DE3413938C2 - Process for the preparation of reinforcing agent-containing compact or cellular polyurethane, polyurea or polyurethane-polyurea moldings - Google Patents

Description

Composite bodies of cover layers and a foam core are known. According to DE-AS 10 61 507 (CA-PS 564 717) is an increase in specific strength of composites achieved by lining the Inner sides of the cover layers with fabrics or fleeces before filling the foamable reaction mixture. The density of fiber webs for Foam core out can be graded zonewise in this way. A disadvantage of this method, however, is that the fabric or nonwoven can not be surrounded on all sides with polyurethane.

Process for the preparation of optionally cellular, elastic moldings with a closed surface layer of polyurethane-polyurea Elastomers - hereinafter abbreviated PU-PH - from one- Shot systems according to the principle of reaction injection molding technology, for example in DE-AS 26 22 951 (US-PS 4 218 543), EP-OS 26 915, EP-OS 69 286 and DE-OS 32 15 907 described. By the same method are polyurea and polyurethane moldings - abbreviated below Called PH or PU molding - according to DE-OS 32 15 909 or after Publication of D.J. Prepelka and J.L. Wharton in Journal of Cellular Plastics, March / April 1975, pages 87-98.

The PU or PU-PH molded body mentioned can also be reinforced with glass fibers become. Process for the preparation of such moldings are for example, by H. Boden et al. in Kunststoffe 68 (1978), pages 510 to 515, or J. Hutchison et al., or S. H. Metzger et al. in Journal of Cellular Plastics Sept./Oct. 1981, pages 263-273.

With fiber-containing fabrics, for example glass fiber mats, Non-wovens or woven fabrics, reinforced moldings can, however, according to the reaction injection molding can not be made because of the mold inlaid fabrics from the high pressure in the mold injected reaction mixture pushed away and / or compressed become.

The object of the present invention was to provide a method which enhances the production of fibrous webs, compact or cellular moldings based on PU, PH or PU-PH elastomers allowed from one-shot systems after the reaction injection molding technique.  

By using polyurethane duromers with a certain stiffness, containing a fibrous sheet, as fibrous Reinforcement agent, this task could be solved.

The invention thus relates to a process for the preparation of reinforcing agents containing compact or cellular polyurethane, polyurea or polyurethane-polyurea moldings by reaction of

• 1a) organic polyisocyanates,
• b) higher molecular weight compounds having at least two reactive hydrogen atoms and
• c) chain extenders and / or crosslinkers in the presence of
• d) fibrous reinforcing agents and optionally
• e) catalysts,
• f) propellants,
• g) auxiliaries and / or additives

in closed molds, wherein components (a) to (c) and optionally (e) to (g) as one-shot systems according to the Reaction injection molding technique, which is characterized is that fiber-containing fibrous reinforcing agents Fabrics of needled or unvarnished mats, Nonwovens, felts or fabrics of textile, carbon, metal or glass fibers obtained by spraying a fibrous sheet with a reactive polyurethane Duromermischung with a viscosity of 200 to 2000 mPa · s at 20 ° C on the Basis of organic polyisocyanates, polyhydroxyl compounds, optionally crosslinking and / or chain extenders and catalysts in such an amount, that the weight ratio of fibrous sheet too Polyurethane mixture is 50 to 95 to 50 to 5, obtained have been used and which has a compressive strength perpendicular to the mat plane of 1.1 to 0.1 N / mm² at 30% compression have.

The moldings produced by the process according to the invention are surrounded on all sides by PU, PH or PU-PH elastomers and have isotropic mechanical properties. Reinforced opposite with glass fibers Moldings are also worth mentioning the following advantages: homogeneous property image, higher strength, toughness and heat distortion resistance.  

Suitable fibrous reinforcing agents (d) are polyurethane duromers, in addition to the content of fiber-containing fabric a compressive strength perpendicular to the mat plane of 1.1 to 0.1 N / mm², preferably from 1.0 to 0.2 N / mm², at 30% compression, a thickness of 1 to 20 mm, preferably from 1 to 5 mm, and a density of 100 to 400 g / cm³, preferably from 150 to 250 g / cm³. Advantageously the polyurethane duromers further have a porosity (free pore volume) of 80 to 95% by volume, preferably from 87 to 94% by volume.

To prepare the polyurethane duromers are polyurethane mixtures with a viscosity of 200 to 2000 mPa · s, preferably of 300  to 1000 mPa · s, at 20 ° C and a starting time of 15 to 240 seconds, preferably from 30 to 120 seconds, at 80 ° C based on organic Polyisocyanates, polyhydroxyl compounds, catalysts and optionally crosslinking and / or chain extenders used.

As organic polyisocyanates are aliphatic, cycloaliphatic and preferably aromatic polyfunctional isocyanates in question. In detail Examples include 1,6-hexamethylene diisocyanate, 1-isocyanato 3,3,5-trimethyl-3-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydrotoluylene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding Isomer mixtures, mixtures of 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanates and polymethylene polycyclohexylene polyisocyanates, 2,4- and 2,6-tolylene diisocyanate and the corresponding mixtures of isomers, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and the corresponding Isomer mixtures, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (crude MDI) and Mixtures of crude MDI and toluene diisocyanates.

Frequently, so-called modified polyfunctional isocyanates, d. H. Products by chemical reaction of the above-mentioned di- and / or polyisocyanates to be obtained. Examples include ester, urea, Biuret, allophanate and preferably carbodiimide, isocyanurate and / or urethane-containing di- and / or polyisocyanates.

However, preference is given to using urethane-group-containing polyisocyanates, for example, with low molecular weight diols, triols, polyoxypropylene glycols, Polyoxyethylene glycols and / or polyoxypropylene-polyoxyethylene glycols, modified 4,4'-diphenylmethane diisocyanate or tolylene diisocyanate, Containing carbodiimide groups and / or isocyanurate rings Polyisocyanates, e.g. B. on diphenylmethane diisocyanate and / or Toluylendiisocyanat- Base, tolylene diisocyanates, mixtures of crude MDI and tolylene diisocyanates and especially mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanates or mixtures of the diphenylmethane diisocyanate Isomeric and polyphenylpolymethylene polyisocyanates.

Polyhydroxyl compounds are preferably polyether polyols a functionality of 2 to 8, preferably 2 to 4 and hydroxyl numbers from 200 to 800, preferably from 250 to 600 use. For improvement In addition, di- and / or trifunctional polyether polyols can be added to the flexibility having hydroxyl numbers from 20 to 200, preferably from 25 to 180 be used with the proviso that the polyether polyol used  Mixtures have a hydroxyl number of 200 to 800, preferably 250 own up to 600.

The polyether polyols are prepared by known methods, for example by anionic polymerization with alkali hydroxides, such as sodium or Potassium hydroxide, or alkali metal such as sodium methylate, sodium or Potassium ethylate or potassium isopropylate, as catalysts or by cationic Polymerization with Lewis acids, such as antimony pentachloride and boron fluoride Etherate, or bleaching earth as catalysts of one or more Alkylene oxides having 2 to 4 carbon atoms in the alkylene radical and a starter molecule, the 2 to 8, preferably 2 to 4, reactive hydrogen atoms bound contains.

Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide, epichlorohydrin and preferably Ethylene oxide and in particular 1,2-propylene oxide. The alkylene oxides can be used individually, alternately one after the other or as mixtures become. Suitable starter molecules are, for example: water, organic dicarboxylic acids, such as. As amber, adipic, phthalic and / or Terephthalic acid, and preferably polyvalent, especially two- and / or trihydric alcohols, such as. Ethylene, propylene-1,2- and 1,3-diethylene, Dipropylene, butylene-1,4-, hexamethylene-1,6-glycol, glycerol, trimethylolethane, propane, pentaerythritol, sorbitol and sucrose.

The polyether polyols may be used singly or in the form of mixtures become.

Preference is given to using polyether polyols with predominantly secondary Hydroxyl groups, especially di- and / or trifunctional polyoxypropylene polyols with hydroxyl numbers from 200 to 400. Well suited also polyoxypropylene-polyoxyethylene polyols having a total content Oxyethylene groups of not more than 30 wt .-%, provided that substantially are bound inside and not terminally and have a functionality of 2 to 3 have.

As polyhydroxyl compounds may also contain hydroxyl groups Polyester, polyester amides, aliphatic polycarbonates and polyacetals with Functionalities of 2 to 8 and hydroxyl numbers of 20 to 400 used become. Due to the high content of primary hydroxyl groups are such Polyhydroxyl compounds very reactive, so they usually used only in the form of mixtures with said polyether polyols become. Due to the numerous variations regarding Type and amount of polyhydroxyl compounds used or in particular  their mixtures can improve the mechanical properties of the resulting polyurethane Duromers according to the intended use almost arbitrarily modified become.

For variation of the mechanical properties of polyurethane duromers If necessary, the polyurethane mixtures may also be crosslinked and / or or chain extenders. Suitable crosslinking and / or chain extenders have molecular weights of 60 to 600, preferably from 60 to 300 and preferably have 2 or 3 reactive Hydrogen atoms on. For example, be considered as crosslinking agents trihydric or polyhydric alcohols, such as. For example, pentaerythritol, trimethylolethane and preferably trimethylolpropane and glycerol, and as Chain extenders araliphatic and / or preferably aliphatic Glycols or glycol ethers having 2 to 14, preferably 2 to 6 carbon atoms, such as Bis (2-hydroxyethyl) hydroquinone, 1,3- or 1,2-propanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, and preferably Ethanediol, 1,4-butanediol, diethylene glycol and dipropylene glycol. The weight ratio of polyhydroxyl compound to crosslinking and / or chain extenders depends on the desired mechanical properties of the final product and may be within the limits of 0 to 200% by weight, preferably from 0 to 150% by weight, based on the weight of the polyhydroxyl compounds, be varied.

To prepare the polyurethane duromers, the organic polyisocyanates and polyhydroxyl compounds and optionally crosslinking and / or chain extenders reacted in such amounts, that the ratio of NCO groups to the sum of the hydroxyl groups 0.7 to 2.0: 1, preferably 1.1 to 1.4: 1, is.

The reaction mixture may further catalysts, the polyurethane formation accelerate, be incorporated. To achieve sufficient flow paths and optionally for penetrating the fibrous sheet with reactive polyurethane Duromermischung should their start time at room temperature sufficiently large and the increase in viscosity at 20 ° C be as low as possible. These requirements are met by polyurethane catalysts based on organic metal complex compounds, which become catalytically effective only at elevated temperatures.

Have proven particularly useful and therefore preferably be used such organometallic complex compounds, which only at temperatures greater than 50 ° C unfold their entire catalyst activity, such as. Metal Acetylacetonate, diacetonitrile diacetylacetonate, diphenylnitrile diacetylacetonate and bis (triphenylphosphine) diacetylacetonate complexes  of metals, such as As iron, cobalt, nickel, zirconium, manganese, vanadium, Molybdenum, zinc, tin, antimony and titanium. In particular, be exemplary called nickel, cobalt and especially iron acetylacetonate. Suitable however, it is also zinc stearate.

The polyurethane catalysts, in amounts of 0.01 to 3 wt .-%, preferably from 0.1 to 1% by weight, based on the weight of the polyhydroxyl compounds, can be used individually or in the form of mixtures application Find. However, the polyurethane catalysts may optionally also with polyisocyanurate catalysts from the group of alkali metal formates, acetates and / or carbonates. In particular, be exemplary called sodium or potassium formate, sodium acetate and sodium carbonate, optionally in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 3% by weight, based on the weight of the polyhydroxyl compounds, be used.

Needled or unvarnished mats are used as fiber-containing fabrics, Nonwovens, felts or fabrics made of textile, carbon, Metal or preferably glass fibers can be produced. Preferably Glass fiber mats with basis weights of 100 are used to 1200 g / m², preferably from 200 to 600 g / m², individually or in several layers are sprayed with the flowable polyurethane mixture. The ratio of polyurethane blend to fibrous web is chosen so that the finished, flat, fibrous Polyurethane duromers 50 to 95 wt .-%, preferably 70 to 90 wt .-% at least a fibrous sheet, in particular made from Glass fibers, contains.

For the production of the surface, fiber-containing usable according to the invention Polyurethane duromers may include the organic polyisocyanates, polyhydroxyl compounds and catalysts and optionally crosslinking and / or Chain extender according to the one-shot process individually by means of metering pumps fed to a mixing head, there intense at temperatures of 20 to 80 ° C, preferably from 23 to 50 ° C, mixed and directly onto the be sprayed fiber-containing fabrics. According to a preferred embodiment However, the above-mentioned starting components in advance the corresponding proportions to two components A and B, wherein Component A preferably the polyhydroxyl compounds, catalysts and optionally crosslinking and / or chain extenders and component B consists of the organic polyisocyanates, united, so that only these two components dosed, promoted and at must be mixed in the mixing head said temperatures.  

The polyurethane mixture becomes uniform on the fibrous web sprayed to avoid long flow paths.

According to a preferred embodiment, this is the fibrous Placed sheet in the open mold and sprayed there. It However, it is also possible that the fibrous sheet outside the Spray mold and then sprayed with polyurethane mixture insert fiber-containing fabrics in the open mold. The weight ratio of fibrous web to polyurethane blend in this case is 50 to 95 to 50 to 5, preferably 70 to 90 to 30 to 10.

To the starting components which can be used for the process according to the invention (a) to (c) and (e) to (g) for the preparation of the compact or cellular PU, PH or PU-PH moldings is to be carried out as follows:

(a) As organic polyisocyanates, the aliphatic, known per se, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates, as already described above for the preparation the polyurethane duromers were described. Preferably also find For this purpose use: urethane-containing aromatic polyisocyanates with NCO contents of from 33.6 to 15% by weight, preferably from 31 to 21% by weight, for example, with low molecular weight diols, triols, dialkylene glycols, Trialkylene glycols or polyoxyalkylene glycols having molecular weights up to 800, modified 4,4'-diphenylmethane diisocyanate or tolylene diisocyanate, as di- or polyoxyalkylene glycols, individually or as Mixtures can be used, for example: Diethylen-, Dipropylene, polyoxyethylene, polyoxypropylene and polyoxypropylene polyoxyethylene glycols. Also suitable are NCO-group-containing Prepolymers with NCO contents of 21 to 9 wt .-%, preferably from 21 to 14% by weight. Furthermore, liquid carbodiimide groups have proven to be excellent and / or isocyanurate-containing polyisocyanates with NCO contents from 33.6 to 15, preferably from 31 to 21% by weight, e.g. Based on 4,4'-, 2,4'- and / or 2,2'-diphenylmethane diisocyanate and / or 2,4- and / or 2,6-toluene diisocyanate and especially 2,4- and 2,6-toluene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and the corresponding isomer mixtures, for. B. from 4,4'- and 2,4'-diphenylmethane diisocyanates, mixtures of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (raw MDI) and mixtures of tolylene diisocyanates and crude MDI.

(b) According to the invention usable higher molecular weight compounds having at least two reactive hydrogen atoms suitably have molecular weights  from 10,000 to 400, preferably from 6,000 to 1,000, and are di- to hexafunctional, preferably di- and trifunctional. Especially proven have and therefore preferably be used polyester polyols with a maximum functionality of 3.5, preferably from 2 to 3, and a molecular weight of 400 to 3000, preferably from 1000 to 2500, and in particular polyether polyols having a functionality of 2 to 6, preferably from 2 to 4, and a molecular weight of 400 to 10,000, preferably from 1000 to 6000. However, polyether polyamines are also suitable and other hydroxyl-containing polymers having said molecular weights and functionalities, for example polyesteramides, polyacetals, such as As polyoxymethylenes and butanediol, and polycarbonates, in particular those prepared from diphenyl carbonate and 1,6-hexanediol Transesterification. The above-mentioned higher molecular weight compounds can be used individually or in the form of mixtures. The connections will be prepared by known methods, wherein u. a. the already mentioned Building components for the preparation of polyhydroxyl compounds for the Polyurethane duromers can be used.

c) used as chain extenders and / or crosslinkers low molecular weight di- to tetrafunctional, preferably difunctional Compounds from the group of aliphatic and / or araliphatic Diols and / or triols, the secondary aromatic diamines, the primary aromatic diamines and 3,3 ', 5,5'-tetra-alkyl-substituted 4,4'-diaminodiphenylmethanes.

Suitable diols and triols advantageously have molecular weights less than 400, preferably from 60 to 300. Consider, for example aliphatic and / or araliphatic diols having 2 to 14, preferably 4 to 10 carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,1-decanediol, Diethylene glycol, dipropylene glycol and preferably 1,4-butanediol, 1,6-hexanediol and bis (2-hydroxyethyl) hydroquinone, triols, such as Glycerol and trimethylolpropane, and low molecular weight hydroxyl groups Polyalkylene oxides based on ethylene and / or propylene oxide and the aforementioned diols and / or triols as starter molecules.

As secondary aromatic diamines may be mentioned by way of example: N, N'-dialkyl substituted aromatic diamines, optionally substituted on the aromatic Core may be substituted by alkyl radicals, with 1 to 20, preferably 1 to 4 carbon atoms in the N-alkyl radical, such as N, N'-diethyl, N, N'- Di-sec-pentyl, N, N'-di-sec-hexyl, N, N'-di-sec-decyl, N, N'-dicyclo- hexyl-p- or -m-phenylenediamine, N, N'-dimethyl, N, N'-diethyl, N'N-diisopropyl-, N, N'-di-sec-butyl, N, N'-dicyclohexyl-4,4'-diamino-diphenyl methane and N, N'-di-sec-butyl-benzidine.  

As aromatic diamines, those are used which are suitable in ortho-position to the amino groups at least one alkyl substituent have liquid at room temperature and with component (b), in particular the polyether polyols are miscible. Have proven themselves further Alkyl-substituted meta-phenylenediamines of the general formulas

in which R³ and R² are the same or different and have a methyl, Ethyl, propyl and isopropyl and R¹ is a linear or branched Alkyl radical having 1 to 10, preferably 4 to 6 carbon atoms is. In particular, those alkyl radicals R¹ in which the Branching point at the C 1 carbon atom sits. As radicals R¹ are exemplary called the methyl, ethyl, isopropyl, 1-methyl-octyl, 2-ethyl-octyl, 1-methyl-hexyl, 1,1-dimethyl-pentyl, 1,3,3-trimethyl- hexyl, 1-ethyl-pentyl, 2-ethyl-pentyl and preferably cyclohexyl, 1-methyl-n-propyl, tert-butyl, 1-ethyl-n-propyl, 1-methyl-n- butyl and 1,1-dimethyl-n-propyl radical.

Suitable alkyl-substituted m-phenylenediamines include, for example: 2,4-dimethyl-6-cyclohexyl, 2-cyclohexyl-4,6-diethyl, 2-cyclohexyl 2,6-isopropyl, 2,4-dimethyl-6- (1-ethyl-n-propyl) -, 2,4-dimethyl-6- (1,1-dimethyl-n-propyl) -, 2- (1-methyl-n-butyl) -4,6-dimethyl-phenylenediamine-1,3. Preferably used are 1-methyl-3,5-diethyl-2,4- or 2,6-phenylenediamine, 2,4-dimethyl-6-tert-butyl, 2,4-dimethyl-6-isooctyl and 2,4-dimethyl-6-cyclohexyl-m-phenylenediamine-1,3.

Suitable 3,3 ', 5,5'-tetra-n-alkyl-substituted 4,4'-diaminodiphenylmethanes For example, 3,3 ', 5,5'-tetramethyl, tetraethyl and Tetra-n-propyl-4,4'-diaminodiphenylmethane.

Preferably used are diaminodiphenylmethanes of the general formula

in which R⁴, R⁵, R⁶ and R⁷ are identical or different and have a methyl, Ethyl, propyl, isopropyl, sec-butyl and tert-butyl, however, at least one of the radicals is an isopropyl or sec-butyl radical have to be. The 4,4'-diaminodiphenylmethanes can also be mixed with Isomers of the general formulas

R,, R⁵, R⁶ and R⁷ are as defined above to have.

Examples include: 3,3 ', 5-trimethyl-5'-isopropyl, 3,3', 5-triethyl 5'-isopropyl, 3,3 ', 5-trimethyl-5'-sec-butyl, 3,3', 5-triethyl-5 ' sec-butyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diisopropyl-, 3,3'-diethyl-5,5'-diisopropyl, 3,3'-dimethyl-5,5'-di-sec-butyl, 3,3'-diethyl 5,5'-di-sec-butyl, 3,5-dimethyl-3 ', 5'-diisopropyl, 3,5-diethyl 3 ', 5'-diisopropyl, 3,5'-dimethyl-3', 5-di-sec-butyl, 3,5-diethyl-3 ', 5'- di-sec-butyl-4,4'-diaminodiphenylmethane, 3-methyl-3 ', 5,5'-triisopropyl-, 3-ethyl-3 ', 5,5'-triisopropyl, 3-methyl-3', 5,5'-tri-sec-butyl, 3-ethyl-3 ', 5,5'-tri-sec-butyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl 5,5'-di-sec-butyl, 3,5-diisopropyl-3 ', 5'-di-sec-butyl, 3-ethyl-5 sec-butyl-3 ', 5'-diisopropyl, 3-methyl-5-tert-butyl-3', 5'-diisopropyl, 3-ethyl-5-sec-butyl-3'-methyl-5'-tert-butyl, 3,3 ', 5,5'-tetraisopropyl and 3,3 ', 5,5'-tetra-sec-butyl-4,4'-diaminodiphenylmethane. Preferably 3,5-dimethyl-3 ', 5'-diisopropyl and 3,3', 5,5'-tetraisopropyl 4,4'-diaminodiphenylmethane. The Diaminodiphenylmethane can used individually or in the form of mixtures.

The chain extenders and / or crosslinkers mentioned can be used individually or used as mixtures of the same or different species become.

The chain extenders and / or crosslinkers and mixtures thereof come in the process according to the invention in amounts of 2 to 60 wt .-%, preferably from 8 to 50 wt .-% and in particular from 10 to 40 wt .-%, based on the weight of components (b) and (c) used.  

e) As catalysts (e) in particular compounds are used which the reaction of the hydroxyl-containing compounds of the components (b) and (c) strongly accelerate with the polyisocyanates. In consideration come organic metal compounds, preferably organic tin compounds, such as stannous salts of organic carboxylic acids, e.g. Tin (II) - acetate, stannous octoate, stannous ethylhexoate and stannous laurate, and the dialkyltin (IV) salts of organic carboxylic acids, e.g. Dibutyltin diacetate, Dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate. The organic metal compounds are alone or preferably used in combination with strong basic amines. Mentioned for example amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl, N-ethyl, N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethylbutanediamine, pentamethyldiethylenetriamine, Tetramethyldiaminoethyl ether, bis (dimethylaminopropyl) urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-azobicyclo- (3,3,0) octane and preferably 1,4-diazabicyclo- (2,2,2) -octane, and alkanol compounds, such as Triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine and dimethylethanolamine.

Further suitable catalysts are tris- (dialkylaminoalkyl) - s-hexahydrotriazines, in particular tris- (N, N-dimethylaminopropyl) -s-hexahydrotriazine, Tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide, Alkali hydroxides, such as sodium hydroxide and alkali metal alcoholates, such as Sodium methylate and potassium isopropylate, as well as alkali salts of long-chain Fatty acids having 10 to 20 carbon atoms and optionally pendant OH Groups. Preferably used are 0.001 to 5 wt .-%, in particular 0.05 to 2 wt .-%, catalyst or catalyst combination, based on the Weight of component (b).

f) to blowing agents (f), which in the process according to the invention optionally may be used, water containing isocyanate groups reacts to form carbon dioxide. The amounts of water that expediently can be used, 0.5 to 2 wt .-%, based on the weight of component (b).

Other useful blowing agents are low boiling liquids which evaporate under the influence of the exothermic polyaddition reaction. Suitable are liquids which are opposite to the organic polyisocyanate are inert and have boiling points below 100 ° C. Examples of such, preferably used liquids are halogenated hydrocarbons, such as methylene chloride, trichlorofluoromethane, dichlorodifluoromethane,  Dichloromofluoromethane, dichlorotetrafluoroethane and 1,1,2-trichloro-1,2,2- trifluoroethane.

Also mixtures of these low-boiling liquids with one another and / or or with other substituted or unsubstituted hydrocarbons can be used.

The most convenient amount of low boiling liquid for production cell-containing PU, PH or PU-PH moldings depends on the density, which you want to achieve and, where appropriate, the co-use of Water. In general, amounts of from 0.5 to 15 parts by weight, based to 100 parts by weight of component (b), satisfactory results.

The reaction mixture may also contain auxiliaries and / or or additives (g). Examples include surfactants, foam stabilizers, cell regulators, fillers, Dyes, pigments, flame retardants, hydrolysis protectants, fungistatic and bacteriostatic substances.

Suitable surface-active substances are compounds which to assist in the homogenisation of the starting materials and, where appropriate are also suitable to regulate the cell structure. Called are, for example, emulsifiers, such as the sodium salts of castor oil sulfates, or of fatty acids and salts of fatty acids with amines, e.g. B. diethylamine or stearic acid diethanolamine, salts of sulphonic acids, z. As alkali or ammonium salts of dodecylbenzene or Dinaphthylmethandisulfonsäure, and ricinoleic acid; Foam stabilizers, such as Siloxane-oxalkylene copolymers and other organopolysiloxanes, ethoxylated Alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters and Turkish red oil, and cell regulators, such as paraffins, Fatty alcohols and dimethylpolysiloxanes. The surface-active substances are usually in amounts of from 0.01 to 5 parts by weight, based on 100 parts by weight of component (b) applied.

As fillers, in particular reinforcing fillers are the conventional common organic and inorganic fillers, reinforcing agents, Weighting means, means for improving the abrasion behavior in paints, coatings, etc. In detail may be mentioned by way of example: inorganic fillers, such as silicate Minerals, for example phyllosilicates, such as antigorite, serpentine, Hornblende, amphibole, chrysotile, talc; Metal oxides, such as kaolin, aluminum oxides, Titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide, zinc sulfide, and asbestos flour.  

Preferably used are kaolin (China Clay), aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and natural and synthetic fibrous minerals such as asbestos and wollastonite. When Organic fillers are, for example, considered: coal, melamine, Rosin, cyclopentadienyl resins and graft polymers on styrene Acrylonitrile based by in situ polymerization of acrylonitrile-styrene Mixtures in polyether polyols analogous to the information in DE-PS 11 11 394, 12 22 669 (US Pat. No. 3,304,273, 3,383,351, 3 523 093), 11 52 536 (GB-PS 1 040 452) and 11 52 537 (GB-PS 987 618) and then optionally aminated, as well as filler-containing polyoxyalkylene polyols or polyamines in which aqueous polymer dispersions in Polyoxyalkylenpolyol- or -polyamindispersionen be converted.

The inorganic and organic fillers may be used singly or as mixtures be used. Preferably used are stable filler Polyoxyalkylenpolyol dispersions in which the fillers in the presence of polyoxyalkylene polyols in situ with high local energy densities crushed to a particle size smaller than 7 microns and this be dispersed at the same time.

The inorganic and organic fillers become the reaction mixture advantageously in amounts of from 0.5 to 50% by weight, preferably from 1 to 40 wt .-%, based on the weight of components (a) to (c), incorporated.

Suitable flame retardants are, for example, tricresyl phosphate, tris-2- chloroethyl phosphate, tris-chloropropyl phosphate and tris-2,3-dibromopropyl phosphate.

In addition to the aforementioned halogen-substituted phosphates can also inorganic flame retardants, such as alumina hydrate, antimony trioxide, Arsenic oxide, ammonium polyphosphate and calcium sulfate for flame retardancy Shaped bodies are used. In general, it has to be useful proved, 5 to 50 parts by weight, preferably 5 to 25 parts by weight of said Flame retardant for every 100 parts by weight of component (b) to use.

Details of the other common additives and additives are the specialist literature, for example, the monograph of J.H. Saunders and K.C. Frisch "High Polymers", Vol. XVI, Polyurethanes, Part 1 and 2, published by Intersciences Publishers 1962 and 1964, respectively.  

For the preparation of the optionally cellular PU, PH or PU-PH moldings become the organic polyisocyanates (a), higher molecular weight compounds with at least two reactive hydrogen atoms (b) and chain extenders and / or crosslinkers (c) in such amounts for the implementation brought that the equivalence ratio of NCO groups of the polyisocyanates (a) to reactive hydrogen atoms bonded to OH, NH₂-, NHR- and CONH₂ groups, components (b) and (c) 1: 0.90 to 1.25, preferably 1: 0.95 to 1.15.

The preparation of cellular and preferably compact PU, PH or PU-PH molded body takes place after one-shot method using the known reaction injection molding technique. This procedure is described for example by Piechota and Röhr in "Integralschaumstoff", Carl-Hanser-Verlag, Munich, Vienna 1975; D.J. Prepelka and J.L. Wharton in Journal of Cellular Plastics, March / April 1975, pages 87 to 98 and U. Knipp in Journal of Cellular Plastics, March / April 1973, pages 76 to 84.

For this purpose, the polyurethane duromers (a) individually or in several Layers are placed in the open mold so that they are separated from the PU, PH or PU-PH mixture on all sides, but at least two, preferably Both side surfaces can be wrapped. The amount of in the Forming introduced reaction mixture is such that the obtained moldings content of fibrous sheet, in particular a glass content of 7 to 70 wt .-%, preferably 20 to 60 wt .-%, based on the total weight and have the microcellular or compact molded body has a density of 0.8 to 2.1 g / cm³, preferably from 1.2 to 1.8 g / cc, and the cellular shaped bodies have a density of from 0.1 to 1.2 g / cm³, preferably from 0.25 to 0.8 g / cm³. The output components are at a temperature of 15 to 80 ° C, preferably from 20 up to 55 ° C, introduced into the mold. The mold temperature is expediently 20 to 90 ° C, preferably 30 to 75 °, optionally it may be advantageous be conventional mold release agents, such as wax or Silicone base, after every 3rd to 10th mold filling to improve the Demoulding, use. The densification levels for the production of microcellular or cell-containing moldings are between 1.1 and 8, preferably between 2 and 8.

The compact or microcellular obtained by the process according to the invention PU, PH or PU-PH moldings are particularly suitable for Use in the automotive industry, for example as body parts, Cover plates, as well as technical housing parts or furniture parts.  

The cell-containing moldings find, for example, as safety covers in the automotive interior or insert for reinforcement of soft integral foams Application.

The parts mentioned in the examples are by weight.

Production Example 1 Preparation of a polyurethane duromer

Component A: Mixture of

40.7 parts of a polyoxypropylene-polyoxyethylene glycol having a hydroxyl number of 28, prepared using 1,3-propylene glycol as a starter molecule and a mixture of 1,2-propylene oxide and ethylene oxide in a weight ratio of 4: 1,
4.1 parts of a polyether triol having a hydroxyl number of 400, prepared using trimethylolpropane as starter molecule and 1,2-propylene oxide,
55.0 parts of dipropylene glycol,
0.1 part of dibutyltin dilaurate and
0.1 parts of triethylenediamine.

Component B: Mixture of diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates (Crude MDI) with an NCO content of 31 wt .-%.

45 g of the polyurethane mixture consisting of the components A and B im Weight ratio 1: 1.45 were with a two-component spray gun on 0.23 m² of a glass fiber mat with a basis weight of 450 g / m² sprayed on and the sprayed fiberglass mat in a mold at Allowed to cure at 23 ° C in 60 min. The polyurethane duromer obtained had

a glass fiber content of 86% by weight a basis weight of 532 gsm a thickness of 3.7 mm a density of 143 g / cm³ a compressive strength perpendicular to the mat plane at 30% compression of 0.18 N / mm² and a porosity of 93.4% by volume.

Production Example 2 Preparation of a polyurethane duromer

100.1 parts of a reaction mixture prepared by intensive mixing at 50 ° C of

100 parts of a hexanediol-1,6-butanediol-1,4-adipate having a hydroxyl number of 56,
35 parts of butanediol-1,4 and
113 parts of 4,4'-diphenylmethane diisocyanate (isocyanate index 1.03)

were at 50 ° C with a one-component spray gun on 0.23 m² one Glass fiber mat with a basis weight of 450 g / m² sprayed on and the Cure sprayed fiberglass mat in a mold at 120 ° C in 60 min calmly. The obtained polyurethane Duromere possessed

a glass fiber content of 54% by weight a basis weight of 889 gsm a thickness of 4.2 mm a density of 211 g / cm³ a compressive strength perpendicular to the mat plane at 30% compression of 0.6 N / mm² and a porosity of 87.4% by volume.

example 1 Preparation of a cellular, polyurethane-containing reinforcing agent molding

Component A: Mixture of

77.8 parts of a polyether polyol having a hydroxyl number of 26, prepared by polyaddition of 1,2-propylene oxide to trimethylolpropane and subsequent addition of ethylene oxide,
19.1 parts of ethylene glycol,
0.01 parts of triethylenediamine in dipropylene glycol (33% by weight),
0.1 part of dibutyltin dilaurate and
3 parts of methylene chloride.

Component B: urethane-modified 4,4'-diphenylmethane diisocyanate with an NCO content of 23 wt .-%.

The polyurethane-duromer, prepared according to the instructions of Preparation Example 2, Was in a tempered to 50 ° C open metallic mold with the inner dimensions 600 × 300 × 3 mm inserted, closed the mold  and via an inlet opening with the aid of a Puromat® 80 Elastogran Mechanical engineering with a 50 ° C warm mixture of 100 parts of the component A and 124.9 parts of component B, corresponding to an isocyanate index of 1.05 charged. The resulting polyurethane molded body was after Removed from the mold for 1.5 minutes. The fiberglass mat was uniformly soaked and in embedded polyurethane elastomer. A shift of the glass fiber mat in the coating of the mold was not found.

The polyurethane molded body had the following mechanical properties:

Glass content [% by weight] 11.7 Tensile strength according to DIN 53504 [N / mm²] 31.3 Elongation at break according to DIN 53504 [%] 10 Tear strength according to DIN 53507 (according to Graves) [N / mm] 170 Shore D hardness according to DIN 53505 62 Heat resistance to Iso-75 / B [° C] 177 Bending modulus according to DIN 53457 [N / mm²] 1470

Example 2 Preparation of a Compact Polyurethane Reinforcing Agent Polyurea molded body

Component A: Mixture of

76.9 parts of a polyether polyol having a hydroxyl number of 26, prepared by polyaddition of 1,2-propylene oxide to trimethylolpropane and subsequent addition of ethylene oxide,
22 parts of 2,4-dimethyl-6-tert-butylphenylenediamine-1,3,
1.0 part of 1,4-diazabicyclo- (2,2,2) -octane in dipropylene glycol (33 wt .-% strength) and
0.1 part of dibutyltin dilaurate.

Component B: urethane-modified 4,4'-diphenylmethane diisocyanate with an NCO content of 23 wt .-%.

The polyurethane-duromer, prepared according to the information of Preparation Example 1, Was in a tempered to 50 ° C open metallic mold with the internal dimensions of 200 × 200 × 4 mm inserted, closed the mold and via an inlet opening with the aid of a Puromat® 30 Elastogran Mechanical engineering with a 50 ° C warm mixture of 100 parts of the component A and 52.6 parts of component B, corresponding to an isocyanate index of 1.05, charged.  

The resulting polyurethane-polyurea shaped body was after 0.5 min removed from the mold. The fiberglass mat was uniformly saturated and all-round encased in elastomers. A shift of the glass fiber mat during loading of the mold did not materialize.

On the obtained PU-PH molded body, the following mechanical properties measured:

Glass content [% by weight] 9 Tensile strength according to DIN 53504 [N / mm²] 19.5 Elongation at break according to DIN 53504 [%] 13.3 Shore D hardness according to DIN 53505 66 Bending modulus according to DIN 53457 [N / mm²] 1250

Example 3

Four polyurethane duromers, prepared analogously to the details of Preparation Example 1, were in a mold at 200 ° C in one minute to a thickness of 3.5 mm pressed and then according to the manufacturing instructions of Example 2 processed to a compact PU-PH molded body.

The resulting polyurethane molded body was removed from the mold after 0.5 min. The Glass fiber mats were uniformly soaked and elastomers on all sides envelops. A shift of the glass fiber mats when loading the Form did not occur.

On the obtained PU-PH molded body, the following mechanical properties measured:

Glass content [% by weight] 31.3 Tensile strength according to DIN 53504 [N / mm²] 23.2 Elongation at break according to DIN 53504 [%] 10 Shore D hardness according to DIN 53505 76 Bending modulus according to DIN 53457 [N / mm²] 5050

Comparative test

An untreated glass fiber mat with a basis weight of 450 g / m² Was inserted analogously to the instructions of Example 2 in a mold and subjected to the reaction mixture described. The fiberglass mat was 30 mm in the flow direction through the reaction mixture at the feed postponed. The molding was unusable.

Claims (10)

1. A process for the preparation of reinforcing agent-containing compact or cellular polyurethane, polyurea or polyurethane polyurea moldings by reacting

• a) organic polyisocyanates,
• b) higher molecular weight compounds having at least two reactive hydrogen atoms and
• c) chain extenders and / or crosslinkers in the presence of
• d) fibrous reinforcing agents and optionally
• e) catalysts,
• f) propellants,
• g) auxiliaries and / or additives

in closed molds, wherein components (a) to (c) and optionally (e) to (g) are processed as one-shot systems by the reaction injection molding technique, characterized in that as fiber-containing reinforcing agents, fiber-containing fabrics of needled or un-needled Mats, fleeces, felts or fabrics of textile, carbon, metal or glass fibers obtained by spraying a fibrous sheet with a reactive polyurethane-duromer mixture having a viscosity of 200 to 2000 mPa · s at 20 ° C based on organic Polyisocyanates, polyhydroxyl compounds, optionally crosslinking and / or chain extenders and catalysts in such an amount that the weight ratio of fibrous sheet to polyurethane mixture 50 to 95 to 50 to 5, have been obtained, and the pressure resistance perpendicular to the mat plane of 1, 1 to 0.1 N / mm² at 30% compression possess. 2. The method according to claim 1, characterized in that one as fibrous reinforcing agents, those having a thickness from 1 to 5 mm and a density of 100 to 400 g / cm³ used. 3. The method according to claim 1, characterized in that one the polyurethane duromers so inserts into the mold, that on all sides of polyurethane, polyurea or polyurethane Polyurea molding compound are wrapped.   4. The method according to claim 1, characterized in that one as higher molecular weight compounds (b) used those which a molecular weight of 400 to 10,000 and a Have functionality from 2 to 6. 5. The method according to claim 1, characterized in that one as higher molecular weight compounds (b) used those which are selected from the group of polyester polyols, polyether polyols, Polyether polyamines, polyacetals, polycarbonates and / or polyesteramides. 6. The method according to claim 1, characterized in that one as chain extenders and / or crosslinkers (c) those used, which has a molecular weight of 60 to 400 and a Possess functionality of 2 to 4. 7. The method according to claim 1, characterized in that one as chain extenders and / or crosslinkers (c) those used, which are selected from the group of primary aromatic diamines, secondary aromatic diamines, aliphatic Diols and / or triols. 8. The method according to claim 1, characterized in that one as fibrous reinforcing agent (d) based on such used by glass fibers. 9. The method according to claim 8, characterized in that one the fibrous reinforcing agent in such an amount employs that the reinforcing agent containing compact or cellular polyurethane, polyurea or polyurethane Polyurea moldings have a glass content of 7 to 70 wt .-%, based on the total weight, possess.