DE1570127A1 - Polymer mixture - Google Patents

Description

Polymer Mixture The invention relates to polymer mixtures, in particular Polymer mixtures of (a) acid interpolymers, (b) graft copolymers with a polydiene rubber as substrate and a hydroxyl-containing polymer as Superstrate and (c) epoxy resins.

The invention aims to create novel polymer mixtures.

Werner's invention aims to create a new class of Polymer mixtures of acid interpolymers, hydroxyl-containing graft copolymers and epoxy resins.

Another purpose is to provide methods of production such polymer mixtures.

These and other purposes are achieved through the creation of mixtures achieved, which contain (A) a graft copolymer made of a polydiene rubber as Substrate and a hydroxyl-containing polymer as a superstrate in a ratio from about 15-200 parts by weight of the superstrate polymer per 100 parts by weight the substrate polymer; (B) an acid interpolymer which either (a) a Acid monomer of the type indicated below contains that with at least one with it interpolymerizable vinylidene monomer is interpolymerized, this acid interpolymer a Parr-3ar softening point below about 2250 ° C and in pyridine at 300 ° C has an intrinsic viscosity of less than about 0.5, or (b) at least one acid monomer of the type given below, that with a nitrile monomer of the type given below Art and at least one vinylidene monomer is interpolymerized with the acid monomer and the nitrile monomer is interpolymerizable; and (c) an epoxy compound which contains several epoxy groups.

The invention is explained in the following exemplary embodiments, but not limited to it. Unless otherwise stated, parts are made given on a weight basis.

Example I (production of graft copolymer latexes) Part A mach the following polymerization approach uses a series of polydiene rubber latexes A-Q to be used as a substrate: Ingredient Parts Water 250 diene X comonomer (s) Y divinylbenzene 0.5 sodium stearate 5 potassium persulfate 0.3 tert.Dodecyl mercaptan 0.4 The water and the soap are placed in a suitable reaction vessel, deoxygenates the soap solution by boiling, cools under nitrogen, adds the remaining Add constituents of the batch and heat to 500 C with agitation until the monomers approximately 95% have been converted into a polymer. The type and quantities the diene rubber and the comonomer (s) are given in Table A.

Part B A series of graft copolymer latices A-Q are produced, adding different amounts of ethylenically unsaturated alcohol and optionally of one or more oomonomers together with 0.2 parts of tert-dodecyl mercaptan aliquots of the polydiene rubber latexes A-Q produced according to Part A are added, which contain 100 parts of rubber solids, and the reaction mixture at 700 a below Agitation is heated until substantially all of the monomer mixture polymerizes is.

Each latex is made by adding 2 parts of a styrenated phenol stabilized as an antioxidant. The type and amount of ethylene unsaturated Alcohols and the comonomer (s) are given in Table A. The graft polymers consist in each case of a diene and optionally a comonomer as substrate and an ethylene-unsaturated alcohol and optionally a comonomer as a superstrate, which is grafted onto the substrate in the specified proportions.

Part a Each of the graft polymer latexes A-Q is in an excess of methanol failed. The solids are filtered off and then dispersed in methyl ethyl ketone, whose amount Fr is calculated that the dispersion has a solids content s about 15 Has weight percent.

Table A Part I Graft polydiene rubber (substrate) (A) copolymerizat- Diene parts comonomer (s) parts latex X Y IA, IJ butadiene 100 without 13, IC, ID, lE, 1 I, IM, IN, 10, butadiene 90 styrene 10 ir butadiene 75 styrene / vinyl 10/15 benzyl alcohol IG butadiene 75 styrene / phenyl 10/15 allyl alcohol IH butadiene 80 phenyl allyl 20 alcohol IK isoprene 75 styrene 25 IL butadiene 90 acrylonitrile 10 IQ butadiene 80 styrene / vinyl (10/10) benzyl alcohol Table A Part II Graft hydroxyl-containing polymer copolymer (Superstrate) (B) parts of sat-latex ethylene- parts comonomer (e) parts B per 100 unsaturated parts of alcohol A IA, IB vinylbenzyl 10 styrene / acrylic 80/10 60 alcohol nitrile IC "10" 70/20 60 ID Phenylallyl- 10 "70/20 60 alcohol IE" 20 "60/20 60 IF vinylbenzyl 10 70/20 60 alcohol IG phenylallyl 10" 70/20 60 alcohol IH "@@@@@@ 10 @@@@" II 70/20 50 Graft hydroxyl-containing polymer copolymeri- (superstrate) (B) parts of sat-latex ethylene parts comonomer (e) parts B per 100 unsaturated parts of alcohol A I I vinylbenzyl 20 styrene 80 60 alcohol IJ Phenylallyl- 100 "- 35 alcohol IK 2-Oxymethyl- 100" - 90 butadiene IL Ethyl-ß- 20 vinyl chloride 80 50 oxyethyl fumarate IM Bix (ß-oxy 25 methyl 75 30 ethyl) fumarate methacrylate IN ß-oxyethyl- 10 ethyl acrylate 90 60 acrylate 10 ethyl-ß- 77 butene-1 23 30 oxyethyl fumarate IP phenylallyl 25 butadiene 75 40 alcohol IQ vinylbenzyl 25 n 75 75 50 alcohol Example II Part A (production of a styrene-maleic anhydride interpolymer) A monomer solution is prepared which consists of 80 parts of styrene, 20 parts of maleic anhydride, 1.5 parts of di-tert-butyl peroxide and 1 part of dodecyl mercaptan.

100 parts of diethylbenzene are placed in a tightly closed container with stirring Introduced into the autoclave and heated to 1750 C.

Then the monomer mixture is added over a period of 2.5 hours introduced into the autoclave in a constant amount per unit of time, the reaction mixture is kept at a temperature of 1750 C. That used as a solvent Diethylbenzene is then vacuum distilled from the autoclave and thereby removed from the polymer mixture. The molten polymer is removed from the autoclave and placed in a flat cooling dish. That According to the Parr-Bar process, polymer has a softening point of 125 ° C and in pyridine at 300 ° C. an intrinsic viscosity of 0.055.

Part B (production of other acid interpolymers) In the part A procedure described in this Example II is a number of further acid interpolymers generated. The composition of the monomer batch, the reaction solvent, the reaction time, (i.e. the period of time in which the monomer mixture is added to the reaction solvent is added) the softening point of the acid interpolymer and the base molar Viscosity of the acid interpolymer in pyridine at 300 ° C. is shown in below in Table B.

Table B Acid interpolymers, part I, in the case of monomer batch reaction solvent game component parts mol% solvent parts II A styrene 80 79 diethylbenzene 100 maleic acid 20 21 anhydride 113 (1) styrene 100 64 cyclohexanone 230 maleic acid 54 36 anhydride IIB (2) styrene 126 62 cyclohexanone 200 ethyl acrylate 27 14 maleic acid-47 24 anhydride 113 (3) styrene 108 50 acetophenone 300 2-thylacrylate 92 25 maleic acid-49 25 anhydride Example monomer batch reaction solution smit tel game Bes tand part parts mole% solvent parts IIB (4) styrene 110 46 cyclohexanone 50 Acrylonitrile 40 32 Diethylbenzene 150 Maleic acid 50 22 anhydride IIB (5) methyl metha- Methyl ethyl ketone 200 acrylate 140 70 maleic anhydride 60 30 IIB (6) styrene 90 35 Methyl ethyl ketone 200 butadiene 60 44 maleic acid 50 21 anhydride part II Reaction softening basic molar game conditions point (Parr bar) viscosity Temp. Hour

IIA 1750 C 2.5 1250 C 0.055 IIB (1) 1450 C 3.0 2050 C 0.21 IIB (2) 1450 C 2.0 1470 C 0.15 IIB (3) 1450 C 3.5 1550 C 0.15 IIB (4) 1450 C 3.0 IIB (5) 1750 C 2.5 IIB (6) 900 C 4.0 Example III (preparation of polymer mixtures) Part A A series of mixtures of an acid interpolymer and an epoxy compound is prepared by adding 100 parts of each of those produced in Example II and in the Table B listed acid interpolymers, various (listed in Table C) Quantities of Epon 828 (this is essentially the diglycidyl ether of bis-phenol A) and 0.25 part of dodecyltrimethylammonium chloride dissolved in 85 parts of methyl ethyl ketone will.

Part B A series of polymer blends is prepared by 220 parts (about 100 parts acid interpolymer solids) of Part A of this Example III prepared solution and various amounts (given in Table C) the solution of the hydroxyl-containing graft copolymer prepared according to part a of Example I The compositions are given in Table C.

Table C, Part I, example of hydroxyl-containing graft copolymer Parts substrate superstrate example IIIA IA 8 100 butadiene) 100 10 vinylbenzyl) alcohol 60 80 styrene 10 acrylonitrile IIB IB. 8 90 butadiene # 100 as Example IIIA 10 styrene IIIC IC 8 as in example IIIB 10 vinylbenzyl alcohol 60 70 styrene 20 acrylonitrile IIID 10 4 as in example IIIB as in example IIIC IIIE ID 8 as in example IIIB 10 phenylallyl alcohol 60 70 styrene 20 acrylonitrile IIIF IE 8 as in example IIIB 20 phenylallyl alcohol 60 Styrene 20 acrylonitrile) IIIG IE 4 as example IIIB as example IIIF IIIH IF 200 75 butadiene as in example 1113 10 styrene 100 15 vinylbenzyl alcohol III I IG 50 as Example IIIH as in Example IIIE In the case of hydroxyl-containing graft copolymer game of parts substrate superstrate example IIIJ IH 25 80 butadiene 10 phenylallyl-20 Phenylallyl-100 alcohol 50 alcohol 20 acrylonitrile IIIK I I 100 as in Example IIIB 20 vinylbenzyl alcohol 60 80 styrene IIIL IJ 20 as in example IIIA 100 phenylallyl 35 IIIM IK 10 75 isoprene) 100 100 2-Oxymethyl- @ 90 25 styrene butadiene IIIN IL 25 as in Example IIIB 20 ethyl-ß-xoy- # ethyl fumarate 50 80 vinyl chloride IIIO Im 10 as Example IIIB 25 bis (ß-oxy) ethyl) fumarate 30 75 methyl metha-3 crylate IIIP IN 10 as in example IIIB 10 ß-oxyethyl acrylate 60 90 ethyl acrylate IIIQ IO 10 as in example IIIB 77 ethyl-ß-oxyethyl fumarate 30 23 butene-1 IIIR IP 10 as in example IIIB 25 phenyl allyl alcohol 40 75 butadiene IIIS IQ 10 80 butadiene 25 vinylbenzyl-10 styrene 100 alcohol 50 10 vinylbenzyl-75 butadiene alcohol Table C Part II Example acid interpolymer EPON 828 game of parts Composition (parts) Example IIIA IIA 100 80 styrene 36 20 maleic anhydride IIIB IIA 100 as in example IIIA 36 IIIC IIA 100 like example IIIA 36 IIID IIA 100 like example IIIA 36 IIIE IIA 100 like example IIIA 36 IIIF IIA 100 like example IIIA 36 III IIA 100 like example IIIA 36 IIIH 113 (1) 100 100 styrene 60 54 maleic anhydride III I IIA 100 as example IIIA 36 IIIJ IIB (2) 100 126 styrene 42 27 ethyl acrylate 47 maleic anhydride IIIK IIB (4) 100 110 styrene 38 40 acrylonitrile 50 maleic anhydride IIIL IIB (3) 100 108 Styrene 43 92 2-ethylhexyl acrylate 49 maleic anhydride IIIM IIB (5) 100 140 methylme thacrylate 50 60 maleic anhydride IIIN IIB (6) 100 90 styrene 36 60 butadiene 50 Maleic anhydride IIIO IIA 100 as example IIIA 118 IIIP IIA 100 as example IIIA 4,5 IIIQ IIA 100 as example IIIA 54 IIIR IIA 100 as example IIIA 18 IIIS IIA 100 as in example IIIA 9 Example IV (Manufacture of glass fiber reinforced Laminates) The polymer mixtures prepared according to Examples IIIB to IIIG are processed into multilayer materials and tested for their bond strength. All resinous polymer mixtures are brought to a solids content with methyl ethyl ketone set of 62 percent by weight. In all cases, a glass fabric (Style 28 from Hess Goldsmith, equipped with Volan A) in a size of 254x965 mm rolled up in a cylinder and immersed in the resin solution for 30 minutes. Then it will be The fabric is taken out and placed between stainless steel rollers that are on a Roll gap of 0.3 mm are set, stretched, In an oven with forced A stream of hot air is used to dry the fabric for 5 minutes at 1250 C to remove the solvent to remove. Each tissue is then cut into 76.2 mm diameter disks. These are put together to form a laminate preform of 80 layers, which is then placed between chrome-plated steel plates for one hour at 1600 C and pressed under a pressure of 70 kg / cm2 and then cooled under pressure 0 Off Three test specimens are cut for each laminate, each having a size of 25.4x25.4x12.7 mm have. Bond strength is determined by the method described in ASTM D-229-58, Paragraph 40-43 is described0 The experiment is carried out three times with each polymer mixture carried out. The average bond strength is reported. The results for the polymer mixtures of Examples IIIB to IIIG and a control experiment, which shows the bond strength obtained when only the acid interpolymer and the epoxy compound used are given in Table D below.

Table D Part I polymer hydroxylhal term graft copolymer mixture of parts substrate superstrate example example control vers. - - - -IIIB. IB 8 90 butadiene) 10 vinylbenzyl) 100 10 styrene) alcohol) 60 80 styrene 10 Acrylonitrile IIIC IC 8 as in Example IIIB 10 phenylallyl alcohol) 60 70 styrene 20 Acrylonitrile IIID IC 4 like example IIIB like example IIIC IIE ID 8 like example IIIB 10 phenylallyl alcohol) 60 70 styrene 20 acrylonitrile IIIF IE 8 as in the example IIIB 10 phenylallyl) alcohol 60 60 styrene 20 acrylonitrile IIIG IE 4 as in the example IIIB as in example IIIF part II polymer-acid interpolymer EPON composite mixture of parts assembly 828 strength example example parts kg play control vers. IIA 100 80 styrene 36 286 20 maleic anhydride IIID IIA 100 as control version. 36 590 IIIC IIA 100 like control vers. 36 649 IIID IIA 100 like control vers. 36 560 IIIE IIA 100 like control vers. 36 700 IIIF IIA 100 like control vers. 36 596 IIIG IIA 100 like control vers. 36 562 Example V Part A (creation of a Styrene-acrylonitrile-acrylic acid interpolymer) A solution is prepared, those of 210 parts of styrene monomer, 66 parts of acrylonitrile monomer, 24 parts of acrylic acid monomer, 80 parts of xylene, 70 parts of n-butyl acetate, 3 parts of benzoyl peroxide and 2.5 parts Di-tert. Butyl peroxide. 25 parts of this solution are placed in a reaction vessel introduced, which is provided with a reflux condenser and a dropping funnel. The reaction mixture is heated to the reflux temperature (about 1200 ° C.). To the remainder of the solution is for a period of from the start of reflux Introduced into the reaction vessel in a constant amount per unit time for 2.5 hours. Thereafter, refluxing is continued for an additional 20 minutes. The thus obtained Solution is cooled to water temperature and mixed with 46 parts of xylene and 43 parts Diluted n-butanol. A resin solution is obtained with a resin solids content of about 40%.

Part B (production of other acid interpolymers) in the im Part A of this example V describes a number of additional procedures Acid interpolymers generated. The composition of the monomer batch is in Table E given.

Table E Acid Interpolymers When Acid Monomer Nitrile Monomer Vinylidene monomer game (parts) (parts) (parts) VA Acrylic acid (24) Acrylonitrile (66) Styrene (210) VB (1) (4) (11) Methyl methacrylate (85) VB (2) "(15)" (35) Styrene (50) VB (3) "(20)" (20) "(60) v3 (4) (10) methacrylic (20)" (70) nitrile VB (5) methacrylic (10) acrylonitrile (10) vinyl chloride (80) acid VB (6) chloroacryl- (15) "(15) vinyl acetate (70) acid VB (7) acrylic acid (10) "(20) (70) VB (8)" (20) (20) vinyl chloride (60) Example VI (Preparation of Polymer Mixtures) Part A A series of mixtures from an acid interpolymer and an epoxy compound are produced, by 100 parts of each of the produced according to Example V and given in Table E. Acid interpolymers, a variable amount of Epon (shown in Table F) 828 (this is essentially the diglycidyl ether of bis-phenol A), and 0.25 part Dodecyltrime thyl ammonium chloride can be dissolved in 85 parts of methyl ethyl ketone.

Part B A number of polymer blends are made by 220 parts (about 100 parts of acid interpolymer solids) of Part A of Example VI produced Solution and one (in the table F specified) variable amount of the prepared according to Part C of Example I. Mixing solution of the hydroxyl-containing graft copolymer, all compositions are given in Table F.

Table F Part I Example hydroxyl-containing graft copolymer game of Parts substrate superstrate example VIA IA 8 100 butadiene) 100 10 vinylbenzyl alcohol 60 80 styrene 10 acrylonitrile VIB IB 8 90 butadiene 100 as in example VIA 10 styrene VIC IC 8 as in example VIB 10 vinyl benzyl alcohol 70 styrene 20 acrylonitrile VID ID 8 as in example VIB 10 phenylallyl alcohol 60 70 styrene 20 acrylonitrile VIE IE 8 as for example VIB 20 phenylallyl alcohol 60 60 styrene 20 acrylonitrile VIF IF 200 75 Butadiene as in example VIB 10 styrene 100 15 vinylbenzyl alcohol VIG IG 50 as in example VIF as in example VIB VIH IH 25 80 butadiene) 10 phenylallyl-) 20 phenylallyl-) 100 alcohol) alcohol) 70 stvrol) 50 20 acrylonitrile VI I I I 100 like example VIB 20 Vinylbenzyl) alcohol 60 80 styrene VIJ IJ 20 as in example VIA 100 phenylallyl) alcohol Example hydroxyl; containing graft copolymer game of parts Substrate superstrate example VIK 1K 10 75 isoprene) 100 100 2-Oxymethyl-25 styrene ) butadiene 90 VIL IL 25 as in example VIB 20 ethyl-ß-oxyethyl fumarate) 50 80 vinyl chloride VIM IM 10 as in example VIB 25 bis (ß-xoy) ethyl) fumarate 30 75 methyl methacrylate VIN IN 10 as for example VIB 10 ß-oxyethyl) acrylate 60 90 ethyl acrylate) VIO IO 10 as for example VIB 77 ethyl-ß-oxyethyl fumarate) 30 23 Butten-1) VIP IP 10 as example VIB 25 phenylallyl alcohol 40 75 butadiene VIQ IQ 10 80 butadiene) 25 vinyl benzyl- ) 10 styrene) 100 alcohol) 50 10 vinyl benzyl) 75 butadiene alcohol Tabel F Part II Example of acid interpolymer EPON 828 game of parts Composition (parts) Example VIA VA 100 70 styrene 36 22 acrylonitrile 8 acrylic acid VIB VB (3) 100 60 styrene 36 20 acrylonitrile 20 acrylic acid VIC VA 100 as example VIA 36 VID VA 100 as example VIA 36 VIE VB (3) 100 as in example VIB 36 VIF VB (1) 100 85 methyl methacrylate 60 11 Acrylonitrile 4 Acrylic acid VIG VB (7) 100 70 Vinyl acetate 36 20 Acrylonitrile 10 Acrylic acid VIH VB (2) 100 50 styrene 42 35 acrylonitrile 15 acrylic acid VI I VB (4) 100 70 styrene 38 20 methacrylonitrile 10 acrylic acid VIJ VB (3) 100 as example VIB 43 VIK VB (5) 100 80 vinyl chloride 50 10 acrylonitrile 10 methacrylic acid VIL VB (6) 100 70 vinyl acetate 36 15 acrylonitrile 15 chloroacrylic acid VIM VB (8) 100 60 vinyl chloride 118 20 acrylonitrile 20 Acrylic acid VIN VB (7) 100 as example VIG 4.5 VIO VA 100 as example VIA 54 VIP VA 100 like example VIA 18 VIQ VB (2) 100 like example VIH 9 example VII (Production of glass fiber reinforced laminates) The according to Example VIA Polymer mixtures produced up to VIQ are processed into multilayer materials and tested for their bond strength. All resinous polymer mixtures will be adjusted to a solids content of 62 percent by weight with methyl ethyl ketone In all cases, a glass fabric (Style 28 from Hess Goldsmith, equipped with Volan A) rolled up into a cylinder with a size of 254x965 mm and 90 minutes long immersed in the resin solution, then the fabric is taken out and between Stainless steel rollers adjusted to a roller gap of 0.3 mm, stretched. In an oven with a forced flow of hot air, the fabric is 5 minutes long dried at 1250 C to remove the solvent, then each fabric cut into slices of 76.2 mm in diameter.

These are put together to form a laminate preform of 80 layers, which is then placed between chrome-plated steel plates for one hour at 1600 O and pressed under a pressure of 70 kg / cm2 and then cooled under pressure. In in all cases showed the produced from a polymer mixture according to the invention, glass fiber reinforced laminate has a higher bond strength between each other adjacent layers as a laminate made with the same solids content a mixture of the acid interpolymer and epoxy resin but without the hydroxyl-containing one Graft copolymer had been produced.

Hydroxylated Graft Copolymers The hydroxylated according to the invention Graft copolymers are made by adding about 15-200 parts by weight of the superstrate monomer polymerized in an aqueous solution, the 100 parts by weight of the polydiene rubber contains, which formed the substrate of the hydroxylated graft copolymer Superstrate monomer consists of an ethylene-unsaturated alcohol to which one or more copolymerizable ethylene unsaturated monomers, one of which is a nitrile monomer can be, can be admixed. The amount of ethylenically unsaturated Alcohol about 1-100 percent by weight, that of the ethylene-unsaturated nitrile zero to about 60 percent by weight and the amount of other copolymerizable, ethylene-unsaturated Monomers are from zero to about 95 percent by weight. The preferred hydroxylated Graft copolymers are obtained by polymerizing about 20-90 parts, in particular 40-80 parts of the superstrate monomer (s) per 100 parts of the polydiene rubber.

The graft copolymerization reaction is carried out with agitation at a Temperature performed at which the initiator used in the system the Initiates copolymerization of the superstrate monomer (s), usually at one Temperature from 40-100 ° a. To substantially complete conversion of the monomer charge To ensure a polymer, you can add an additional polymerization initiator to the system to add. However, this additional initiator is often superfluous because it is not used initiator that is still present from the production of the polydiene rubber, and / or active sites on the chain of the polydiene rubber are capable of polymerization initiate the monomer charge.

The reaction is preferably carried out in the substantial absence of one the previously produced polydiene rubber latex added bi'rnulsifier carried out, because the grafting efficiency is reduced by such an added emulsifier The emulsifier already present in the polydiene rubber latex is usually sufficient as a dispersant for the graft copolymerization reaction. If necessary, can However, the aqueous dispersion an emulsifier in an amount of up to about Add 2% of the weight of the superstrate monomer mixture. With this limitation the amount of emulsifier added, a high degree of grafting efficiency can be achieved, As a result, there is usually at least 80% of the superstrate in the graft copolymer chemically bonded to the substrate. Since not converted from the graft copolymer If gum cannot be extracted, the polydiene gum appears to become completely chemically bound with the superstrate.

In the Reaktiollsgenliseh for the graft copolymerization can optionally further additives may be included, for example polymerization regulators (chain transfer agents) and stabilizers.

Superstrate of the hydroxylated graft copolymer The superstrate of the hydroxylated graft copolymer contains (a) about 1-100, preferably about 5-25 percent by weight of a chemically bound, ethylene-unsaturated alcohol, (b) zero to about 60, preferably zero to about 30 percent by weight of a chemically bonded, ethylene-unsaturated nitrile and (c) zero to about 95, preferably about 40-90 percent by weight, one or more other, chemically bound, copolymerizable, ethylene-unsaturated Monomers.

A19 Ethylene-unsaturated alcohols are the ethylene-unsaturated ones and polyvalent monomers are suitable. In the monomer can optionally also Hydroxyl may also contain other functional groups. These alcohols can therefore can be selected from a large class of substances.

These include aromatic alcohols, e.g. vinyl benzyl alcohol, 2-phenylallyl alcohol, vinyl-β-oxyethylbenzene, β-oxyethylstyrene, etc .; aliphatic Alcohols, e.g. 3-oxybutene-1, allyl alcohol, 4-oxypentene-1, methallyl alcohol, 2-oxymethylallyl alcohol, 2-chloromethylallyl alcohol, etc .; Oxydienes, z * BO 2-Oxymethylbutadine-1,3, 2,3-bis (oxyme thyl) 1,3-butadiene, etc.; Oxymono and polycarboxylic acid esters, e.g. 3. Ethyl-ß-oxyp ethyl fumarate, bis (ß-oxyethyl) fumarate, ß-oxyethyl acrylate, butyl-ß-oxypropyl fumarate, ß-oxypropyl methacrylate, ß-oxypropyl crotonate, bis (ß-oxyethyl) itaconate, ethyl-ß-xoyäthylmaleate, o (-oxymethyl methyl acrylate etc .; oxymono- and polycarboxylic acids, e.g.

# -Oxymethyl acrylic acid, # -Oxymethyl cro tonsic acid, oxymethylfumaric acid, Oxypropyl maleic acid, etc .; Oxyamino and amido monomers, e.g. o (-oxymethylacrylamide, N-oxymethyl acryl amide, N-oxymethyl maleimide, N-ß-oxypropyl maleimide, ß-oxyethyl acrylamide, 2-oxymethylallylamine, etc., # -oxymethyl acrylnitrile, etc. Various of these alcohols are used in the examples. However, you can get equivalent results by any other of the alcohols identified above or mixtures thereof be replaced.

Suitable ethylene-unsaturated nitriles are acrylonitrile and methacrylonitrile and their mixtures.

The suitable ethylene-unsaturated monomers can be selected from a large number of Class of vinyl and vinylidene monomers can be selected. These include olefins, e.g. ethylene, Propylene, isobutylene, 3-ethylbutene-1, butene-1, pentene-1 etc., mono- and polycarboxylic acid esters, e.g. B. methyl methacrylate, ethyl acrylate, diethyl maleate etc., mono- and polycarboxylic acids and their anhydrides, e.g. acrylic acid, methacrylic acid, Crotonic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, etc .; Vinyl- and vinylidene halides, e.g. vinyl chloride, vinyl bromide, vinylidene chloride, etc. Particularly preferred are aromatic monovinylidene compounds, e.g. B. styrene, as well as substituted alkyl styrenes, e.g. B. ortho-, meta- and paramethylstyrene, 2,4-dimethylstyrene, Paraethylstyrene, etc .; aryl substituted halostyrenes, e.g., ortho, meta and Parachlorostyrene or bromostyrene, 2,4-dichlorostyrene, 2-methyl-4-chlorostyrene, etc .; and mixtures of these compounds with one another and with # -methylstyrene. Using of mixtures that contain K-methylstyrene, the proportions should be such that that the i-methylstyrene does not exceed about 70 ffi of the total weight of the superstrate forming monomers. In the examples, various of the above indicated, ethylene-unsaturated monomers indicated.

However, you can get equivalent results from everyone else monomers identified above or mixtures thereof are replaced.

Substrate of the hydroxylated graft copolymer The substrate of the hydroxylated Graft copolymer is a polydiene rubber that is (a) about 40-100, preferably about 75-100 Weight percent of a chemically bound conjugated diene and (b) zero to about 60, preferably zero to about 25 weight percent of one or more others, chemically contains bound, ethylene-unsaturated monomers.

Suitable conjugated dienes are butadiene, isoprene and their Mixtures.

The suitable ethylene-unsaturated monomers can be selected from a large number of Class of vinyl and vinylidene monomers 0 This class was mentioned above given on the basis of the monomers for the superstrate. In a preferred embodiment the substrate contains the conjugated diene in chemical association with a copolymerizable one Monomer obtained from an ethylenically unsaturated alcohol or an aromatic monovinylidene compound exists in the sense indicated above. In particular, you can have both a Ethylene-unsaturated alcohol as well as an aromatic monovinylidene compound, especially styrene. In this last-mentioned embodiment contains the polymeric diene rubber substrate (a) about 40-99, preferably about 75-99 weight percent of the chemically bound conjugated diene, (b) about 1-60, preferably about 1-25 percent by weight of the chemically bound, hydroxyl-containing Monomer and (c) about 1-60, preferably about 1-25 weight percent of the aromatic Monovinylidene compound.

The invention is not directed to any particular method of manufacture of the polydiene rubber limited. In the examples, polymerization is carried out free radicals worked in aqueous systems. However, satisfactory ones are obtained as well Results when you æOB. with anionic or cationic catalysis in aqueous or organic systems works. It can therefore diene rubber made from monomer combinations which are not easily polymerizable with the help of, for example, free radicals are. You can also use monomers that are not copolymerizable with butadiene or isoprene are, use together with other copolymerizable monomers which can be used with both e.g. are copolymerizable to form terpolymers.

In various embodiments, the copolymerizable ethylene-unsaturated monomers can be olefins, e.g. ethylene, propylene, isobutylene, 3-methylbutene-i, butene-1, pentene-1, etc .; Mono- and polycarboxylic acid esters, e.g. B.

Methyl methacrylate, xethyl acrylate, diethyl maleate, etc .; Mono- and polycarboxylic acids or their anhydrides, e.g. acrylic acid, methacrylic acid, crotonic acid, fumaric acid, Maleic acid, maleic anhydride, itaconic acid etc., vinyl and vinylidene halides, zOBO vinyl chloride, vinyl bromide, vinylidene chloride etc., aromatic monovinylidene compounds, e.g. styrene, as well as substituted alkyl styrenes, e.g. ortho-, meta- and paramethylstyrene, 2,4-dimethyl styrene, paraethylstyrene, etc.; aryl substituted halostyrenes, e.g. Orthostyrene, metastyrene and parachlorostyrene or bromostyrene, 2,4-dichlorostyrene, 2-methyl-4-chlorostyrene etc .; and mixtures of these compounds with one another and with # -methylstyrene, aromatic alcohols, e.g.

Vinylbenzyl alcohol, 2-phenylallyl alcohol, vinyl-ß-oxyethylbenzene, β-oxyethylstyrene, etc .; aliphatic alcohols, e.g.

D-oxybutene-1, allyl alcohol, 4-oxy pen ten-1, methallyl alcohol, 2-oxymethylallyl alcohol, 2-chloromethylallyl alcohol, etc .; Oxydienes, e.g. 2-Oxymethyl butadiene-1, 3,, 2,3-bis (oxyme thyl) -butadiene-1,3, etc .; Oxymono- and polycarboxylic acid esters, e.g.

Ethyl-ß-oxyethyl fumarate, Bix- (ß-oxyethyl) fumarate, ß-oxyethyl acrylate, Butyl-ß-oxypropyl fumarate, ß-oxy propyl methacrylate, ß-oxypropyl crotonate, bis- (ß-oxyethyl) itaconate, ethyl ßoxyethyl maleate, # -Oxyme thylm thyl acrylate etc .; Oxymono- and -polycarboxylic acids, z03. # -Oxymethyl acrylic acid, ; -Oxymethylerotonic acid, Oxymethylfumaric acid, oxypropyl maleic acid, etc. oxyamino and amido monomers, e.g. i-oxymethylacrylamide, N-oxymethylacrylamide, N-oxymethylmaleimide, N-ß-oxypropylmaleimide, β-oxyethyl acrylamide, 2-oxymethylallylamine, etc., γ-oxymethylacrylonitrile, etc. Various these ethylene-unsaturated monomers are used in the examples. You can however, with equivalent results from any other of those identified above Monomers or their mixtures are replaced.

If appropriate, one can use in the preparation of the substrate polymer use a chemical crosslinking agent. In general, amounts of up to are sufficient about 5% based on the weight of the rubber-forming monomers. A crosslinking agent content from 0.5-1.25 * is particularly advantageous.

In the context of the invention, any crosslinking agent can be used, which can react with the rubber-forming monomers. Such wetting agents are natural known. They include B. divinylbenzene, diallyl maleate, diallyl fumarate, diallyladipate, Diallyl phthalate, allyl acrylate, allyl methacrylate, diacrylates and dimethacrylates from polyhydric alcohols, for example ethylene glycol dimethacrylate, etc.

In the preparation of the hydroxylated graft copolymers, the Polydiene rubber commonly used in the form of freshly made latices or from Latices that have been stored in an inert atmosphere. These latices can by any of the known polymerization processes carried out in aqueous emulsion which are customary for the production of such latices. In general the monomers are emulsified in water, with the help of a micelle-forming Emulsifier, which is preferably in an amount of about 2-7 percent by weight The monomer is used0 Then one can in the presence of a water-soluble Free radical polymerization initiator or a redox catalyst Polymerize at 0-80 ° C. The reaction mixture can use a polymerization regulator (chain transfer agent), e.g. a higher alkyl mercaptan such as dodecyl mercaptan. Such an agent is usually used.

Acid interpolymers (component B (a)) The from the acid interpolymer existing components of the compositions of matter according to the invention, which are in the Examples I-IV illustrated consist essentially of one essentially homogeneous interpolymer from (a) 20-45, preferably 20-35 mol of an acid monomer of the class #, ß-ethyl enunsaturated polybasic acids, anhydrides of, ß-ethylene unsaturated polybasic acids and their mixtures, and (b) 80-55, preferably 80-65 mol% at least one vinylidene monomer which can be interpolymerized with said acid monomer is.

Typical examples of the acid monomers used in the acid interpolymer can be used are maleic acid, maleic anhydride, malaleic acid, Fumaric acid, citraconic acid, citraconic anhydride, itaconic acid and itaconic anhydride. Typical examples of vinylidene monomers, used in the acid interpolymer are mono-uad diolefins, for example ethylene, propylene, butene-1, Isobutylene, butadiene and isoprene; Vinyl halides, e.g. vinyl chloride and Vinyl bromide; Vinylidene halides, for example vinylidene chloride; Vinylidene aroma. hydrocarbons and halogenated derivatives thereof, for example styrene; Vinyl naphthalene; ring alkyl substituted styrenes, e.g., o-, m- and p-methylstyrene, 2,4-dimethylstyrene; ring halogen substituted styrenes, e.g. o-, m- and p-chlorostyrene, 2,5-dichlorostyrene; ok-alkyl-substituted styrenes, e.g. B. # -Methyl styrene, # -ethyl styrene; Acrylic acid and methacrylic acid esters of alkanols with 1-18 carbon atoms, e.g. methyl methacrylate, Butyl methacrylate, ethyl acrylate, dodecyl acrylate; Acrylonitrile; Methacrylonitrile; Acrylamide, Methacrylamide, vinyl alkyl ketones such as vinyl methyl ketone and vinyl butyl ketone; Vinylalkylä ether, for example vinyl methyl ether and vinyl butyl ether; Vinyl ester of carboxylic acids which have 1-18 carbon atoms @, for example vinyl formate, Vinyl acetate, vinyl stearate, vinyl benzoate, etc. The acid interpolymers are preferably which are used in the compositions of matter according to the invention, from interpolymers a maleic anhydride and a vinylidene aromatic hydrocarbon, in particular Styrene.

In the compositions of matter according to this feature of the invention The acid interpolymers used differ from the usual acid interpolymers on three important points. First, the acid monomer and the vin are jlidene monomer in the polymer chains in the molar proportions given above, i.e. 20-45 Mol-% acid monomer and accordingly 80-55 mol vinylidene monomer, irregular distributed, not in a molar ratio of 1: 1 egg in the polymer chain regularly alternating monomer groups. The structure just described is typical of the known acid interpolymers of this type. Second are the acid interpolymers are homogeneous and are the acid monomer and the vinylidene monomer essentially in all polymer chains in connected to the molar ratios given above. The acid interpolymers are particularly important essentially free of (a) simultaneously formed interpolymers in which the acid monomer and the vinylidene monomer are linked in a molar ratio of 1: 1 and the two monomer groups in the polymer chain regularly with one another alternate, and from (b) simultaneously formed homopolymers of vinylidene monomer. Third, the molecular weight of the acid interpolymer is so low that the Interpolymers (1) when determined by the known Parr-Bar method Softening point below about 2250 ° C., preferably below 205 ° C., especially in the range of 60180O C and (2) in pyridine at 300 C an intrinsic viscosity below 0.5, preferably below 0.40, acid interpolymers with such softening points and intrinsic viscosities have a number average molecular weight less than about 10,000, preferably less than about 5000. for the production of acid interpolymers, which meet the requirements of the invention are particular polymerization processes necessary. These homogeneous acid interpolymers are preferably used in one Solution polymerization processes produced in which the acid monomer and the vinylidene monomer in the molar ratio desired in the interpolymer, of the polymerization reaction are fed. Furthermore, the monomers are essentially in the polymerization medium introduced in that amount per unit of time in which they polymerize so that they polymerize essentially immediately upon entry into the polymerization medium. In this way of working, the formation of a 1 interpolymer avoided with alternating groupings.

To achieve an acid interpolymer with a Parr Bar softening point and an intrinsic viscosity in the desired range, the polymerization process is carried out at temperatures above about 800 C, preferably in the range 140-170 ° C in solvents by acting as polymerisation regulators (chain transfer agents) for this A number of solvents can be used for this purpose. Aromatic ones are preferred Hydrocarbons such as xylene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene and the same. It is also useful to use relatively large amounts of peroxides as Polymerization initiators, for example benzoyl peroxide and the like, in quantities for example 0.1-5, preferably 0.5-2 parts of initiator per 100 parts of the To use monomers. In viral cases it is advisable to use molecular weight regulators to be used preferably in the form of polymerisation regulators (chain transfer agents), for example mercaptans, terpenes and the like, in amounts of for example up to 10 parts, preferably 0.5-5 parts per 100 parts of the monomers. That in part A of Example II described polymerization process for producing the acid interpolymer A represents the currently preferred procedure for producing from an acid interpolymer existing component of the compositions of matter according to this feature of the invention represent.

Acid interpolymers (component B (b)) The acid interpolymers which form components of the compositions of matter according to Example V-VII are interpolymers of (1) 2-30 and preferably 4-12 percent by weight of at least one acid monomer of the formula in which R is selected from the class hydrogen, halogen atoms and alkyl groups having 1-4 carbon atoms, (b) 2-40, preferably 8-20 percent by weight of a nitrile monomer of the class acrylonitrile, methacrylonitrile and mixtures thereof, and (3) the remainder of at least one Vinylidene monomer that is interpolymerizable with the acid monomer and the nitrile monomer. The monomers suitable as the third component of the acid interpolymers include mono- and diolefins, for example ethylene, propylene, butene-1, butadiene and isoprene; Vinyl halides such as vinyl chloride and vinyl bromide; Vinylidene halides, for example vinylidene chloride; Vinylidenarom.kohlenwasserstoffe and halogenated derivatives thereof, for example styrene; Vinyl naphthalene; ring alkyl substituted styrenes, e.g. B. o-, m- and p-methylstyrene, 2,4-dimethylstyrene; ring halogen-substituted styrenes, for example o-, m- and p-chlorostyrene, 2,5-dichlorostyrene; alkyl substituted styrenes, e.g. o (-Methyls tyrene, o (-ethylstyrene; acrylic acid and methacrylic acid esters of alkanols with 1-18 carbon atoms, e.g. methyl methacrylate, butyl methacrylate, ethyl acrylate, dodecyl acrylate; acrylamide, methacrylamide; vinyl alkyl ketones, e.g. vinyl methyl ketone and vinyl butyl ketone; vinyl alkyl ethers, for example Vinyl methyl ether and vinyl butyl ether; vinyl esters of carboxylic acids which have 1-18 carbon atoms, for example vinyl formate, vinyl acetate, vinyl stearate, vinyl benzoate, etc. Preferred acid interpolymers are the interpolymers of acrylic or methacrylic acid, acrylonitrile and styrene, methyl methacrylate or a mixture of Styrene and methyl methacrylate.

The acid interpolymers used in the compositions of matter according to the invention preferably have a low molecular weight, e.g., below 10,000, especially in the range of about 1500-5000, although this is not strictly necessary. Acid interpolymers of this type can according to that described in Example V, Part A. Process are produced.

Epoxy compounds All epoxy compounds with two or more epoxy groups can be used in the compositions of matter according to the invention. Preference is given to epoxy groups which contain two or more epoxy groups with the following structure: Typical examples of such epoxy compounds are polyglycidyl esters of polybasic acids according to US Pat. No. 2,866,787, polyglycidyl esters of polyhydric phenols according to US Pat. Nos. 2,467,171, 2,506,486, 2,640,037 and 2,841,595 and polyclycidyl ethers of polyhydric alcohols according to the USA Patents 2,538,072 and 2,581,464. Preferred epoxy compounds are the polyglycidyl ethers of dihydric phenols, the structure of which can be represented by the following formula Here n is an integer in the series 0, 1, 2, 3 .... and R represents the divalent hydrocarbon radical of the dihydric phenol. Epoxidized flaxseed oil, epoxidized soybean oil and other epoxidized drying oils disclosed in U.S. Patent 2,569,502; epoxidized polyolefins, e.g. B. vinylcyclohexenedioxide, dicyclopentadiene oxide and divinylbenzene oxide; epoxidized polyunsaturated monoesters; epoxidized polyunsaturated polyesters according to the laid-out Australian patent application 11 826/55, glycol bisexodihydrocyclopentadienyl ether according to US patent specification 2,543,419; epoxidized novolac resins; and epoxidized liquid diene polymers, for example epoxidized liquid polybutadiene according to US Pat. No. 2,946,756.

Further suitable epoxy compounds can be found in the USA patents 2 992 193, 2 971 942, 2 949 438, 2 938 875, 2 936 292, 2 918 439, 2 917 469 and Belgian patent 588 068.

The acid interpolymers forming component B (a) and the Epoxy compounds are in the compositions of matter according to the invention in such Proportions contain that per carboxyl group of the acid interpolymer on average 0.2-1.2, preferably 0.4-1.0 epoxy groups are present. When calculating this It is assumed that one anhydride group is equivalent to two carboxyl groups is.

The component consisting of an acid interpolymer B (b) B (b) and the epoxy compounds are in the compositions of matter according to the invention present in such proportions that per carboxyl group of the acid interpolymers on average at least 0.4, preferably at least 0.6 and in particular at least 0.8 epoxy groups are present. When using the epoxy compound in such Amount that per carboxyl group of the acid interpolymer B (b) is significantly more present as an epoxy group hardly leads to any particular advantage.

One of the special features of the compositions of matter according to the invention is that at elevated temperatures in the order of 1490 C the Acid interpolymer and the epoxy compound react with one another, so that the Compositions of matter can be thermoset without the need for a catalyst is. On the other hand, at moderate temperatures up to about 400 ° C. there is no significant Reaction between the acid interpolymer and the epoxy compound. As a result of this Properties can be produced by the compositions of matter according to the invention and be stored for a long time, up to at least about a year, without that they thermoset or gel in the container in which they are stored.

If necessary, you can use small amounts of a catalyst, to the reaction between the acid interpolymer and the epoxy compound accelerate.

Various types of catalysts are suitable for this purpose. Quaternary ammonium compounds, for example lauryltrimethylammonium chloride, are preferred. As catalysts in the compositions of matter according to the invention can also other amines, e.g. B. lutidine, collidine, pyridine, benzylamine, benzyldimethylamine, 1,8-diamino-p-menthane, as well as their N-substituted ones obtained by alkylation Derivatives, e.g., N, N, N ', N'-tetramethyl-1,8-diamino-p-menane and N, N'-dimethyl-1,8-diamino-p-mene than can be used, or a polyalkylene polyamine, e.g. B. ethylenediamine, diethylenetriamine, Triethylenetetramine etc. Tin compounds can also be used, for example Tin (II) octoate and dibutyltin di-2-ethylhexoate. When the epoxy groups of the epoxy compounds Ring epoxy groups are, as for example in the dicyclopentadiene dioxide, it is sometimes it is useful to use Lewis acids as the catalyst, e.g. BF3 or p-2oluenesulphonic acid.

When using catalysts, their amount is usually about 0.1-5.0, preferably 0.5-2.0 percent by weight of the acid interpolymer has been shown that the curing behavior of the resin compositions according to the invention Can be modified if they are a phenol, a carboxylic acid and / or an anhydride a rtyearboxylic acid is added. Such hardening modifiers increase the Gel time and lead to a higher final hardness, that is, they increase the heat resistance. Typical modifiers are phenol, resorcinol, novolac resins, salicylic acid, resorcyclinic acid, Benzoic acid, adipic acid, phthalic anhydride, maleic anhydride and pyromellitic anhydride. The phenolic modifiers are usually in a range of 0.1-5.0, preferably 0.5-2.0 parts per 100 parts of the acid interpolymer is used. The modifiers consisting of carboxylic acids and carboxylic acid anhydrides become usually in an amount of 0.5-10, preferably 2.0-5.0 parts per 100 parts of the acid interpolymer is used.

Applicability The compositions of matter according to the invention are in particular for the production of impregnation agents for laminates, as well as adhesives, Pressing, spraying and coating compounds are suitable.

The impregnation and coating compositions according to the invention exist from an organic solvent in which the hydroxyl-containing graft copolymer, the acid interpolymer and the epoxy compound in those given above Shares are resolved. In these masses, any organic solvent can be used the usual solvents in which all components are soluble or are used are dispersible. These solvents include, for example, the aromatic ones Hydrocarbons, the halogenated aromatic hydrocarbons, alcohols, Ethers, ketones, esters and any mixtures thereof, for example xylene-butanol mixtures, Ketone-ester mixtures etc.

In addition to the organic solvent, the hydroxyl-containing graft copolymer, the acid interpolymer and the epoxy compound can be according to the invention Tberzugssassen also pigments, extenders, fillers, matting agents and like included. Any pigments can be used as opposed to are insensitive to the acid interpolymer, for example titanium dioxide, copper phthalcyanine, Ultramarine blue, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, zinc chromate, Soot and the like.

Films made from the coating compositions according to the invention can be prepared according to the customary Processes are applied, for example by spraying, brushing, rolling, Dipping, etc. The wet films can be removed by heating at elevated temperatures in of the order of 1490 C or preferably 177 C or more for a short time Cured for a period of the order of 60 minutes, depending on the curing temperature werden0 The coating compositions according to the invention are particularly suitable for coating of metal surfaces, for example primed or unprimed steel, Aluminum, chromium, nickel, brass, copper, etc. The compositions of matter can can also be used to cover other surfaces, e.g. paper, Cardboard, leather, textiles, glass, porcelain and other vitreous materials, as well as plastics such as polyesters, methacrylate polymers, styrene polymers and the like 0 The films produced from the coating compositions according to the invention have the following properties after curing: They have (a) good adhesive strength on primed or unprimed metal substrates, (b) high hardness, (c) high gloss, (d) good color properties, and (e) excellent durability against solvents and corrosion. The hardened ones stand out in particular Pilme has unsurpassed resistance to alkaline detergents the end. This resistance is several orders of magnitude higher than anything else before known organic coatings. The alkali resistance of the films is so excellent, that they are used for certain purposes, for example for the inside of washing machines and the like, can be used in place of porcelain-clad steel.

Molding and injection molding compounds can be produced by using the hydroxyl-containing Graft copolymer, the acid interpolymer and the epoxy compound with one finely divided Filler, for example glass, asbestos, paper, Mixes wood flour and the like. The molding and injection molding compounds obtained in this way can pressed or processed by injection molding and by heating to temperatures above cured at around 1490 ° C. Laminates can be produced by using a Web with a mixture of the hydroxyl-containing graft copolymer, the acid interpolymer and impregnated the epoxy compound and the impregnated web at elevated temperature, especially cures under pressure, as described in Example IV. The train can consist of paper or a textile fabric. It preferably consists of high melting points Fibers, for example glass fibers, metal threads, asbestos threads, nylon threads or threads from other high-melting polymers.

In the production of such laminates, the reinforcement sheet with a dispersion of the hydroxyl-containing graft copolymer, the acid interpolymer and the epoxy compound impregnated and to reduce the content of the impregnated Sheet of volatile substances heated to temperatures of up to around 93 ° C. Since the Do not cure temperatures according to the invention, you can reduce the content of volatile Reduce substances to very low values, for example less than 2%. In most cases it is useful to impregnate the web so that they are about Contains 30-50, especially about 35-45 ffi resin solids. Then an or several layers of the resin-impregnated sheet are placed on a base and about For 15-60 minutes at an elevated temperature, e.g. B. from 121-2040 C under one Pressed pressure of 3.5-70 kg / cm2, so that the layers are connected to each other and the resin is cured. Since there are no volatile substances when the resin system cures Fabrics are formed, one can produce Schichitoffe that have a high density and Possess strength.

The compositions of matter according to the invention can also be used as adhesives to connect different surfaces, e.g. wood, paper, textiles, Metals and the like can be used. For connecting such surfaces to one another the planes with a mixture of the hydroxyl-containing graft copolymer, of the acid interpolymer and the epoxy compound coated and the action exposed to heat and pressure 0 The one between the parts to be joined Adhesive can expediently be heated dielectrically.

The compositions of matter according to the invention can also be used for various used for other industrial purposes. For example, the material compositions Suitable as a binder in the production of dense, high-quality grinding wheels. You can get good looking, shiny coatings on plywood and other wooden surfaces obtained by covering the surface with the said compounds and then the coatings cures while the assembly is held under pressure. The compositions of matter can also be used in the resin-impregnated paper for air filters such as those used in automobile engines can be used, serve as resin binders, or in place of phenol-formaldehyde resins as a binding agent for sand intestines in foundries.

The above description, in particular the exemplary embodiments serve only to explain the invention. Many modifications within the scope of the concept of invention are obvious for the Pachmann.

Claims (17)

Paten tanaprüche: 1st gene, characterized by (A) about 1-250 parts by weight of a graft copolymer made of polydiene rubber as a substrate and a hydroxyl-containing polymer al @ sup @ rstrat in a ratio of about 15-200 parts by weight of superstrate polymer per 100 parts by weight of substrate Polymer, where the substrate polymer is a rubber-like polymer of about 40-100 percent by weight of a conjugated diene of the class butadiene, isoprene and mixtures thereof, and accordingly about 60 to zero percent by weight of at least one vinylidene monomer that is copolymerizable with the conjugated diene, since the superstrate polymer is a polymelizate of (1) about 1-100 percent by weight of an ethylenically unsaturated alcohol, (2) zero to about 50 percent by weight of ethylene-unsaturated nitrile and (3) zero to about 95 Percent by weight of at least one vinylidene monomer terpolymerizable therewith is (B) 100 parts by weight of an essentially homogeneous interpolymer of class (a) In t erpolymerisate with (1) about 20-45 mol% of an acid monomer of the class #, @ - ethylene-unsaturated polybasic acids, anhydrides of #, ß-ethylenically unsaturated polybasic acids and their mixtures, and accordingly (2) about 80-55 mol- % at least @ ten @ of a vinylidene monomer that is interpolymerizable with the acid monomer, the interpolymer having a Parr-Bar temperature below about 225 ° C and in pyridine at 300 ° C an intrinsic viscosity below about 0.5, (b ) Interpolymers from (1) about 2.30 percent by weight of at least one acid monomer of the formula where R is selected from the class hydrogen, halogen atoms and alkyl groups with 1-4 carbon atoms (2) about 2-40 percent by weight of a nitrile monomer of the class acrylonitrile, methacrylonitrile and their mixture @ and (3) the remainder at least one vinylidene monomer, which with the acid monomer and the nitrile monomer are interpolymerizable; and (C) an epoxy compound which contains a plurality of epoxy groups and is present in an amount such that d @. per carboxyl group of component (ß) (a) there is an average of 0.2-1.2 epoxy groups present and per carboxyl group of component (B) (b) at least 0.4 epoxy group is present. 2. Mixture according to claim 1, characterized in that component (C) has several epoxy groups with the structure contains. 3. Mixture according to claim 1, characterized in that the component is dio (B) is an interpolymer of styrene and maleic anhydride. 4. Mixture according to claim 1 or 2, characterized in that @ the Component (B) is an interpolymer of styrene, acrylonitrile and acrylic acid. 5. Mixture according to claim 1 to 4, characterized in that the The substrate of component (A) is an interpolymer of butadiene and styrene. 6. Mixture according to Anupruch 1 to 5, characterized in that dat3 dan Superstrate of component (A) is an interpolymer of tyrene, aoryl nitrile and vinylbenzyl alcohol is. 7. Mixture according to claim 1-5, characterized in that the Juperstrat component (A) is an interpolymer of styrene, acrylonitrile and phenylallyl alcohol is. 8. Mixture according to claim 1 to 4, characterized in that there is a sub Component (A) was joined by an interpolymer of butadiene, styrene and vinylbenzyl alcohol is. 9. Mixture according to An @ pruch 8, characterized in that @ the superstrate of component (A) an interpolymer of styrene, acrylonitrile and vinyl benzyl alcohol is. 10. Mixture according to Anupruch 1 to 4, characterized in that the Component (A) substrate is an interpolymer of butadiene styrene and phenylallyl alcohol is 11. Mixture according to claim 10, characterized in that the superstrate of daii Component (A) is an interpolymer of styrene, acrylonitrile and phenylallyl alcohol is. 12. @ coating and impregnation @ mass, characterized in that, an organic liquid medium (A) about 1-250 parts by weight of a graft copolymer of a polydiene gum @ ii as substrate and a hydroxyl-containing polymer as superstrate in a ratio of about 15-203 parts by weight Superstrate polymer per 130 parts by weight; ubtrt-Pol vmeri sat, whereby the subutra t-polymerisate a rubber-like polymer of about 40-100% by weight of a conjugated diene of the class butadiene isoprene and mixtures thereof, and dementia about 60 to zero percent by weight of at least one copolymerizable with the conjugated diene is vinylidene monomer, the superstrate polymer in polymer consists of (1) about 1-100 percent by weight of an ethylene-unsaturated alcohol, (2) zero to about 50 percent by weight . nt is an ethylenic, saturated nitrile and (3) zero to about 95 percent by weight of at least one vinylidene monomer polymerizable therewith; (B) 100 parts by weight of an essentially homogeneous Interpol® polymer of class (a) Interpolymers with (1) about 20-45 mol% of an acid monomer of class #, ß-ethylene-unsaturated polybasic acids, anhydrides of #, ß- Ethylene-unsaturated polybaci., Chen acids and their Gemi @ ch @, and accordingly (2) about 80-55 mol% of at least one vinylidene monomer, since, with the acid monomer is interpolymerizable, the inter polymerisat @ incn Parr-Bar-Erw has a calibration point below about 2250 ° C. and in pyridine at 300 ° C. has a grunamolar viscosity below about 0.5, (b) interpolymers from (1) about 2-30 percent by weight of at least one acid monomer of the formula where R from the class hydrogen, halogen atoms and alkyl. groups having 1-4 carbon atoms are selected (2) about 2-40 percent by weight of a nitrile monomer of the class aorylnitrile, methacrylonitrile and mixtures thereof and (3) the remainder of at least one vinylidene monomer which is interpolymerizable with the acid monomer and the nitrile monomer; and (c) a spoxy compound which contains several epoxy groups and is present in such an amount that there are on average 0.2-1.2 epoxy groups per carboxyl group of component (B) (a) and per carboxyl group of component (B) (b) at least 0.4 epoxy group is present. 13. @ coating and impregnation compound according to Anupruch 12, characterized in that that component (B) is an interpolymer of styrene and maleic anhydride. 14. Coating and impregnation compound according to claim 12, characterized in that the tlis component (B) is an interpolymer of styrene, acrylonitrile and acrylic acid is. 15. Laminate, characterized in that a reinforcement sheet is impregnated and bonded with a waraghardened resin mixture, which essentially consists of (A) about 1-250 parts by weight of a graft copolymer from (inem polydiene rubber as subs and a hydroxyl-containing polymer as superstrate in the Ratio of about 15-200 parts by weight of superstrate polymer per 100 parts by weight of substrate polymer, where the substrate polymer is a rubbery polymer and about 40-100 percent by weight of a conjugated diene of the class @utadiene, isoprene and deron mixture and accordingly about 60 to zero Percent by weight of at least one vinylidene monomer copolymerizable with the conjugated diene, the superstrate polymer is a polymer of (1) about 1-100 percent by weight of an ethylene-unsaturated alcohol, (2) zero to about 50 percent by weight of an ethylenically unsaturated nitrile and (3) zero up to about 95 percent by weight of at least one vin that can be interpolymerized with it is ylidene monomer; (B) 100 parts by weight of an essentially homogeneous Interpol @ mericate of class (a) Interpolymers with (1) about 20-45 mol% of an acid monomer of class #, ß-ethyl unsaturated polybasic acids, anhydrides of # #, ß- Ethylene-unsaturated polybasic acids and their mixtures and accordingly (2) about 80-55 mol% of at least one vinylidene monomer which is interpolymerizable with the acid monomer, the interpolymer having a Parr-Bar softening point below about 2250 C and in pyridine at 300 C has a green molar viscosity below about 0.5, (b) interpolymers au (t) about 2-30 percent by weight of at least one monomer of the formula where E is selected from the class hydrogen, halogen atoms and alkyl groups having 1-4 carbon atoms (2) about 2-40 percent by weight of a nitrile monomer of the class acrylonitrile, methacrylonitrile and their mixtures and (3) the remainder of at least one vinylidene monomer, which with the acid monomer and the Nitrile monomer is interpolymerizable; and (c) an epoxy compound which contains several epoxy groups and is present in such an amount, since there are an average of 0.2-1.2 epoxy groups per carboxyl group of component (B) (a) and per carboxyl group of component (3 ) (b) at least @ 0.4 epoxy group is present. 16. Jchiohtstoff according to claim 15, characterized in that the Component (B) is an interpolymer of styrene and maleic anhydride, 17th Laminate according to Claim 15, characterized in that component (B) is one Interpolymer of styrene, acrylonitrile and acrylic acid is.