DE1694782A1 - Polymer mixtures - Google Patents

Description

DR.-ING. BY KREI5LER DR.-ING. SCHDNWALD DR.-ING. TH. MEYER DR. FUES COLOGNE 1, DEIGHMÄNNHAUS

Cologne, 8, £ »1967 AvK / Äx

Princeton Chemical Research _f Inc. F “0, Box 652” Princeton * New Jersey (ü.S.A ”)

Polymer mixtures

The invention relates to mixtures of methaoryl nitrile homopolymers and copolymers with vinylidene homopolymers and copolymers as well as mixtures with condensation resins, such as phenolforaldehyde compounds and polyurethanes

Relatively little work has been done in the field of methacrylonitrile polymer applications because these polymers are rigid, resinous compositions with negligible flow properties or similar properties, and thus minimally thermoplastic. Polymethacrylonitrile is inherently more thermoplastic than acrylonitrile polymers, however, the limited * thermal stability of these polymers, the problem of yellowing, and other factors have prevented the use of polymethacrylonitrile as a pre-paste or fiber. When typical polymethacrylonitriles ^{are heated to 200 0} G, they change color from yellow to light red, and when they ^{are heated above 25O 0 0,} they degrade to about 85% monomer. Like polyacrylonitrile, polyacrylonitrile does not form any monomer during pyrolysis. It is assumed that this is due to a crosslinking of the polymers by Van der Waala "real forces or hydrogen bonds via 3 ~ a" tertiary hydrogen atoms.

Polymethacrylonitrile shows little deformation when it is is heated in boiling water for a long time, but the polymer usually becomes cloudy this class are also found in low-boiling ketones, such as acetone and methyl ethyl ketone, as well as in high-boiling ones Ketones, such as cyclohexanone, are soluble. They are also soluble in acetic anhydride, ithylaeetacetat,! Furfural, nitromethane, Nitropropane and pyridine. Monomeric methacrylonitrile, methyl ethyl ketone and methylene chloride are in the hot state also solvent.

Polymethacrylonitrile is not badly affected, though it, at room temperature a week in aqueous 30 $ iger Sulfuric acid, 10% sodium hydroxide, 10% sodium chloride and 20 # ammonium hydroxide is held. These polymers dissolve in concentrated hydrochloric acid Hydrolysis and formation of polymethacrylic acid, which is precipitated by adding water.

Polymethacrylonitrile-butadiene copolymers have a comparison rubber-like properties to acrylonitrile-butadiene copolymers, however, less elastic recovery. They are softer and have poorer solvent resistance and lesser "nerve".

Similar problems that have arisen so far in terms of physical Properties revealed by polymers are sometimes dissolved by mixing polymers, thereby creating some improvements in properties, but usually at the expense of other properties, "In thermoplastic materials, the blending of poly-." .. kidneys generally lead to a deterioration in tensile strength and tensile modulus values However, different polymers is not always successful because the individual components of a intended mixture incompatible may be or only a limited tolerance within a narrow quantitative ratio Have components. This mixing also has the advantage

an improvement in the properties of the various Individual components of these mixtures, however, are those The results achieved are sometimes very different and in certain cases cannot be foreseen. Here is to note that mixtures of incompatible polymers are cheese-like and have poor strength properties »

Certain commercially available resins generally cannot be used in the form in which they are supplied “For example, polyvinyl chloride is usually difficult to process as such. So it becomes common softened or also copolymerized with other eonomers to achieve certain processing properties as well to improve physical properties «Both methods have inherent drawbacks. For example, there are plasticizers expensive and wont wander or evaporate, leaving an embrittled material back as it ages The strength properties are often retained by copolymerization th, the softening temperatures and. the resistance to chemical attack and environmental influences worsened. A mixture of single polymers generally gives certain improvements in properties, but at the expense of other properties. The mixing of thermoplastic masses has in general result in a deterioration in tensile strength and tensile modulus values.

The combination of different mixtures of polymers or copolymers is associated with a lack of compatibility and consequently poor physical properties as an insurmountable obstacle, even if the combination the properties of the individual components would be advantageous in a mixture. Among the methods of improving the Compatibility of these compounds includes combining them in a common solvent. It is true in certain In cases, no segregation was found in the solution, but the compatibility of the mixture in the dry

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PiIm lost after evaporation of the solvent, whereby as a result of the practice or the training of "cheese-like" Properties of unusable products are obtained.

The invention addresses these and others To eliminate difficulties that have arisen up to now · The invention relates to a method and a mixture of substances directed that allow methacrylonitrile homopolymers and / or copolymers for areas of application use, xfor which these compounds have so far been considered unsuitable were β The invention enables a "change in the Solubility, solvent resistance, acid resistance and heat resistance of methaoryl nitrile polymers and -oopolymers »The invention is also based on a Process for the preparation of compatible blends of methaeryl nitrile polymers and copolymers directed over a wide range of proportions of the Mixing ingredients are compatible, and where volatile plasticizers that are lost through migration or volatilization are not required to prevent the physical properties of these polymers and copolymers to improve. According to the invention, mixtures of methacrylonitrile polymers and copolymers are obtained, in which the compatibility with other known resinous compounds by internal modification of these Methacrylonitrile compounds can be improved. the Resin-like mixtures according to the invention based on methacrylonitrile polymers are not yet suitable for use in Contemplated applications where these resins are used in combination with known reactive resins will.

Products with the aforementioned advantageous properties are according to the invention by mixing Methacrylonitrile polymers and copolymers obtained with various polymers, with the physical properties of the mixtures compared to the properties of the individual constituents

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parts are improved. The individual ingredients are over a wide range of proportions compatible, and in many cases the physical properties are synergistically increased * lie methaoryl nitrile polymers according to the invention include polymethaoryl nitrile and Methacrylonitriloopolymeaie and - »terpolymers with α-methylstyrene, Styrene, vinyl chloride, vinylidene chloride, aoryl esters, Methacrylic acid esters, butadiene, vinyl acetate, fumaric acid esters, Maleic acid esters, crosslinked polymers and Graft polymers of methaprylonitrile-styrene-butadioen, in particular Graft polymers of methacrylonitrile and styrene Methacrylonitrile butadiene polymers, and chlorinated ' Methacrylonitrile polymers, namely copolymers of Methaoryl ™ nitrile with vinyl chloride, vinylidene chloride, 2 * chloroethyl vinyl ether, 2-Ohlor-t, 3-butadiene, 2-Ohloraorylaten, Ohlcrmaleic acid esters and chlorofumaric acid esters.

The invention is particularly directed to mixtures of the foregoing Methacrylonitrile polymers with polyvinyl chloride, urea formaldehyde, Phenol-formaldehyde, epoxy and isooyanate resins.

According to the invention it was found that mixtures of substances with good optical clarity, tensile strength and flexibility be obtained ■ when polyvinyl chloride with linear Methacrylonitrile-Styrene-Butadiene-Eerpolymeren is mixed · | Good clarity and flexibility are continued within Amount ratios between polyvinyl chloride and the perpolymer as well as within wide proportions within the terpolymer itself The ratio of polyvinyl chloride to terpolymer changes the tensile strength of the mixture increases inversely with the butadiene content, i.e. the tensile strength values increase with it decreasing butadiene content in the total mixture The exact Ratio of polyvinyl chloride to the oil polymer or that Ratio of methacrylonitrile to styrene to butadiene im Terpolymers themselves depend on the intended use

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application of the polymer mixture from »This is an extremely advantageous feature, since mixtures, the combination of which are required for the various processing operations, 2 · Β. Calendering, extrusion, film manufacture and application of coatings that are cut to size can be easily manufactured.

It has also been found that by blending polyvinyl chloride with linear methacrylonitrile-styrene-butadiene polymers or methaorylnitrile-butylaeryla * - *; Copolymers Surprisingly, a clear synergistic effect on the physical properties is achieved, and r that the mixtures have higher tensile strength values than the individual polymers. Cross-linked derpolymers and graft polymers of methacrylonitrile, styrene and butadiene show the same synergism in mixtures with polyvinyl chloride.

In addition to the suitability for pressing "for blow molding, the extrusion molding, for the production of coatings u * the like. The polymer mixture with synergistically increased tensile strength values can also be used in the construction sector, for the manufacture of boat hulls, car parts, furniture, etc. Further applications emerge from the examples in Table II. "Further valuable products can be obtained if mixtures which contain the remaining multiple bin-P fertilizers are crosslinked due to the presence of a conjugated diene.

It has also been found that the mixtures according to the invention of polyvinyl chloride and methaeryl nitrile polymers have better melting and flow properties than polyvinyl chloride alone. Ficht weichgemaohtes or hard polyvinyl chloride usually has poor 3Pli © ßeigenseha £ T8N _f the so far prevented its use for the production of! Moldings UNAE commodities. This disadvantage is eliminated by the polymer mixtures according to the invention

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The polymer mixtures according to the invention have the other Advantage that they have a higher dimensional stability under heat than hard polyvinyl chloride * The extent of this Superiority depends on the particular methacrylonitrile polymer and the mixture used in a given polymer mixture Quantity from *

It was also found that polymer mixtures, the moderate to have good compatibility and good properties, from mixtures of these methacrylonitrile polymers (ΜΑΗ) with polyurethanes can be produced. These mixtures are

en within a wide range of composition / very

clear to slightly cloudy »The degree of flexibility and |

Rigidity of these mixtures depends on the composition lld on the proportion of the individual polymer components. Mixtures with a high polyurethane content have good adhesive properties and excellent abrasion resistance, while mixtures with a high content of MAK polymer (especially hard MAF polymer) improved flexibility and impact strength have compared to the MÄE polymer alone.

It has also been found that these methacrylonitrile polymers with both epoxy and phenol-formaldehyde prepolymers can be mixed within a wide range of proportions, mixtures

of high strength can be obtained, which is advantageous for the g

Suitable for a wide variety of applications, e.g. for the production of adhesive bonds, laminates, protective coatings, Foils, electrical insulation and cast and pressed parts *

It was assumed that the most varied of chlorine-containing Polymers of methacrylonitrile or acrylonitrile "with each other as well as with other chlorine-containing polymers are compatible. This was subsequently done through the manufacture several mixtures of this type confirmed «It was found that the internal modification of the acrylonitrile and Methacrylonitrile compounds compatibility with others chlorine-containing polymers, ζ · Β · polyvinyl chloride and its

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Equivalents, e.g., vinylidene chloride, vinylidene chloride copolymers Uodgl ”, improved by applying .one Such a method will solve the problems related to the compatibility in solution and the incompatibility occur as a dry film in various known mixtures, avoided because the mixtures of chlorinated Acrylonitrile and methacrylonitrile polymers and copolymers with other chlorine-containing polymers within substantial other ranges of proportions are compatible.

The proportions of methacrylonitrile polymers and ^ * -oopolymers to polyvinyl chloride, phenolic, epoxy and urethane resins and their equivalents in the mixtures according to the invention can be within very wide limits, for example the ratios can be 1:99 to 99 s1 its equivalents, however, will be so; chosen so that maximum properties in terms of tensile strength, tensile modulus, compatibility USW _{0 are obtained} for the intended use of the respective mixture.

Preferred embodiments of the invention are shown in the following examples. Various mixtures of methacrylonitrile homopolymers and methacrylonitrile-a-methylstyrene copolymers with polyvinyl chloride were made. The compatibility of the components of the mixtures has been determined within a wide range of proportions. Furthermore, the tensile strength, the The modulus of elasticity and the dimensional stability are measured when heated.

It is surprising that copolymers of methacrylonitrile and α-methyl styrene are compatible with polyvinyl chloride, and thus form clear mixtures, since polystyrene and copolymers of styrene and methacrylonitrile form cloudy mixtures and polymethacrylonitrile alone is cloudy. The compatibility could therefore neither the phenyl radicals of oc-methylstyrene can still be assigned to the methyl radical alone *

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Examples 1 - 3

A solution of 10% by weight of high molecular weight polyvinyl chloride (PVG) in cyclohexanone is produced * to ^ ige solutions (by weight) of methacrylonitrile (EÄN) y & -Methylstyrene (cc-MS) (80 * 20), polymethacrylonitrile (PMAH) and Styrene (SM) / MAN (75 * 25) in methyl ethyl ketone are slow stirred into separate parts of the above-mentioned PVG solution, until each solution has 2 parts by weight of PYG and 1 part by weight Methacrylonitrile polymer contains * The results obtained are listed in Table I below.

Table I. Appearance
des Ge «-
misehes Ent
mixture
at the
Stand - - Appearance of
GieSfölie * at
game MAN polymer crystal
clear no very clear, strong,
flexiM, harder
handle 1 ΜΔΝ / α-MS 80/20 quite
easy
cloudy no very slightly cloudy,
strong, flexible IVJ PMAN ' easy
Cloudiness no slight cloudiness,
strong, flexible, .3 SM / MAN-75/25

* Air-dried at room temperature, then dried overnight under reduced pressure at 65-7O ⁰ G · I

The compatibility of the various polymers and copolymers of polymethacrylonitrile is not only surprising, but the strength, flexibility and clarity of the blends are also properties that are in themselves unexpected are. The exceptional clarity of the copolymers of methacrylonitrile and prepared according to Example 1 Alpha methyl styrene is particularly advantageous when used these mixtures for the production of pollen in the packaging area, where clarity and firmness are important.

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Examples 4-14

Mixtures of PYO with PMAN and MAN / ct-MS-80/20 in various proportions are produced by mixing the dry, powdery polymers on a roller mixer at 182 ⁰ O until the mixture is homogeneous.In some cases, 1 % By weight of a stabilizer ("Thermolite 31", manufacturer M & T Chemicals), based on PVO, added. Test specimens are produced by pressing. The results of the tests are given in Table II below.

Table II PVO, weight ./ Train train Strain, at MAN polymer MAN polym Parts firm module.
kg / om ² game 100/0 ability,
kg / em 3n357 Ψ 80/20 779 29.736 3.6 4th PMAH 67/33 503 25,940 2.0 5 PMAH 50/50 405 22,400 1.7 6th PMAN 33/67 458 22,700 2.0 7th PMAN 20/80 * 384 20,300 1.8 8th PMAN 10/90 * 226 22,070 1.3 9 PMAN 20/80 * 300 23,100 1.6 10 PMAN 28.6 / 71.4 * 469 22,425 2.4 11 MAN / a-MS-
80/20 0/100 * 363 19,750 2.0 12th MAN / a-MS-
80/20 0/100 355 20,035 2.0. 13th - 560 10.9 14th

* The sample contains 1 wt .- # stabilizer. («Thermolite 31"), based on PVG.

Examples® 4-10 illustrate the improved physical Properties obtained by using polymethaoryl nitrile homopolymers mixed with polyvinyl chloride can be obtained. This particular homopolymer can, like these examples show how to improve the tensile modulus of Polyvinyl chloride can be used. Examples 11 and 12

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however illustrate the synergistic effect that achieved when using the copolymer of methacrylonitrile and cc ~ methylstyrene in combination with polyvinyl chloride , whereby the tensile modulus of the hybrid is significantly increased This result is particularly surprising in view of the fact that copolymers of methacrylonitrile and oc-methylstyrene are exceptionally brittle and both the tensile strength and the modulus of elasticity in tension wow like the Elongation of these copolymers cannot be measured. Normally it cannot be expected that by blending a brittle material into a somewhat thermoplastic one Material, e.g. high molecular weight polyvinyl chloride, improved physical properties are obtained » It was attributable to the fact that a brittle material, when used in a mixture, had the physical properties, ζ · Β. the modulus of elasticity in tension and the tensile strength, would worsen. It is particularly significant that in Example 11 The smaller amount of methacrylonitrile not only improves the tensile properties of PVC, but also improves one Mixture with improved elongation results in »

Examples 15-23

The influence of the addition of PMAN on the thermal stability (T _d ) of PVC is shown in the following

Table III · - i

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(Table III Example ITr ₉ Weight ratio PMAH / PVO 15th 100/0 16 80/20 17th 67/33 18th 50/50 19th 33/67 20th 20/80 * 21st 10/90 * 22nd 0/100 * 23 0/100

99.0 - '.. 98.5 '94, 5 94.0 85.0 79.5 83.0 80.0 83.0

* Sample contains 1 wt «<- # stabilizer (" Thermolite 31 "), based on PVC.

Examples 15-23 above illustrate the improvement in heat distortion resistance brought about by Mixing of polymethaoryl nitrile homopolymers with polyvinyl chloride can be achieved, whereby the processing properties of the mixture is improved. Me temperature, Up to which the mixtures are dimensionally stable is crucial important in molding where the flow of thermoplastic material in the mold is required to be removed To fill cavities in complicated shapes * Thermoplastic masses that retain their shape up to high temperatures do not look too complicated to deform Moldings, especially ^ ean balance between the temperature at which the pjeess mass is thermally degraded and the temperature until ζ ti which it retains its shape, must be maintained · ■

Srgebnisse, the "a-t Gömlsdhen Iran Me thaorylnitril-butyl Copolymörefi (iiAJf-ButyJö ^ triacrylate) init polyvinyl chloride receive η. werdöni filndmalog denlenigen * which are obtained with the öe * mixtures of methacrylonitrile and α-methylstyrene according to Examples 11 and 12. A copolymer of and butyl acrylate with a ratio of the monomers im

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-finished polymers of 53 * 47 are mixed with a Polyvinylohloriil in proportions of 99 * 1 to 1 »99, whereby the distances between the individual mixtures are each IQ Gew _f -rope, a« B · 90 * t0i 80 * 20., ,. · 20 ^ Β0, 10) 90 etc. Solutions and mixtures are prepared in accordance with the "Examples 1 <-3 4-14 *. Both the." available »The ratio of MAIi to butyl aorylate can be varied between 8S * 15 and 15 * 85, whereby in practice the same results are obtained. Instead of butyl aorylate, ethyl acrylate 2-ethylhexyl acrylate and its equivalents can be used * I The mixtures with polyvinyl chloride show a synergistic effect in relation to the tensile strength and the tensile modulus; ■ '. ■ \;

The processability of this mixture becomes the following experiments described further,

Examples 24 '' 33 '

To evaluate the ease of processing, in each case

1 g of the powdery polymer mixture on an aluminum, slide exactly in a circle of specified diameter

Pressed for 2 minutes at 177 ^° G and 280 kg / cm ^2. A comparison

the durometer and the thickness of the slices obtained gives a relative measure of how light these polymer blends are flow. The results for mixtures of PVO with PMAli / ä-lS ~ 80/20 are given in Table IV below ^^. - ■ .- '., - ν -: ...-, -. '-.' .. ■■■■ ■

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Table IY MAH polymer / By Thickness ,, mm t 0.43-0.56 example ΜΑΗ-polymer PVC * knife 0.38-0.51 Mr" mm 0.38-0.51 0/100 45 0.28-0.48 24 - - - ■ 10/90 47 0.33-0.51 25th PMAH 20/80 47 0.25-0.43 26th MAH / a-MS-80/20 20/80 48 0.28-0.46 27 - PMAH 28.6 / 71.4 48 0.33-0.48 28 MÄH / a-MS-80/20 33/67 50 0.36-0.48 PMAH 50/50 51 0.3-0.46 30th PMAH 67/33 52 31 PMAH 80/20 52 32 PMAH 100/0 54 33 PMAH

»All samples contain 1 wt .- # stabilizer (" Thermolite 31Λ based on PVO.

The evaluation of the various mentioned in Examples 24-33 Mixtures resulted in optimal processing properties that were not a significant improvement over represent modified vinyl chloride homopolymers. These examples further illustrate the advantage of the invention Mixing, in which molding compounds are obtained that are used for the production of molded parts with complicated Shapes can be used and satisfactorily complex and distant in shaping Fill areas of the mold at reduced press temperatures. This property also represents an economic advantage when shaping these mixtures »

Methaoryl nitrile equivalent polymers used in manufacture of mixtures with polyvinyl chloride that can be used are polymethacrylonitrile, the copolymers are methacrylonitrile (MAH / a-methylstyrene, styrene / teAH, MAtf / tiayloride, MAH / Vinylidene chloride, MAH / styrene / a-methylstyrene, MÄH / acrylic acid ester, MAH / tiethaoryl acid ester, M & H / butadiene, ΜΑϊί / α-methyletyrene / butadiene, MAH / vinyl acetate u * w · The area

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usable proportions of the MAN polymer to polyvinyl chloride can be between 1:99 and 99: 1. These polymer blends can be used to produce coatings, Foils and lasers are used or pressed or extruded «Sheets and plates of these polymer mixtures can be shaped and used in the building and construction sector, for furniture, boat hulls, auto parts and as a cheap replacement for polyester fiberglass «,

A copolymer of methacrylonitrile and α-methylstyrene is produced in which the individual components are present in the finished polymer in a ratio of 80:20 mol- $. Mixtures of this polymer are weighted with polyvinyl chloride ratio of 50:50 prepared according to the method described in Examples 1-3, the individual components being dissolved in solvents before mixing. A crystal clear solution is obtained, which is then cast into a film which also has the same clarity, proof for the compatibility of the components of the mixture both in solution and in the dry film · _Σ

The copolymer of methacrylonitrile and α-ethyletyrene is also dry blended with polyvinyl chloride in proportions of 5:20 and 8:20, as described in Examples 4-24. These polymer blends exhibit also excluded i drew compatibility. They have similar physical properties to the mixtures prepared according to Examples 11 and 12.

According to the! Invention, the proportions of components in the copolymer of Methäörylni-feiiil and <x-Metayl _r styrene can within wide limits of 90f! 0 ^J to 10 * 90 mol ~? SJ · lie In addition, the mixtures of this Gopolymeren 'with polyvinylchloride In Quantities of 90110 to 10:90 mol # produced.

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The mixtures of copolymers of methacrylonitrile and CC-Me thy! styrene with polyvinyl chloride are made by mixing of dry powders, solutions and dispersions manufactured and for the production of foils * packaging material, Protective coatings, molded ilen., Extruded parts uοdgl * used »

Polyvinyl chloride is usually difficult to process. It is therefore usually plasticized or with others Copolymerized vinyl monomers. Both methods have their own drawbacks. Plasticizers are expensive and maintain too migrate or volatilize, leaving behind after aging) an embrittled material «By copolymerization are often the ability properties that Softening temperature and resistance to attack deteriorated by chemicals and environmental influences * Accordingly, polyvinyl chloride is mixed with linear polymers of methacrylonitrile, styrene and butadiene, whereby Mixtures are obtained which have high optical clarity, tensile strength and flexibility »

The following examples describe master polymers of methacrylonitrile, Styrene and butadiene, their production and their advantageous use for increasing physical Properties of vinyl chloride polymers.

Examples 34- * 39

Methacrylonitrile-Btyrene-Butadiene Terpolymers are used in Room temperature produced as latices, being an emulsion is used, the freshly boiled softened water and ffiseh distilled monomers with the below in Table V contains the compositions

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Tabel V 35 36 37 38 39 example 34 90.0 90.0 90.0 90.0 90.0 water 90.0 1.8 1.8 1.8 1.8 1.8 Duponol MB 1.8 18.75 17.5 20.0 22.5 15.0 Methacrylonitrile 12.5 6.25 n, 5 20.0 22.5 15.0 Styrene 12.5 25.0 15.0 10.0 5.0 20.0 Butadiene 25.0 0.15 0.15 0.16 0.15 0.15 K ₂ S ₂ O ₈ ■ 0.15 0.25 0.25 0.25 0.25 0.25 Dodecyl mercaptan 0.25

• Sales, fo 27.8 42.5 12.3 54.1 61.9 6.4

The polymerizations are carried out for a period of up to 18.5 hours, * ο The reactions are terminated by introducing 0.05 parts of hydroquinone dimethyl ether. The terpolymers are deposited by coagulation with a mixture of aqueous ammonium chloride, methanol and isopropanol and treated with 0.05-0.10 parts of N-phenyl-β-naphthylamine as an antioxidant

Examples 34-39 illustrate various methods and compositions for the manufacture of terpolymers, the methacrylonitrile, styrene and butadiene in different Molar ratios included «These examples also show that the proportions of the monomers within further Ranges can be changed, with terpolymers obtained with ■ different proportions of the monomers and consequently can be "tailored" to the various applications.

Example 40 below shows that the compositions of the polymers mentioned in Examples 34-39 essentially correspond to the monomer ratios used in the preparation of the terpolymers. - ""

Example 40

Samples of the terpolymers prepared according to Examples 34-39 are suspended in methyl ethyl ketone. Each terpoly

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mere is easily soluble and gives a clear, gel-free Solution, a sign that the terpolymers are linear. A comparison of the infrared spectra obtained from this slide Terpolomereη were added, showed that the monomers are polymerized into the polymers in approximately the proportions that are based on the monomers used are to be expected

Examples 41-46

A solution of 10 wt _o - $ high molecular weight polyvinyl chloride (PVC) in cyclohexanone is manufactured. In separate Por P-tions of this solution are solutions of 10 wt .- $ of the terpolymers of Example 34-39 were stirred in methyl ethyl ketone in such amounts that each terpolymer in amounts of 10, 20 »30 and 50 wt _o - $ of the total mixture available istβ All mixtures are crystal clear. If they are left to stand, no segregation can be observed. Films cast from these mixtures are air-dried for a few hours at room temperature and then kept in a vacuum oven at 50 ^° C. over a laugh. All films with all proportions of PVC to terpolymer are crystal clear and have high flexibility and strength,

Examples 47-52

Mixtures of PVC with the terpolymers according to Examples 34-39 with proportions of 90:10 and 60:40 are prepared by placing the dry polymers on a roller mixer at 163-168 ° C are kneaded until the mixtures are homogeneous. All mixtures are made with 1.5 wt ..- ^ stabilizer ("Thermolite 3 t ', manufacturer M & T Chemicals) j related made on PVC. All of these blends have been found to be satisfactory for the manufacture of pressed parts 171-177 ° C can be used.

Examples 41-52 illustrate the compatibility of polyvinyl chloride with those of Examples 34-39

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produced terpoljmereiu foils with h@TTorragen.der Clarity and improved tensile strength and andsren excellent physical properties are thereby obtained.

Besides noting that by mixing clay polyvinyl chloride with linear terpolymers of methacrylonitrile! Styrene and butadiene blends with improved physical properties Properties are preserved »it was found that these terpolymers in addition to the methaeryl nitrile butyl acrylate copolymers Surprisingly, a pronounced synergistic effect on the physical properties of the mixtures result in |

Linear terpolymers of methacrylonitrile, styrene and butadiene are prepared in the manner described in Examples 34-39, the proportion of methacrylonitrile from 12.5-45 mol #, the proportion of styrene from 12.5-45 mol $ and the proportion of butadiene is varied from 10-50 mol $. The products made in this way are mixed with polyvinyl chloride, the proportion of which varies between 50 and 90 GeWe-jS * solutions of these mixtures as well as cast films made from these solutions are crystal clear, a sign that these compounds both in the solution and in the dry film are compatible "the ingredients used for making these mixtures are also t dry blended in the manner described in examples 4-14 AEEN manner.

It was found that these _r terpolymers can be mixed with 1-99 "~ $ polyvinyl chloride. The composition of the terpolymers varies within wide limits; the scope of the invention includes terpolymers in which the proportion of methacrylonitrile is between 10 and 80 mol $, the proportion of styrene between 10 and 80 mol ~ and the proportion of butadiene between 10 and 80 mol 70 mole # varies. The styrene is also wholly or partially replaced by methyl styrene and its equivalents. «Small amounts of polymerizable vinyl

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derivatives can also be incorporated into the ferpolymer will.

In the case of mixtures of these ferpolymer with polyvinyl chloride synergistic effects are also observed as noted in Examples 53-59, i.e. the values the tensile modulus and tensile strength are higher for the mixtures than for the individual components. Based on these These polymer blends have unique properties for the production of molded parts from hard polyvinyl chloride, ZoBc pipes, hoses, bottles and containers, as well as other molded parts. In addition, mixtures of this type are used for packaging, foils, electrical insulation, Protective coatings, laminates, moisture and vapor barriers, as well as for iConstruction parts, furniture and devices with and without the addition of pigments and fillers.

Except for the aforementioned purposes, the synergistic Polymer mixtures from the terpolymer of methacrylonitrile, Styrene and butadiene and the copolymer of Methacrylonitrile and butyl acrylate with polyvinyl chloride also in the building sector, for the manufacture of boat hulls, Auto parts, furniture and the like can be used. These polymers are particularly advantageous in applications where increased Rigidity is required for the molded parts made from these mixtures, as they are due to residual unsaturated places. " by adding a conjugated Diens, namely butadiene, are present, hardened can be.

The copolymers and polymers based on methacrylonitrile are not limited to the aforementioned monomers. In the copolymer, the butyl aerylate can be completely or partially replaced by ethyl aerylate or 2-ethylhexyl acrylate. In the terpolymer, styrene can be completely or partially replaced by other vinyl monomers * e.g. * a-methylstyrene and the yiny! Toluenes additionally zix methyl methacrylate, acrylic

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- now ^r

- ■ 21 * ■■ '■: ■: -. ■ - . -;> _: -. "■■, ■

nitrile and the like , and the butadiene can be completely or partially replaced by other known conjugated dienes, e.g. isoprene, chloroprene, piperylene, 2,3-dimethyl butadiene and their equivalents.

Various mixtures of methaorylnitrile-styrene-butadiene terpolymer and methacrylonitrile butyl acrylate copolymers are produced. The synergistic effect regarding the tensile strength and the tensile modulus and elongation illustrated by the following Examples 53-59, which are compiled in Table VI *

Table Vl

Example composition tensile modulus, elongation, Br- · '·' strength- kg / cm ² ^

53 Polyvinyl chloride (PVe) ^a 355 19th .750 2.0 54 90 PVO +10 terpoly
more 6D " 570 24 .530 5.3 55 60 PVC + 40 terpoly
more 6D 597 24 .110 4.6 56 90 PVC + 10 terpoly
meres 3B 381 Λ§, j 090 5.5 57 Methacrylonitrile /
Butyl acrylic; t - 53/47 303 14th .235 112.0 58 90 PVC + 10 Methaory1-

nitrile / butyl acrylate -

53/47 437 20,840 3.0

59 60 PVC + 40 Methaoryl- - nitrile / butyl acrylate 53/47 389 7.0 18.910

a) Contains 1% by weight of stabilizer "Thermblite 31", based on on PVC. All mixtures contain 1.5% by weight of stabilizer »Ihermolite 31», based on PVC.

b) The terpolymer 6D contains methacrylonitrile, styrene and Butadiene in a ratio of 45i45: 1O *

o) The terpolymer 3B consists of methacrylonitrile, styrene and butadiene in the ratio of 37.5: 12.5150.

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Example 53- illustrates the tensile strength and modulus of the polyvinyl chloride used in making the Mixtures mentioned in Table VI were used. the Examples 54-56 illustrate the benefit provided by Addition of a terpolymer of ethaeryl nitrile, styrene and butadiene. zu polyvinyl chloride is achieved, -The increase The tensile strength and the modulus of elasticity are important in this context in both examples the properties of the mixture far exceed the properties go beyond that from the sum of the individual components were expected *

P Example 57 illustrates the tensile properties of unmixed Methacrylonitrile-butyl acrylate copolymers, while from Examples 58 and 59 the synergistic properties, obtained by blending such a copolymer with polyvinyl chloride. example is particularly significant in this regard, as an addition of 10 parts of methacrylonitrile-butyl acrylate copolymer a greater increase in tensile strength and tensile modulus of a mixture with Pölyvinylohloria ^ acts as an additive of 40 ropes of such a copolymer.

The illustrate the same synergistic effect following Examples 60-63. Mixtures of PVC and MAN / SJS / BD ^ are made in proportions of 10:90 and 30j70. The tensile strength and tensile modulus of these blends as well as the polymers alone are given in Table VII below *,

• PVC Table VII Tensile strenght,
kg / sm ² . 1 64 7 Tensile modulus, kg / cm example
Br. 100 maf / sm / bd 352 17,575 60 90 0 562 _ 24,250 6t 80 10 626 23,550 62 0 20th 281 18,280 63 100 109 83 1 /

For comparison, the following are the physical properties of the TerpolyBeren stated alone,

Taüelle VIII train Train- Strain, example composition firm module* 4, JJr, ability,
kg / cm ^ kg / cm ² 7 ° 288 19 * 05.0 1.8 64 MAN / SM / BD-45/45/10 230 12.090 13.7 65 _: MAH / SM / BD-40/40/20 low estimated high 66 MAH / SM / BD-25/25/50 (estimated 3 * 515 ( estimated soft rubber— 70) 100) like elastomer,

similar to unvulcanized rubber

As various homopolymers, copolymers and Terpolyjnere methacrylonitrile sometimes incompatible with chlorinated resins such as vinyl chloride polymers Vinylidenehloridpolymeren and their equivalents are "searched for a method and composition _$ by this incompatibility problems can be avoided" It has now been found that by using a chlorinated methacrylonitrile polymers, as described above, the compatibility of such a compound in a mixture with vinyl chloride resins and their equivalents is improved,

Examples of chlorinated methacrylonitrile polymers which fall under this aspect of the invention are copolymers in which methacrylonitrile is copolymerized with vinyl chloride, vinylidene chloride, 2-chloroethyl vinyl ether, 2-chloro-f, 3-butadiene, 2-chloroacrylic acid esters, chloromaleates and puma rates and their equivalents Examples of polymers with which the above polymers can be mixed are boylvinyl chloride, vinyl chloride-vinylidene flour, vinylidene chloride-methacrylonitrile, vinyl chloride-vinyl acetate, chlorinated polyolefins, vinyl chloride-aerylic acid esters, vinyl chloride-vinyl ethers, vinyl chloride-dialkyl fumarate and maleate _and nd their equivalents.

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- 24 -

Various blends of chlorinated methacrylonitrile poly mers with various vinyl chloride and vinylidene chloride copolymers and homopolymers were made * The results obtained are shown in the following examples described * »

Example 66

A copolymer that contains 63% methacrylonitrile and 37% vinyl chloride and has an intrinsic viscosity of 0.4-5, measured in methyl ethyl ketone at 25 ° G, with an im Commercially available polyvinyl chloride resin of average Mixed molecular weight. 10 parts by weight of this copolymer of: methacrylonitrile and vinyl chloride are with 90 parts by weight of vinylidene chloride on one Two-roller mixer mixed with heated rollers become 60th GeWeIIe of this methaerylnitrile-vinyl chloride copolymer and 40 parts by weight of vinylidene chloride in the mixed in the same way «The polymethacrylonitrile vinyl chloride copolymer showed no evidence of incompatibility with vinylidene chloride in these areas.

Example 66 illustrates that by internal modification

• of methacrylonitrile polymers, for example by copoly-

• merization with vinyl chloride, the compatibility of this Nitrile polymers with resinous materials that too chlorinated, e.g. with the vinylidene chloride polymers mentioned in this example, can be improved.

For example, the methacrylonitrile-vinyl acetate copolymers mentioned here manufactured according to one embodiment of the invention as follows

Example 67 .

In a 1 1 resin flask equipped with a stirrer, thermometer, ■ Nitrogen inlet tube, reflux condenser and two dropping funnels is provided, 250 ml of softened water are used and 1.0 g of sodium lauryl sulfate ("Duponol ME"). In

10983 1/1647

a mixture of 70.0 g methacrylonitrile and 30.0 ^ vinyl acetate is added to one of the dropping funnels. In the second Iropftrichter © is given in mixture of 50 ml of demineralized water and 1.0 g KpSgOs "The contents of the flask is heated under nitrogen at 56 ⁰ C. The nitrogen atmosphere is maintained during the entire course of the reaction. The Monomerenggmisch and catalyst solutions are added simultaneously within 6 hours into the flask · It is allowed to polymerization 48 hours after completion: addition of the monomers and the ^ Soög-Iiclsung pass off, "The reaction temperature during this time 56 to 58 ⁰ O liaeh this time the polymer is coagulated with an aqueous iosodium chloride solution, washed and dried overnight under reduced pressure at 55 ° Pressed A clear, water-white, strong, flexible is obtained. The infrared analysis of the obtained product reveals, as expected, strong carbonyl and nitrile absorption bands. This confirms that the polymer obtained is a polymethaorylnitrile-vinyl acetate copolymer.

The quantitative ratio of the monomers in the preparation of the above-described copolymers can be within wide limits. The amounts of Oomonomeren may be the same, or any of the comonomers can be used in a \ relatively heights · Share

Example 68

The molecular weight of the various polymers used according to the invention was determined by measuring the intrinsic viscosity. These viscosity measurements are carried out using a 0.5 $ solution of the polymer in methy1 ethyl ketone at 25 ⁰ C ". The results obtained are hereinafter referred to.

109831/1647.

ο. 35 0, 31 0, 34 0, ο, 0.53, .0. 37 53 29 31 41 ι.29 (two different samples 0, O, 0,

MAN polymer Border viakositäl;

Λ MAN / SM / BD ■ '.- 25/25/50

B MAN / SM / BD - 37 _r 5 / 12.5 / 50

G MAN / SM / BD - 12.5 / 37.5 / 50

D MAN / SM / BD - 30/30/40

B - MAN / SM / BD - 35/35/30

$ MAN / SM / BD - 40/40/20

G MAN / SM / BD - 45/45/10

H polymethacrylonitrile (PMAN)

I PMAN of H after chlorination
' (21tSfo Cl)

Ea has also been found to be homopolymers and copolymers of methacrylonitrile with both epoxy and phenol formaldehyde prepolymers can be mixed within wide proportions, whereby pressed masses of high strength, wedge *, which can be used for the most diverse Applications are suitable, ζ «Β. for gluing, production of substances, protective coatings, pollen, electrical insulation and of cast or injected molded parts. In terms of the physical properties will be a certain & rad of synergistic build-ups in these blends.

As examples of Methacrylnitrilpolymeren that can be used in this ψ Ausführungsf <JRM of the invention are genanntj polymethacrylonitrile (PMAN), styrene (SM) / methacrylonitrile (MAN), ΜΑΝ / α-Methylstyröl, MAN / butadiene, MANAiöjlchlorid, MANyVinylidenchlorid, UAE / ^ tnylaQe-tat, MAN / frumaric or maleic acid ester, MAN / acrylic or methacrylic acid ester. Suitable epoxy and phenol prepolymers are, for example, a bisphenol A-epichlorohydrin resin ("Epön 828", manufacturer Shell Chemical Co.), epoxidized fatty acid ("Epon 872", manufacturer Shell Chemical Cc), phenol formaldehyde ("Burez 1 ^ 956" , Manufacturer Durez), cycloaliphatic epoxy resin ("Ciba X8200 / 103", an epoxidized cyelohexane derivative) and the like.

109831/1647

Various mixtures of these Spoxy * and / or phenol-formaldehyde prepolymers are uftter use of polymethacrylonitrile or methacrylonitrile-styrene copolymers used as Mtrilharze. The polymer blends with polymethacrylonitrile appear to be tougher than the polymer blends with the corresponding methacrylonitrile-styrene copolymers (25 /? 5).

Example 69

A xylene solution of an epoxidized one containing $ 75 pesticides Fatty acid ("Epen 872") is treated with methyl ethyl ketone (MEE) diluted to a pesticide content of -50 $ A "

Sufficient amount of this solution is slowly added with stirring to 15 / fc of polymethacrylonitrile (PMAH) in MEK to obtain a mixture of PMAIi and epoxidized fatty acid in a weight ratio of 95: 5. The mixture is clear and the films cast from it , are clear, flexible and strong ■■ - ■■ "

Example 70

Solutions of PMAJT in MEK are mixed with 0-50 wt. bisphenol A epichlorohydrin resin "Epon 828". All mixtures are essentially clear and the films cast therefrom are also essentially clear, strong and flexible. These g Mixtures! Also have good adhesion to wood.

Example 71

A mixture of PMAC and epoxidized fatty acid "Epon 872" in a weight ratio of 67t33 is applied to the example described manner · Then there is enough tributylamine stirred in to harden all of the epoxidized fatty acid · Films cast from this mixture »are somewhat cloudy and stiffer than the corresponding uncured foils. The mixture shows excellent adhesion to wood.

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Example 72

A solution of a styrene-methacrylonitrile copolymer (SM / μγ, weight ratio 75/25) is with. ei & em cycloaliphatic Epoxy resin (Durez X8200 / 103) mixed. The solution is practically clear. One poured from this mixture Foil is crystal clear mixtures that represent stiff to sticky, non-stiff materials, with increasing epoxy content can be produced using this method.

Example 73

The experiment described in Example 72 is used repeated by PMAIi in place of SM / MAN-75/25. Clear solutions are obtained. The films cast from it are clear to slightly cloudy. The polymer blends with PMAN are tougher than the corresponding polymer blends with SMAAU-75/25.

Example 74

Solutions PMAN in MEK be at 0.20 percent - mixed $> phenol-formaldehyde resin "Durez 15956".. The mixtures obtained are clear. Cast films from these blends are transparent, strong and flexible, after they have been dried at room temperature in air and then overnight under vacuum at 55-6O ⁰ C.

Examples 69 and 74 illustrate the compatibility of polymethacrylonitrile with epoxy and phenolic resins, while Examples 70 and 71 demonstrate excellent bond strength of mixtures of polymethacrylonitrile and epoxy resins, particularly on wood.

Examples 72 and 73 also illustrate the compatibility of epoxy resins with the polymers according to the invention, in particular Styro1-methacrylic copolymer (75:25), there clear films can be obtained from these mixtures, as well of mixtures with polymethacrylonitrile, the latter giving somewhat tougher films

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Although epoxy resins are generally intended to be blended with homopolymers and copolymers !! of methacrylonitrile are suitable, has been the aforementioned cycloaliphatic epoxy resin "öiba-X82OO / iO3" used in some experiments. Dieäes Harz has the following structure:

Except for the mixtures prepared according to Examples 64-68 are similar mixtures with polymethacrylonitrile and the cycloaliphatic epoxy resin in weight ratios of 90:10 to 1Oi90 produced. On the in Examples 64 to 68, mixtures of styrene-methacrylonitrile copolymers are also used (75:25) made with the cycloaliphatic epoxy resin, the weight ratio being from copolymer to epoxy resin 90s 10 to 10:90. All mixtures of the homopolymer of polymethacrylonitrile and the copolymer of styrene prepared in this way and methacrylonitrile with the epoxy resin give solutions and 'cast films that are crystal clear, a testament to the excellent Compatibility of these mixtures in solution and | in the dry film »

Polymethacrylonitrile and the hard mathacrylonitrile-styrene copolymers, e.g. those of styrene and α-methylstyrene, and their equivalents have improved processability, Adhesion, flexibility and strength when mixed with 1-35 parts by weight of the cycloaliphatic epoxy resin will,. Because of these improved physical properties, the polymer blends are suitable for production of molded parts, flexible foils and protective coatings, especially outdoors, where weather resistance is important.

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16947

The mixtures of homo- and copolymers of methacrylonitrile with phenol-formaldehyde resins described so far are produced in various proportions. However, it has been found that mixtures containing 10-40 wt - ° ß> of methacrylonitrile containing polymer containing 90-60 wt .- $ include phenol-formaldehyde resins, are suitable as adhesives and molding resins with improved impact toughness..

Mixtures of 40-90 _o - $ polymers which contain methacrylonitrile, with phenol-formaldehyde resins were found to be high-quality protective coatings, and binders with increased adhesiveness ο

"In accordance with the invention, it has also been found that various Urethane resins (i.e. condensation products of polyisocyanates with polyols) are also compatible with homopolymers and copolymers of methacrylonitrile.

As MAN polymers that are used for the production of blends with Polyurethanes that can be used are, for example, polymethacrylonitrile (PMAN), styrene (SM) / MAN, MAN / oc-methylstyrene (a-MS), MAN / vinyl chloride, MAN / vinylidene chloride, MAN / butadiene, MAN / acrylic acid ester, MAN / methacrylic acid ester etc. Likewise, the composition of the polyurethanes, i.e. the quantitative ratio of polyearboxylic acid, polyol and polyisocyanate used for their preparation, within next * Limits are »

The mixtures obtained have not only excellent compatibilities but also excellent adhesive properties and can as such for the manufacture of adhesives be used. A certain synergism is also present in this regard and in other physical properties of the Determine mixtures. These mixtures of polyurethanes with homopolymers and copolymers of methacrylonitrile are suitable can also be used as an extender for the more expensive polyurethanes in a wide variety of applications. Conversely, polyurethanes can as a non-volatile plasticizer for improvement

109831/1647

the flexibility and flow properties of hard Methacrylonitrile polymers are used «

The following examples illustrate various blends of polyurethanes with homopolymers and copolymers of methacrylonitrile. .

Examples 75-77

A solution containing 10% by weight of a polyurethane made from adipic acid, 1,4-butanediol and p _T p ^l -diphenylmethanediisooyanate ("Estane 5740 ', manufacturer BFGoodrich) is prepared. In separate portions of this solution, 10 stirred $ solutions of PMAN, MAN / oc-methyl styrene (80:20) and SM ₇ aian (75:25) in. Methylk'eton until each G-2 wt eraisch _e polyurethane parts by 1 part by weight of MM -Polymer contained The results obtained are shown in Table IX below.

Tabel IX Ent
mixture
at the
Stand Appearance of
Cast film at
game
ITr. MAN polymer Appearance
of the Ge
mix no crystal clear,
strong, not
stiff 75 PMAN crystal
clear no slightly cloudy,
strong, not
stiff 76 MAN / a-MS-80/20 easy
cloudy no slightly cloudy j
strong, not
stiff 7? SM / ivIAN-75/25 easy
cloudy

The aforementioned polyurethane from adipic acid, 1,4-butanediol and aromatic diisocyanate ("Estane 5740") has excellent compatibility with those of the present invention methacrylonitrile polymers used in solution and in films, in particular with a weight ratio of 50:50, However, the constituents of these mixtures are also within a very wide range of proportions of poly-

109831/1647

methacrylonitrile to polyurethane from 99: 1 to 1:99 compatible. The invention includes polyurethanes in general, that is _, those which are produced from dicarboxylic acids, diols and diisocyanates and have essentially the same compatibility with polymethacrylonitrile *

The blends of polyniethacrylonitrile with polyurethanes have various uses. ZoB. polymethacrylonitrile has with 1-40 wt _o -% polyurethane polymethane exceptional flexibility which is attributed to the polyurethane, so f is assumed as a plasticizer and / or processing aid is effective because polymethacrylonitrile as such has poor flow properties. Mixtures of polyurethanes and polymethacrylonitrile can be used to produce water- or crystal-clear films, protective coatings and molded parts. Zobo toys, appliances, containers "are used" u _o etc. For this polymer blend made products have better toughness and abrasion resistance and strength than polystyrene polyurethane mixed with 1-40 $ methacrylonitrile iann an excellent adhesive and as Üherzug used with improved strength characteristics. Coatings of this type generally improve the wear resistance of foils or artificial leather

A comparison of example 75 with the examples 76 and 77 shows that homopolymers of methacrylonitrile are more compatible with polyurethanes than copolymers of methacrylonitrile. These mixtures also have excellent properties as adhesives and coating compounds.

The invention includes, as a novel product, terpolymers of Methacrylonitrile, styrene and butadiene and a process for improving the physical properties of polymers of methacrylonitrile and styrene by polymerizing monomers of this class and their equivalents with butadiene and / or its equivalents.

10 9 8 3 1/16 4 7

1894782

The homopolymers of styrene and methacrylonitrile as well as their copolymers are hard thermoplastic compositions with limited flexibility and tendency to embrittlement * These properties have several disadvantages in many cases where these nitrile polymers are used as such for various purposes where a wide range of Good physical properties are required _for namely tensile strength, modulus of elasticity in tension, flexural strength, water resistance, solubility in cheap solvents and the like.

These homopolymers and Oopolymeren of styrene and methacrylic nitrile ι are aug due to their poor flexibility and relatively high brittleness, in general, to applications, such as deformation limited by extrusion, calendering or other known molding method for thermoplastic compositions

Various copolymers and terpolymers have been made to date been to eliminate some of these difficulties. A polymerization with other monomers is not always desirable, since the ■ reaction rates of the different Comonomers cannot be predicted with sufficiently high accuracy, so that in some cases the copolymerized proportion of the comonomers is less than

the proportion of comonomers present at the beginning of the reaction. Also, it is not possible with reasonable accuracy To predict the degree of branching, the duroh mixing different Monomer could be achieved in the production of copolymers. For example, high degrees of branching could be used occur in a copolymerization process, in which a gel-containing polymer is formed. Gels usually occur when attempting to dissolve the polymer in a solvent and appear to be insoluble Particles in the solution. These gels are also useful in the production of molded parts or calendering films noticeable as flaws, those as stains in wrapped foils

109831/1647

or are visible as rough spots in parts of the mold * ■ The gel is usually a highly branched or partially crosslinked polymer as opposed to a linear one Polymer, the formation of which is sought "

According to the invention it is possible to avoid these and other difficulties of the known processes and to produce terpolymers of methacrylonitrile, styrene and its equivalents and butadiene and its equivalents which do not have the previous disadvantages. The invention enables homopolymers of styrene and methacrylonitrile and their copolymers to be modified, with polymers having reduced rigidity and brittleness and improved flexibility being obtained. The invention also enables the production of polymers of methacrylonitrile which are essentially linear and free of insoluble and infusible branched gel particles, have improved pleating properties under the action of heat and / or pressure, are easy to extrude or inject and are suitable for the production of components or Coating compositions are suitable and can be crosslinked, as a result of which the chemical resistance and the pestability properties of these polymers are improved. According to the invention, elastomeric polymers of methacrylonitrile can also be produced which are amenable to further internal modification _r through which excellent adhesive properties are achieved «

Products with these properties are produced according to the invention by adding methacrylonitrile in the presence of styrene or its equivalents and of butadiene or its equivalents is polymerized. The difficulties of the known Processes and products are avoided by using small amounts (5-25% by weight of butadiene are polymerized in such a way that a linear terpolymera of moderate molecular weight and high Flexibility is maintained. However, larger amounts of butadiene, e.g. 5-75 parts or 5-50 parts by weight, can also be used will. Since the terpolymers are linear and a

1 09831/1647

are moderate in molecular weight, they may be easily dispersed or dissolved before use, if necessary. In addition, these products flow easily under exposure of heat and pressure so that they are better for processing by pressing and injection molding and for the production of foils. You can use known methods, e.g. injection molding, Pressing and blow molding, easily processed into good everyday objects or into sheets, foils, Hoses, profiles uodgl »are extruded, or they can be processed into thermoplastic films in a known manner by calendering. From these terpolymers produced films have good optical clarity and

are easily heat-sealable and can also be carried with them |

Poly '

itself and other thermoplastic materials, e.g. pyrolefin, such as polyethylene, propylene and the like «,, are welded. These Properties are particularly advantageous in the packaging sector * Terpolymers of this type are also suitable in the form of Organosols or LatdoBs for the production of protective coatings as well as for the production of laminates. Optionally, these polymers can also be based on the C-0 double bonds, which are present as a result of the copolymerization of butadiene are easily crosslinked. Through networking chemical resistance and strength properties of these products.

Linear methacrylonitrile-styrene-butadiene terpolymers, in |

which have a butadiene content of 25-75% by weight are elastomers, They are relatively less sticky at lower levels Butadiene and become increasingly sticky with increasing iji Butadiene content. These terpolymers can thus be applied to the various applications, e.g. as adhesives, binders, coating agents, coatings for pressure-sensitive adhesive strips and Protective coatings are "cut to size" · While the latex form is desirable for these polymers, they can optionally easily converted into organosols. The polymers according to the invention can by known processes

10983 1/1647

1894782

Spray-dried and, depending on the polymerization and drying conditions, in finely divided masses of. certain Particle size can be converted · In this powder form the polymer is suitable for the production of figmented or non-pigmented or filled molding compounds, or it can be relatively volatile, relatively unsolvafcigating Liquids with the formation of organ sols “PlastisoIe can be dispersed with these polymers are made by relatively non-volatile organic liquids are mixed in that make up the polymer dissolve at elevated temperatures.

The presence of methacrylonitrile in the terpolymer contributes to hardness and wear resistance, as they are not present to this extent in conventional styrene-butadiene copolymers. Equivalents of conjugated bees other than butadiene can also be used, namely isoprene, chloroprene, 2,3-dimethyl— 1 :, 3-butadiene, etc. · the styrene may be entirely or partially substituted in the vinyl Eahmen the invention, by "aromatic derivatives, for" Bo oc-Methylstyro}., can be Tinylnaphthalin u _e like replaced. Yinyltoluole. In addition, other olefin or vinyl monomers can be polymerized as modifying agents in the context of the invention.

Some preferred embodiments of this aspect of the Invention are described in the following examples »

Examples 18 ~ 83

Methacrylonitrile ^ styrene-butadiene serpolymers are used in Room temperature as an emulsion using fresh boiled softened water and freshly distilled monomers, with the following in table χ mentioned monomer mixtures is assumed *

109831/1647

Table X 79 80 .0 8T 0 82 0 83 example 78 90.0 90 ,8th 90 8th 90 8th 90.0 water 90.0 1.8 1 , 5 H 0 U 5 1.8 "Duponol MB" * 1.8 18.75 17th , 5 20, 0 22 5 15.0 Methacrylonitrile 12.5 6.25 17th , 0 20, 0 22 0 15.0 Styrene 12.5 25.0 15th , 15 10, 15th 5 * 15th 20.0 Butadiene 25.0 0.15 0 f25 0, 25th O, 25th 0.15 K ₂ S ₂ O ₈ 0.15 0.25 0 o> O, 0.25 Dodecy! Mercaptan 0.25

Revenue, $ 27.8 42.5 12.3 54.1 61.9 6.4

The polymerization is carried out by adding 0.05 part Hydroquinone dimethyl ether canceled. The polymerization time is not longer than 18.5 hours. The terpolymers are made by coagulation with a semisch of aqueous Ammonium chloride, methanol and isopropanol obtained and with 0.05-0.10 parts of H-phenyl-ß-naphthylamine as an antioxidant treated.

Example 84 _f

Methyl ethyl ketone is added to samples of the polymers prepared according to Examples 78-83. All polymers are readily soluble and form a clear, gel-free solutions, a sign that the polymers are linear * i A comparison of the infrared spectra of films of this Serpolymerenzeigt that the monomers in the polymers in approximately. Proportions are incorporated which were to be expected on the basis of the monomers used in the polymerization reaction *.

Example 85 :

Samples of the produced according to Examples 78 and 79 Polymers are sandwiched between metallized polyester foils ("Mylair", manufacturer du Pönt), Älumißiöafglieft and unbleached Kraft paper pressed · Öttte adhesive is made

and the polymer cannot be easily rubbed off from the lens wearer «

Example 86

Foils are produced by pressing samples according to the Examples 81 and 82 prepared polymers. These films have higher strength and clarity and are less yellow than comparable films made from acrylonitrile butadiene styrene terpolymers,

Example 87

Films which are produced by pressing samples of the polymer produced according to Example 80 can be ^{bonded by pressure to themselves, to metallized polyester films (Mylar 11} ), polyethylene and their equivalents. These films can also be used to make laminates from these dissimilar materials using pressure alone or pressure combined with mild heat.

Example 88

Films are made from a latex of Example 82 Cast Polymers »The foils have a moderate degree of" continuity "and are stronger and harder than Films cast from acrylonitrile butadiene styrene latioes will"

Example 89

The experiment described in Examples 78-83 is repeated with the difference that chloroprene instead of Butadiene is used as in Example 78, essentially the The same results are obtained with the polymers produced in this way obtain"

Example | fe

The experiment described in Example 89 is repeated, but with t »ä-dimethyl-» i _t 3-butadiene instead of butadiene

* 39 -

is used · Essentially the same results are obtained «·

Example 91

When using isoprene instead of butadiene in Example 89 gives similar results

Example 92 . ■ .. '

Polymerization procedures described in Examples 78-83 " is, using "-Methylstyrene Place of styrene repeated. A polymer is obtained which have essentially the same properties as those in | Example 78 has obtained polymers, evidence of the Suitability of a-methylstyrene for these purposes *

Example 93

Yiny toluene is used in place won ec-methy! Styrene used in the process described in Example 92 try! ,. Essentially the same results are obtained, evidence that a-lethylstyrene and ¥ i &yl1; o! «Ol are equivalent for the purposes of the invention * '

Example 94

When using yinylnaphthalene instead of α-methyl- | styrene in Example 92, similar results are obtained. A slightly different polymer is used due to the bulkiness the liaphthalene component received "

The term "polymers" used here includes terpolymers of methatsryinitrili styrene and butadiene and theirs jiguivalentea.

The proportions of methacrylonitrile / styrene / butadiene in the process according to the invention are preferably 25-45 s 13 /: 5-50, but the proportion of butadiene and its equivalents can also be 5-75 to 5-25 parts by weight ,. . ■, "

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Claims (14)

P ate η ta η s ρ rü che . (I) Polymer mixtures containing a mixture of 1 ») methacrylonitrile polymers and 2.) polyvinyl halides ^ polyurethanes, epoxy polymers, phenol-formaldehyde polymers, Vinylidene halides or polyurea formaldehydes. 2. Polymer mixtures according to claim 1, wherein the methacrylic nitrile polymer a copolymer of methacrylonitrile with acrylonitrile, Styrene, α-methylstyrene, vinyl toluene, vinyl chloride, Vinylidene chloride, acrylic acid esters, methacrylic acid esters, butadiene, vinyl acetate, dialkyl fumarates, dialkyl maleates, Isoprene, chloroprene, piperylene and / or 2,3-dimethy! Butadiene, is. 3. Polymer blends according to claim 1 and 2, wherein the second Chloride polymer polyvinyl chloride, Wtä $ WmXiiffl &, vinyl chloride-vinylidene copolymer, vinylidene-acrylonitrile copolymer, vinylidene chloride-methaeryl nitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-alkyl acrylate copolymer, chlorinated polyolefin, vinyl chloride-divinyl ether copolymer, vinyl chloride-dialkyl maleate copolymer is. 4, polymer mixtures according to claim 1 tois 3 containing about 1 to 99 percent by _e - # Methacrylnitrilpolymer and 99 to 1 wt .- ^ second polymer. 5. Polymerengeiaischs according to claim 1 to 4, wherein the methacrylonitrile polymer is a methacrylonitrile-styrene-butaene terpolymer » 109831/1647 • - ki - 6. Polymer mixtures according to claim 5> wherein in the terpolymer the proportion of methacrylonitrile between Io and Bo Mol- #, the proportion of styrene between Io and 80 mol * - # and the The proportion of butadiene is between 10 and 70 mol «#. 7. Polymer mixtures according to claim 1 to 4, wherein the Methacrylonitrile polymer a copolymer of methacrylonitrile and at least one acrylic acid ester is * 8. Polymer mixtures according to claim 7, wherein the monomers in molar ratios of about 85; 15 Ms 15 j 85 \ available. 9. Polymer mixtures according to claim 1 to 4, wherein the Methacrylonitrile polymer a copolymer of methacrylonitrile with vinyl chloride, vinylidene chloride, 2-chloroethyl vinyl ether, 2-chloro-1,3-butadiene, alkyl-C2 «chloro) aaryiates, Dialkyli (chlorine) maleates or dialkyl (chlorine) fumarates is. 10. Polymer mixtures according to claim 1 to 4, wherein the second polymer is a condensation product of adipic acid with p, p ^l -Diphenyltnethandiisocyanat or toluene diiso- , cyanate 1st. . " 11. Polymer mixtures according to claim 1 to 4, wherein the second polymer a polymerized epoxidized fatty acid, a polymerization product of bisphenol A and epochlor · » hydrin, the polymerisation product of the epoxy of the formula 109831/1847 or the polymerisation product of the epoxy of the formula is. 12. Polymer blends according to claim 11, wherein the methacrylonitrile polymer in an amount of about 10 to 9o wt .- ^ the total polymer content of the polymer mixture is present, 13. Polymer mixtures according to claim 5 * wherein the terpolymer is essentially linear and essentially gel free. 14. Methods of improving tensile strength, tensile modulus, the dimensional stability in the heat and the processing ability of methacrylonitrile polymers according to claim 1 and the * second polymer according to claim 1, characterized in that that one has about 1 to 99 parts by weight of methacrylonitrile polymers blends with about 99 to 1 parts by weight of the second polymer. 109831/1647