DE2216718A1 - Process for modifying the rheological properties of polymers, polymers produced by the process and apparatus for carrying out the process - Google Patents

Description

Procedure "", gum Codification of the raeological properties of Polyaeran, polymers and devices produced by the process "ar üurchführun" de "Verfeiirene.

Coded polymers, especially polyolefins with improved Flow properties and occasionally improved adhesive properties compared to the polymeric Grundiaater "ial, a.B. the polyolefin, which is used as the starting material, are obtained in the extrusion press by a controlled reaction, which often includes degradation. This is done an initiator injects under conditions of either maximum distribution or intensive mixing, whereupon noticeable changes the rheological behavior, i.e. the molecular weight distribution, take place in the starting polymer. According to some

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ExecutionMormea are also coaomers based on the base material grafted on during the mining process *. In these cases BMUH receives excellent new graft polymers with favorable Smelting properties and other useful properties,

The present invention relates to the chemical and / or physical modification of polymer materials in an extrusion press.

In particular, the invention relates to the formation and use of a special reaction zone within a Extruder, wherein the reaction conditions can be selected and maintained so that one has the following effects achieved: 1) Instant, intensive mixing of added reaction participants with a polymer or 2) intensive distribution of added reaction participants in one Polymer, with both gears achieving special rheological changes one through the extrusion press • I allow moving polymers.

Three particularly important process parameters that are in short Time that can be regulated are shear force, pressure and teiapevature. It has now been found how such hegulations are to be made, so there are various surprising and useful results result.

According to a preferred embodiment of the invention Help respondents introduced into the special reactionazone under conditions that maximize effect within result in a minimum of time. ϊ; ΐη polymer can not only be in its Theological properties, i.e. in molecular weight and flow properties can be changed, but simultaneously chemical modifications can also take place. For this purpose, additional starting materials are chemically combined with the

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- "9 * - *

$ 221671

Polymer umgteetxt, especially new grafted ones Polymers with a shorter chain length than the starting polymer

receives.

It is known that polymers can be modified in an extruder by placing them in it "at elevated Semperaturen with or treated without the addition of an initiator. It is also known that such reactions take place in extrusion presses Eonomers or polymer chains on the base polymer to graft on.

It has now been found to have extraordinary advantages in terms of Process sequence and product quality can be achieved with the training and use of special reaction ions and conditions within an extruder. Kau can operate at relatively low temperatures and high throughputs. The resulting grafted products are new and have unusual properties. Furthermore, the Process efficiency improved.

FIG. 1 shows an echeeatic view of a forward-leaning Extrusion press eur implementation of the process according to the invention, in which an initiator of a decompression device is fed will.

FIG. 2 shows a schematic view of a further preferred one Extrusion press, which provides a thin film zone with shear force under high pressure conditions for effect the polymer reactions and an extremely good mixing .

Figure 5 shows a schematic view of a special ^U Egan "-iiischers, which is incorporated in the device according to FIG.

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be it "earth came",

The present invention relates to a rheological or chemical and ideological modification process Properties of a polymer that is usually feet at room temperature. The procedure is through a combination marked at the following levels:

Introduction of the polymer into an extruder with a moving extruder screw of various core cross-sections, which results in a reaction zone,

(b) creating an overpressure in the extruder while the polymer is passing through,

(c) application of heat, in addition to mechanical processing, to convert the polymer into liquid form,

(d)! Transport of the liquid polymer into a reaction zone inside the extruder! in which the polymer volume • ο it is regulated that it is smaller than the volume of the Reaction ions, causing a pressure reduction in this Zone arises,

(e) Introducing into this reduced pressure zone in which the polymer is essentially liquid, one of the the following materials:

(1) a reactive compound or reactive twists,

(2) a free radical initiator, or

(3) a combination of (1) and (2), in a measurable change in theological and / or chemical properties sufficient quantity and

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(f) Transport of the resulting modified polymers through the rest of the extrusion process.

An essential feature is the sealing or closing the high pressure and high vision keaictionsaone or the rivet pressure reaction zone with a device such as a.B. a cap that shows the implementation of the lleaktionezone concludes. Such a device is generally used in conjunction with a subsequent depressurization.

According to a preferred embodiment, the cap consists of a portion of the screw core which has an enlarged cross-section, thereby preventing gaseous reactants from being You can leave the action zone easily a suitable device is, for example, a commercially available Egan mixer.

The sealing of the reactants is preferably accompanied by a subsequent venting of gas at a reduced rate Pressure, with vaporous components being removed. The capping also prevents vaporous reactants prematurely removed from the reaction zone.

By venting or venting the gas, unwanted ones are prevented Pressure increase, corrosion caused by reactive vapors, the formation of bad-smelling products, corrosive products, easily decomposable products and the like.

The inventive method is based on all polymers applicable that can be processed in an extrusion press, especially on thermoplastics such as nylon, polyester, polycarbonate, engineering plastics and acetals. It is particularly suitable for polyolefins with 2 to 8, preferably 2 to 5 ^ Carbon atoms, including copolymers of olefins

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other monomers, * .B «vinyl monomers, in which 4er olefinic share of 4 predominantly part is a component.

The method is also applicable to elastomers, especially polyolefins, but are .bestimmt on silicone elastomers and the like A distinction should be made between polymers whose properties g largely by the Xthylengehalt and those polymers whose properties largely by the content of 0,. - Cg olefin can be determined.

This distinction lies mainly in the fact that polyethylene and ethylene-containing polymers are among certain Simultaneously crosslink and breakdown conditions in the reactor under which C -, - and higher polyolefins do not crosslink, however, are dismantled.

In the following description, therefore, reference is occasionally made to different process conditions that are to be used if the essential polymer properties are determined by the ethylene content.

The method according to the invention can also be applied to all types of elastomer that can be processed in an extrusion press. All examples are more natural Rubber, polyisobutylene, butyl rubber :, chlorobutyl rubber, polybutadiene, butadiene-styrene rubber, ethylene-propylene-castomers, ethylene-propylene-diene terpolymers and Mixtures of these with one another and with thermoplastic polymers are called. Mixtures of elastomers and thermoplastics in any quantitative ratio, particular improvements are made by the process according to the invention.

In particular, polyolefins, both plastic and elastomeric in nature, but also other thermoplastics are used for purposes

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eggs, for which the bigenecliatft of good flowability during processing is important. The 1st ia »b« son4ere the Pail in the production of foils, fibers, with injection molding and the like »

In numerous technical applications there is a narrow one Holektlar weight distribution cheaper than a wide one. at .some slaetosera and plastics of low molecular weight suitable eich R v / Hu for measuring the molecular weight distribution However, the swell, defined below, is a more useful hatred. Generally show tight Molecular weight distributions tend to be lower Viscosities and improved molding properties.

The best way to achieve the desired narrow molecular weight distribution would be to control the polymerization in such a way that this molecular weight distribution is obtained directly. So far, however, no effective method for the corresponding polymer synthesis is known.

It has now been found that in numerous polymers, especially polyolefins and especially polypropylene, polybutylene and, within certain limits, also polyethylene (if there are no excessive crosslinking reactions) the molecular weight distribution can be narrowed by using controlled Procedural Mafinahaen using the following Embodiments of extrusion presses described bring about excellent mixing or dispersing of the reaction participants.

Once the polymer is in the molten state, at a suitable temperature and at a significantly reduced pressure compared to a first oosing zone of the extrusion press or a zone with high shear force in the case of a thin polymer film (with high

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Print) know initiators of various kinds. and there then occurs rapid dispersion or dispersion of the Initiator or other heating participant in the polymer. Badurch let it be possible to have intense reaction at very courses Occasionally, it can be achieved in the reaction zone.

In most cases, due to the controlled degradation, the length of the individual polymer molecules is approximately the same the desired narrow molecular weight distribution and, at the same time, a reduction in molecular weight result. Iristallinity and other desirable properties of the polymer are retained.

Instead of or in addition to the above-described change in the Kolekulargewichtsverteilung can be reactive with the introduction and / or i> polymerizable monomer it in the presence of suitable catalysts or initiators (usually it is the same compounds, the downsizing of the polymers cause) tin-grafted cause and usually, but not always, a polymerisation of such monomers at the active sites, which result from the special reaction conditions in the reaction zone at this point in time aa polymer.

The method according to the invention is particularly remarkable in that it is a simultaneous method for the first time Narrowing of the molecular weight distribution, which can be determined by the smaller increase in shape of the polymer or the better flowability, and to achieve "an inner. hopping degrees lying half of a wide range Provides.

Much of the resulting graft polymers are new. “For example, no graft polypropylene has been produced yet

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ait- o, b5 "to Zo G * w * ~ # t ^ fi |) grafted component bit Sehmelsfliefcgeechwindigiceittn (MlK) γβ" et ** 5 Μ © 1ooo _g irors-wise more ale 2o bie loo «», whereby £ iet «# Sefca * X * i] U * ßge« 0liw ± 2iä ± gltelt ■

us »ninÄaatene 5o? t higher lies ale dig d «8 Grandpolyaieren, and kit For» BUiiahmtr:

which are at least B o _t o5 ·: ßunheita lower ale äi «

the basic polymer.

With a relatively narrow division of weight ^; are new x »ä rorteilkaft. Bi * Beseie & ming ^H rel * tiT'- beiidht calibration ftxtf tag Qrundpol ^ mer directly to a Syntheße ent-Btammt, ie before measurable Spaltwag _r degradation, chain termination or the like. Occurred.

The meieten Gy "bia Og-Polyelefinen provides cross-linking is not a problem · In äthylenhaltigen PolTreeren or polyethylene slightly different methods can be used, au avoid networking · These include the creation of activated sites mm polyethylene by initiators which do not promote Veraetssng , '* · £ · gaseous oxygen * · substance, organic 2limver1 »; i3iäu $ g« &; orgtoiechs Sohwefalrerbindungen, Hitaestabilisatoren, acid anhydrides and dgX «

Furthermore Bfcn either initiators or die.Monomeren separated from the other component _# D * H · the Konomer or initiator, and before this · "retract μ that the Reaktica rather grafting al" leads iur networking, like * one you came to Control the temperature in such a way that the negation is kept to a minimum «<* · *

The method according to the invention is very flexible, it is in numerous variants can be carried out according to the intended purposes.

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Of course, you can also add monomeric cleansers, whereby graft copolymers are obtained in which the graft chains comprise at least two different Konoraere (aufrer the monomers of the base polymer).

You can also graft substances that are not polymers form. For example, substances can be grafted on that act as antistatic agents, light stabilizers, agents for photo-degradation, Core builders, / lamiühlenuner, nitzestabilisatoren, plasticizers, Lubricants, dyes and the like act. Mn »<eg for Carrying out this variant consists in making an unsaturated site available, in connection with Ddt sterling hindrance in the monomer, so that only one monomer is grafted onto a reaction site. Me polymerization is not qualified. Monomers that directly iait the functional grafting materials react, also practice the above Punctures satisfactorily.

The preferred class of monomer for the production of graft polymers according to the present invention has functional groups such as diacid groups, hydroxyl groups, Nitrile groups, amine ester groups, polyether sequences, imide groups, Amide groups, glycyl groups, iipoxy groups or the like, in addition to at least one multi-subject bond

You can then use functional groups in the extrusion press or later reacted with other codifying agents in order to change the properties of the graft polyfine and about heat stabilizers, light stabilizers or absorbers, Xernformer, lubricant, anti-photo degradation agent, flame retardant, Antistatic agents, plasticizers or the like. To give.

The graft polymer usually contains from 0.02 to 20, preferably

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o, 1 WLe 1o and especially preferred ο, 2 * & Ls S Hew «, ^ graft fraction.

When suitable Honomerer ies for HersteirLuag · Pfropfenteile can additionally sur aforementioned Jex change the rheologiechen properties advantageous improvements of Hafteigenßchaften äes Jolpaersa · achieving KrfinÄungsgemäö can therefore polymers produced ₃ AEIE practically on all substrates liable, even when using relatively little graft component , d, h _e V / o or less, based on the total polymer "Numerous non-polar! polymers such as 2 * 3, the polyolefins h FTSN not good to metals and other materials such as Sämststoifen," .B. Nylon, polyesters ^ fluorhaltigeii polymers "<ma figi * furthermore they take no par oat offe," paintings, fiber cables ₉ Ketallplattierungeji, overprints, etc. "on. By modification with the corresponding monomer according to the present invention, products can be obtained which have all of the above-mentioned properties that are lacking in the basic polymer.

The bo modified materials may still for all purposes for which the unmodified material (base polymer) is used · are needed so they can, for example foamed etisolen au Pl and I ^J ulvem V9rartt * surmounts, "u colloidal Gemiechen dispersed," mulgiert , extruded vani. be deformed in any way.

The preferred monomers for modifying are unsaturated Cono- and polycarboxylic acids (C-- to C ^) with preferably at least one olefinic double bond, as well as the anhydrides, salts, esters, Xther, amides, nitriles, thiols, 'thioacids, Glycidyl, cyano, hydroxy, glycol and other substituted derivatives of these acids

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Examples of acids, anhydrides and acid derivatives include: maleic acid, fumaric acid, himinic acid, itaconic acid, citraconic acid, acrylic acid, glycidyl acrylate, cyanoacrylate, hydroxy-Cj to C _2o -alkyl methacrylate, acrylic polyether, acrylic anhydride, methacrylic acid, crotonic acid, Mesaconic acid, angelicic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, himinic anhydride, (5,6-i) ndo-raethylene- & -tetrahydrophthalic anhydride), acrylonitrile, methacrylonitrile, sodium acrylate, calcium acrylate and MagneBivunacrylate.

Other monomers which may be used alone or in admixture with one or more of the carboxylic acids or carboxylic acid derivatives, the Cp-C are ₅ '-Vinylmonomeren, e.e. Acryloxide, acrylonitrile and monoriny! Aromatic compounds, i.e. styrene, chlorostyrenes, bromostyrenes, ci-methylstyrene, vinylpyridines and the like

Other useful monomers are C.- to C ^ Q vinyl esters, Vinyl ethers and allyl esters, e.B. Vinyl butyrate, vinyl laurate, Vinyl stearate, vinyl adipate and the like, as well as monomers having two or very vinyl groups, e.B. Bivinylbenzene, ethylene dimethaorylate, triallyl phosphite, diallyl cyanurate and iCriallyl cyanurate

Thus, in general practically all materials are those with the base polymer, in particular among free-radical ones Conditions and at the melting temperature of the base polymers can react, suitable for the purposes according to the invention.

In addition to the unsaturated is called a functional group. However, the functional group does not have to be present, see as an example the * suitable monomers styrene or ethylene.

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It was also found that "in the manufacture according to the invention of graft polymers when used in sufficiently small quantities as nucleating agents act and thus shorten the lateral span within the the hardening of the polymer and the formation of the solid plastic enter from the melt. These proportions also increase the clarity of the polymers ez *, they are therefore in used in the appropriate cases, e.g. ·.;. in the preparation of of foils, bottles and the like. Ber kerr-forming effect is observed at very low concentrations of the graft polymers as an additive in other polymers.

Of course, the usual additives can also be used with the modified polymers are used, including conventional heat stabilizers, lubricants, antioxidants, Antistatic agents, dyes, i'lammheramer, plasticizers » Preservatives, processing aids and the like, furthermore fibrous and non-fibrous fillers or reinforcing agents including giss, silica, plastic powder » Metal powder and wires.

The usability of the graft polymers according to the invention is very extensive because these products have good bonding and adhesive strength own. They can be printed and by editions decorated, furthermore electroplated, hot-pressed, painted and coated by vacuum metallization

From the polymers according to the invention, in particular from with Tapes made from acrylic acid-grafted polypropylene are particularly suitable for fastening nail straps to nail straps (nail stacks).

Such tapes are also suitable for lacing and other things

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Purposes where good adhesion and strength are required, especially when they contain 1o to 7o wt. 56 clastomeres.

For further processing, the polymer products according to the invention can be blow molded using extrusion or injection preformed, calendered, centrifugally cast, for overmolding, for powder coating, compression molding, i'ornipressen or Extrusion presses can be used, furthermore they can be Foam processed, injection-molded, mechanically deformed, rotationally pressed, pressed with reinforcement, thermally deformed, impregnated in webs and the like. The Polymers according to the invention are particularly suitable as coatings or fil-like laminates on other polymers, for example as laminates grafted with glycidyl acrylate Polypropylene on nylon, Iylar and the like.

It is emphasized that the base polymers also include substituted polymers. In the «backbone dee polymers can thus before grafting by functional groups such as chlorine atoms, hydroxyl groups, nitrile groups, ksteramine groups or Like. Be substituted.

Furthermore, polymers that are grafted with monomeric substances, in particular those with functional carbonic acid groups, »Usätalich be networked in kcnveational Welse or under Use of Hetal3 «alaen can be fed to an ionomeric crosslinking.

Products that are initially processed during processing are desirable flow very easily and then harden very rigidly after processing by crosslinking. The products manufactured according to the invention can be used in this way. Come one If crosslinking is taken into account, the molecular weight of the poly-

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meren by using · larger! sings of the free radical initiator, ie from ο, οί? öew to 5, -. #, "gange polymer are based on the Off ~ drastically reduced polymers having intrinsic viscosities of d, east and less, ie 5oo to 6000 - _{9 are} preferably I000 to 5oo and particularly preferably 25oo and 4500 ei ?, are particularly suitable for crosslinking after the grafting described.

low molecular weight polymers can not only be crosslinked, but also detailed and otherwise on the production of Surface treatment can be processed.

According to the present invention, poles can therefore not only 5weeks lowering the molecular weight and narrowing the Molecular weight distribution treated and thus fed to traditional plastic uses, but can rcan also produce polymers that can be used as coating agents " and additives to fuels, lubricating oils, lubricants and spray oils as viscosity modifiers, sludge inhibitors and antioxidants are suitable.

For example, α-olefins, e.g. Ethylene-propylene copolymers, whose viscosity was reduced to a certain extent and which received a narrow molecular weight distribution, excellent additive properties when used in lubricating oils within a wide temperature range

The modified polymers in accordance with the present invention excellent «.ls additions. You grant to others Polymers, even if they are present in small quantities, are unusual Properties even when these other polymers differ from the modified additive in terms of melt flow rate differ considerably. In general, can

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tie polymers according to the invention advantageously nit other polyolefins, that is thermoplastics and Klae tomer s in amounts of o »6d1 to 99», preferably o _(o1 to 2o and special bevoreugt o, o1 to to wt .- ^, based on the weight of the resulting mixtures , mix.

According to a particularly preferred embodiment of the invention, a polymer of 0p- to Cg-cono-olefin or a copolymer thereof is grafted with acrylic acid. The polymers of the Cn- to Cg-cono (X-olefins are polyolefins denotes, and in the description of the present invention this term includes the co-polymers of the C ₂ - to 0 _Q -föono-0 (-olefins with each other and with other monomers as well as the homopolymers,

Auoh polymers that contain diolefins such as butadiene or isoprene, are suitable. The polyolefins are mostly produced using a catalyst with a transition metal, however They can also use bit Phillipe catalysts, or cationic anionic initiators or according to the free-radical method Production of the C ^ -Og polyolefins are known and form not part of the present invention.

Suitable polyolefins both plastic and elastic in nature and low or high density polyethylene, polypropylene, palybutene-Ί, poly-3 ~ «* thylbutene-1, poly» 4-ethylpentene * l ₍ mixed polymers of monoolefins and other olefins (mono * or diolefins) or vinyl monomers such as ethylene / propylene Klschpolpolymer, or with one or more other monomers, aB SPDM, Xthylene / butylene copolymers, Ethylcn / Vinylacetateopalynere, Ethylan / Äthylaerylat copolymers, propylene / 4-methylpentene «l-copolymers and the like.

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"Copolymers ¹¹ or composite polymers are understood to mean products made from» wet or several monomers or substituted derivatives thereof *

The polyolefins avoided in accordance with the invention contain propylene and / or ethylene, i.e. which are "the preferred materials." Polypropylene and polyethylene. The starting polymer of the invention The method preferably has a Schaele index (Ml) of 0.1 Ms 4o, preferably 1 to 4o and particularly preferably from 1.5 to 4o, or a melt flow rate « speed (KKi) between about 0.1 and 50, preferably between o, 1 and 5, ο and particularly preferably between ο, 5 and 2, These melt flow rates approximately correspond to Average molecular weights (viscosity average) from about 15o ooo to? Oo ooo.

In the production of usually solid polymers from 1-olefins, certain rheological properties are often used for control purposes, one of these rheological properties being the melt index or the melt flow rate, which characterizes the processability of the polymers and gives an approximate indication of the molecular weight. The melt index of polyethylene is usually determined according to ASTM D-1238-652. In this ^r j? Eet. the Bxtrudiergeechwindigkeit in grams per 1o minutes (is at 19o ° C under the weight of a piston ₉ whose diameter 9 »465 determines now is through a mouthpiece of 2 _(o86 mm diameter and 8 ₉ ooi laundri Läng ·) and, together with its Stamp weighs 216o g. *.

The melt flow rate (MFR) of polypropylene is determined using the same procedure, but the temperature is 23o ° C (ASTM D-1238-65T)

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The device used to determine the melt index is called "Dead-weight Piston Plastometer" in the ASTM manual ·

In general, polypropylene from the reactor has a melting flow rate below 1, while with polyethylene from the reactor the melt index is about 0.4 to 40. , \

The preferred monomers which _{are grafted onto C 2} bis (^ polyolefins and other polymers in accordance with the present invention are maleic anhydride, acrylic acid, methacrylic acid, glycidyl acrylate, acrylamide, hydroxy C _... to C 20 alkyl methacrylates and their Derivatives. Other monomers that can be used are mentioned in the present description. Other monomers can be mixed with these, such as maleic anhydride, styrene, acid esters, salts and the like preferred.

The grafting reaction is initiated by a free radical initiator, which preferably consists of an organic * per compound. Particularly preferred peroxides are t-butyl perbenzoate, dicuayl peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne (Lupersol 13o), * t, * ( '-Bis (tert.- butylperoxy) dlieopropylbeniol (TulCup R) or other free radical initiators with a half-life temperature of more than 80 ° C. and mixtures thereof In general, the higher the decomposition temperature of the per compound, the more favorable it is.

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Tiger 1 is used in an extrusion press 1 with a cover section 2, a reaction section 5 and an end section CMH1 4.

Grafting carried out

Polypropylene is introduced into the feeding zone 2 of the strand preparation 1 via a funnel 5. The Kxti'uderechnecke. 6 in the loading zone 2 can be in different be designed in a conventional manner, for example with a charging part 7, a Überganj; steep 8 and a first part 9.

In the protective zone 2, the polypropylene is heated by heating devices 1o to a cylinder temperature of 2o4 to 54? and preferably heated 2O4 to 288 ⁰ C.

The Jixtrmderechneck · 6 has a grain which has a reduced cross-section 11 at the beginning of the rsaktlonosons 3. Dadmrch 3 susätsliches volume and a drop in pressure in the Keaktionss ^ a · raises produced d _w h "a · Dekompreseion so that a portion of the polymer epexieller * j ^% ea abnormally high pressure in the extruder auegeaetst * dc.

The feed line 12 connects the reaction zone. with the An initiator, which preferably consists of a peroxide atsht, and an · »active monomer (in some cases this will be P «r« xyä used alone). Ia Pail the special present The design phone consists of acrylic and the Initiator from "VulCup R". ■.

By injecting the initiator or the mixture of initiator and monomer at this point, the low pressure in A careful dispersion of the initiator in the polypropylene is effected in an extremely short period of time

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actual cleavage or degradation of the polypropylene result. Appropriate settings of the polypropylene feed rate and screw speed must be maintained.

According to the preferred embodiment, the initiator and Acrylic acid introduced into zone 3 as a liquid chemical. If only a dismantling is sought, then luan only gives an initiator or initiator of zone 3 dissolved in a solvent.

F-8 was found to degrade the polypropylene noticeably takes place when the counter pressure against the PlüseigkeitsgemiBCh Aue initiator and acrylic acid in the injection line 12 is less than about 7 atm and preferably about 0 atm.

The pressure in line 12 therefore gives an indication of whether the propylene feed speed and screw speed are set accordingly for the respective product.

2eil of the extruder, which is beneist by the heaters 13 has a temperature zwiechen about 71 and 232 and preferably 121 to 232 ⁰ C. The Extruderechn "cjce 6 in the rear part of the neaktionszone 3 can have any cross-sectional de" core comprise the appropriately, for pumping and, if necessary, additional mixing and for the regular reaction participants, the reaction is allowed to end.

Decompression part 3a of the screw follows immediately «In transition part 3b with gradually increasing cross-section of the screw core and finally a metering zone 3c with a constant cross section «iee Sc'r.raubenkems.

? C 3? ή 2 / »", ^r ! ε 2

The extruder screw 6 then has a fusion seal (also called cap) 14 on which deviate from the free Initiator and acrylic acid from the reaction zone 3 prevented.

The screw 6 also has a second compression zone 15 behind the cap I **.

Line vent 16 (to the possibly vacuum ^ n ^ sica is above the jjekonipressionszone 15 »for the purpose of eliminating excess noise or fumes. One works without the Entlüftuiig 16, so the cap 14 and the decompression zone 15 are not applicable.

The grafted copolymer or rio polymer blend is then passed through a metering zone 4, from which it is extruded via a nozzle 17 on the extrusion press 1.

The barrel temperature, which is produced by the heaters 18 in the metering zone 4, is 177-288 and preferably 177-232 ⁰ C.

According to FIG. 2, an extrusion press 2o with a charging zone 21, a keaction zone 22 and an unddosierungszone 23 for carrying out the grafting process according to the invention used. In this embodiment, the initiator and acylic acid are injected through an injection port 24 at one end introduced, on which the extruder screw 25 has a core 26 of a very large cross-sectional diameter. The gap between this part of the screw core and the interior of the extruder 2o is very small and varies with size the extruder. For example, this gap concerns a 5, o8 cm-> xtruuer 127-127o, preferably 254-635 and particularly preferably 254-5o8 / u.

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In a further embodiment according to FIG Piece of enlarged cross-section or the mixing device 26 shown, in the circumference of which several channels are incised »This results in several channels without an exit, below l) The polymer is jerked out of the inlet channels and over the outer surface is pressed into the outlet channels. Instead of this other suitable means can also be used.

The novelty and the progress of the invention lie in the Combination of such a kischvorrichtung with means for Introducing the reactants at a relatively early stage in the extrusion process.

In any case, as well as when a device is used Figure 2 as well as Figure 3 »the polymer forms a thin liquid film under relatively high shear forces, compared to the conditions in other parts of the extrusion press.

Initiator and / or acrylic acid are used with pressures between 14 and 35o or in particular between 35 and 246 atmospheres injected due to these high pressures and due to the fact that that only a thin polypropylene film is present in the high shear zone 27 of the reaction zone 22, there is intensive and immediate mixing with noticeable degradation of the polymer.

The extruder 2o also has a cap 29 and a Vent 3o. As in FIG. 1, however, these two parts can also be omitted.

As can be seen from the embodiments according to Figure 1 and Figure 2, can extrusion presses of different design for carrying out the graft polymerization according to the invention

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fahreriB are used. The common league of all Extrusion is that instant mixing of initiator and acrylic acid with the polymer, i.e. polypropylene, takes place. le-r extremely high Kish ^ raä, the that Characteristics of the invention is characterized by a noticeable poljraer degradation made visible. This polymer degradation becomes noticeable through a substantial increase in the melting rate or the solids index of a copolymer, compared to the base resin. The narrowing of the Molecular weight distribution 5 can be seen from the fact that the The increase in shape of the grafted copolymer is less than that of the base polyolefin used to produce the copolymer was used*

Linige high molecular weight; Polymers, e.g. The polyolefins, when pressed through a capillary nozzle of relatively short length, produce an extrudate whose diameter is greater than the diameter of the capillary.

This property of the polymers is called "normal increase" (the swell) denotes and numerically in the ratio between The diameter of the extrudate and the diameter of the capillary are printed out ^ Both the extrudate diameter and the capillary diameter become the extrudate diameter used). According to the present description, the "standard increase defined as follows"

Increase in shape = (e)

^D o where D = octrudate diameter

D = capillary diameter

The numerical value of the norm increase is also of the geometry of the nheometer, m which the polymer passes through the capillary

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is pressed, depending. Me specified in the following 'colors numerical values were obtained with a height meter, whose kheoraeter cylinder has an inner diameter of 9.5 now owned. The specified temperature was accurate to + 1.1 (J set, the tolj ^ mer was through a capillary with an inside diameter "of 0.7666 mm and a length of 25.55 mm pressed. The intrittangwinkel the capillary was 9o °.

The kessungen were carried out by removing the polymer pushed through the capillary by means of a plunger that operated at constant speed or constant shear rate (y) from 13.5 to 333.3 seconds * "worked.

The polymer was through the capillary in normal room temperature

(21.1 to 26.7 ⁰ C) printed.

The measurement of the increase in shape is often used to establish a giObes Measure of molecular weight distribution in polyolefins. Polymers with a high increase in shape have a broader molecular weight distribution than polymers with a low increase in shape.

The polymers according to the invention thus have gains in shape which are less than the gains in shape of the base materials. They are products of a statistical cleavage process which leads to a reduction in molecular weight and which they possess therefore a narrower molecular weight distribution than the base polymers.

Ks is to be mentioned that grafted polymers with unusual high Schinelz flow index (i.e. from about 2o to 1000) as well can be made using an ausganys polymer with a Schinelz flow index of the -vleichezi range, where . one grafts conventionally and / or dismantles additionally.

2098 U 3/0762

BAD GRONAL

The free-radical initiator in amounts corresponding o, o5 to 5, preferably o, p2 to 2, and "most preferably o _t o2 bit 1, o wt .- #, based on the polymer, are used..

The conomer to be grafted on is used in amounts of 0.1 to 100 preferably from 0.15 to 50 and particularly preferably from QjI to 25 wt .- ^, based on the base polymer, applied. A particularly preferred range is between 0.1 and 1 »$ 5. At these levels, high graft conversions are achieved. Also, the adhesive properties are compared with the Base polymer, greatly increased, even with such small amounts of graft.

In general, initiator and monomer are mixed and at the same time admitted, with the exception of the i'all in which as polyrcer polyethylene or a predominantly ethylene containing Copolymer is present.

new graft polymers according to the invention bind by various important properties marked. These include:

(1) A melt flow index of 3 to 1,000, preferably of »More than Io to 25t>» special preferred from 2o to 25o, by at least 5056 or more, preferably 10056 or more and more preferably at least 150 or more higher than the melt index or melt flow rate of the starting polymer, which has a melt index or a melt flow rate of non-plus-size to 15o (measured according to ASTM D-1238-65T) «

(2) Content of S pQlymerized Pi'ropf ComGnomer of o, o2 to 2o, preferably 0.1 to 1o and particularly preferably from O ', 2 to 8 wt .- #, based on the total amount of the graft Co-

2098A3 / 07S2

polymeric (it should be mentioned here that the advantageous effects of grafting are observed with a relatively low content of grafted comonomer, ie, V / o and less).

(3) I norm increase of at least 0.05, preferably at least 0.1 units less than the iorrazunahine des (round polymer, particularly preferably of ο, 15 units less than when Grunäpolyraer.

example 1

Polypropylene with a melt flow index of 0.4 vmrde over Put the MnL filling funnel according to -iJ'igur 1 into an extruder introduced. Into the injection line with a side opening 12 a mixture of acrylic acid and peroxide (VulCup H) was used in the different approaches in the table I specified quantities filled. In the case of mixtures A to G, acrylic acid and peroxide were produced with practically no counterpressure added to the injection line 12, which was located above the decompression zone of the screw.

For Mixtures H through K, however, acrylic acid and peroxide were fed into a standard extruder with the reaction zone filled with polymer and considerable pressure the melt was present against the injection line. the Other conditions under which the graft copolymerizations were carried out are listed in Tables I and II below refer to.

209843/0762

Table I »
(without pressure )

Product · A B C D. E

Cylinder temperatures, ° C 217-254 27I-254 271-254 271-254 • 271-254 271-254 271-254 Loading zone I5I-204 160-204 I5I-204 151-204 146-204 151-204 151-204 Reactor zone. 252-204 252-204 252-204 252-204 252-204 252-204 ' 252-204 N> Dosing zone 41.7 40.8 43.1 44.9 '43.1 ^ 40.8 40.8 O
CO Output kg / hour I6O 16Ö 160 160 160 160 160 co
4 >> Screw speed, rpm 15th 15- 15 ■ 50-55 15th 15th co g peroxide / 1,000 g acrylic acid 3.26 6.22 6.46 6.50 6.35 " -8.9 9.92 CD amount of acrylic acid injected,
Wt .-? S 2.66 5.85 5.58 5.29 6.05 -7.5 8.60 ^v Total amount of acrylic acid im
Prod.,% By weight 81 94 86 84 95 87 fo acrylic acid conversion 0. • 0 0 0 0 0 0 Melt pressure against Injek
management, at

Table lit
(with full pressure)

Product _H__ __I_ _J_ "-JL

Cylinder temperatures, C

Loading zone 271-254 271-254 27I-254 271-254 ro
CO Reactor zone 149-204 149-204 I49-204 149-210 I. Dosing zone 252-204 252-204 252-204 232-204 Output kg / hour 36.3 41.7 56.5 41.5 Very speed, TJpM 160 160 I6O 160 σ
CD g peroxide / 1,000 g acrylic acid 15th 15th 15th 15th co
GO amount of acrylic acid injected,
Weight-fo 5.84 6.70 7.85 9.96 / 07 Total amount of acrylic acid im
Product, Gev.-fo 5.18 5.82 6.96 • 8.96 CJ)
IO io acrylic acid conversion 85 87 89 90

Melt pressure against injection line, at 150 x-N-400 I50-5OO 300-5OO

Eb has been found that "monomeric at .biinarbeitung of graft in amounts of about 5 percent -.. 3ind $ or less of the total graft polymer relatively high ITrawandlungsgrade be reached for grafting ■ In about 15 to 2οGew .- ^ conversions low" ie they are "from 5o to 8056.

As can be seen from the tables above, the proportion of acrylic acid in the copolymer *! - is related to the amount of oil injected. The total conversion of acrylic acid ¹ into polymer is relatively high under both test approaches.

Example 2

The mixtures obtained according to Example 1 "were examined. The careful dispersion and mixing of the initiator, which causes a noticeable degradation of the polypropylene in the mixtures A to G ″ can be seen from the lower one Increase in shape and the higher melt flow rate.

In contrast, the polypropylene-acrylic acid graft copolymers show H to K increases in shape which are either equal to or higher than the increase in shape of the basic Pblypropylen-GrundiBaterials, they suffered very little molecular weight loss. It can be seen from this that there is no noticeable degradation in mixtures H to K during the grafting of the acrylic acid.

The increase in the melt flow rate of the grafted Copolymers A through G compared to melt flow rate of the base resin, you can see, that a noticeable Degradation has occurred, in contrast to the small increase in melt flow rates for the grafted copolymers H to K-.

The experimental data for -fcorm increase and melt flow- speed are summarized in Tables III and IV below (the acrylic acid content has been reduced to the closest Whole number rounded up or down):

209843/0762

Table hit

ro ο co

product

MFR

Weight ^ acrylic acid, approximate shape increase at 204 ° C

13.5 sec

γ - 33.8 sec y »67.7 sec

-1 -1

-1

7 - 135.3 sec Ύ - 338.3 sec

-1

-1

Basic material

0.4

0 '

1.67 1.76

1.85 1.94

2.53

6.5 11.2 10.6 10.2 49.7 11.4 13.3 5 6 6 6 6 9 9

1.35 1.35 1.35 1.42 1.50 1.35 1.20 1.35 1.35 1.35 1.42 1.50 1.35 1.27 1.42 1.35 1.35 1.42 1.50 1.35 1.42 1.50 1.42 1.35 1.42 1.50 1.50 1.42 1.67 1.76 1.59 1.59 1.85

Table IYt

product

MFR weight per acrylic acid, approx.

Shape increase at 204 C Ύ = 13.5 sec " ¹ T- 35.8 sec 'Y- 67.7 sec

-1

-1

T = 135.3 sec

-1

338.3 sec '

-1

0.9
6th

0.8 6

_K

1.7 9

1.67 1.67 1.67 1.76 1.76 1.85 1.85 1.94 1.94 1.94 1.94 2.22 2.22 2.32 2.32 2.75 2.53 2.64 2.75 3.32

■ - 33 - \;

Example 3

For oars division, the effect of fillers, in particular Chrysotile aabest and glass fibers, became polypropylene-aerylic acid graft copolymer E according to Example 1 with non-j-ottii'isiertem Polypropylene homopolyiner, which is a SehmelssiTie ^ eschwindi ^ speed of about 5 ", compared. The mechanical characteristics of the graft copolymers compliant with the certification are essentially grounded more improved than the Jiagenschai'ten of a filler-containing, non-modified polypropylene homopolymers. The results of the experiment are summarized in the sections V and VI. .

2088A3 / 07Ö2

Table V;

Izod notch Izod impact strength, secant tensile strength, heat deformation toughness cm.kg/cm (ft.l "w / in. 5» 4) Flexibility, ₂ mungstempera-

module kg / cm door Ta. "

¹⁸ 5 ke / om

18.5 kg / οία, C sample 22.2 ⁰ C 22.2 ⁰ C -17.8 C -28.9 CM kg / cm

Polypropylene +
25 fo chryotile asbestos 3.24 49.68 25.38 24.30 24.0 416 78.4

$ 6 polypropylene

_o aoryl acid grafted,

C ₀ + $ 25> Chrysotile-As-

CD best 2.75 55.62 31.86 30.78 28.8 492 88.0

-c- 1

^CJ polypropylene + 35 Ί ⁰ v>

^ Chrysotile Asbestos 3.83 38.88 23.76 23.22 29.6 422 96.0 ^

c ^ 1

_o Polypropylene with 6 fo

rsj acrylic acid grafted,
+ 35 i ° chrysotile asbestos 4.05 65.34 37.20 36.72 35.2 580 101.0

IS3 N)

sample

Polypropylene + 50 chrysotile asbestos

Table Vl: 5.4) Secant-
Bending Tensile strength
ability, ₂ Izod Notch
tenacity Izod impact strength,
cm.kg/cm (ft. Ib / in. , 9 ⁰ C module
M kg / cm kg / cm ' 22.2 ⁰ C 22.2 ⁰ C -17.8 ⁰ C -28

2.92

Polypropylene grafted with 6 $ acrylic acid, + 50 io chrysotile asbestos 4.21

Polypropylene + 20 io

Fiberglass (3.2mm) 9.19

Polypropylene ** grafted with 9 $ acrylic acid, + 20 io glass fibers (3.2 mm) 12.42 ⁺

⁺ Application method; ⁺ Mixture G.

24.30 18.36 18.36 39.1

48.06 35.64 33.48 44.3

45.90 '38, 88 37.20 36.2

56.70 45.3 37.20 41.6

447

620
700

820

Heat deformation temperature b. 2 c 18.5 kg / cm,

101.8

114.0 102.4

148.0

Example 4

The process for the preparation of product A according to Example 1 was repeated with the exception that - that instead of Acrylic acid glycidyl acrylate is widely used. liae resulting modified graft copolymers possessed an unusual degree •• ■ aftun ^ on aluminum foil, polyester (> :. ylar) and hylonlolie with back deformation at? p2 ° 0. The results of the experiments are summarized in Table VIl; -. nji: en'- · e:

Table VII

Sample peel strength krj / cm

Aluminum foil T.vlar

Polyiropylene over 0

Polypropylene-g- ^ lycidyl acrylate ii, i6 to the 'J'est to

fixed.

example 5

The general procedure of Example 1 was repeated with the exception that instead of acrylic acid, calinic anhydride has been used / ended. Las maleic anhydride became the polypx-opylene to ^ e ^ and the initiator (dicumyl peroxide UCP or LUPLnSOL 13oL) was added to benzene or xylene directly added to the polymer melt.

read outgoing polypropylene had a flow index of about ο, J3.

The experimental conditions and results are in the following Tabel. VIII listed:

3/076 1

BAD ORiQiNAL

^s product Peroxide-
Solution em. Graft polymers *
initiator Tabel YIII: product Maleins «-
aniijdrid
grafted MFR
(250 ⁰ C) L.
H . Xylene
Xylene 0.16, DCP ■
0.14 PCP *
Time one., -
anhydride
ins ^ es. 0.27
0.28 69
71. N benzene Atm. 0.15 DCP with maleic anhydride. 0.55
0.45 0.25 51 0 benzene air
H ₂ 0.14 DCP 0.27 0 ii, 5 ' ro P. benzene air 0.14 DCP Maleins.-
anhidrid
additive 0 0.25 46 Q. benzene Il 0 1.0
1.0 0.28 0 ' 1.2 ;: - R. benzene H ₂ 0 1.0 0.25 0 1.1 S. benzene air O, O85L 0 0.51 0.24 60 T benzene N ₂ O, O85L 1.0 0.58 0.21 56 CJ 'U benzene V 0.25 x DCP 1.0 0.55 0.42 56.9 ■ V benzene air 0.29 DCP 1.0 0.58 0.55 - • W .Benzene Il O, O85L 1.0 0.09 —— M. 1.0 _- ti 5.0 5.0 5.0.

Table VIII (continued *

Peroxide-
Solution · sm. Atm. initiator *
Maleins.-
anhydride-
additive product Maleins.-
anhydride
grafted MFT
(25O ° C) I. product benzene air O, O44L 1.0 Maleins, -
anhydride
total 0.17 59.0 CD X benzene Il O, O84L 1.0 0.25 0.20 57.4 ¹ Y benzene Il O, O89L 1.0 0.28 0.22 54.8 Z benzene It O, O52L 1.0 0.29 0.17 24.5 AA benzene Il O, O47L 5.0 0.55 0.20 26.2 BB benzene It O, O94L 5.0 0.55 0.29 64.2 CC benzene ti 0.088L 5.0 0.41 0.26 69.8 DD benzene Il O, O44L 5.0 0.40 0.20 55.9 EE benzene H 0.1OL 0 0.55 - 57.9 FP ' benzene Il 0.05OL 0 - - 15.5 GG benzene M. O, O45L 0 - - 17.6 EH benzene Il O, O87L 0 - 55.2 II benzene Il 0, O49L 1.0 - 0.15 55.0 JJ 0.26

As can be seen from the table, one obtains according to the invention a good degree of circulation for the maleic anhydride grafting as well as high melt flow rates.

Example 6 '■' "..-.

The product V was with a; Asbestos filler reinforced and in different hig-enscuaften with analog; reinforced Grund-jolypro: ylen verrliciien, the jüx'results are over Table IK can be seen.

20-9 6 4-3 / 0 70 2

BAD ORiQiNAL

ro ο cd

sample

Izod notch toughness

22.2 ⁰ C

Polypropylene + 35 <fo chrysotile asbestos 3.40

polypropylene grafted with maleic anhydride + 35 io chrysotile asbestos 3.94

Table IX:

Izod impact strength, secant tensile strength om.kg/cm (ft. Lb / in. 5.4) flexibility, ₂

module kg / cm

22.2 ⁰ C -17.6 ° C -28.9 ° CM kg / cm ²

40.5 25.92 23.22 24.0 453

59.94 41.04 35.64 26.1 525

V / arm deformation s t temp e rature b. ρ 18.5 kg / cm, c

82.0

83.0

from the table above, one obtains jBäi improved stiffness »SelilagJEäligkeit. and tensile strength, while the heat distribution of (Trunü-Polypropylen ver is equivalent.

uqji vor-atebena applied tew filler or glass fibers _{so that} various internal cracks were obtained.

Bia riaeologigeiie "Mß ^ ßseiiafte" of lroaukten are, in falgeiiien ^ afeeilej k vmü B

? 0 9 ü t * 3/0 7 S 2

Table Δί

predominantly ethylene-containing polymers

Melt index MI

Reduction of the II - increase

at the start

0.05-50

1-10

0.05-100 0.05,1000

0.05-250

1-10

»Ind. 0 -0.05 * preferred, 0> 0.1, "especially Tj preferred 0 - 0.15 ·

aind. 0-0.05 »yorzwgsw. 0-0.1, ■ fees, preferably 0-0.15

0-0,0.5, predominantly, 0-0.1, especially preferred 0-0.15 0-20,000, preferably 0-XQOO, bes »preferably 0-500

0-20 000, vorzttgsw. 0-1000, especially preferred 0-500

0-20 000, preferred, Q-IQOO, especially preferred Q -. 500

Table B:

predominantly C 1 - to C _fl -containing polymers.

at the start

MFR

a. End of diminution in shape gain

MFR increase

0.3-0.9 3-1000, preferably 3-300, especially preferred 3-200

0.91-5.0 5-1000, preferably 5-300, especially preferably 5-200

5.01-10 15.5-1000, preferably 20-300, especially preferably 25-250

10.1 - 150 15 - 1000, preferably 20-300, especially preferably 25-250 at least 0.05, preferably 0.10, especially preferably 0.15

at least 0.05, preferably 0.10, especially preferably 0.15

at least 0.05, preferably 0.10, especially preferred 0.15

at least 0.05, preferably 0.10, especially preferably 0.15

at least 1000, preferably 1500, especially preferably 2000

at least 500, preferably 7OO, especially preferably 9OO

At least 300, preferably 400, especially preferably 750.

at least 50, preferably 100, especially preferred

Claims (1)

Claims (a) Introduction of the polymer in an extruder with movable A displacement screw with a different core cross-section that delimits a reaction zone, ("b) induction of positive pressure in the extruder during Passage of the polymer, (c) application of heat in addition to mechanical processing to convert the polymer into liquid form, (d) Transporting the liquid polymer into a reaction zone iniiex'halb the extruder, in which the polymer volume adjusted so that it is smaller than the volume of the Kealctionezone, creating a reduced pressure in this zone arises, (e) Introduction of reduced pressure in this zone in which the polymer is essentially liquid, one of the following materials (1) a reactive compound or compounds, (2) a monomer or monomers, (3) a free radical initiator, or (4) a combination of the above components in order to be measurable Change in theological and / or chemical properties 209843 / 07S2 Shafts of the polymer in sufficient quantity, and (f) Transporting the resulting modified polymer through the rest of the extrusion process. 2. A method for codifying the theological or ¹ chemical and theological properties of a polymer usually fesstöh at room temperature, characterized by the atufenί (a) Linfünruth d @ g polymers in an extruder with movable displacer & ehiieeke different core cross sections,. the one i - .. eakti © n§iä6iie limits _t (b) Generating an overpressure in the extruder during Passage of the polymer, (c) Use of Iiitgf in addition to the mechanical processing ^ to transfer the i'olylflejL 'ifi liquid i'örm s5ü _t (d) l'ränsiJört of flüsgigen polymers by a Änfangsteil the Reäktiöns2ö: fte _t Weichöm in it under high shear forces transferred into a relatively thin liquid film, (e) Introduction of iii this initial part of the reaction zone, in which the polymer under high shear forces in the form of a thin j ^ ilras is one of the following materials (1) a reactive compound or reactive Links, (2) a homomer or monomers, (35) a free radical initiator or (4) a combination of the above components, in for-measurable Change in the rheological uiad / or chemical rligen- üc? iaften sufficient-henge, and 209 34 3/0782 g "" MN ". (f) Transport of the resulting modified polymer through the remainder of the extrusion process. 5. Method according to claim Z, characterized in that the cross section of the iichneck kernel is relatively large in the initial part of the reaction tones. 4. The method according to claim 1 or 2, characterized in that the polymer is a C ₂ - Ms Cg-olefin polymer. 5. The method according to claim 1 or 2, characterized in that, that the polymer is a thermoplastic polymer. 6. The method according to claim 1 or: 2, characterized in that that the polymer is high or low density polyethylene, 7. The method according to claim 1 öier 2, characterized in that that the polymer is polypropylene * 8. The method according to claim 1 or 2, characterized in that the polymer polymethylpentene, isotactic polypropylene, Polyallomerfe, polybutylene or mixtures thereof are used . 9. The method according to claim 1 or 2, characterized in that that the polymer is an elastomer. 10. The method according to claim 8 _f, characterized in that the elastomer is an ethylene-propylene copolymer or an ethylene-propylene-Uien terpolymer. 11. The method according to claim 1 or 2, characterized in that that the monomer is unsaturated and as functional groups Contains carboxyl groups or derivatives thereof. 2098 43/0762 12. The method according to claim 1 or 2, characterized in that that acrylic acid or a derivative thereof is used as a monomer. 15. The method according to claim 1 or 2, characterized in that the monomer haleinäureanhydi'id or a! Derivative. '
of which used. 14. The method according to claim 1 or 2, characterized in that that glycidyl acrylate is used as the monomer. 15. The method according to claim 11, characterized in that
the resulting modified polymer then through
further reactions in i'orin the esterification, i.'neutralization, amide formation or imide formation is modified. 16. The method according to claim 1 or 2, characterized in that that the free radical initiator in the absence of is introduced by free radical reacting monomers. 17. The method according to claim 1 or 2, characterized in that that the free radical initiator in the presence of is introduced by free radical reacting monomers. 18. The method according to claim 1 or 2, characterized in that the entrance part of the iieakt ions zone under a relative
low pressure. 19. The method according to claim 1 or 2, characterized in that last polymer from a mixture of a thermoplastic
and an! elastomer. 20. The method according to claim 1 or 2, characterized in that that the polymer is an ethylene-containing polymer. 2OS 8 U / Ο? «-.MDOFWlNAL Hi 2216716 21. Graft polymer from a basic polymer with o, o2 to 2o.-Ev /.- 'C graft component, with a melt index or an ochmels flow rate of 1 to 1ooo, which is at least 25y-> higher than that of the base polymer, and a ± Ornz.unahune, which is at least a 0.05 units lower than never an increase in the basic polypi'ir. 22. Polymer according to claim 21, characterized in that the base polymer is a Ο., - to C ₁ -Pqlyo efin and the grafted y IO ' Proportion of the polymer p.ich is derived from an unsaturated carboxylic acid or a derivative thereof. 23. Polymer according to claim 21 or 22, characterized in that the base polymer is plastic » 24. Polymer according to claim 21, characterized in that the base polymer is elastomeric. 25. Polymer according to claim 21, characterized in that the base polymer is a mixture of> Jlastoiaeren and plastics. 26. Polymer according to one of claims 22 to 24, characterized characterized in that the unsaturated carboxylic acid present is acrylic acid or a derivative thereof. 27. Polymer according to one of claims 22 to 24 _f, characterized in that maleic anhydride or glycidyl acrylate is present as the unsaturated carboxylic acid derivative. 28. Polymer according to claim 21 or 23 to 26, characterized in that that the base polymer is an ethylene-containing polymer. ? τ » \ * P; L ? / O 7 f , - ■ BAD ORiSINAL train? % reWtiteung des? e, procedure according to, claim t _t duroh £: s »i Kitt el-» % 4st i-xt ^^ i ^ rschBeelct. with e _; ine.m germ -tai «y ^ wit 4et iit at Yerbie & uBg manufactures Outside 'and " Middle" pit iron, S. teg ^ Uefe iffi. S5yltn4ep sng ^^ riaet is » so they 4at material. (o) a ^ a thin pölym ^ ifiliii ¥ €> ^ iegt ^ MeIe ^, © ick in the zone dea ^ yli ^ de? ^ befi ^ d ^ t «mcl © iaeii, Aniaiigsabsehni v / ei at, the · d. \ * rq: h one; making a thin film 3 corner core of "enlarged cross-section, is limited, by which the material is sheared between Z, ylinderv / and and clßia snail segment is taken, and 2 C 3 8 4 3 ·. i. ' 7 S 2 ". (d) an opening that establishes a connection between this initial section of the -. eaktioitslcanimer and aera exterior of the 51. Reactor according to claim 29 or 2o, characterized in that the reaction karaner has a '.ondabsehnitt, dex * durefc a © cross-sectional area of the screw core be _; renst will, aie only we, ni _f ·; The inner section of the Aylinean is smaller, so that gaseous materials evolved in the Kanazier are indexed on the main bus of the chamber. 32 «reactor according to claim> o, characterized in that the Hittel sur Manufactuiif: the d "Unnen film from one fty'lintier- or cone ©; meRt consists Riit expelling urid Access end in longitudinal orientation within aes Cylinder, creating a liquid between the i.xtruder cylinder and the segment under 1 is seized, the t (1) has measuring grooves on the surface of the access end * the one dead before the expulsion end (2) aa ejector end on the surface has ejector rolls that end dead before the entrance end, and (3) Film careers within the kille that is the inner wall des Extruder2ylinde; r weight touch « hsso ri.esearch and j.iiPineering Company Linden, N.J., Dr. ILJi WoJH (■ lawyer) BAD ORIQiNAL