DE1570938A1 - Process for the preparation of aqueous latexes of graft mixed polymers from acidic vinyl or vinylidene monomers on olefin polymers - Google Patents

Description

Eonte ca | ini_ Speie ta Gener ale.peil l.'lnäy s tria_ Minerariu.

Appropriate for the preparation of aqueous latices from graft clip oly beers from acid vinyl or vinylidene monoj; ters on olofin polymers

The invention relates to a process for the production of aqueous latices of graft copolymers of acidic vinyl or vinylidene monomers on olefin copolymers and olefin copolymers as well as the use of these latices for various purposes, in particular for bonding elastonic polymers of ethylene with α-olefins and optionally with one cyclic or acyclic diene with substrates or layer carriers consisting of natural or synthetic fibers, surface oxidized metal surfaces and glass fibers, as well as the molded parts obtained in this way ₀

It is known that in the usual production of emulsions - graft compounds of natural or artificial kautoohukeji, the monomers to be grafted on must be able to swell. It is also known; _r that if a large amount of soap is used, the monomers will tend to polymerize. Where are homopolymers

Surprisingly, it has now been found that the water i acidic monomers in the presence of an aqueous one eiiieü saturated alcoholic-alpha-olefin copolymers

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large quantities obei'flächenaktiver means which must be present in amounts of i can be copolymerized or a weakly unsaturated Terpolyseren and said copolymers "or terpolymers geff-iOpft despite the use of ₅ to the production of emulsion to allow the to be grafted or terpolymers Olefincopoiymeren «.

The subject of the invention is a process for the division of aqueous latices from i-graft polymer, which is characterized. that saturated amorphous ethylene-olefin copolymers or weakly unsaturated olefin terpolymers in aqueous emulsion with an anionic surface-active agent for graft polymerization with a water-soluble acidic vinyl or vinylidene aenomer in the presence of a free one. Hadical "forming initiator, which is optionally miscible with an anion-active surface-active agent. The invention further comprises the use of these latices for various purposes as well as a process for the pre-bonding of elastomeric polymers or terpolymers with incompatible substrates or Layer supports, for example natural or synthetic fibers, using the above-described aqueous latices and subsequent mixed vulcanization. The scope of the invention also includes the vulcanized objects obtained by vulcanization bonding using the latices according to the invention.

The following water-soluble vinyl or vinylidene monomers, for example, are also suitable for grafting in an aqueous emulsion according to the invention: acrylic acid. Methacrylic acid, its alkyl esters, mixtures of acrylic and methacrylic acid, units of acrylic or methacrylic acid with their alkyl esters, sorbic acid, muconic acid, grotcic acid and their alkyl esters.

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or vinylidene monomers are used in amounts of 1-50 SeW ₀ --ϊοίΐβη per '00 6ev / - parts of the copolyraeren or terpolymers present in the aqueous emulsion «,

The amount of monomers to be grafted on can be all at once or can be added successively in several portions during the reaction. Mixtures of different Monomers are used

Initiators which are capable of forming free radicals can be used for the graft polymerization; z, B- organic beroxides and hydroperexides »organic biasso compounds, such as benzryl peroxide, p-chlorobenzoyl peroxide» bicumy! peroxyti. Ci-t-liutyl peroxide, t-butyl hydroperoxide _s Cuaiolhyurcpercxyd, Üiazctutyronitril, DiarcEUiino1: en2or_ etc. Peroxydgeraisclie, eg Acetyibenzoyiperoxyft or inorganic PercXySe ₅ , also high potassium oil and alcohol in Acsersir

Also suitable as initiators are hex mixtures, consisting of the abovementioned peroxides and a medium, ZrB, PerrQBiiifet _s Eisenacetyiacetoriatj lenamiii etc / _{c t} "consisting". When using redox mixtures

t the implementation of Pfrcrfreakticn never tel a Semperatursiie they -as "when using orgasmic African peroxy the alone applicable -

Ssr initiator will be in rising from Ο.1-Ό before £ Ugsue: *. Se ** cn - ^£ - @ ew - ropes prc'CO ropes nasty Gopojymeren or te ^ gsl ^ aerer. used IDe? Initiator must in Bsiälsi & iis ter he added v; ith _s be dispersed _ "", s, B .. as Lösuog in an organic solvent such as benzene UolucZ-y ^ α Biaethylphthala or AEEA gleisljei? BEonomereii, which is on sisp-fix-pf en - 33 initiator can rail; An anti-surface active agent can be used in the same amount or in a lower amount than the initiator - / ends up / ira.

157Q93B

The copolymers of ethylene as α-olefins and the weakly unsaturated terpolymers are obtained using catalyst systems which are soluble or dispersed in coal-fired fuels and which consist of a transition metal compound, in particular a vanadium compound, and an organometallic compound of aluminum, are examples of preferred catalyst components vanadium tetrachloride _r oxychloride 'and acetylacetonate and Aluminiumtriäthy1, aluminum tri-t-butyl and Aiumini "umdiäthylmonochlorid.

Of the copolymers of ethylene with ct-Oifoinen are the copolymers of ethylene with propylene or butene-1 with an ethylene content of 2C-80 lfol - # and a molecular weight between 5OrOOO and 500,000 preferred "

The weakly unsaturated olefin interpolymers. which are grafted are the terpolymers of ethylene with α-olefins and cyclic or acyclic dienes with conjugated or non-conjugated double bonds? Particularly preferred are the terpolymers of ethylene with propylene and cyclooctadiene-3 and of ethylene with propylene and bicyolopentadieno terpolymers which contain 1-butene or 1-pentene olefin and eutadiene, isoprene or 1,4-hexadiene as diene; can also be used «These terpolymers are characterized by the presence of 0,05- '; double bonds per 100 carbon atoms or by a diene content of i-20 Eol- #, characterized by an ethylene content of 2C-83 UaX ~ <p and a molecular weight between 50 = 000 and 500 * 000.

To achieve high graft values, terpolymeres must be used that are free of substances that hinder or in any way limit the grafting reaction can. ζ, Β, the anticxydants and the minor ones Kengen on diolefins or on diolefin-rich oligomers,

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which are previously present in the crude polymerization products. For this purpose, materials; which are suitable for the production of graft copolymers, "For example in the laboratory by extracting the crude polymerisation products with acetone in one • Kumawaga extractor can be obtained «

An aqueous latex is made using a copolymer or terpolymer (either raw as such or washed with acetone), ₅ to this latex are added while the mass is agitated; - the monomers or monomers to be grafted on and then the free radicals initiator optionally in admixture with an anionic surface active agent "of suitable anionic surface active agents, the ammonium salts of the sulfates of alkylphenols and Polyäthylenoxyäthanol _r Katriumlaurylsulfat, sodium and Kaliumoleate _{5 0} are stearate -palmitate.und ~ for the preparation of the latex

Older aqueous latex of the oopolyraeren of ethylene with α-olefins is produced as follows: A 1-30 percent by weight paste of an ethylene-C4-01 efin copolymer is mixed in a carbon dioxide solvent with a solution of Ί-3Ο wt. parts of an anionic surfactant per 1-00 GeWo portion of the copolymer in a V / assermenge emulgiertj which is as high as or lower than the weight of serving as a solvent the hydrocarbon ₀ This hydrocarbon is from the resulting emulsion by distillation under reduced pressure removed the aqueous emulsion is then again concentrated by distillation under reduced pressure at 25 ~ 5C $, preferably 40-45 / 0 ₀ dry ingredients

This concentrated emulsion can, if necessary, be stabilized by adding an inorganic phosphorus salt “eg, sodium phosphate, polyphosphate, etc.”? to avoid lump formation. The graft polymerisation 009812/1596 __,

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v / is then attached to the copolymers in emulsion !! carried out by the concentrated aqueous I & tuleion of the copolymer _P, the acidic VinyX or vinylidene monomers to be grafted and the organic or inorganic; Free radical initiator contains "heated to a temperature in the range of 25-15O ⁰ C". When the polymerization is finished, thin and homogeneous latioes of high stability have formed.

The graft copolymer obtained in this way contains Q, 1-4C # polymer chains from the vinyl or vinylidene monomer The best results in terms of adhesion are obtained using latiees of copolymers., which contain 2-25 $ of the grafted acid polymer "

The graft products mainly consist of polymer chains, obtained by polymerizing the polar monomer that predominates on the terpolymer chains is grafted in the position in which free radicals are formed by chain transfer {tertiary carbon atoms or unsaturated groups) "

The raw product also contains a certain amount of free polar homopolymer, the formation of which is due to low molecular weight free radicals. which originate from the homolytic degradation of the radical initiator, while the high molecular weight free radicals _% which are bound to the polymer chain are mainly used for the grafting reaction and only to a very small extent for the crosslinking of chains * The crude graft product therefore consists of grafted molecules that are formed by polar polymer chains that are grafted onto the copolymer or terpolymer chains; from an ungrafted polar homopolymer and possibly; from small amounts of unreacted copolymer or terpolymer ”.

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The aqueous latices of the graft copolymers have that Appearance τοη thin and homogeneous materials "on high mechanical stability *

The aqueous latices produced in accordance with the invention form pliable felts, ¹ which are able to adhere to various substrates, so that these materials can be used in the field of watercolors.

Bio ability of the Cartoxy! Groups with polybasic Bubstaneen, eg polyamines, polyvalent metal oxides, etc. _e . react with crosslinking of the material, makes it possible to produce Latises filr: e from these, which have good elastomeric properties and liqhe solvent resistance and adhere firmly to pelaric or metal surfaces as well as to natural and synthetic fibers.

The KlebeigeiiäScliaftisB of the films produced from the gem & © latises the invention are obtained _r allow their use for contact gluing from 3: ~ he same areas issit or different properties · s> B ^ for bonding lCohlenwasserstoffelast'omereii from olefins {. s »Bc of lthyIen-a-0iefin-Copol3 ^r mereii or serpolymers, which are used for the graft polymerisation ewei-iiea) with natural ccier synthetic Maseru * z ^ a terbinden von Hol-s? with metal, for the production of non-woven fabrics, and on the imitation leather area *

the film _{s obtained} by peeling off the water is not sticky. The latices are suitable as a sex aid. sB «. as a waterproof finish _s for the non-iron finishing of fabrics and as a softener for resins «4i @ mn crease-proofing - they can also be used in the paper industry for the surface treatment * of finished products« ■ ·

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In the manufacture of objects made of a rubber layer and one made of cellulose fibers Layer, it is extremely important to have an adhesive bond to achieve which seibot is particularly strong under the sharp thermal stresses (such as occur, for example, with dynamic stress) " It is well known that these problems occur, for example, in the manufacture of car tires, conveyor belts and drive belts and rubberized fabrics.

According to earlier proposals by the applicant, the problem

the adhesion
In / between olefin copolymer and textile fibers by using solutions of ethylene-propylene copolymers which have been prepared with organic solvents and which are chlorosulfonated or grafted with oleic acid and both on the fiber - especially if these are made with conventional phenolic resins treated as well as on the elastomeric layer as such, i.e. able to adhere to the unmodified layer = although satisfactory results were achieved with this procedure, it was, however, very desirable in the presence of aqueous mixtures instead of organic solutions to work, which are often dangerous due to their ■ flammability, volatility and the possible formation of explosive mixtures with air

It has now been found that very strong bonds can be produced if the adhesive used is an aqueous, solvent-free dispersion of a phenol-aldehyde resin and a stable aqueous latex of an elastomeric polymer of ethylene which has an acid group containing vinyl or vinylidene monomers is grafted. is used, which is an ion-active surface-active Contains agent and has been aged for 0-80 hours before use *

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The process of bonding elastomeric ^. Polymers of ethylene with incompatible documents or layer

* Carriers, like natural and synthetic fibers, consists in mailing the fibers with an aqueous dispersion pretreated as described above,

- · then applied to the pretreated parsers are a layer consisting of a mixture of ^{1, s} containing the elastomeric polymers of ethylene, vulcanizing agent and reinforcing filler, and finally the whole by heating to 110-22Q ⁰ Cy preferably at 140-180 ⁰ C vulcanized "

To prepare the aqueous dispersion of the latex is the graft polymer with an aqueous solution of a polyvalent phenol and an aldehyde mixed ₀ The ratio between the Pfropfmischpolymeren and the mixture of the polyhydric phenol and formaldehyde may be within very wide limits - for example between O ","?: ''. ' and 1: 1, based on weight. The mixtures of polyhydric phenol and formaldehyde contain these components in weight ratios of Q, 1: 'i "The preferred polyhydric phenol is resorcinol, and the aldehyde used is formaldehyde =.

Since the graft polymerization reaction itself can also take place through crosslinking of the olefinic polymer used, it is possible, if necessary, to limit this phenomenon by adding a substance to the original latex together with the monomers and the initiator which is able to act as a chain transfer agent are halogejiierte or halogenfroie hydrocarbons ζοBo carbon tetrachloride, carbon tetrabromide, chloroform, methylene chloride, tetralin, cumene, and other halocarbons in amounts of 2-20 parts per 100 parts of the latex present in the copolymer ₀ These optional ver ~

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BATH

Applied organic substances will be used after graduation The graft polymerization removes the latex by distillation under reduced pressure. “The aqueous latex; of the graft polymer is stable and can last for months without Changes are saved »

If the resorcinol / formaldehyde resin solution is added to the latex of the Graft polymer is added, is the aging time this resin in the presence of the latex is of particular importance for achieving good end results the bond, it was found that to achieve the best bond values between those treated with the suspension Pasern and the polymer, especially in the case of a heat treatment, an aging period of the suspension τοη 70-80 Hours, preferably 55-70 hours is required A longer aging period leads to the formation of gels *

The parsers are or tissue v / earth with the fortigen adhesive dispersion treated in a usual manner, ζ, 33, by dipping, brushing, etc _t The treated parsers are allowed to constant weight dry * You will then be in the most appropriate manner according to the various known methods merged with the mixture based on the copolymer or the terpolymer, which contains the vulcanizing agents, dchc an organic peroxide as free radical initiator and an acceptor for free radicals, such as sulfur, and optionally reinforcing fillers and additives. When using the vulcanizing agent can also Serpolymeren based on sulfur and accelerators used ^»f The whole mass is then vulcanized according to known method in a press at temperatures of 11C-22Q ° east, preferably from 14C-18O ° C.

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Peel tests according to the ASTtI D-'876-61-T method were carried out on the material obtained in order to determine the strength of the bond between thin fabric and rubber. The adhesive strength achieved by the method according to the invention is good at high temperature and. What is even more important, still achieves very good values ^{at a higher temperature (90 0 C),}

As reinforcing fillers for the Ethyien-a-Oiefin copolymer and any carbon blacks or mineral fillers are used / ended?

The organic peroxide is used in the process of vulcanization in amounts of O ₅ I - O Ge \ ** - parts per 100 parts of the copolyraeren or polymer and the sulfur in an amount which is less than half the amount by weight of the feroxide used , second hand,.

The tests were carried out with a commercially available rayon strip carried out, the per cn 12 cord knots of 0.65 inches in diameter

Bg i ep i el, J.
A) Production of an aqueous polymer paste

100 g of an Xthyien-SropYlen-Copolyraeren with a GrenzvislcoBltät of Ί.96 x * O cm ^ / g. determined in toluene

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3O ⁰ C, and a propylene content of 62 mol ~ $ are with 900 g of toluene angerührtr To the thus obtained paste 12 g of the ammonium salt of the ßulfats of an alkyl phenol-Polyätliylencxyäthanols with an active substance content of 55 $ ^ trade designation "Phenopon Co 436 "and 900 g of water. The cheese is then treated for 15 minutes with a mechanical diffuser (" Ultra lurrax "). A homogeneous-looking emulsion is obtained from which the solvent is removed by distilling off the toluene-water azeotrope under pressure of 40 mm Hg is removed under nitrogen while the mass is stirred. The aqueous emulsion is then concentrated by steam distillation under reduced pressure to a dry residue of 37 $ <>

B) graft polymerization

'■ 70 g of the latex prepared according to', A) are mixed with stirring into a mixture of '! With continued stirring, 12.1 g of freshly distilled and pure acrylic acid dissolved in 14 g of deionized water are slowly added to the mass. The air is removed by bubbling nitrogen through the till ”. The flask is placed in a bath maintained at 85 ⁰ C _bath%, while the mass is stirred under an inert gas * Kach 6 hours, the polymerization terminated "from the flask are 2'2 g of a low-viscosity latex discharged, from which 3 g of coagulum and 209 g of a homogeneous latex and a dry residue of 35 $ are separated off by filtration. Io g of the latex are made with acetone

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• coagulated and the precipitate washed with water until the free polyacrylic acid is removed. _T - Acrylic acid chemically bound to the polymer, determined by salting out the residue with alcoholic potassium hydroxide after extraction with water, is 10.6 $, 1 g of the residue is after extraction with Water treated for 5 hours with 500 g of boiling toluene, an insoluble gel being formed which, after drying, made up 50% of the original material

C) Preparation of an adhesive mixture using the graft copolymer and adhesive agent 83 g of the latex of the ethylene-propylene copolyraerene grafted with acrylic acid according to Example i (B) v / earth mixed with 129 g of a solution _{r has} the following composition and before Use after 1 hour of aging:

Resorcinol 11g

35% formaldehyde 68 g
Oil ratio

Resorcinol / formaldehyde 0.125

Water 100 g

3 Above I sodium hydroxide Ig

The weight ratio between the solids in the solution and the solids in the latex is 0 _? 87c-

Kaeh. aging for 72 hours immersed the square rayon fabric in the adhesive mixture and dried by evaporation of the .Wassers in a heating cabinet at 8Q ⁰ C "The total amount of the adhesive to the tissue dry adhesive is 5 <fo ₀ The treated fabric is placed between two Layers one

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the following composition:

Ethylene-propylene copolymer of a · Kooney viscosity JiI (Ί · .'4) at! CO ⁰ of 2Q, propylene content 62 LIoI- ^

JSAF kiss "50» »

Sulfur 0,? "*

Dicumy peroxide 4 ^H ""

The coated fabric is placed in a press for 30 minutes

2 vulcanized under an eruption of 40 kg / cm at a temperature of HO ⁰ U - the following values were determined at different temperatures: ■,

Temperature. ⁰ O peel test

20 6th _; 3

40 4.3

60 3; 8

90 4.0

J)) Comparative example: Production of an adhesive mixture using a non-grafted copolymer and adhesive tests ο

79 g of the according to example. 1 (A) manufactured latex ,, consisting of an ecraision of an ethylene-pifopylene-oppolymer, v / orden mixed with '.'29 g of a solution that has the following composition and was aged 1 stunt before use:

Resorcinol 1-1 g

35% formaldehyde '-Tg

Eesorcinol / forraaldehyde molar ratio 0.5

Water . '0Og-

3Oily sodium hydroxide ■ g

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42.2 g of water are added to the mixture of latex and solution. The weight ratio of the solids in the solution to the Peststoffen in the latex is Oi 59c After an aging period of 4SS hours is immersed the square rayon fabric in the adhesive mixture and then by evaporating the Yfassers in a heating cabinet at 8Q ⁰ C dried The total amount of the tissue adherent dry adhesive is 5 * £ _t

The treated tissue is between two layers one Mixture of the following composition laid

'' Ethylene-propylene copolymer,
Kooney Viscosity IJL V - ^) - 20 at 'CO ⁰ C.

Propylene content 62 JSo \ - & ¹ QO parts by weight

ISAF soot 50 «'«

Sulfur Oj3 ^v "

4 n 'w

The coated fabric is vulcanized for 30 minutes in a press under a pressure of 40 kg at a temperature of "40 ^<. The adhesive value is 0.8 kg / cm at 23 ° C <·

Bl g of the example * '. (B) latex of an ethylene-propylene copolymer grafted with acrylic acid are mixed with 29 g of a solution _? which has the following composition and aged 1 hour before use l@sor.cin 11g

35% formaldehyde

17th

■ 7 g

Kolverhitltnis Heso £ cin / j? Ox7 & aldehya Oy 5

Water . 100 g

1 §

fm, dea deals cli ai * s latex «ad solution are 3Y _S .7 g 17g

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given. The weight ratio between the solids in the kesorcinol formaldehyde solution and the polyethylene in the latex is 0.59. Hach versohiedenen ^ Altöirungezeiten the square cloth is in the adhesive mix Ge v immersed and then by evaporating the water dried in an oven at 80 ⁰ C. The total amount of dry adhesive adhering to the strips is $ 5. "Projes for the adhesive cans are produced in the manner described in the preceding examples". The results of the adhesive tests are compiled in the following table

Aging time.
St do

24

Temperature during the experiment,

20 40 60 90

20 40 60 90

Adhesive strength kg / cm

7.2 5.3 3.5 1.5

8.5

5 * 1 4.4

20 40 60

90

9.0 5.1 4.5 3.5

On the in example '. (A) described V / eise v / ird an aqueous emulsion of an ethylene-propylene copolymer is produced which has a limiting viscosity determined ^{in toluene at 3O 0 C}

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'tat of 1.73x10 ² cm -' / s tat ^{and contains} 50 Iol- $ £ propylene. The aqueous solution is up to a Srockenrückstand of 42.0 $ £ concentrated to 75 gd © a latex obtained, a solution of 3 g 0 * Natriummetahexaphosphat in 5 g V / ater · -geg _e ben ₀ While stirring, a dispersion of a mixture vonOj6 & g benzoyl peroxide and, 0> 5 g of the surface-active agent mentioned in Example 1 ("Phenopon öo 436") in 6 g water and then a solution of β g acrylic acid in 13 g water Euhrerj cooler and gas distributor equipped animal neck flask given ₀

The air is displaced by bubbling nitrogen through the mass. The flask is ^{immersed in a bath kept at 85 0} O while the mass is stirred under inert gas. After 6 hours, the polymerization is complete. 1C6.5 g of a thin latex are removed from the flask, from which no agglomerates can be filtered off. The dry residue of the latex is 36 ₉ 4 ° The acrylic acid chemically bound to the copolymer » g9 contributes $ 10, determined by salting out the coagulated product with alcoholic potassium hydroxide after removal of the free polyacrylic acid by wax with water

1 g of the residue obtained after extraction with Vfasssr and 5 hours of treatment, Rait 5OQ g boiling iDoluol a gel _s the off after drying 50 $ of the original material

* "'■ ■ · -" "'" ■ - / = * - ■ ■ ■■ power o ■

80 g of the latex of the ethylene propylene copolymer grafted with acrylic acid are mixed with 129 g of a solution, has the following composition and has been aged for one hour before use '. .

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Recorcin,. 11 6

Formaldehyde 17 g

Resorcinol / formaldehyde ratio 0.5

Water 100 g

30% sodium hydroxide 1 g

To the mixture of latex and solution is added 41 grams of the weight ratio between the solids in the resorcinol forraaldehyde solution and solids in the latex is 0.59.

After 48 hours aging time the square rayon fabric is dipped in the adhesive mixture and then dried by evaporating the water in a drying oven at 80 ⁰ C "The adhesive to the strip total amount of dry adhesive is 555. On Etie in the above examples \ described 7eiso samples prepared for Klebteste The Klebv / ert is 7 kg / cm at 25 ⁰ Co

In the manner described in Example 1 (A), an aqueous emulsion is a Xthylen-propylene Copolyraeren produced having a specific in-toluene at 3O ⁰ C intrinsic viscosity of 1,96x1 Q ² cmVg and 62. Hol-0 contains Prppylen "The aqueous emulsion is prepared by Destillation.auf and the water bath under reduced pressure to a Troclcenrück-, stand by 4J, 8 $ concentrated ,, 75 g dec latex prepared iwerden with stirring to a dispersion of a mixture of 0.675 .1 gjBenzoylperoxyd und.1 g of overall in example 1 / - (?!? henopbn Co 436 ')' called surfactant in \ 8 g of water ^ egebexio then a solution of 4.75 g · Kethacrylsäure in 15.5 g of water is added slowly stirred the crowd. The mixture is placed into a four-necked flask provided with) stirrer, condenser and gas distribution * Dio air is

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etttferntf, internally nitrogen άμταϊι the mass bubbled to 3 flasks. is placed in a bath held ^{at 85 0 O.} iie Masee stirred under an inert gas sphere

!] 3ie polymerization is completed after 6 hours, "From the piston v / Ground 105 g © ines dünailUssigen Xatex entnpinsaen, from the strength and lump-104g eiiies liömogen looking ■ ait" a frockeorUckstasid of 35 | be separated S _e

l-Ö g'des iatex be with acetone feoagulierto Bie precipitation is washed with water until free © di Polymetliacrylsäure away _c Me to the verse - <§ñ & © te ^ Cosol fmere chemically bound Methscrylsäui * emeng © is 9 $ 5f > _s determined by searing out the liicketanäes with alcoholic potassium hydroxide after extraction with? fess @ i% - 1 g ä © s liiekstaiiclgs © i gives after extraction with water and 5-stage treatment ait 500 g boiling salti ©! "unl« 3sliel \ © © el © _s -die after ds® f $ Materials EMSsi'3icIiea _t

75 g öes üates: fisa sit 15 © tliacrylsäiir © grafted I.tli, yl @ ji ~

®a ait 129 g aiissr Isö

E rmrü®a ait 129 g

The following Saaeriaeiisetsimg laat imö "τθγ äera 'Oebraueh * --Hours Aged? Mrfles.

Resorcinol x 11 g

3Seiger formaldehyde '7 g llolvex ratio "Sesercin / Foriaaldehytl 0.5

\ 7assor '00 -g

s Sodium Hydroxide 'Ig

46 g of water are added to the mixture of latex and solution. The ratio between the pesticides in Löstang and the pesticides in latex is Q _? 56 _C after an aging period of 40 hours, the square Eej * on - Sewebe is dipped into the adhesive mixture and then elurcli evaporation of the water in a heating cabinet free 80 ⁰ O *

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dried. The total amount of adhesive adhered to tissue amounts to

The treated fabric becomes one between two layers Mixture of the following composition placed:

Ethylene propylene copolymer

Kconey viscosity LILj +) at 100 ^c C = 25 _f '

Fropyl egg content 62 KoI-J-S 100 Gev /, - parts

ISAF carbon black 50 ""

Sulfur * 0.3 ""

α, α'-bis (t-butylpercxy, -diisopropy! benzene (peroxiraon)

'.'. Gu ^ -ig; 1.6p. Parts by weight

The coated fabric is in a Presue for 30 minutes

ο
vulcanized under a pressure of 40 kg / cm at a temperature of HO ^{0 C.} The probe tack value is 4.5 kg / cm at 25 ⁰ C

On the in example '. (A) an aqueous emulsion of a terpolymer of ethylene, propylene and cyclooctadiene - '. 5 is prepared, the one in toluene at

ο 2 ^

30 C has a certain intrinsic viscosity of ', .6'x'iO cur / g and' 2 KoI- ?? Cyclooctadiene- ': .5 and 57 EoI- ?? Propylene contained. The aqueous emulsion is concentrated to a dry residue. To 230 g of this latex, a solution of '. _t 66 g of benzoyl peroxide in 2Q g of toluene and then a solution of '5 g acrylic acid in 36 g Yfesscr. which contains 2 g of the surface-active agent mentioned in Example 1 ("Phenopon Cc 436"). The mixture is placed in a four-necked flask equipped with a stirrer, condenser and gas distributor. The air is removed by bubbling nitrogen through the lass . The flask is placed in a ^{bath kept at 85 0} C, and the mass is stirred in an inert gas atmosphere, -

009812/1596 ^% Λ

The polymerization is over after 6 hours. 314.5 g of a thinly liquid latex are removed from the flask, from the 1.5 g of agglomerate and 3''3 g of a homogeneous-looking latex with a dry residue of 3% 4 ^c / £ by PiI-

v .'- ground.

tration separated / 10 g of the latex v / ground with acetone "The precipitation is coagulated until free 'polyacrylic acid is gewaschen- removed with water, - the Acryisäuremenge _s which is chemically bonded to the terpolymer, is _2? 6 £, be, -stimmt by -Aussalzen the residue with aqueous potassium hydroxide to extraction with Wascer _c · 1 g of the residue obtained after extraction with -water and ~ 5 hours of treatment with 500 g of boiling toluene insoluble gels, "" after drying $ 85 of the original material-matter,

■ 97 g of the terpolymer grafted with acrylic acid ύοχι ethylene, propylene and cyclooctadiene-I, 5 v / earth mixed with 153 g of a solution that has the following composition and before use '! Hour has been aged:

Resorcinol ..1Ig '

35% formaldehyde 17 g

Resorein / formaldehyde ratio. 0 _P 5 water 124 g

3Ofoiges iiatrium hydroxide 1g

After an aging period of 72 hours, the rayon fabric is square in the adhesive st off getaucirt mixture and then evaporating the water-'in a heat sch rank at 80 ⁰ G-dried ,. The total amount of dry adhesive adhering to the fabric is 5fo _a

The treated tissue. ' is between two layers of a mixture, based on an ethylene-propylene-cyclooctadiene-I _? 5 ~ terpolymers, which have a propylene content of 48 MoI- ^ ₃ an Oyelccctadien-f, 5 content τοη 2.3 Uol-fo and a Mooney viscosity ML (IH). "-" of 27.5 at IQO ⁰ O hato the

00 98 12/1596 - - "-

Mixture has the following composition:

Terpolymeric HAP carbon black

Zinc oxide Stearic acid phenyl-ß-naphthyianine tetramethylthiuram disulfide Mercaptobenzothiazole disuifide sulfur

OO Weight Parts 50 It Il 3 Il Il J: .5 " Il ■ It It - Il It Il It Il I »

ras coated tissue is placed in a press under a

2 - ο -

Vulcanized pressure of 40 kg / cm at a temperature of IpQ G 50 Mi * th. The Klebv; ert is 5 kg / cm at 25 ⁰ Cn

To in Example 1 (A v-described manner / ith an aqueous emulsion of an ethylene-propylene Oopolymei-en forth asked · which has a specific in toluene at 3 3 ⁰ C intrinsic viscosity of 1p37x "O cirrVg and 50 LIo L-. jS propylene contained The aqueous emulsion is concentrated to a dry residue of 4-dfo .

A solution of 1.5 g of sodium hexametaphosphate in 5 * 5 g of water is added to 397 g of this latex. Then in the cash register 3 _f 45 g of benzoyl peroxide. 16 g of freshly distilled methyl acrylate and a solution of 16.5 g of acrylic acid in 50 g of water are stirred in ₀ The mixture is poured into a four-necked flask equipped with a condenser, stirrer and gas distributor ... The air is removed by blowing nitrogen through the / is bubbled Checkout "the flask is placed in a bath maintained at 85 ⁰ C bath while the mass further stirred under an inert gas atmosphere v / ill be _c

The polymerization is over after 7 hours 540 g /. one

0098 12/1596 -;

Slightly thin latex are removed. In the filtration no agglomerates are separated off _c The separated latex has a Irockenrückstand of 36 ₅ 5 ^f /> -. The amount of acrylic acid and kethyl acrylate. which is chemically bonded to the copolymer. is 12 $, expressed as acrylic acid and beatircmt by salting out the coagulated product with alcoholic potassium hydroxide after removal .the free polyacrylic acid by washing with water _t

"G dös extracted with water residue gives after 5 hours of treatment with 500 g of boiling toluene insoluble gels, the 'make up after drying''i'. I of the starting material *

SO g of the latex of one with acrylic acid and methyl acrylate grafted Ethylene-Propylene-Copol.ymeran were with '; 29 g mixed with a solution of the following composition:

Rcscrcin 11 g.

'35i * igc.r PorrcaldehYä / -. 11 g

Resorcinol / fonaaldehyde ratio 3.5

Water * CO g

The same sodium hydroxide. .G

The oeniseh made of latex and solution became 4 '? g V / asfjer gegeben- Ka ch of aging TO hours, the hanaels- • Usual auadratische rayon "Gev / ebe in the adhesive mixture dipped and then by evaporating the water in a heating cabinet at 80 ⁰ G _t dried on the above in the In the manner described in the examples, test specimens were produced to measure the adhesive value that? kg / cm at 25 ^P C amount

009812/1596 _R ._

BATH

AJ_ Hjer_ßt.pllun & des ^ aqueous. Latex, .des, Terpolymer An aqueous latex is prepared from ethylene using a terpolymer. Propylene and cyclooctadiene ~ 1.5 produced with the following germ count: Mooney viscosity IJL (1 + 4} at '00 ⁰ O 55 Limiting viscosity in toluene at 30 ⁰ O ^ 1.61x10 ezr / g propylene content 57% 4 col- #

Oyclooctadiene content 1 _? 39 llol ~ $ S

! en Impurities .. * that hinder the grafting reaction can were removed from the terpolymer by placing the crude polymer in a Xumagawa extractor for VTO hours was extracted with A2oton.

"■ CO s of this material are suspended in 900 g of toluene" To the paste obtained in this way: 2 g of Penopon 00 436 and 900 g of deionized water are added. The mass is then treated for 15 minutes in a mechanical emulsifier ί "Ultra-Turraxj. A homogeneous-looking emulsion is obtained, from which the organic solvent is removed by: distilling off the Tcluol ~ / 7ascer- / .. 2eotrop3 at a pressure of 40 mm Hg under nitrogen and with stirring. The aqueous emulsion is then distilled by afc- concentrated by water until an emulsion with a dry soot of V- $ .5 is obtained.

To> 52 g of the latex produced according to Λ, 3.45 g of Eeiiao.ylperoxyä mixed with ..42 g of the surface-active agent penopon CO 436 mentioned in Example "■ A) are added as a dispersion in 20. g of water mass is maintained in motion, and a solution "on 1. 42 g Matriumhexametaphosphat in 2j g water and then with a solution of 37.5 g of a mixture of 8Oj5 acrylic acid and 20 ^ methacrylic acid in 66 g deionized V / ater offset The 'mixture is placed in a four-neck reactor? the

009812/1596

Reflux- '. ■. "'. ■ _.

is provided with a stirrer / cooler and gas distributor «. The air is removed by passing nitrogen through the mass ο The flask is placed in a ^{bath kept at 85 0} O "while the mass is constantly agitated under inert gas. The polymerization is completed for ₆ hours 0 From the flask ' - 501 g of latex are removed, from which 4 g of coagulum are filtered off, The latex is thin, has a homogeneous appearance and a dry residue of 37% "": Q- g of the latex are coagulated with acetone »The precipitation is washed with warm water until the free homopolymers are removed α The amount of acid chemically bound to the polymer is 9 ₅ 2 ^ ₅ determined by salting out the residue with alcoholic potassium hydroxide after extraction with "- 'water ρ

A dispersion of a mixture of 0.61 g of benzoyl peroxide and 0.5 g of the surface-active agent mentioned in Example 1 A) ("Penopon CO 436") in 5 g of water is added to 67 g of the latex produced according to Example 7 A), the dry residue of 41.5 $ hat * Then a solution of Op 21 g of sodium hexametaphosphate in 5 g of water and a solution of 5 g of crotonic acid in 39 g of deionized water are added * The mixture is placed in an animal neck reactor equipped with a stirrer, reflux condenser and gas distributor _o the air is displaced by nitrogen is bubbled through the mass ο the flask is placed in a bath maintained at 95 ⁰ C bath, while the mass is kept in motion in an inert gas "is beendet- Kach.6 hours the polymerization ·. "From the piston 122 of a low-viscosity homogeneous latex discharged with a dry residue of 2,758 $ g., 10 g of the latex in acetone coagulated" Die! Precipitate is washed well with water until the free acid is removed * _a The amount of Crotonic acid previously bound to the polymer is 4 ^ 9 determined by salting out the residue with alcoholic potassium hydroxide after extraction with water.,

, 009812/1596 ' _BÄD

In the manner described in Example 7 A), using the terpolymer described there and extracted with acetone, an aqueous latex with a dry residue of 45% is obtained. 5/5 made- Sine solution of a Gemi- '. · Rope of ¹ _? 22 g Bcnzöyiperoxyä and 0 _? 6 g of the surfactant mentioned in Example 1 A) in 10 g v / water are added to 140 g of this latex while the mass is kept in motion. Then a solution of Op6 g of ijatriumhexametaphosphat in 0 g of water and a solution of 12 , 5 g of freshly distilled crude methacrylic acid in 36 g of deionized water was added. The mixture is placed in a four-necked reactor equipped with a stirrer, reflux condenser and gas distributor ₀ The air is removed by pearls one nitrogen through the mass can _e The flask is placed in a constant bath maintained at 95 ⁰ O bath, while the mass is continuously The polymerization is completed every 6th hour under inert gas.

2'0 g of latex are taken from the flask, from which 1.5 g of coagulated material are filtered off = the grafted latex has a thin, homogeneous appearance and a dry residue of 37 / ^ 10 g of the latex is coagulated in acetone _c The precipitation is carried out washed with warm water until the free polyether acrylic acid is removed. The amount of methacrylic acid chemically bound to the polymer is 12.2 $, determined by salting out the residue with alcoholic potassium hydroxide after extraction with V'ascer. ■ *;

• In the manner described in Example 7 A), an aqueous latex with a residue of 41.5 pounds using an Ethyler.-Propylene-Cyelocctadier.-I _P 5 terpolymer is prepared from impurities; which can hinder the grafting reaction by 17C ~ hour 009812/1596 "

Extraction of the crude polymer with acetone in one Kumagawa Extractor: Was., 'The Terpolymer had the following key figures.

Mooney viscosity WL (1t4) at 100 ⁰ O 27 " Limit viscosity in toluene 'at 3Q ⁰ O 1, Ββχ'ΊΟ cayg

Propylene content 47 _; 9

Gyclooctädien content · - ', 5 1.C8

To 260 g of this latex, a dispersion of a mixture of / .3.2 g of benzoyipercxide and "..6 g of the surface-active agent (" Penopon 43ό ") mentioned in Example 1 A) in 32 g of V / asaei- is added during the mass is kept in motion-- With further agitation, a solution of. ';, "4 g of sodium potassium phosphate in 29 g of water and a solution of 28 g of freshly distilled pure acrylic acid in 44 g of deionized water are added, The mixture is placed in a four-neck reactor equipped with a stirrer, reflux condenser and gas distributor. The air is removed by bubbling nitrogen through the mass. The flask is placed in a .gehaltenes at 85 ⁰ C ead, while the spot wirdr kept under inert gas in. The movement polymerization is complete after 6 hours. 499 g of a thin latex of homogeneous appearance and with a dry residue of 36-5 $ are removed from the flask. Io g of the latex are coagulated with acetone. The precipitate is washed until free polyacrylic acid has been removed. The amount of acrylic acid chemically bound to the polymer is Io.2j5 _f determined by salting out the residue with alcoholic potassium hydroxide after extraction with water.

The product can be used to bond cellulose fibers (z _t | _{c of} the kind used for the manufacture of tires) with saturated or weakly unsaturated ulefin elastomers, which are inherently incompatible with cellulose fibers *

009812/1696

^ OHlGiHAL

In the manner described in Example YA), an aqueous latex using a crude is ethylene-propylene-dicyclopentadiene terpolymers prepared which χ an intrinsic viscosity (in toluene at 30 ⁰ C) of 1.61 10 crr / g and 48 mol Contains propylene and 1 liter of dicyclopentadiene. The emulsion is concentrated by distilling off toluene and water until an aqueous emulsion with a dry residue of 36% is obtained. A solution of 1.66 g of benzoyl peroxide in 20 g of toluene and then a solution of 15 g of freshly distilled acrylic acid and 2 g of the surface-active agent mentioned in Example A) in 46 g of water are added to 230 g of this latex with stirring gegebei in a four-necked flask equipped with a stirrer, reflux condenser and Gasvcrteiler _r the air is removed by allowing nitrogen aiming by the cashier. The flask is placed in a structure kept constant at 85 ⁰ O, while the mass is kept constantly in motion under nitrogen. The polymerization is sworn after 6 hours from the piston v are / Ground 314 g latex discharged, filtered from the '* jpg coagulate The latex looks thin liquid from undhomogen and has a dry residue of 31-$ 5 - By Abd, struggling water closed elastic films are obtained, which adhere firmly to a glass substrate. This film has the following mechanical properties:

Tensile strength 54.15 kg / cm ²

Biu; elongation

Ug of the latex are coagulated in acetone, The coagulated Product is washed with water until the homopolymer (polyacrylic acid, is removed. The amount of chemically attached to the polymer Bound acrylic acid is $ 12.6, determined by salting out the residue with alcoholic potassium hydroxide after extraction with water, .

00 9 812/1596

An aqueous emulsion of an ethylene-propylene Cyclooetadien- 'manufactured terpolymers having an intrinsic viscosity (in toluene at 3O ⁰ C) τοπ' to in Example 7 A-described Magi χ -.61 'O ² cm ³ / g and 2-3 Hq1- # Cyclooctadien-i, 5 and 48 mol $ S propylene contains ₀ The aqueous emulsion is concentrated to a dry residue of 36 $ / To 230 g of the latex obtained, a solution of I _{3 is added with constant movement of the mass} 66 g of benzoyl peroxide in 20 g of toluene and then a solution of 15 g of acrylic acid in 2 g of the surface-active agent mentioned in Example 1 A) and 46 g of water are placed in a four-necked flask equipped with a stirrer, reflux condenser and gas distributor. the air is removed by nitrogen passes through the mass ₀ the flask is placed in a bath maintained at 85 ⁰ G bath, while the mass is kept in motion in an inert gas. The polymerization is over after 6 hours ~ 314-5 g of latex are removed from the flask, from which Ί.5 g of flakes and 313 g of latex with a homogeneous appearance and a dry residue of 31 »4 / '3 are filtered off ,," · 0 g of the latex are coagulated with acetone "the precipitation is gcwacchen with water until the free-polyacrylic acid removed is ο the amount of the chemically bound to the polymer of acrylic acid is _2? 6 $ _f determined by salting out of the residue with alcoholic Käliumhydroxyd after extraction with water * 1 g of the residue, which, after extraction with water, is treated with 500 g of boiling toluene for 5 hours, forms a gel which is insoluble in toluene and which, after drying, represents 85% of the starting material.

97 g of the acrylic acid-grafted latex of Ä'thylen-propylene Oyclooctadien-1 _r 5-terpolymers with 153 g of a solution mixed the .gealtert one hour prior to use v / was orden and has the following composition:

0098 12/1596

-. ■ "■ '- ... ■■. ^BAD ORIGINAL

~ 30 -

11 G 1570938 Resorcinol G 35fo ± gcT formaldehyde 124. G \ 7asser Λ
I. G 3 Above sodium hydroxide Resorcinol / formaldehyde-IIolver- 0.5 ratio

After an allowance of half an hour this will be
Reyongewebe immersed in the thus prepared glue mixture, followed by evaporation of the Yfassers in an oven at 8O ⁰ C dried The total amount of the adhesive to the tissue dry adhesive is 57 $ -

The treated fabric is between 2 layers of a mixture based on an ethylene-propylene-cyclooctadiene-I _r 5- terpolymer with a Frcpylene content of 48 LIoI- ^ ₅ a cyclooctadiene - "'ö content of 2 _: 3 MoI- ^ and a Mooney viscosity LlL ('+4) of 27.5 at IQO ⁰ C. The mixture has the following composition:

Terpolyraeres' CO

HAF carbon black - 50

Zinc oxide 3

Stearic acid 0-5

Phenyl ~ i3-naphthylamine '

Tetramethylthiuram disulfide 1

Mercaptobenzothiazole disulfide 1

Sulfur 2

The layer structure is in a press for 50 minutes under a pressure of 40 kg / cm and a temperature of ⁰ C 1:50 vulkanisiertr The strength of the bond is 5 · kg / cm at 25 ⁰ Co

009812/1596

Claims (1)

' _s .) Process for the preparation of aqueous Laticea von graft polymer, characterized in that saturated amorphous ethylen-ft-olefin copolymers or weakly unsaturated olefin interpolymers in aqueous emulsion with acidic agents, water-soluble vinyl or vinylidene monomer in the presence of a radical-forming agent and an anionic graft polymer to be subjected 2.) Method according to claim 1, characterized in that; that as acidic vinyl or vinylidene monomers, acrylic ,. Methacrylic, Sorbic, muconic and crotonic acid, the alkyl ester of which is so \; ie Mixtures of these compounds can be used. "3V) ancestors according to claims 1 and 2, characterized in that the vinyl or vinylidene monomers are used in amounts of 1 to 5o Ggv /, - iieilen / 1 OO 'file copolymers or terpolymers , ■ *"'. "■ ; ■) "■ Method according to claims 1 to 3, thereby gekenrizeichnot, * that the radical formers in "narrow from 0.1 to 10 GeWc-'files, preferably 1 to 4 Gcw ^ ropes / 100 parts Co- or lerpolymcros uses viordcn> 5c) Process according to claims 1 to 4, characterized in that that the radical generator is used dissolved in an organic solvent, 6 _e ) Process according to claims 1 to 5 »characterized in that the amount of deα used surface-active agent 009812/1596 SAD smaller or at most equal to the range of the radical creator, int ) Method according to - "Claims 1 to 6, characterized in that that as ethylene-ci-olefin copolymers are preferred Ethylene-propylene or ethylene-I3utene (1) copolymers with an ethylene content of 20 to 8o mol - '/ »and a molecular weight from 5o «ooo - 5oo, ooo are used- ) Method according to "claims 1 to 6, characterized in that that as weakly unsaturated olefin i'erpolymero is preferred Terpolymero with 2ο - 8o KoI-5 ^ ethylene one Molecular weight of 50,000-5,000,000 ends, which, in addition to ethylene and propylene, are 1 to 2o mol- '/ j cyclic or contain acyclic dienes. 9.) Method sun bonding of amorphous copolymers or terpolymers of ethylene and oc-olefin and optionally cyclic or acyclic dienes with natural or synthetic fibers or woven fabrics made of, for example, polyamides, polyesters, Heyon and / or cellulose _s characterized in that the fibers or tissue with an aqueous lösungsnittelfroien, anionic-containing gealterton dispersion of a phenol-aldehyde Hames and a stable aqueous latex pretreated with an amorphous _r acidic vinyl or Vinylidenmononeren grafted Äthylenelastomeren, then a mixture of the amorphous co or Serpolymeren, Vulkanisationsmittcln and applying reinforcing fillers and vulcanized at temperatures between 11o and 22o ° C, preferably 14o ° and 1Bo ⁰ C. 009812/159 6 ~ 33 - ft-) Method according to claim 9 »characterized; that one uses a Pfropfolastoineroa that o, 1 to 4o # _; preferably 2 to 25 5 » _r lionojuerketten from acrylic acid; Methacrylic acid and / or its alkyloaters contains- ft _; ) Process according to Claims 9 and Lo, characterized in that the dispersion used for pretreating the fibers or fabrics ages before use Io bic 80 hours, preferably 55 to 70 hours 0098 12/1596