpO) an EEW. The ensuing exotherm was intercepted by lowering the oil heating and maintaining the reaction temperature of between 130 and 135 ° C. After one hour at reaction temperature having an EEW of 632 was measured (2.53% EpO). After an additional 1, 5 hours reaction time, the EEW Con t 884 (1, 81% EpO) The reaction mixture was cooled and filled at about 70 ° C. This gave a clear, pale yellow and very viscous liquid with the following characteristics:

EEW: 941 g / eq (measured)

Viscosity: 268 Pas (at 22 ° C)

OH number: 29.4 mg KOH / g

Reaction products according to the invention based on polyols and epoxides can be used as raw materials for the production of the novel polyurethanes.

For this purpose, initially the components of the polyol component (polyols, chain extenders rer, zeolite paste, defoamer reaction products according to the invention from polyols and polyepoxides, etc.) by means of a SpeedmixerTM the company Haunschild for 20 sec were mixed at 800 RPM and 40 sec at 2000 RPM and after the degassed vacuum and heated to 50 ° C. To the mixture the appropriate amount was then added to degassed isocyanate (50 ° C) and mixed for 40 sec at 2,000 RPM in SpeedmixerTM. The reactive mixture was then placed in a heated to 50 ° C mold to prepare test plates with a thickness of 2 mm. After casting, the temperature was raised to 80 ° C and stored, the materials for 2 hours at this temperature. Thereafter, the test panels were removed from the mold and after a 7-day storage under standard climate tensile bars were punched out from these test sheets and the tensile strength and elongation according to DIN 53504 is determined. Another part of these tensile bars were then stored in water vapor, and then determines the tensile strength and elongation according to DIN 53504 for 5, 10 or 15 hours at 130 ° C.

table 7

B32 B33 B34

Poly 9 5,000

Material B 27 81 000

Material from B 28 76,000

Material B 30 81 000

KV 15,000 15,000 15,000

ZP 3,500 3,500 3,500

DF 0.500 0.500 0.500

Kat2 0,001 0,001

Cat6 0.003

8. Examples of the prior art (tests V14-V16 and B35)

For the experiments, V14 - V16 & B35 the corresponding amounts of Polyol 6 were initially charged with epoxide 2 and homogeneously mixed at room temperature in a 500 ml four-necked flask equipped with stirrer, nitrogen inlet and cooler. After homogeneous mixing of the components of a sample was taken to the viscosity of the mixture at 23 ° C to be determined. Then, when the temperature in the experiments were V14 & V15 increased to 60 ° C and held at this temperature for 3h, analogously as described in US 4,647,624 Example 2. Fig. After the 3 hours, the mixture was cooled and the viscosity again. Similar procedure was at V16 and B35, but in this case a temperature of 130 ° C was used for the synthesis of B35 and 5 the mixture was added when 100 ° C Cat. After 3 hours at 130 ° C, the materials were cooled V16 & B35, and determines the viscosity of the mixture at 23 ° C again.

table 8

V14 V15 V16 B35

Poly 6 285,00g 180,00g 180,00g 179,25g

Epoxy 2 15.00g 120,00g 120,00g 120,00g

Kat 5 0.75 g

Viscosity at 23 ° C

to mix 1290 2670 2670 2650

[MPas] viscosity at 23 ° C

after 3 h / 60 ° C 1300 2580

[MPas]

Viscosity at 23 ° C

after 3 h / 130 ° C 2560 6760

[MPas]

As seen from Comparative Examples V14 - V16 can be seen, the viscosity of the mixture does not change, since there is no significant reaction between the polyol and polyepoxide takes place. In the case of B35 a significant increase in viscosity can be observed. This means that none of the structures of the invention were produced in the described examples of US 4647624, but it still is a mixture of polyol and polyepoxide, analogously as described in Comparative Examples V4 & V5. The materials which reflect described in V4 & V5 state of the art back and show poor Langzeithydrolyse properties.

That for the preparation of the novel reaction products of polyepoxides and polyether polyols, a corresponding catalyst is required V16 and B35 visible - Further, from Examples V14.