DE1546911A1 - Process for impregnating porous surfaces - Google Patents

Description

'' Yün porous ObeC '! "Groaning The invention 6.) a process for impregnating vcn porous surfaces. The invention is based on the knowledge that opposing : 3säna (e m14 porous upper girls in a surprising way p7 "can straighten" if you have the impregnation through Beakr. len the impregnation components to the impregnation n., i.: @. @ _ w4-aclen surfaces erzengfi, ie, more precisely, if .axi the surfaces to be impregnated with polymer-soluble, inoromeric verbs areas I t was found "that in itself dIg., e way be2, cc) x @ der: j dicY @ zm and fixed iris bags o The method JAr invention is characterized in that the surfaces with polymerizable, ethylenically un- saturated monomers are treated and that the monomers by a catalyst system applied separately to the surfaces consisting of (a) an organic hydroperoxide, an organic ring peroxide or an inorganic hydroperoxy acid and (b) an oxidizable; Sulfur compound polymerized in situ will. The impregnation of a porous surface takes place according to the invention according to the fact that the surface with polymerizable Monomers and in the following as so-called first and second compounds gen designated compounds is treated, which the poly- cause merization of the monomers. According to a preferred embodiment Fahrungsform the method of the invention is initially through Dissolving a first compound in a polymerizable vinyl monomers a batch A prepares, in which the to be impregnated Body is immersed. The body treated with batch A. is then exposed to the action of the so-called second connection, whereby the polymerization of the monomers of batch A is directed. The so-called second connection can Ren advantageous embodiment of the method of the invention can also be used in the form of approach B, which among other components such as fillers and the like. may optionally also contain polymerizable monomers. It has also proven to be advantageous if the approaches A and 'r3 polymeric compounds are added. The method of the invention also enables porous materials Impregnate and glue in one operation. So can be used, for example, in the production of laminated bodies, such as plywood or veneer wood, the layers-same- be closed in good time and connected to one another. The ones on the. Laminated bodies produced in this way are characterized by their large size Strength. They are also extremely waterproof casual and, depending on the monomers used, towards the Resistant to the effects of solvents. According to the procedure of Invention impregnated laminates are therefore particularly suitable for the production of components. The method of the invention is suitable see also in a particularly advantageous manner, for example, impregnation ren and possibly at the same time for joining textiles For example , using the method of the invention achieve extremely water-resistant impregnations. Suitable polymerizable, ethylenically unsaturated Monomers are all compounds in question, the one or several groups of the formula: contain. Suitable polymerizable c-ethylenically dew-saturated monomers with the specified group are, for example, the Vinylvex ° - bonds with the group, wi: a for example Acryj.säurF ", Met.hae:, # ylic acid, esters and amides of Acids ,, z.ü. Methy ".airylatD Methylmetharrylat, Ethyleneglyk °; 1-, diaerylat, Acrylamidp Methacrylamid, N-Alkyl- and N, N-T'ial) .: yl # amides of acids, such as N-methylacrylamide, N, N-dimet, hyl --- acrylamide; N-methyl methacrylamide; N, N-dimethyl methacrylamide usd o. Other polymerizable ethylenically unsaturated monomers are for example dlaleic anhydride maleic acid, fumaric acid acid, diesters, amides and estamides of maleic and pumaric acid, Maleimide and the like. The vinyl ethers, such as, for example, are also suitable Methyl vinyl ether = ethyl vinyl ether #, propyl vinyl ether; Butyl. vinyl ether and the like., 9 Also vinyl ester, such as. be: .sp @ Le, lswe @. @@ V @. @ @@ c @ r @ .: vavy Vitaylace @ ca @, @ t @@. r @@@ pr'ob @ r @@ naf.3 V @ '@ @ ty1- @ bu: yrat and dx @@. @ ° g..k. - .ee: L @ $ r ::: ei @ clym @ oris @ r @@ ar.e är: tlyler: sct @ unsaturated Monr., Fiw: .ce sJo @ A: -err.ier . Ve .., b.ixadungen "as sp3. @: Z_.Ye.:@e Styrene, p @ At.; Et .., am: .nostyrolp x> -Meti.4,, V; @sty ", ol., l azAcetoxystyr (: pl and rt @. @ gl @@ To the suitableex: @ p, #. Yme ° i :: "ä erbaren ,, äthy.Ef #, qIsch uys @ Esät tiger- Moisonie.ren include rmh V: rta: 1.ndangen, such as acrylo- ni: r1. t "Methaeryl @) r @ -i. trril AK @ dergb., 1 Hal: og-anq, perbi_ra @ it: nge n, @t: ie 1'e =; ra.luoxäth & lean @: @@@, or # ax.f: laorä, thylerx E.xad Üergl, as well as in- de-, e connections,) wle t, eis ~ ') lelsweise Ätky 6er & ls: _ @><@ ty en,. N®'iinylimide, isopropeny! a:; e @; atu: ml dergio. Egg. Re variety of suitable polymerisieg ° b: ire33, ä @ 9hyleriisct unsaturated monomers tb - ijcien by the @ 5 @ $ = me @ .: are reproduced if: R is a hydrogen or halogen atom or an alkyl or Aryl group; X whine: hydrogen or halogen atoms or hydroxy-s ALeoxy-g Aryloxy- ,: Garboxy- .. Alkoxycarbonyl-, Aryloxycarbonyl-, Acyloxy, cyano, aryl or carbamoyl groups and together: Groups, the formula. Particularly suitable polymorisable knomers can be obtained by the Formula: were reproduced, where R has the meaning given and V represents: A substance of water; or Halzgenatom or a Hydroay-, Alkoxy - t Aryloxy-, carboxy-, -alkoxycarbonyl =, aryloxycarbonyl-, acyloxy-y Cyano, ary! Or carbarmyl group or a group of the formulas: in which n is a number such as 1 or 2 and R3 is a has divalent hydrocarbon group when n = 1 or has the meaning of a trivalent hydrocarbon group, if n = 2 j If R in the given formulas consists of a halogen atom, so this consists preferably of a fluorine, chlorine or Bromine atom. If R represents an alkyl group, this has preferably 1 to about 8 carbon atoms and is for example a methyl, ethyl, propyl, isopropyl, butyl, pentyl, Hexyl, heptyl, octyl, 2-xthylhexyl or derglo. Consists R consists of an aryl group, this preferably consists of one mononuclear, earbocyclic ring with 6 to 10 carbon atoms, for example a phenyl, tolyl, xylyl, 2,4-diethyl - # phenyl ring or the like. If X and X 'represent alkoxy or alkoxyoerbonyl groups , see above the alkoxy groups preferably have 1 to about 8 carbon atoms and consist, for example, of a methoxy, Xthozy, Propoxy, isopropoxy, butoxy, pentoxy, hexoxy, heptoxy, Octoxy or 2-ethylhexoxy group. Place X and X 'aryloxy- or aryloxicarbonyl groups, the aryloxy groups have preferably 6 to about 10 carbon atoms, via it for example wise for phenoxy, tolylozy, xylyloxy or 2,4-diethylphenoxy groups is the case. If X and V have the meaning of acyloxy groups, they have these preferably have 1 to about 10 carbon atoms and consist for example aua Formrlosy-, Aoetoxy-, Propionyloxy-, Butyryl- oxy, iyobutyryloxy, yalerylosy, or benzoyloxy groups X and X # the meaning of halogen atoms ,. so these exist preferably from fluorine, chlorine or bromine atoms. Have X and X9 the Meaning of aryl groups, they consist of vorzugswelee mononuclear, carbocyolic aryl groups with f to about 10 carbon atoms, for example phenyl, tolyl, xylyl-s 2,4-diethylphenyl groups and the like If X and X 'have the meaning of carbamoyl groups, then these consist of unsubstituted carbamoyl groups ,, N-mono- substituted carbamoyl groups or N "N-disubatituated Cgrba- moyl.gruppena The carbamoyl groups can, for example, subst.- be caused by alkyl r.dex, aryl groups with up to about 10 Carbon atomsx, hew ° pie = 5 by methyl, ethyl "brs @ pyl" Isopnopyl-, butyl- "# s- <ü @ -Rtyl @. Tert-butyl-, phenyl-s Toly :: .-. Xyxyl and other groups., The nitrogen atom. the carbamoyl group kfinn continues to be part of eJres heteracyclic ring, for example a morphcline "pyridine or piperidine ring." The group Rs preferably consists of a divalent or dr = eivalent organic residue with up to about l. (? carbon-- atoms. Suitable divalent radicals are, for example, methylpn-; Ethylene-; Progylen-; Tetramethylene; 2,2-D1 methylpropylene-; 1., 2-phenylene-; 1,3-ptienylene-; 1,4-phenylene radicals and the like Advantageous trivalent organic radicals are, for example 1.2. 3-propanetriyl; 1.2, 4-butanetriyl; l., 3, 5-pentanetriyl and like r The invention is essentially based on the knowledge that non-aqueous palymerizable, ethylenically unsaturated Monomers in situ in contact with surfaces to be impregnated can be very easily polymerized if they are bonds in contact - are broken? - that are in bestixstm- @ er Add white points and use them as the first and second bond are designated, Connections that come into question as so-called “first connections” consist of organic hydroperoxides, inorganic hydro. peroxy3 acids ƒder the organic ring peroxides (transannu? ar per- oxdes), such as Ascaridr) 1. Suitable so-called second Compounds consist of oxidizable sulfur compounds with ii0. at least one oxygen breath or one sulfur a @ om, that is bound to a sulfur atom Suitable organic hydroperoxides are connections with the e GrY: ppe -C-o0H, -6n of the ties of 42 @ i'.IV, 1'.`.727f . = IG6.i111@Z Single bonds exist, in contrast to double bonds a carbonyl group in organic persons. Many of the Seelg net, en organic klydr® peroxides can be broken down by the following Display formula: Herein R2, R3 and R4 individually represent hydrogen atoms or Alkyl or aryl groups with up to 20 carbon atoms or together with the carbon atom on which they sit, one carbocyclic ring. The alkyl groups can optionally be substituted or from cycloalkyl groups with 1 to about 20 Carbon atoms, preferably 1 to about 10 carbon atoms exist. Unsubstituted alkyl groups are, for example, methyl, Ethyl- " propyl-, Iaopropyl-, butyl-, sec-butyl-, tert-8uty: 1- groups and the like .. Positions R2, R3 and R4 substituted alkyl groups, they preferably have 1 to about 10 carbon substance atoms and consist of benzyl, 4-methylbenzyl, 4-methyl benzyl, 4-isopropylbenzyl groups and the like .. Positions R2, R3 and R4 represents cycloalkyl groups, these consist, for example, of Cyclohexyl-, 4-methyloyclohexyl-, 2,4-dimethylcyclohexyl-, 4- Ethyloyolohexyl, 4-propylcyclohexyl and 4-isopropyloyclohexyl groups o If R2, R3 and R4 represent aryl groups, these can be substituted tuated and not substituted. Have suitable aryl groups especially 6 to 20 carbon atoms and preferably 6 to about 10 carbon atoms and consist, for example, of Phenyl®, u-tolyl-, m-tolyl-, p-tolyl-, 4 = ethylphenyl-, 4®prolsyl-. phenyl, 4misopropylphenyl, xylyl groups and derglo. Form R2, R3 and R4 with the carbon atom on which they sit i, a carbooyelic ring, this can consist of 5 to 7 carbon There are atoms of matter. In this case, for example, Pinan hydroperoxide or pinene hydroperoxide. Suitable first compounds are thus, for example, Viethyl «J hydroperoxide, ethyl hydroperoxide, isopropyl hydroperoxide, tert.- Butyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, benzyl hydroperoxide, diphenylmethylhydroperoxide, triphenylmethylhydro- peroxide, a-pinentiydroperoxide, ascaridol, perehromic acid and others Suitable second compounds are, for example, sulfur dioxide, sulforyl chloride, thionyl chloride, diethyl sulfite, dibutyl sulphite, sulfur monoxide, sulphoxylic acid, sulphurous acid, and iter- sulphurous acid, (hydrosulfuxous acid) thicischulphurous acid, Esters of acids, such as sulfenic acid and sulphinic acid, organic sulfinyl halides, such as, for example, methylsul: f1, nylw Chloride, ethylsulfinyl bromide, propylsulfinylochloride, phenyl aulfinyl halide and the like, organic sulfonyl halides such as for example Ilethylsulfonylbromid, Xthyl, sulfonylohlorid, Propylsulfonyl fluoride, phenylsulfonyl chloride and the like "Als It has proven particularly advantageous to use as the second connection gen to use such connections, in which the worthiness of the Sulfur is not greater than 4 and in which at least one Oxygen atom or a sulfur atom bound to a sulfur atom that is. Compounds preferably used include also compounds with 6-wextigem sulfur, which SGhwefelcüoxyd free when in contact with an initial connection come. Such connections can be represented by the Formula: wherein X2 represents a halogen atom such as a Fluorine or chlorine atom and R5 is a halogen atom or an organic one Group, z tH. an alkyl group having 1 to about 8 carbon atoms or an aryl group with 6 to about 10 carbon atoms o Züi der-- like compounds .-- belong Sulfury3.chlorid "_. Methy: 1a;: tfun; -. a Chloride, ethyl sulfonyl chloride, butyl sulfonyl fluoride etc. Become.to implement the method of the invention approaches A and H are used, they can be packed in tubes, bottles, aers? Sol- containers, spray bottles, squeeze bottles and (? ergl "autbewahrx will. Approach A then consists of a first connection and a polymerizable vinyl monomer. The so-called first Vrrbin # n As a result of approach A, it does not itself have any catal, ytical effects - and can therefore be considered non-catalytic, the Poymeri satiOxi (: i.nM conductive connection. For the Ansat = z ß it is important "that this one connection contains, which riciit catalytic, the Pi, lymerl, - =. ation introductory connection of Anse.tzes B added; ie "the approach 19 must one of the so-called? wide connections mentioned above keep. Mlengen and type (ler used so-called. First and breathed, second connection must be such that the Coincidence of approaches A and f? a Kata'.ysatox combination,: @ tion arises, which beivt) iel svre4 so at temperatures of less P as 500C a polymeric salt of tar monomers brings about, with approx Polymerization rncigli @ -f, ;; @ quickly sVartäfind «oll, cj..h. na-all Possibility should rne '@r as 50% of the % 4onomeren in bearander.-: a short time. It turned out that! the polymer = I ott: zgr = - cIzwindi ability depending on the composition; ung of approaches 11 and F3 -: rrr;. @ zhieden can be. Extenders, iligments, thinners can be added to approaches A and B and a number of other ingredients are added will, Those needed to carry out the method of the invention Amounts of so-called first connection and so-called second connection, which initiate the polymerization can be very different be. For example, the first connection only needs in Traces to be present, that is, for example, in amounts of about 0.00001 wt. xen. However, the first connection can also up to about 15% by weight based on polymerizable, ethy- lenisch unsaturated compounds may be present. The amount the so-called. Second connection can be between about 0.01 to about 1,000 mol % e, based on the first @ compound, lie. As a rule, large surpluses are generated at the second connection used when used alone. This is for example the case when it consists of gaseous sulfur dioxide or gaseous sulphonyl chloride. .When making eggs of achieht-shaped material, it is play wise possible to proceed in such a way that for the production of approach A one or more of the first compounds in one or more non-aqueous polymerizable; Ethyle- never unsaturated hionomer types can be dissolved. Approach A can then point to one or more surfaces of the to be impregnated elements are applied, whereupon the elements with are brought into contact with each other and the effect of the so-called Q second connection. That way becomes a in situ polymerized layer obtained in an unexpected is formed in a short time. Although the seats A and B have an extraordinary Developing a lot of responsiveness is the starting point A and B are extremely stable on their own. In this way is it possible to use approaches -A and B over long periods of time, For example, to store for several months without being in the Approaches changes occur or the ability to react lost when one approach comes into contact with the other approach- goes. An impregnation system consisting of approaches A and ß has the following composition, for example: Approach A: Approach B: 50-33.3 parts acrylic acid - 50-33 parts acrylic acid 0-l6,? Parts of ethyl acrylate 0-16 ,? Parts methyl acrylate 5-20 parts of polyvinyl acetate 5-20 parts of polyvinyl acetate or polymethyl metha- or polymethyl methacrylate crylate 0.5-2.0 parts of t-butylhydro- 0.5-2.0 parts of sulfur dioxide peroxide 0.25-0.5 parts thioglycolic acid The impregnation process can take place within a period of can be initiated one second after contact of approaches A and B, the polymerization over a period of 10 minutes takes place at least 50 times. For example, one or more Kinds of vinyl monomers such as an acrylic acid ester or mixtures of acrylic acid esters with an organic hydro peroxide, as in the case of t-butyl hydroperoxide with each other mixed. Will this mix with a mix consisting of one or more types of vinyl monomers, e.g. an acrylic acid amide or a mixture of acrylic acid amides and acrylic acid and sulfur dioxide brought into contact, the poly- merization occurs almost suddenly and is within a period of time from 1 to 10 minutes essentially completed up to 50 times. None of the mixtures used shows before the contact bring an activity to the mixes. In one embodiment of the method of the invention for example, the surface to be impregnated with a not aqueous mixture an annular peroxide, for example Ascaridol and acrylonitrile monomers treated, whereupon a Treatment with another mixture consisting of aeryl nitrile monomers, sulfur dioxide, dissolved polymethyl acrylate and diethyl sulfite follows. In this case, for example wise more than 50 x of the monomers within a period of 2 minutes in polyacrylonitrile, while the entire Polymerization is complete within : t minutes. As mentioned earlier, the two approaches can be suspended Particles of solids, fillers, pigments, reinforcements agents, plasticizers , stabilizers and other additives to achieve special properties, dissolved synthetic @ polymers and / or natural polymers keep. Approaches A and i3 can for example be about 5 to about 99 x consist of the polymers to be polymerized. here The proportion of catalyst components can, for example, be between 0.00001 to about 10 or 15 wt. % E, based on the poly- merizable monomers. According to an advantageous embodiment of the * method of the- Invention can, for example, use the following approaches A and B the following connections can be used: Approach A: Compounds with one or more hydroperoxy groups as well polymerizable vinyl monomers of at least one compound types and possibly non-catalytically active riiods: t- fication means. Connections with at least one ringLdr = migen peroxide group (transannular peroxide group) and vinyl monomeric at least one type of vinyl monomer and given if non-catalytically active modifiers an additive Sentence A can therefore consist of, for example: 1o an organic hydroperoxide, such as te- £ 3utyl- hydroperoxide, cumene hydroperoxide, p-bienthanum hydroperoxide b Diisopropylbenzene hydroperoxide or ethyl hydroperoxide and Vinyl monomers of at least one polymerizable vinyl monomer type. 2. An inorganic hydroperoxy acid such as Perahromic acid and vinyl monomers of at least one poly- merizable vinyl monomer type. 3. A ring-shaped (transannular) peroxide, such as wise ascaridol and vinyl monomers at least one poly- merizable vinyl monomer type. Suitable modifying agents added to batches A. consist, for example, of compounds with easily removable hydrogen atom, such as phenyl acetonitrile, cumene, ethyl acetoacetate, diethyl malonate and the like., This also includes thermally relatively stable peroxides, such as ditertiary butyl peroxide, dibenzaldiperoxide, Tertiary butyl peracetate and the like. Further modifiers are for example inorganic pigments and fillers such as also organic pigments, dyes and fillers. Farther can be added to solutions or dispersions more natural or synthetic polymeric substances. These polymers can be chemically inert or be involved in the reaction that occurs during Bringing approaches A and 3 into contact takes place. The approach 13 consists in an advantageous manner of a mixture a compound with a tetravalent sulfur atom and poly- merisable vinyl monomers and, if necessary, modifications resources. Approach 3 can optionally also be assigned compounds which contain a divalent sulfur atom, such as for example sulfur monoxide. Furthermore, approach 3 Have sulfur-containing compounds, the sulfur release dioxide, such as sulfuryl chloride. Suitable modifiers for the loading approach I3 are made of natural and synthetic polymer materials, Pigments, dyes, fillers, plasticizers and the like .. To carry out the method of the invention, for example wise the following approaches A and 8 are used A: t-butyl hydroperoxide + polymerizable monomers B: sulfur dioxide + polymerizable monomers A: t.-Butylhydroperoayd + polymerizable monomers * dissolved Poly »r 13: sulfur dioxide + polymerizable monomers + dissolved Poly »r , A: t-butyl hydroperoxide + polymerizable monomers + dissolved Polymar + finely ground bentonite clay B: sulfur dioxide + polymerizable monomers + dissolved Polymer + finely ground bentonite clay A: Cudol hydroperoxide + di-t-butyl peroxide + monomer 8: keraaptosuccinic acid + dibutyl sulfite + monomer A: p-menthane hydroperoxide + phenylacetonitrile + styrene + maleic acid anhydride B; Sulfur dioxide + styrene + maleic anhydride + sodium bisulfite addition product of methyl ethyl ketone A: t-butyl hydroperoxide + diisopropylben $ ol hydroperoxide + 2-ethylhezyl methacrylate + polyoctyl acrylate + triethylene glycol diacrylate a: sulfur dioxide + xethyl acrylate + polyoctyl acrylate + triethylene - glycol diaerylate A: t-butyl hydroperoxide + di-t-butyl peroxide + methyl acrylate + finely ground clay filler + 2,2-dimethylpropandioldiacry- lat B: sulfur dioxide + potassium bisulfite addition product of acetone + Clay filler + methyl acrylate + 2,2-dimet, hylpropandioldi- acrylate. As already mentioned, the approaches A and ß described in packed in separate tubes or bottles or wash bottles be. If batches A and B contain polymeric substances, so can these have been made, for example, from vinyl chloride, .. Acrylic and methacrylic acid esters, substituted and not substituted acrylic acid amides and methacrylic acid amides, buta- diene, propylene, ethylene, styrene and various polymerizing available monomers. Furthermore, approaches A and B poly- esters, polyamides, polyurethanes and polycarbonates added will. Finally, approaches A and B can also be natural Resins, alkyd resins, phenolic resins, modified and unmodified decorated resins and the like can be added. So in the Monomers, for example, are dissolved polyvinyl acetate, poly vinyl format, cellulose esters such as cellulose acetate or cellulose acetate butyrate and cellulose ether. The polymers can thereby-in amounts of 1 to 75 ßew.-xen, based on the Weight of monomers used. The following are intended to play into the method of the invention illustrate in more detail: Example l: 400 g methyl methacrylate, 40 g methyl acrylate and 6.5 g t-butyl liydroperoxyd were together to form batch A mixed, -which approach A in a container of 15.24 x 15.24 x 5.08 cm was brought. In the mixture was then a Piece of porous poplar wood measuring 8 x 8 x 0.5 am and weighing brought by 22 g. The container was then placed in an airtight lockable chamber brought. Then the Chamber Evacuated to a vacuum of 180 mm for 2 minutes, whereupon it was filled with nitrogen. The evacuation was made repeated three times. During this time the piece of wood became thoroughly impregnated with the mixture of batch A. The wood- piece was now removed from the mixture and off for 30 seconds. left to drip. After draining, the impregnated wooden piece brought to another chamber, which was filled with sulfur dioxide gas was filled. Immediately upon contact of the monomers with the sulfur Dioxide started the polymerization, which after 10 minutes almost was too finished. The impregnated product obtained consisted of a copolymethyl methacrylate poplar wood body, which has a weight of 39.6 g. This body was extremely water- constant, 50% more durable, more rigid and splintered when nailed not. The process was able to work with equal success with other monomers be repeated. Styrene, vinyl chloride, vinyl acetate, acrylonitrile and cyclohexyl methacrylate. With equally good Mixtures of these monomers have also been used successfully. Example 2: m @ n @ mnmw To form batch A, 400 g of methyl methacrylate, 200 g Methyl acrylate, 2 g di-t-butyl peroxide, 5th-g-butyl hydroperoxide and 20-g ethylene glycol diacrylate mixed together, with this Mixture was made as described in Example 1, a piece of one treated with three layers of Pöhrenholz existing plywood. To The piece of wood was drained of the impregnation mixture brought into a chamber containing a gas mixture of 10 x sulfur Dioxide and 90 x nitrogen contained, The polymerization of the Monomers within the porous wood was essentially after Finished 10 minutes. The impregnated wood obtained was above the action of water and organic solvents including the action of solvents for polymethyl Resistant to ethacrylate. The piece of wood was 20 times heavier become. The increase in strength and rigidity was about 30%. The wood was suitable for building outdoors, e.g. for building clothing of buildings and the like. The impregnation even held was exposed to water heated to 800C for 2 hours. Example 200 g acrylonitrile, 100 g methyl acrylate and 50 g diethylene glycol diaerylat were with 2 g of benzoyl peroxide, 2 g of methyl ethyl ketone peroxide and 2 g of pt-lenthanum hydroperoxide mixed. This mixture was used as batch A for impregnating pine wood. The pine wood was cut into 4 mm thick panels, which were passed through two salts whose distance from one another which was 3.5 mm. The rollers dipped into approach A. The rollers pressed the wooden panels together and pushed open this way the air trapped in the pores out of the Plates. After pressing, the pores were with the Liquid of batch A filled. Owned the wooden panels after this treatment a thickness of 3.8 mm and contained 10 % by weight of batch A in the pores of the wood. 100 g of acrylonitrile, 50 g of ethyl acrylate and 25 diethylene glycol; diacry did with 0.5 g of sulfur dioxide and 0.1 g of triethylamix mixed. This mixture represented approach 8, which means that Pine wood treated with batch A has now been treated. The wooden panels or strips of wood that are im- were impregnated, were passed through a chamber in which Spray nozzles were arranged covering both surfaces of the wood sprayed with batch B. Immediately after spraying on of approach a, the wooden panels or strips of wood were through rollers passed through, a distance of 3.2 mm from each other During the grouting process, approaches A and 3 mixed together, causing the polymerization to start The wooden panels obtained had a thickness of 3.5 mm. The polymerization was essentially after 10 Finished within minutes, the material obtained had a 50 x increased strength and is particularly suitable for lamination for purposes of manufacture with water-resistant adhesives of plywood, to the high demands on their Resistance, i.e. for example to manufacture for boats, concrete molds and for cladding exterior walls, which requires special water resistance is . Example 4: Three pieces of pine wood 4 mm thick were made, as in He Example 3 described, treated with approach A. The pine Wood tires were then also, as described in Example 3, sprayed with approach B. Immediately after spraying were the wooden pieces are stacked on top of each other, with the piece was placed between the two outer pieces in such a way that the grain direction of the middle piece of wood perpendicular to the grain direction of the outer wooden parts came to rest. The one on top of the other layered pieces of wood were then placed in a press, where they under a pressure of 70 kg / cm2 to a total strength of 10.1 mm were measured. The pressing time was 10 minutes. In this way a triple laminated wood was obtained, this by means of a cross-linked polymer made of Acryloa nitrile, methyl acrylate and diethylene glycol diacrylate impregnated was. The product obtained had a density of 0.95 and consisted of about 30 x all polymers. The material was opposite impermeable to hot water and dry heat up to 250 ° C. Due to the improved strength and rigidity _ the material produced was about 2.54 em "thick five layers of existing plywood. The impregnated material can be used for lining floors, for wall coating, for Use roof cover and as a component. Furthermore, the Material an @ excellent building material for the production of Boats and can also be used, for example, to lay out Use the holds of Lattkraftwagen and the like , Example 5: 2 mm thick walnut wood layers * were mixed with a mixture (Approach A) treated that existed. from 200 g polymethylmetha- crylate, dissolved in 800 g of methyl methacrylate and 12 g of disopropyl benzene hydroperoxide, the wood layers were made by rolling leads whose distance from each other was 1.5 mm "After the wooden layers had been pressed to a thickness of 1.7 mm at the front and 15 wt, -% e of batch A contained, they were by a Chamber that contained sulfur dioxide gas immediately after contact with the sulfur dioxide, the polymerization continued which was almost finished within 5 minutes. The get- material was used to produce a three-layer standing plywood is used, in which only the outer layer consisted of walnut wood, which was im- had been impregnated. The surface made of walnut wood the plywood turned a deep brown color after using it a variety of different commercially available polishing agents The wood turned out to be used for decorative purposes in the usual way lacquered walnut wood as superior, that before-- Partial appearance of the impregnated material has its reason in that the impregnation of the wood is deeper and more complete than is the case with impregnating agents made from solvents mediums are applied to the wood surface, Example 6: Approach A described in Example 5 was used in Example Manner described 3 to 1.0 mm thick H ol zpl att en poplar, Fever tree, mahogany, oak, pondorosa and rosewood applied. The wooden panels were then loaded with an approach B which is composed of 94 9 methyl methacrylate, 5 x polymethyl methaerylite 0.8 x dibutyl sulfite and 0.2% sulfur dioxide consisted. The treatment Treatment took place as described in Example 4. The wooden panels were then, also as described in Example 4, to min- at least two layers of 1.5 mm thick pine wood applied, In this way, extremely decorative panels were bears witness to the appearance of equipped Owned wooden panels. The thickness of the finished panels was 3 mm. However, the panels had a strength and rigidity that is, as they have about 0.625 cm thick plywood sheets: # - n, which were produced in the usual way. Example 2 mm thick wooden slats made of green pine wood with a damp activity content of 38% were placed in a drying oven, by circulating nitrogen to a temperature of 228 ° C was heated. After the wood has dried and after the When the wood reached the temperature of the stove, the wood plates are removed from the oven and immediately placed in a Approach B immersed, which consists of a mixture of 99 % methyl methaarylate, 0.8 % diethyl sulfite and 0.2 % sulfur dioxide was standing. During the cooling, the mixture of batch B sucked into the pores and gaps in the wood. After the Wooden panels on 230C were the gaps and pores more than closed Filled 50 times with the mixture from batch B. The specific The weight of the wooden panels was 82 x the specific weight of the originally green wooden panels. The wood panels were then treated with an approach A, the from 94 x methyl methacrylate, 4 x acetyl peroxide and 2 x cumene hydroperoxide existed, the described in Example 3 Spray method was used. After spraying the approach A the plates were passed between two rollers, the were arranged at a distance of 1.5 mm from each other. By pressing the panels impregnated with approach A and the application of batch A became a mixture and an intimate one Contact of the two impregnation components achieved. the Polymerization was almost complete within an hour completed. The material obtained consisted of polymethyl methaerylate impregnated Föhrenhol with a thickness of 1.7 mm, - The panels were in an excellent way for making water-resistant plywood. Example 8: A wall made of concrete blocks was made with a mixture consisting of 75 x methyl acrylate, 12% acrylic acid, 10% divinyl benzene, 2% t.-dutyl hydroperoxide and 1 x acetyl peroxide (approach A) treated. On the same side, the concrete blocks were mixed with a mixture consisting of 75.5% riethylacrylate, 12% aerylic acid, 10 x di- vinylbenzene, 2% silicone oil (Dow Corning 200 Fluid, Manufacturer Dow Corning Corporation) and 0.5% sulfuryl chloride (batch 8) treated. The concrete blocks were treated at the same time in such a way that the Misehungen_from separate containers by a spray device provided with a double head The concrete blocks were sprayed, causing the droplets of the Approaches A and 8 on the surface of the concrete blocks together mingled. The polymerization of the monomers began, aäs the droplets of approaches -A and B onto the porous surface of the concrete material, due to the polymerization of the Monomers, the pores of the concrete blocks were networked terpolymer made from methyl aerylate, aerylic acid and divinyl benzene sealed. The acrylic acid reacted with the calcium and magnesium ions of the concrete, creating an excellent Adhesion was achieved, the silicone oil remained in the polymer and accumulated in the outer surface, creating a non-wettable surface was obtained. The received Concrete impregnation was both water resistant and water resistant repellent . Example 9: The procedure described in Example 8 was used for impregnation of the Nalkst'ein masonry of a house applied, the masonry could be impregnated in this way to be water-resistant. Example 10: no r The procedure described in Example 8 was successful for Waterproof equipment of a cast concrete wall used, which was later covered with a damp layer of earth. Example 1I: - The procedure described in @: 3example 8 was successful for waterproofing a wall made of bricks turns, which was later partially covered with wet soil. Example 12: - A cotton fabric weighing 161 g0.836 m # and a plain weave was with a solution of an approach A impregnated, which consisted of 30 % polyethyl acrylate, 60 Ethyl acrylate, 9 x acrylic acid and 1 x Ascaridolo The impregnation took place in such a way that the fabric passed over two rollers was spaced 7.62 cm apart as well as under a 6.35 mm thick, beveled spreading knife through it, the one in the middle between the two rollers was arranged. The position of the spreading knife was such that the fabric was pressed 1.27 cm below the plane that was pushed by formed on the top surfaces of the rollers. The bevel of the spreading knife was such that when the tissue an open angle of ß0 through the surface of the Tissue and approximately 1/4 inch (6.35 mm) of the surface of the spreading knife. sers was formed. The fabric was perpendicular led to the spreading knife, whereby the viscous solution des- - Approach A was applied to the fabric and the spread knife the impregnation mixture into the spaces between the Fabric squeezed, leaving little or no impregnation compound remained on the surface. Immediately after approach A in the had been pressed in, the tissue passed into a chamber in which an atmosphere of gaseous Thionylchloride (Approach_B) _ was maintained «Upon contact polymerization of the monomers continued with the thionyl chloride which was essentially completed within 3 minutes. In this way, a fabric was obtained which was coated with a mixture consisting of polyethylene acrylate and a copolymer of Ethyl acrylate and acrylic acid had been impregnated. The impregnation renation led to incomplete closure of the tissue, so that a flexible material was obtained that was resistant to air and water vapor was porous. The presence of acrylic acid components in the polymer caused that the polymer swelled by about 200% on contact with water, making the fabric airtight, as the spaces between of the tissue with puffy or swollen polymer stuffed. Was the impregnated material with a finishing agent treated on a silicone basis, a material was obtained which is used to manufacture waterproof rainwear was suitable. The material was porous to water vapor and As a result, it turned out to be the known, in the usual way superior to coated fabrics. Also owned the material a resistance to water that was better than that of fabrics that are only water-repellent Equipments had been treated due to the Sealing of the interstices-by the action of Water swollen polymers Example 13: rrr @ r @ Single-porous paper with a density of 0.73 was made in the following wisely impregnated with approaches A and B. The approach A consisted of 80 × tdethyl methacrylate 10 x 2,2-dimethylpropanediol diacry lat 8 x lauryl acrylate 1 x a-pinene hydroperoxide 1 x methyl ethyl ceramic peroxide Approach B consisted of 80 × methyl methacrylate 10 x 2,2-dimethyl propanedione diacrylate 9 x lauryl acrylate 0.1 x mercapto succinic acid 0.4 x sulfur dioxide 0.5 x dibutyl sulfite The paper was run at a speed of 91.4 m / minute continuously withdrawn from a roll and by means of a guide rollers and rollers under a coating device out, from which batch A was applied. The paper The track was then passed through a roller, which e'urch Apply a low pressure excess liquid slip pressed off. Then, within a second, the paper bahr became passed through a chamber in which dcs on both sides Papers of approach A was sprayed on. Upon contact of the 1'ompo- components of the approach ü with the components of the approach A pcly- The monomers merized. The polymerization was within a few seconds ended up to 90 times . The paper web was picked up by a second role. Within a All the conomers were polymerized within an hour. In this way became a polymer impregnated paper of one density of 1.08. The paper was not attacked by water and could only be achieved with solvents for non-cross-linked Moisten the polymethyl methacrylate. The paper was suitable in excellent way of waterproofing a wide variety of Objects, for example for the production of decorative coatings of wooden parts, washable wooden panels, exterior coatings' and the like .. Example 14: Through a dipping process, leather was first made with the following Approach A impregnated and then subjected to a 90 x off Nitrogen and 10 x gas consisting of sulfur dioxide set. Approach A consisted of 69% butyl acrylate . 20 % ethyl acrylate 10 x acrylamide 10% polyethyl acrylate 1 % ascaridol The impregnated leather was suitable for the production of water- resistant shoe soles and the like. t3eis @ 1 1 Following the procedure described in Example 14, leather was im- . impregnated with: Approach A 69 % butyl acrylate 10 x didethylene glycol diacrylate 20% butyl rubber 1 % t-buty7 hydroperoxide Approach H $ 6 x nitrogen 4% phosphine 10% thionyl chloride Example 16: A doll fabric weighing 170 g / 0.836 m2 was gender quietly impregnated. First, the fabric was made with a treated liquid approach A, which consisted of: 10 X acrylamide 10 % Aerotex Resin M-3 (manufacturer Ameräcan Cyaraamid Co. 88 % ethyl acrylate 1 x t.4Dutylhydroperokyd 1 % phosphoric acid The fabric was then passed through two rubber rollers, to remove excess liquid from batch A. That Wet tissue was then passed through a chamber equipped with a Was filled with 80% carbon dioxide and 20% sulfur field dioxide. After the tissue has been in the chamber was essentially completely in the monomers transferred a polymer. The tissue was then put into a 120 ° C heated oven. Because of this exposure to heat, that became Polymer of the fabric cross-linked and chemically attached to the wool fibers bound. A woolen fabric was obtained which had a different improved resistance to wrinkling and the Influence of that he possessed. Cross-linking of the vinyl polymer in the fabric can occur through Use of a divinyl compound, such as glycol diacrylate, divinylbenzene, z'riallyl cyanurate, etc. can be achieved. i3eisoiel 17: ras @@ wa A viscose rayon fabric with a dish of 122 9 / 0.886 m2 was impregnated by applying the following liquid to the fabric Approaches A and 3 was carried out, Approach A had the following composition: 50 x vinyl pyridine 48% styrene 1 ascaridol - 1 x benzoyl peroxide After immersing the tissue in the liquid batch A, the Fabric passed through two Gusrmiwalzen, through which over- The excess liquid was removed, whereupon the tissue was removed passed through a bath of the liquid batch 3 , which is fed as follows sammer: was set: 50 x vinyl pyridine 49% styrene 0.5 % sulfur dioxide 095% triethylamine The fabric was then passed through rubber rollers to the unpolymerized sand parts of approach B $ u distant, whereupon the fabric was dried. In this way was partially with a copolymer of vinyl pyridine and styrene impregnated fabric. The surface of the Tissue could be stained with acidic dyes. Example 18: @@ rs The most varied of porous objects, such as wood, Tree trolls, synthetic, plastic materials and porous, inorganic Chemical substances can be impregnated according to the methods of the invention at least in part, which gives them properties of the Record sentences A ®der d. For example, it is possible Treat wood with a 3% hydroperoxide solution and then to dry. After the treatment, the dry wood has development properties that correspond to the properties of hydroperoxides speak and can be used as a porous body as well as approach A be det. In the present case, the wood with the approach d implemented, which consisted of: ä $ i Y3n @ ethyl ether 0.5% sulfur dioxide 0.5 f tributylamine The approach r3 was pretreated by dipping, - 2 wooden pieces in the liquid batch B applied. The dive time was 3 hours. After immersion, var @ were excess Ienomers removed by evaporation. After the one described Procedure the wood was impregnated with an olyeir @ a, ge, which made up 25% of the total weight . Example 19: A 1.2? cm thick wood fiber board with a density of 0.4 treated with the following approaches A and d: Approach A 9 $ styrene 1 uenzoyl peroxide 0.5% cumene hydroperoxide 0.5 x manganese naphthenate Approach r3 90% nitrogen 10% sulfur dioxide The mixture of batch A was by means of a spray device applied to both surfaces of the fiberboard. The spraying happened under considerable pressure to impregnate the upper To support surface pores. The fiberboard was then turned into a Chamber brought with the nitrogen-sulfur dioxide mixture was filled. After a residence time of 2 minutes , the Plate removed from the chamber. The record was up to $ u one Impregnated depth of 3.17 mm and exhibited a water-resistant Surface coating on.

Claims (1)

Patent claims 1. Method for impregnating porous surfaces, thereby - that the surfaces with polymerizable, Ä.thylenisch unsaturated monomers are treated, and that the monomers are applied separately to the obex surfaces by a tes: catalyst system consisting of (a) an organic aydro- peroxide, one. organic fling peroxide or an inorganic one Hydroperoxy acid and (b) an oxidizable sulfur compound in seats polymerized willows. 2. The method according to claim 1, characterized in that the Surfaces initially with a mixture of polymerizable, ethylenically unsaturated monomers and an organic one Hydroperoxide, an organic ring peroxide or an inorganic cal hydroperacid and then with an oxidizable Sulfur compound are treated. a method according to claim 2, characterized in that the Surfaces initially with a mixture consisting of monomers, a per-compound and polymeric substances are treated. Ao method -according to claims 1 to 3, characterized in that that as polymerizable, ethylenically unsaturated monomers Compounds Compounds of the following formulas are used will: - where mean: R hydrogen or Ha.7ogeriatome, alkyl groups with 1 to about $ Carbon atoms orer hry? groups with 6 to about 10 carbon material atoms; X in common: A group of formulas X and X9 individually: Hydrogen or halogen atoms; Hydroxy, carboxy or Cyano groups; Alkoxy groups with 1 to about 8 carbon atoms; Aryloxy groups of 6 to about. 10.r 'atoms; Alkoxyarbonyl groups with 2 to about 9 carbon atoms; Acyloxy groups rni t 1 bs' JC = atoms; Aryl groups with @@ up to 2twä '0 C ° arb4mrjvl-prfi.ipp ¢ rr mIr: `k bI == n" @ya 20 C-atom; or groups of formulas in which R has the given meaning li aej nen divalent carbon residue, and N die Zai. _-: l or?. represent. 5. Process according to Claims 1 to 4, characterized in that that as organic liydroreroxyd a peroxide of the formula: is used, where mean: I2, R3 and R4 individually: What eratoffatnme, alkyl groups with 1 to about 20 carbon atoms or aryl groups with 1 to about 20 carbon atoms or together: with, the carbon atom on which they sit, a 5 to 7- membered «zarbocyclic ring. , 6a Proceeding according to Pnap: -iIIhen 1 to 5, thus marked- the <e? .is oxy (i able sulfur compound vert @ exi, @@ E, @ a) iron 4-valued visual cell connection with miixdeetdg :: aga :; Oxygen bound to a sulfur atom a @ r.cam cdex, b) a compound of the formula: where mean: X2 is a halogen atom. 5 R is a halogen atom, an alkyl group with 1 'lis et # wa $ carbon material atoms edev tene aryl group with fi up to about 10 carbon fabric fatomen a Method according to Ansp,? 1, ü. -, hen! 1 to 6 "ctadur ^ h - @ ekenn, eichneta that as an oxidizable *>: sulfur compound, shale dioxide is present - r- is turned. 8o adhesive for carrying out the method according to claims 1 to ?, Consisting of a storable batch A containing an organic hydroperoxide, an organic ring peroxide or an inorganic hydroperoxyacid and a storable one Approach 13, containing an oxidizable sulfur compound, whereby. at least one of the approaches polymerizable, ethyl contains unsaturated monomers.