DE1814073A1 - Polymer mixtures, processes for their production and their use - Google Patents

Description

PATENT LAWYERS

Dr. D. Thomsen

Dipl.-Chem.

H. Tiedtke

Dipl.-Ing.

G. Bühling

Dipl.-Chem.

18U073

8000 MUNICH 2

VAL 33

TELEPHONE 0811/226894

TELEGRAM ADDRESS: THOPATENT

Munich ü December 19C8 case Q. 2o 711 / T 2925

Imperial Chemical Industries Limited London / Great Britain

Polymer mixtures, processes for their production and their use

The invention relates to mixtures containing polyethylene terephthalate, which are improved into molded articles Impact strength can be processed.

Polyethylene terephthalate of sufficiently high molecular weight is a high-melting, easily crystallizable one Polymer that has found wide use as a film and fiber-forming material. His success in these applications is based at least in part on the substantial improvement physical properties by stretching

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18U073

of the film and the Pasern can be obtained, whereby the polymer in oriented crystallized form is more advantageous Morphology preserved. Vienn it by melt molding is processed into articles with one or more sections of such a strength that they hardly against However, the polymer is in amopheric form or metastable with respect to temperature unoriented crystalline form of. generally unsatisfactory Morphology, which is expressed in low impact strength.

A mixture according to the invention has now been developed, which can be processed into shaped objects with improved impact strength.

According to the invention, the mixture contains

(1) polyethylene terephthalate,

(2) a rubber material containing at least one amorphous or weakly crystalline synthetic polymer or mixed polymer of high molecular weight, that essentially to form a separate phase dispersed therein in polyethylene terephthalate is insoluble and that a glass chew

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schuk transition temperature below O ⁰ C and a dynamic shear modulus of not greater than 5 χ lo ^

ρ
dyn / cm and

(3) at least one polyfunctional compound, including a compound is to be understood with at least two groups, -OH and / or -COOH, under the Conditions of the melt molding process, (or those under the conditions of the melt molding process can be dissociated to such a connection),

and wherein (2) 1 to 5oSi of the total weight of (1), (2) and

(3) forms.

The mixture can be processed into a molded article by melt molding, and the desired shape To obtain advantage, it is necessary that the preparation of the mixture and its processing aim at the molded article can be carried out so that the rubber material is finely dispersed in the molded articles thus obtained separate particles is present.

Melt molding is a molding of the mixture in which it is e.g. pressed into a mold or through a molding (e.g. an extruder) at a temperature

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above the melting point of the polyalkylene terephthalate s guided and then cooled below the melting point or allowed to cool while it is with the shaping Surface, or with the shaping surfaces in Touch stands. Examples of such melt forming processes are extrusion, melt casting, and compression molding However, injection molding is by far the most preferred method.

In the melt-molded products obtained from these mixtures, groups, each containing two or more individual polyethylene terephthalate chains, have been linked to one another by molecules of the polyfunctional compound to form chain-extended ethylene terephthalate polymers, which are understood to mean a polymer having macromolecular units, each of at least two polymer chains are formed, each consisting essentially of repeating ethylene terephthalate units (ie at least 90 # of the units forming the polymer chain have the structure -OCH ₂ CH ₂ OCOArCO-, where Ar is a p-phenylene group), and each chain has a different chain linked by a chemically distinct entity derived from the polyfunctional compound. The molded article therefore contains a base material of extended chain ethylene terephthalate polymers having rubber material particles finely dispersed therein.

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The expression polyethylene terephthalate, as it is used with respect to the mixtures according to the invention, is not only to be understood as the homopolymer of ethylene glycol and terephthalic acid, but also mixed polymers in which z.3. some of the ethylene glycol residues have been replaced by other diol residues, for example diethylene glycol, and / or some of the tereph- | thal acid residues are replaced by other dicarboxylic acid, such as isophthalic acid, provided that _t the Äthylenterephthalatreste form at least 9o # mole of the polymer chain. However, it is generally preferred to use the homopolymer.

It is preferred that the polyethylene terephthalate used in the mixtures according to the invention have a molecular weight, corresponding to an intrinsic molar viscosity, as defined below, of at least ^ o ml / g (0.21 decilitre / gram), measured in o -Chlorophenol at 25 ⁰ C, and in particular of at least 6o ml / g (0.6 decilitre / gram), in order to form shaped articles of desired physical properties. On the other hand, very high molecular weight polyethylene terephthalate can prove difficult to mold because of its very high melt viscosity.

The fundamental molar viscosity is understood to mean the value, 9098 30 / U 33

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that by plotting values of the fraction

t - t_

where t is the flow time of a "c" g per 100 ml of solution of the polymer in a given solvent using a standard viscometer and t is the flow through time of the same volume of pure solvent through the same viscometer under the same conditions, against the concentration c for different c values and F.xtrapolieron the curve obtained versus zero concentration. All fourth fundamental molars given below Viscosity are based on measurements of solutions of the polymer in o-chlorophenol at 25 °. The above specified Breakage is sometimes referred to as the reduced viscosity of a given concentration of solution.

In order to be suitable as the rubber material for use in accordance with the invention, the synthetic polymer must or high molecular weight interpolymers as follows Meet requirements.

(1) It must be amorphous or at most only weakly crystalline, which means that there is no more than one

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shows weak crystallinity on X-ray examination. That is, the crystallinity pattern consists, if any, of a series of diffuse bands.

(2) It must have a glass-rubber transition ^{temperature below 0} ° C. as measured by differential thermal analysis at a rate of temperature change of 5 ° or less per minute.

(3) It needs to have a dynamic shear modulus of not larger than 5 χ Io dynes / cm. The dynamic shear modulus is at 20 ° C measured by the torsion pendulum method using a frequency of about 1 rotation per second.

(4) It must be substantially insoluble in polyalkylene terephthalate to form a separate dispersed phase therein. In general it can be said that if the calculated Solubility parameter of the interpolymer of the denirpi of Polyethylene terephthalate differs by more than 0.2, is essentially insoluble therein. The solubility parameter is calculated by the Small method, as described in the Journal of Applied Chemistry, Volume 3, 1953, pages 71 to 8o is.

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The mixed polymer must of course also be able to the temperature at which molding is carried out without decomposition to withstand to such an extent that the molded products are rendered worthless. If necessary, it can be in branched and / or networked to the extent necessary to prevent it severe deformation of the rubber particles during the preparation of the mixture is sufficient.

The rubber material preferably has in or on its macromolecular chains groups which correspond to the polyfunctional Compound can react under melt molding process conditions, in which case at least some of the particles of the phase dispersed in the articles produced in this way on the ethylene terephthalate polymer base material. with an extended chain are graft-polymerized by means of molecules of the polyfunctional) compound and the shaped ones obtained in this way Articles generally show particularly useful improvements in impact strength. Such grafting can through exhaustive extraction of a sample of the molded article in o-chlorophenol can be determined. If the presence of polyethylene terephthalate in the residue by IR investigation can be determined, then a grafting has taken place. Extraction is closed under exhaustive extraction Understand until no further weight reduction of the residue occurs.

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It has been found, however, that toughness improvements are desirable can even be obtained where the rubber material with the polyfunctional compound or cannot react with the polyfunctional compounds in the mixture.

Examples of groups that may be reactive with the polyfunctional compound are hydroxyl and OH groups of carboxylic acids, both primary and secondary amino groups, thiol groups, anhydride groups, and epoxy groups. Synthetic rubber materials with OK groups on the macromolecular chains, e.g. in hydrolyzed ethylene-vinyl acetate copolymers, are preferred, but because of the ease with which they can be prepared and their ready reactivity with isocyanates, the preferred polyfunctional ones are compared Compounds are particularly preferred to use rubber copolymers of ethylene and as at least one of the mixed monomers polymerized therewith a hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid, in particular acrylic acid or methacrylic acid. Appropri.gerv. ^r else obtained oxide 2-hydroxyalkyl esters of these acids, by reaction thereof with ethylene oxide or higher alkylene l. The product of ethylene oxide is 2-hydroxyethyl ester; are the products of a higher oxide with the formula Ch ₂ - CHR., in which FL is an alkyl group

9 0 9 8 3 0/1: ';

18H073

one or both of the compounds with the formulas

? OiI

Hp = CH-COOCHp-CH C

and

CH ₂ = CH-COOCK-Ch ₂ OH K

where R is Π (in acrylic acid) or CK, (in methacrylic acid). So is ::. B. insane Case of the reaction of propylene oxide the product either the 2-hydroxy-n-propyl ester or the hydroxyisopropyl ester or their mixture.

Examples of such copolymers are those of ethylene with 2-hydroxyethyl methacrylate (obtained e.g. from the reaction of ethylene oxide and methacrylic acid), of ethylene with one or more suitable hydroxypropyl methacrylates (obtained by reacting propylene oxide and methacrylic acid) and ethylene with methyl methacrylate and one or more of the Hydroxypropyl methacrylates.

Examples of other usable synthetic rubber materials can in particular under polyisobutylene and irregular copolymers of ethylene with propylene or advises Propylene with a non-conjugated diene or with an or

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several esters of acrylic acid and / or methacrylic acid with e.g. alcohols containing up to 8 carbon atoms and / or ir.it one or more vinyl alkane costs, e.g. under Mixed polymers of ethylene with methyl methacrylate, ethyl acrylate, n-3-butyl acrylate, 2-ethylhexyl acrylate and / or vinyl acetate found v / earth.

The amount of rubber material used in the blend is generally from 1 to 5o wt -.% Of the sum of the .Kengen of polyethylene terephthalate, of the polyfunctional compound and of the rubber material. Little or no benefit is obtained with amounts below 1% , however, with amounts greater than about 50%, an inversion of the phases can occur with a tendency to disperse the ethylene terephthalate polymer into a rubber base and noticeably reduce the modulus of the molded articles In general, it is preferred to use 5 to 35J5, and especially 5 to 15Js, such amounts providing the optimum balance of toughness and modulus in the molded articles.

The polyfunctional one found in the mixtures according to the invention Connection is characterized by the fact that it

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a compound with one or more functional components is or is thermally or in some other way dissociable in such a compound, so that it is with at least two Groups each of which is either -OK or -COOH. Examples of such functional components are carboxylic acid groups, Anhydride groups of carboxylic acids, acid halo-P-genides, z: B. Acid chloride and acid bromide groups, epoxy groups and isocyanate groups.

. Preferred examples of usable polyfunctional compounds are polycarboxylic acid anhydrides, polyepoxides, Polyisocanate and compounds that are thermally or otherwise 'i'. 'also under the conditions of the formation process for polyisocyanates are dissociable, which are hereinafter referred to as polyisocyanate producers. Under-the-expressions poly carboxylic acid anhydrides, Polyepoxides and polyisocyanates are organic "see compounds to be understood that contain two or more carboxylic acid anhydride (CO-O-OC-), epoxy or. Contain isocyanate groups.

It is preferred to use such polyfunctional compounds that are not used at the processing temperatures are highly volatile, and it is particularly preferred to use those that have a minimum of by-product formation react. Particular examples of the latter group are those compounds with isocyanate-epoxy and / or anhydride groups

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pen as functional components and uretidione dimers and higher molecular weight uretidione oligomers of polyisocyanates.

The use of polycarboxylic acid anhydrides, e.g.

of tetra- or higher-functional carboxylic acids, is |

notable where it is particularly desirable to avoid discoloration of the molded articles. Examples of the preferred aromatic compounds are liromellitic dianhydride, naphthalenetetracarboxylic dianhydrides,. for example the 1,1,5,8-isomer, the 2,3,6,7-isomer and the 1,2,5,6-isomer, mellitic acid trianhydride, perylene-3, ^ , 9 » lo-tetracarboxylic acid dianhydride and dianhydrides the formula

where Y is a direct bond, -0-, -SO ₂ -, -CO- or divalent hydrocarbon radical, such as -Clip- or -CCCK,) ^ -, for example 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and be 2,2'j 3,3'-isomer, bis (3, ^ ~ dicarboxyphenyl) alkane dianhydrides, v / i ο the dianhydrides of 2,2-bis (3, ⁱ } -dicarboxyphenyl) propane, bis (3, ⁱ l -dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxy-

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Jit

phenyl) ether dianhydride and benzophenone-3,3 ', 4, V-tert-tetracarboxylic dianhydride. Ethylenetetracarboxylic dianhydride can also be listed. By far the preferred polyanhydride is pyromellitic dianhydride.

The polyfunctional compound preferably contains Groups that can react with both -OH and -COOH groups. In this class are polyisocyanates and Polyisocyanate producers especially noteworthy as they are not only with both -OH and -COOH groups under Bildunc of urethane or amide bonds react (or compounds with such a reactivity when heated deliver), but also react with the bonds formed in this way, e.g. to form acylurea and allophanate members can. Much greater improvements in physical properties can be achieved by using '' of these compounds than by using the others above cited polyfunctional compounds are obtained.

Examples of diisocyanafcen are

(A) Polymethylene diisocyanates, for example those with the formula OCN (CK ₂ ) _n NCO, where η is a positive integer, for example from 4 to 2o, where tetramethylene diisocyanate, kexamethylene diisocyanate, dodecamethylene diisocyanate and eicosane-l, 2o-

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18U073 β -

diisocyanate examples are

(b) Derivatives of these compounds in which one or more of the hydrogen atoms of the ethylene groups have been replaced by monovalent hydrocarbon groups, for example 4-butylhexamethylene diisocyanate or 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanates, the like

(c) Derivatives of (a) or (b) in which one or more of non-adjacent methylene groups have been replaced by -O-, -S- or -NR-, where R is hydrogen or a monovalent hydrogen radical, e.g. OCN (CK ₃ ) _£ 0 (CHg) ₂ NCO,

--- = (d) mononuclear and condensed polynuclear diisocyanates, e.g. toluene-2, ⁱ l-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, S-iso'cyanatomethyl ^ 'jS ^ -trimethylcyclohexyl isocyanate and naphthalene diisocyanate,

(e) SuIfony! diisocyanate, f

(f) silicon and phosphorus diisocyanates and in particular

(g) Diisocyanates having the formula OCN-Ar-X-Ar-NCO, wherein each Ar group is a divalent, preferably mononuclear, aromatic The nucleus is in which one or more hydrogen atoms are replaced by inert monovalent groups, for example alkyl, alkoxy or halogen groups, and X is a direct one, if desired Bond or a divalent atom or a zx ^ monovalent group

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pe is, for example -0-, -S-, -SO ,, -, -SO-, NR ¹ - (where R 'is a monovalent hydrocarbon group) -CO- and divalent hydrocarbon groups such as the alkylene group. Examples of (g) are the 3,3'-, 4,4'- and 3,4'-diisocyanates of diphenyl-- "'methane, 2,2-diphenylpro'pane and diphenyl ether, 3,3'-dimethyl - '^ ■ 4, ^' - diisocyanatodiphenyl. And ^^ 'rDimethoxy-iljA'-diisocyanatodiphenyl.4,4'-Diisocyanatodiphenylinethane gives good results and is readily available.

. Where it is desired to use a diisocyanate and the color of the product is important, it has been found advantageous to use compounds which are essentially non-volatile under the reaction conditions and in which the isocyanate groups are linked to non-aromatic carbon atoms, For example, in the case of k _t H '-diisocyanatodicyclo- w hexylmethane isomers and mixtures thereof, 2,5-dimethyl-p-xylene diisocyanate, 1, * l * -di (2-isocyanatoä ¹ thy 1) -2,5-dimethy! benzene and tetramethyl -p-xylylene diisocyanate. When used, however, the mixtures generally require somewhat longer residence times in the melt during the molding process than is the case with aromatic diisocyanates, except when a catalyst is added.

Examples of diisocyanate producers are as follows Diisocyanate derivatives: Epolymerurethanes, Uretidiörididere and higher

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1814-73

Oligomers, cyanurate polymers, urethanes and polymer urethanes of cyanurate polymers and thermally dissociable Schiffsche Dasen adducts. Particularly preferred examples are uretidione dimers and higher ligomers, e.g. the uretidione dimer and higher Oligomers of diisocyanates of the (g) -type and in particular of * J, 4 '-diisocyanatodiphenylmethane.

The amount of the polyfunctional compound _which} of the invention is suitable for incorporation into the mixtures according depends in part on its nature. Where it can only react with -OH and / or -COOH groups, the maximum improvement in properties is generally achieved when just enough polyfunctional compound is present to react with all of these groups, amounts above and below this amount usually 'lead to a reduction in the benefit obtained. If the polyfunctional compound, on the other hand, can react not only with -COOH and -OH groups, but also with the products of these reactions, for example in the case of polyisocyanates and their derivatives, proportions can be considerable Excess over the stoichiometric amount, based on the number of groups in the original mixture which react with isocyanate groups, can advantageously be contained in the mixtures. The amount to be used is also a puncture of the relationship between the intrinsic viscosity of the polyethylene terephthalate ~

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Al '' * '

lats in the mixture to be formed and the desired basal molar Viscosity of the ethylene terephthalate polymer base stock with an extended chain in the objects formed from the mixture. In general it is all the more. polyfunctional compound required, the higher the intrinsic viscosity which is required in the base material of an article molded from polyethylene terephthalate having a specific intrinsic viscosity. Also, it is all the more polyfunctional to produce a given increase in intrinsic molecular viscosity Connection required, the lower the intrinsic molar viscosity of the polyethylene terephthalate.

In the preferred Pallj where the rubber material with the polyfunctional compound can react, the mixture can advantageously contain an excess of polyfunctional compound take up more than the amount necessary to react with the polyethylene terephthalate is desirable.

The specific amounts of polyfunctional compound required in an individual case can be determined by simple examination, but in general, 0.05 to Io Cevj.-S of a mixture of polymer, rubber material and polyfunctional compound have been found to be sufficient for most cases , with the use of about

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- isu-

o is 5 preferably up to 5 £.

The mixtures according to the invention can by any üblixsliea Kischarbeitsweise, but preferably through Melting a mixture of polyethylene terephthalate, rubber material and polyfunctional connection and by submission the mixture produced a mechanical kisch effect e.g. in an extruder, in the screw of an injection molding device with screw conveyor or in a Mill.

Alternatively, e.g. the components of the mixture in be dissolved in a suitable solvent such as diphenyl ether , Nitrobenzene or tetrahydrothiophene-l, l-dioxide, the solutions can be mixed and either the solvent, e.g. by evaporation, removed or the mixture is precipitated, e.g. by breaking the solution into all of its components non-solvent is poured.

The components of the mixture can be used in one simple operation or, if desired, in two or more separate ones Operations are mixed. E.g. the polyethylene terephthalate, the polyfunctional compound and the rubber material are mixed together, for example in an extruder or in the screw of an injection molding machine

909830/1433

1 | 14QI3

- 4α »-

with screw feed. However, it can produce improved results be obtained when the polyethylene terephthalate and the Rubber material must be melt blended before the polyfunctional compound is added. For example, the polyethylene terephthalate and the rubber material are slipped together in an extruder, and then the polyfunctional connection with the resulting extrudate are melt mixed, for example in a further extrusion, if desired in an injection molding device can be effected with a screw feed. In another alternative, the polyethylene terephthalate can be mixed with rubber material mixed in excess of the amount desired in the finished mixture, e.g. in a Schneeken extruder, and can then be mixed with further polyethyleneterephthalate. thalate and polyfunctional compound are mixed, e.g. in a further extrusion, if desired in the screw of an injection molding device with screw feed - can be activated. Other ways of forming the mixtures are familiar to the person skilled in the art, ·,. . .:

The blends can be fabricated into shaped articles by any suitable melt molding process provided that the chewing material in the resulting molded article is separate in the base material of the chain-extended EthyleriVerephthalate Polyncren finely dis-

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j τψιικψ "-je ,, j

pergated particle is found. The required dispersion can be achieved during the formation of the mixture or during the cutting process. The making of this Dispersion can be achieved in, for example, the ingredients dissolved in a suitable solvent and again failed v / earth. However, it can be achieved more conveniently by the mixture of polyethylene terephthalate and Rubber material having an appropriate level of shear stress g is subjected '. This can be done at any stage during the formation of ilischungs, z.3. in the snail an extruder. It can alternatively or additionally in the molding device itself, e.g. in the screw of an injection molding device be effected with screw feed or in a screw extruder. The average size of the rubber, particles in the molded article is preferably 10 "microns or more, e.g. 0.5 to 10 microns, as they are very useful Improvements in impact resistance can be obtained. However, if the size is too small, the improvement in '

Impact strength can be reduced. Particle size monitoring can be achieved, for example, by measuring the extent of the mixture applied shear stress is varied, e.g. by changing the mixture viscosity by changing it before Temperature or change in other extrusion conditions.

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Another is the impact resistance improvement obtained according to the invention The overriding factor is the basal molar Viscosity of the chain extended ethylene terephthalate polymer iin molded object. It is preferably at least 50 ml per g (0.5 decilitre gram) and in particular 65 to "85 ml per g (0.65 to 0.85 decilitre gram). The value of the intrinsic molar viscosity depends mainly on the temperatures at which the polyethylene terephthalate is used in the molten state in the presence of "the polyfunctional compound with which it reacts, and the total times it is exposed to these temperatures. In general there is initially a tendency that the intrinsic viscosity of the chain-extended base polymer increases with time, the rate of increase is generally greater at higher temperatures. After an initial period of time, the duration of depends on the amount of polyfunctional compound present and the temperature to which the mixture is subjected, the intrinsic molar viscosity reaches a maximum and then decreases as a result of competing thermal degradation reactions a consequent adverse effect on the physical properties of the product. Generally fall with Increase in temperature, both the time to reach a maximum fundamental molar viscosity and the maximum achievable

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basal polar viscosity from; therefore, it is preferred to avoid using high temperatures or extended residence times in the mixing and molding processes. Temperatures of 255 to 29o ° C. with total residence times of 30 seconds to 15 minutes at these temperatures are preferred.

The change in intrinsic molar viscosity with the time is also due to the concentration of polyfunctional Compound controlled, the increase of which tends to increase the amount of time required to achieve maximum effect However, above the optimal value it can reduce the ir.axiinally achievable extent of the effect.

Ho the rubber material with the polyfunctional compound however, is the effect of varying the manufacturing conditions on the ultimate properties of the molded product is generally less prominent, which allows greater flexibility of operation.

The advantage according to the invention can be achieved both if the base material of the molded article in crystal lized as well as when it is in amorphous form. However in the latter form, the objects generally have a

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fairly low processing temperature maximum, and it is therefore it is generally preferred that the base material be in crystallized state is present. To ensure that the chain-extended polyethylene terephthalate base material present in this preferred form in the molded articles, one or more of the following procedures may be used be applied.

(1) The article can be molded in a mold heated to at least 100 ° C and preferably 12o to 17o ° C. Temperatures above 2oo ° C are avoided preferably ver ^w, when a degradation of the polyethylene terephthalate to be kept to a minimum. The article should be held in the mold for a sufficient time to allow crystallization; Times from a few seconds up to 2 to 3 minutes are generally adequate.

(2) Alternatively or in addition, the molded article may be subjected to a heat treatment after molding. Temperatures of about 120 ° to about 200 ° C. are suitable and times of up to about 40 minutes are usually adequate.

(3) The mixture can be as little as possible, e.g. not

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more than lo ° C, above the melting point of polyethylene terephthalate during the formation process, e.g. in the tube of the extruder or the injection molding machine.

Before shaping, a lceimbildendes agent added to the mixture for crystallization acceleration to λ thereby reducing the required residence time in the hot mold, or required for the heat treatment period of time. It has been found particularly desirable to include a nucleating agent in cases where a hot mold is used. The type and amount of nucleating agent required to be effective depends to some extent on the nature of the catalyst residues in the polyethylene terephthalate. If the polymer used contains a sufficient concentration of insoluble catalyst residues, no further nucleation need be necessary. On the other hand, if the catalyst residues are soluble in the polymer, it will generally be desirable to add a nucleating agent. The nucleating agent is preferably a very finely divided inorganic material. It has been found that talc and pyrophyllite are particularly effective and can even increase the nucleating effect of insoluble catalyst residues. Concentrations of about o, ol to about 2% are usually appropriate, with the particle size

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size preferably as fine as it is, e.g. 2 microns or less measures.

The nucleating agent can be used during the formation of the Polyethylene terephthalate or at any later stage.

All components of the Itonsungsnischuns are preferably due to the known harmful VTirkunc ^v on moisture molten polyethylene terephthalate as dry as possible. The mixture is also kept as dry as possible and it is preferred to take steps to exclude moisture during the molding process.

To forming mixtures can contain, in addition to the _t content of the polyethylene terephthalate of the polyfunctional compound, the rubber material and possibly a = nucleating agent also "£, ewünschtenfalls further constituents, such as heat and light stabilizers, lubricants, dyes, pigments, means for detaching from the Shape and fillers, such as finely powdered metals, finely powdered ketal oxides, graphite, HuS, ground glass and molybdenum disulfide.

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It is particularly preferred to incorporate fibrous reinforcing agents such as asbestos fibers and especially glass fibers. Where glass fibers are incorporated, it is advantageous in view of the physical properties of the molded article to be formed to mix them with the polyethylene terephthalate before the latter is brought into contact with the polyfunctional compound. The parsers are can, for example, 5 to 60 wt -.% To form the mixture, however, be preferred concentrations 2o to ko%. Short fibers are preferred.

Although the preferred use of mixtures according to the invention in their processing is too thick-walled Objects by melt molding, in particular injection molding, lies, they can also if desired to other shaped Objects, e.g. threads or fibers, are processed.

The invention Xi is illustrated by the following example explained, with all amounts and percentages being expressed by weight.

example 1

There were 90 parts of dry polyethylene terephthalate granules 909830/1433

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With an intrinsic molar viscosity of 58 ml per g (ο, 58 dl. g " ¹ ), in a drum with 0.15 parts of talc, 0.8 parts of III-diisocyanatodiphenylmethanuretidionoligomercm and 10 parts of an irregular, weakly crystalline copolymer of ethylene (7o, 2 wt .- 'g) and methyl methacrylate (29.8 Gev;. · -}?). Mixed, which has a melt flow index at 19o ° C of 3.1 (ASTM test Dl 238), a glass rubber -transition temperature of -33 ° C each had a dynamic shear modulus of less than 5 χ lo ^ dyn / cm and a solubility parameter that deviated from that of polyethylene terephthalate by at least 0.2.

The uretidione oligomer used in this and the examples below was prepared as indicated below. ^, ^ '- Diisocyanatodiphenylmethane, which had been distilled under vacuum, was dissolved in dry chlorobenzene and 4-dimethylaminopyridine (0.5% by weight, based on the diisocyanate, was added as a dimerization catalyst. The pale yellow solution was added at room temperature 2 Stirred for hours and left to stand overnight The precipitated oligomer was filtered off, washed with a little dry chlorobenzene and dried ^{at 55 ° C. in a vacuum oven.}

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ISi ", ■■■■ '! M-"

The nit of a drum ground mixture vmrde then passed through a screw extruder having a diameter of 3,2o cm promoted Thus a screw speed of revolutions per minute at a pipe temperature of 26o C and wherein the residence time in the tube about 1 1/2 minutes. The extrudate was quenched in cold water, granulated * and dried in an air oven at 120 ° C overnight.

Part of the extrudate is then mixed with o-chlorophenol extracted to separate the rubber from the ethylene terephthalate polymer which went into solution. It vmrde the basal molar Viscosity of ethylene terephthalate polymer measured; it is given in the table below.

Thereafter the extrudate in a 57 g-Stübbe injection molding apparatus (2 oz) 6 was "ter applied to a tube temperature of 265 ⁰ C un- one on IIIo ⁰ C heated mold and a Ablcühlzeit of 3o seconds to form 51 only" χ mm Rods measuring 3 mm in diameter were injection molded, the residence time in the tube was about 3 minutes. Parts of various molded products were extracted with e-chlorophenol to separate the rubber from the ethylene terephthalate polymer, as described above

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of the polymer is measured, and the average value is in given in the table below.

There were ran the injection molded bars with a notch having a radius of 0.25 ¹ J, a depth of 2.79 min and ¹ I Einein angle of bo °, cut into 3 mm χ 51 mn measured edge provided and the impact strength at 22 ° C using a Hounsfield-Charpy type impact tester. The average result of a number of measurements is shown in the table below.

For comparison purposes, the above was used Procedure repeated using identical conditions and an identical mixture with the exception of that the ethylene-methyl methacrylate copolymer is omitted <■ was. The test results of samples of this mixture are given below.

existing basal molars basal vis Notch impact Ethylene ethyl viscosity kosity of toughness ρ methacrylate of the extru- injection molded (kg cm / cm) Mixed polymer dats in ₁ Product ml / g ml / g (dl.g " ¹ ) (dl.g-1) no 72.6 (Ο.726) 60 (0.60) 2.58 Yes 8o> o (0.800) "84 U", W. 3.63

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ΊΛ -

By comparison, the notched impact strengths of objects obtained with non-modified polyethylene terephthalate having an intrinsic viscosity of 0.60 and 0.84 are about 2.2 and 2.9 kg cm / cm ² .

Example 2

There were 100 parts by weight of polyethylene terephthalate granules with an intrinsic molar viscosity of 58 ml per g (0.58 dl.g) and 200 parts by weight of an irregular, little crystalline copolymer of ethylene (92% by weight) and f-hydroxy methyl methacrylate (8% by weight ) ) with a reduced viscosity of 1.7 (measured on a liquid solution in chloroform at 25 ⁰ C), a glass-rubber transition temperature below ^{0 0} C and a dynamic shear modulus of below 5 χ

0 2 a

Io dyn / cm in a Iddon-screw extruder with a throughput diameter of 3,2o ^ cm mixed at a pipe temperature of 260 ⁰ C and a screw speed of 60 revolutions per minute, the residence time in the tube was about 1 1/2 minutes . Then 225 parts by weight of this extrudate were mixed under similar conditions with a further 775 parts by weight of polyethylene terephthalate granules having an intrinsic viscosity of 58 ml per g (0.58 decilitre gram) to form an extrudate which had a weight of 15% by weight. Mixed polymer, based on

909830/1433

161.4073

Total weight of the extrudate.

The resulting extrudate was quenched in cold water, Granulated and dried over Nactt in an air oven.

There were then introduced portions of the extrudate in a 57 g-Stübbe injection molding apparatus (2 oz), where it with lime (o, 5 weight - the polyethylene terephthalate%, based.) And various proportions vmrden of Diisocyanaturetidionoligomeren used in Example 1 mixed. The mixture was then injection molded at a barrel temperature of 265 ⁰ C using a mold temperature of 17o ° C and a cooling time of 3o seconds to form 51 mm.χ 6 mm χ 3 mm measured rods. The residence time in the tube was about 3 minutes. .

Tests were carried out on the bars to determine the Rubber particle size in the mixtures (by optical microscopic examination), the percentage of crystallinity of the mixtures (using x-ray diffraction measurement), the intrinsic molar viscosities of the ethylene terephthalate polymer in the blends and the notched impact strengths of the rods (un-

609830/1433

- 2fr -

ter facing of, as described in example 1 ^ with notches of samples provided with a radius of 0.254 mm on an impact tester of the Kounsfield-Charpy type). The achievements are compiled in a table below.

Uretidionoli- ■ by Crystalline crund molars ml per g Notch 'gomercs, % _{} re} . cut nity viscosity .G-D impact on d.C-ev ;. one. liche (50 •in tough mixture of ^: Chews (dl speed Polyethylene ' schuk (kg cn / terephthalate ' particulate (o, 52) cm ² ) and rubber Size (u) (o.74) nothing 4th 45 52 (o, 76) 2.1 (1) 1.5 5 46 74 (o.86); • 5.9 2.0 5 41 76 (o.99) 7.1 2.5 H 47.6 86 8.7 2.5 M. 47.6 99 11-, 5 (2)

The mixtures labeled (1) and (2) were exhaustively extracted with cold o-chlorophenol, and the insoluble one Material was examined by IR spectroscopy. Polyethylene terephthalate was discovered in the residue of (2) but not in the rubber phase of (1).

In comparison, the notched impact strengths of

909030/1433

objects made from unmodified polyethylene terephthalate are shaped and have an intrinsic viscosity · corresponding to those have in the table given above, about

2, oj 2.6; 2.6; 3, ο and 3.3 kg cm / cm.

Example 3

It was dry polyethylene terephthalate granulate with a base molar viscosity of 65 ml / g (0.65 dl.g) in a drum with an irregular _? weakly crystalline Kautschukterpolymeren, which had a melt flow index of 1.5 »a glass Xautschuk-übergangsteir.peratur below 0 ⁰ C, and a dynamic shear modulus of less than 5 x lo ^ dyn / cm and ethylene (77 wt .- ^), ß-IIydroxyäthylmethacrylat (Ii; Gew. -%) * and methyl methacrylate (9 Gev; .- ^) contained, mixed to form a mixture containing equal amounts of the two components. This mixture was conveyed through an Iddon screw extruder with a diameter of 3.2o cm at a tube temperature of 250 ° C. and a screw speed of 55 revolutions per minute. The extrudate was granulated and dried over power in a vacuum oven at 1 * Jo ° C.

Thereafter, proportions of the extrudate were among the same Conditions as stated above with dry polyethy- lenterephthalate granules to form 1, 5, 15 and 25% by weight

909830/1433

of the terpolymer-containing mixtures.

These mixtures were combined with the Ge 5o \ i .-% of the terpolymer containing the original mixture with a drum with 2 wt -% ground 4, -4-diisocyanatodiphenylmethane (14DI) and in a 57 g-Stübbevorrichtung (2 oz) at a. tube temperature of 265 ⁰ C using mm on a cooled to 2O ° C to form Fsildung of 51 χ χ 6 mm injection molded 3 mm ä measuring rods. The bars were

1-closing-stündices heating at 1 ^ iO ⁰ C teilv; else crystallized.

It became the ßrundmolar viscosities of the ethylene terephthalate polymers measured in the molded products; they are given below.

The injection molded rods were notched, as described in Example 1, and the * Impact strength on a Hounsfleld-Charpy type impact tester certainly. Average values are given below.

An optical microscopic examination of the molded mixtures for determining the rubber part size carried out. The test results are given below.

809830/1433

18H073

I.
Examine i Terpolyneres, basic chung; Ge \ -: .-% dor 1-are Vis ι mixture kosity of the ge j formed t Product in nl each _r (, 'ι ~ -l)

25 5o

average rubber particles
size (μ)

5o (o, 5o) 48 (o, 48)

Notch

speed
(kg cm /
cm)

23.2
17.8

approximate dwell time in the ■ shaped tube

not

1 76 (ο t 3 4th ,8th C. ■ lin.) Λ 5 77 (ο , 76); 7th , 2 2 B. 15th .. 56 (ο , 77) ' 6th 11th , 7 2 .C .56) 2

+ 'An optical examination showed that a partial Reversal of the rubber phase and the ethylene terephthalate polymer phase had taken place.

Example 4

The procedure of Example 3B is repeated, with however, the residence time in the tube of the injection molding machine was increased to 3 1/2 minutes. The intrinsic viscosity of the ethylene terephthalate polymer in the molded articles had increased to o.97, the average rubber

909830 / U3

particle size was about 3 microns and the impact strength had increased to 8.9 kg cm / cm.

Example 5

There was an equal mixture used in Example 3 \ Gev; maybe portions of the polyethylene terephthalate and the terpolymer prepared as described in this example. As soon as they were dried, portions of the extrudate were ground with a drum with talc, more dry polyethylene terephthalate granules and various amounts of MDI and, as described in Example 3, re-extruded to form fishbones, the 10 wt .- # of the terpolymer, o, 5 # Talk, based on the weight of the polyethylene terephthalate, and 3,5 and Io wt -.% (based on polyethylene terephthalate and A terpolymer) of MDI contained. The residence time of the material in the extruder was about 1 1/2 minutes. .

The extrudates were granulated, dried and placed in a 57 g Stübbe device using a tube temperature of 250 ° C., a mold heated to 140 ° C. and a cooling time of 50 seconds in the mold to form 51 mm. χ 6 ran χ 3 mm measuring rods injection molded. The material in advance

909830 / U33

18U073

Directional tube time spent was about 3 1/2 minutes. The notched impact strengths of the rods, erund moJLars, viscosities of the ethylene terephthalate polymers and the average sizes of the rubber particles of the blends became as above described, determined. The results of these investigations are compiled in a table below.

MDI
(Gew.-SO

intrinsic viscosity of the molded product, ml / g (dl.ß " ¹ )

average rubber particle size

Notched impact strength ₂ . (kg cm / cm)

5
Io

58
86
9o

(o, 53) (o, 86) (o, 9o)

3 to

5
5

5 »oo ■ 5.69

3.83

Example 6

80 parts by weight of that in Example 3 were used dry polyethylene terephthalate granulate mixed with 2q parts by weight of a ^ dried melt-extruded mixture, the same weight share. of the same polyethylene terephthalate and of the ethylene terpolymer used in Example 3,

909830/14 33

Methyl methacrylate and ß-hydroxymethyl methacrylate, and extruded under the conditions described in this example.

The extrudate was dried, granulated and mixed with a drum with 0, ^1, J Ge \ i .-% Mellithsäuretrianhydrid. Ä this mixture was injection molded partially crystalline rods were hergestellt.Die rods in the manner described in Example 3, tested as described above, with the following results were obtained. The intrinsic molar viscosity of the ethylene terephthalate polymer was 50 ml per g (0.50 dl.gf), the average Charpy notched impact strength of the rods was 4.1 kg cm / cm. The average size of the rubber particles dispersed in the articles ranged from 4 to 5 &

Example 7

There were 522 parts by weight of dry polyethylene terephthalate gray lathe an intrinsic molar viscosity of 65 ml per g (0.65 dl.g) with a drum of 478 parts by weight 6.3 mm long Glass fibers mixed and passed through an Iddon screw extruder with a diameter of 3> 2o cm at a tube temperature of

909830/1433

265 ^° C. and a screw speed of 55 revolutions. promoted per minute. The extrudate was comminuted and dried, and portions were mixed in a drum with various amounts of the mixture described in Example 3 of equal parts by weight of polyethylene terephthalate and the terpolymer and 0.5% by weight of both talc and MDI and re-extruded in Iddon extruder at 265 ⁰ C and a screw speed of 55 revolutions per minute. Under these conditions the time spent by the material in the extruder was approximately one and a half minutes.

Blends were prepared in this manner, each Io Gcw .- ^ fiberglass and terpolymer Io wt - contain "glass fiber -.% Terpolymer and 25 wt .- / j glass fiber and 15 parts by weight of terpolymer and Ji Io · wt. . There were, a further 2.5 wt .- /! ^ MDI was added to each of these mixtures which were then processed using the conditions given in Example 5 to form both 51 mm 6 mm 3 mm and 51 mm χ 9 rr.rn. χ 3 rm rods were injection molded.

It became the rubber particle size, the ■ basal molar Viscosity of the ethylene terephthalate polymer and the Charpy impact strength determined for each mixture according to the method described above. The bending module of each mini

9 O 9 8 3 Q / U 3 3 ^BAD ORIGINAL

by bees of the 51 mn χ 9 ran χ 3 mm measuring rods in a standard pressure gauge. The rod was placed with its larger surfaces horizontally in a three-point loading _{device in which bending by vertical movement of a pair of knife edges that were 31 4} 5 r; jn apart and were in contact with the lower surface of the rod, causes relative to a fixed knife edge located in the middle of the opposite rod surface. The movement of the outer knife edges relative to the middle one proceeded at a speed of 2.5 mm per minute. The modulus was calculated from the initial slope of the force-deflection curve.

The results of these measurements are shown below. For comparison, measurements of injection-molded samples are also given, which correspond to the above-mentioned with the I would be similar to that of the rubber and / or the glass fiber was omitted.

909830 / U 3 3

Te! 'Polymer ο ξ

(Gevi .-% of the mixture)

Io Io

Io

Glass fiber (Gc \ -: .-% of the mixture)

Io

25th

Io

£ run-in-molar viscosity of the molded product. Nl per C (dl.cT ^X )

average rubber particles C ^r ö ft °

99
82

85
86
96

(o, 99) (ο, 82) (ο, 85) (ο, 86) (ο, 96)

5
3

Kcrbschlnc "toughness

(1: C cn / ciii ")

(k ^. / cm ² )

Ιο, 6 · 2,4ί | χ Io

ί H

Ip, 3 ^{: 1} I, οο x Io

8.5 * 2.36 χ Ιο ''

5.7 1.78 χ Ιο * ¹

3.1: 2, .6α χ ίο ¹ '

Example 8

There were 35 parts by weight of dry polyethylene terephthalate granules with a base molar vicocity of 65 ml per c (0.65 oil) with a Troranel with 15 parts by weight of one with
DVA (I) designated copolymers were extruded, v; while the procedure of Example 3 was followed. The granulated powder dried extrudate with a Tror.rael ir.it 2 Gev. ^r .- # T-TDX
table, spritzceGossen and then crystallized using the procedure described in Example 3.

This procedure was repeated to make music with different other mixed polymers specified below obtain.

Tests were carried out with the prepared porridge of each mixture to determine the crund molar viscosity of the
ethylene terephthalate polymers, the rubber particle size and the Charpy impact strength of the objects. The results are given below.

<o {mixed polymer ο Ι co j

Basic molar viscosity ml per g (1 " ^ϊ )

average
Rubber particles
size (u)

Kerbschla £ - tough.it ₂ (kc cn / cm)

co ι

üVA (l) ZVA (2)

87 (o, 87)

81

8o (o, 8o)

3 to H 6 to 7
Ji to 5

6, β

6.6

7.3 7.2

BAD OftKSINÄL

1814013

Eg all of the following "rubbers" were used.

EVAC1): Sehwach-crystalline polymer of mixing 7 ^ 1 wt '..-% ethylene and 2o by weight. ;; Vinyl acetate with a Sehmelzflußindex of 3 ₄ 5 at 19o ° C, a glass-rubber überganßstemperatur of -26 ^Q C and a dynamic modulus of seer Weni £ he than 5 x

ο ρ
la "'dy-n / gin.

SVA (2): Sehv.'ach-liristallines MiGChpolymeres. from ethylene. (36% by weight and vinyl acetate (1 ^% by weight ) with a Schm, el2, flow index of 2 ^ o at 19o ° 0 ,, a glass-rubber transition temperature below ⁰ ° C and a dynamic S .chermodul. by wenicer

η ρ

as 5 x Io dyn / cm *

EEA (I): Sehwaeh-crystalline unresel-like: mixed polyraeres from ethylene (.87 Gev; .- p) and ethylene acrylate (13 GeM .-%} with. A melt flow index of 2.5 at 19-o ^ö 'C, ..- a glass-Kaut-GChuk transition temperature of -47 ' ⁰ C and a dynamic shear

O 2

module of less than 5 x Iq dyn / enr «

ΞΕΑ (2>;: As with £ ΕΑ (1>, jedo-eh 7'8 ^ ethylene wnä'22% - containing ethyl acetate and with a melt flow index of 18.5 19o ° C and a glass-rubber transition stone temperature of - H

,, _ 1.8U.073

ro

- ι

Example 9

At each of a series of experiments were f.er.ischt 9o parts by weight of dry granular polyethylene terephthalate (grundr.olare viscosity Ü5 ml per g (ο, β5 dl.g)) r.it Io Gevrichtsteilen a Kautschukniaterials given below and d under Verv; endunc of an Iddon screw extruder with a diameter of 3.2o cm. at a tube temperature of 25o ° C and a screw speed of 7o turns per IC continuous - to mixed. The resulting extrudates are granulated, _{dried 3} and mixed in a ratio of 2 parts by weight I'DI to 93 parts by weight of extrudate. The mixtures were injection molded in a 57 g Stubbe machine (2 oz.) To aν; ei 'V.'ege-n, as given below.

A. 1/2 part weight of talc was added to 100 parts by weight of the mixture. The mixture was then injection molded ⁰ C and a cooling time in the mold of ¹ Io seconds at a tube temperature of 255 ⁰ C, a Rohrverweilzeit of 6 minutes, a Formter.peratur of ILO.

3. The mixture was at a tube temperature of 25d C a tube residence time of β minutes, a mold temperature of

909830 / U33

18U073

20 ° C and a cooling time of 5 seconds. Thereafter, the molded articles were kept for 1 hour to crystallize the ethylene terephthalate polymer. annealed.

There were 51 nx with both working methods. χ 6 mm χ 3 r.rr, r: CGsenae rods cjeforrr.t. The rods are used to carry out the test. the rubber particle c ^ oe (by optical examination) j the "round polar viscosity of the)". ethylene terephthile: "_; .tpolyrr.eron ^ wa to determine the - XeraschlacsMhic ^ eit of the rods (by a method of operation described above). The results:; c · are compiled in a table below.

Zs v.'ux'den the following rubber materials: used, all of which are at most schv; acn.crystalline and each of which has a Gias-rubber transition temperature below ⁰ ° C. and a dynamic shear modulus of less than 5 x io ^y

ρ
dyn / cm.

Experiment A: "Inrecelmüßices mixed polymer from 7 ^: 'Gev: .- /" ethylene and 2o Gev /.- ί vinyl acetate, in which at least 95 C-ev; .- f' of the vinyl acetate units had been hydrolyzed to vinyl alcohol. The melt flow index of the polymer was 1.0 by meter at 190.degree.

909 ^ 30 / ^ 4 33 <

^, ... ift'V BADORiQlNAL

Experiment B; ünre "elir: äßices Mischpolyr.ercs from 31 Gev /.- 2

Ethylene and 9 OCV / - ^ methacrylamide with a Cchmclzflußindex of 1, _S} ^ err.essen at 19o ° C.

Experiment C: UnregelnaAices interpolymer from 7o wt -%.

Ethylene and 30 wt .- ^ methacrylic acid with a Schrcelzflussindex of S.9 at 19o ° C.

Experiment D: Polyisobutylene does not have a molecular weight

according to Staudin ^ er of about 2oo,000.

" Experiment S: Irregular mixed polymer of ethylene (62.5% by weight b) and. Propylene (37.5% by weight - ^) with a. Sea flow index of 0.5" at 19% ⁰ %,

Experiment P: Irregular 1-I.schpolymeres from 60 ethylene, 55 wt .- # propylene and 5 wt .- ^ of a C-mixture of 4-methyl- and 5-methyltetrahydroindenes with an intrinsic viscosity of 1.5 "at 25 ⁰ G measured in "carbon tetrachloride.

attempt ί
t
1 grunamolar
Visibility ■
nl ie_g j Kerosene
sähigiceit_ ~.
(leg cm / cm "): through the chnit t- 'porn
iiche rope arrows
chen size (p.) "v / eise B. _ ν. ^ (0.5?): 5.4 3. A. B. 3 : 75 (0.75) ί 6.8; 3; A. ^: C 70 (0.70) I. 4.0 \ 1 - 2 [λ D. 100 (1.00) j
I. 9.2 "j oriented
Pill up;
su one through
knife of 4 u 60 (Ο, βΟ) 4.4 2-3 7i (o, 7i) \
J
ί , 7.5
t in flow
direction
directed
jüliipsoide

BATH ORIGINAL

9-09830 / 1433

- i ⁹ 8t4073

AtGpiol 10

Attempt. A. A dispersion was prepared from 15 parts by weight of the terpolymer used in Example 5 in 85 parts by weight of the polyethylene lerephthalate used in Example 3, in which first a 50:50-1 mixture was formed and then further polyethylene terephthalate was added as described in Example 3. I) JS dried granulated extrudate was then in a 57 g Stübbe device (2 oz ") in the presence of 2 wt -.- fj MDI using a tube temperature of 255 ° 0, a tube residence time of 6 minutes, a ? or: temperature of 20 C and a cooling time of 3? ογε of 5 seconds to form 5-ί ΓιΏ χ 6 mn χ 3α.η measuring rods injection molded. These were tempered for 1 hour at 140 ° C. before they were subjected to tests for notched impact strength, intrinsic viscosity of the ethylene terephthalate polymer and rubber particle size.

Experiment B. The procedure of Experiment A was repeated, but the DI was omitted.

The following results were obtained:

909830 / U33

"18H073

Attempt basolar notch phlagrv average

Viscosity ζ i ähigke ii-- --- Kau t s oliul: tei 1 c e n

nl per g (kg cn / cm) size (μ) (cLl.g- ')

A 55 (0.55) 13.3 5 'B 55 (0.55) 4.0 5

Example 11

In 3s, a dispersion of 10 parts by weight of the copolymer used in Example 9A and 90 parts by weight of polyethylene terephthalate with a triolar viscosity of 65 ml per g (0.65 dl 2 ") was produced by a simple extrusion, v / ie in the example 9 "was described. Thereafter, talc (0.5 G-ev /. -Fj) was added to the dried, granulated extrudate and porklings, both with and without the addition of 2% by weight > KDI, were removed from the liquid .g manufactured. In a 57 g Stübbe device, the injection

conducted c "b.ei a tube temperature of 255 ⁰ C, a Rohrverweilzeit of 6 Hinuten, a Pormtemperatur of 140 ⁰ C and a cooling time of 40 seconds, the moldings (51 mn χ 6 mm χ 3 mm measured rods: ft GÜS £. ) v / are tested as in Example, the results given below being obtained.

ω LZ) I basic molar impact average σ present viscosity toughness «rubber particles- ^ nl per S (kg cm / cm) size (γ)

nl per S ₁ (kg cm / cm) size (γ.) (dl g) "

ω no 55 (0.55) 2.7 4

yes 59 ^ (0.5S) - ' 5.4 3

18U073

Example 12

The mixtures given below were prepared in order to determine the influence of the rubber particle size on the impact strength of the mixtures. Both Z-Iisdrangen were produced in such a way that: 3 they contained 15% by weight of the terpolymer used in Example 3. Mixture (A) was prepared by extruding 15 parts by weight of rubber Susannen with λ w5 parts by weight of polyethylene terephthalate, 2 parts by weight of 131 and 0.5 parts by weight of talc. Zs, a Iddon-screw extruder having a diameter of 5.20 cm at a Eohrtenperatur of 265 ⁰ C and a screw speed of 60 revolutions per minute is used, wherein a Rohrverweilzeit was obtained from about 1 1/2 minutes. The extrudate urde granulated v /, dried, and in. A 57 g-Stübbe device sprayable at a Hohrtemperatur of 265 ⁰ C, a Rohrverweilseit of 3 Hinuten, a "Pom of 14O ⁰ C and a cooling time in the mold of 48 seconds "poured. The briquettes were 51 mm 6 mm 3 mm rods.

Mixture (B) v / urde by the preparation of a dispersion from equal parts by weight of rubber and polyethylene terephthalate and then adding more

90 9 8 30/1433

Ϊ8Η073

Polyethylene terephthalate was made using the double extrusion procedure described in Example 3. Thereafter, the extrudate was mixed with 2 wt .- ^ HDi and placed in a 57 g Stübbe device (2 oz.) At a tube temperature of 255 ⁰ G, a pipe residence time of about 9 minutes, a mold of 20 ⁰ C and a cool down time Injection molded in the fora of 5 seconds to form £ rods measuring 51 mm 6 mm 3 mm. The bars were annealed at 140 ⁰ C for one hour to crystallize the Äthylenterephthalatpolvneren.

The briquettes of (A) and (3) -were basic molar. Viscosity of the ethylene terephthalate polymer and Xerb impact strength tested and were visually determined investigated the quality of the rubber dispersion. It results shown below were obtained.

™ Try basic impact area and through viscosity Toughness ρ cut the Kautschukral per g-, (kg cm / cm) particle size

Ui s)

A 57 (0.57) 4.5 1 - 350 μ, average

greater than 20 u

B 55 (0.55) 13.2 1 - 30 [deg.] Average

about 5 u

0/1433. BATH

Ί8Η073

Example 15

A dispersion of 10% by weight per liter of the iDerpolant used in example 3 in polyethylene terephthalate was prepared for 3 seconds with a green viscosity of 65 ial per g (0.65 dl 2) by means of the double extrusion process described in the example . The extrudate was injection molded in a 31 c-Stübbe device (2 os.) With 2 wt .- ^ KDI to form disks with a diameter of 1 ', λ-cn -and a thickness of 3 nm, with the addition a Edge of the disc periphery formed. The riohrtenperatur the S'ornungsvorrichtung was 255 ⁰ C and the Verv / eiiceit about 9 I-Iinuten, the temperature of the porn 20 ⁰ G and the cooling time 20 seconds. The fcheiben were getrernpert one hour at "140 ⁰ C were 50 πα χ 6 mn;. ■; 3 na ness end

a * aa cut the slices, taking the long axis either parallel or perpendicular to the direction of flow of the polymer was in the form during the injection. These were tested for their impact strength in the manner already described. It became the following received results.

Notch impact strength (kg cra / cKi "")

Axis parallel to _ _u

Current 9.3 - 1.0

Axis perpendicular to

Current 3.0 - 1.0

909830/1433

18U073

i .j pi el 14

"Js v / urde a series of dispersions in B. icoiel '■ j> used avay len-I-le thy Ine thaorylat-beta-Hydr oxy ät hy 1-;:. Ethacrylate: I'er polymer in s Polyathylenterephthalt ::. the double Extrusioncarbeiteweiae described in this. example tz prepared. Ts were 5, 10 and 15 wt .- ^ of fe (Derpolyr "older-containing dispersions prepared. this vrarden with a Sronnel 2 Ge \! .- ^c / -> 12DI and injection molded in a 57 g Stübbe device (2 oz.) To form 51 -in χ 6 i: r. Χ '-j raa measuring rods. The maximum temperature was 255 ?. ⁰ G and the omtemperatur 20 ° C the Abläihlungsseit was 5 seconds, and it was a series of 2OiI. dwell times Angev / ending samples vmrden before testing for one hour at 140 ⁰ G tempered were the grundnolare viscosity of Äthj ^. lenterephthalate polymers, the impact strength of the rods and the average

! Cautschuliteilchensro ^ e in the mixtures Destiirjr.t, where The results are presented below in a (Table zui, aair;

are.

09830/14 33

■■■ '"■' ■ '" ■. " ^{Ly! Ϊ́} ' ^ι · ^: !!! ΐ» ^! 4 »'·, Ι · ¹ '

C-ev. '. - ;; j
f Z ο hr ve rv; e 11-
zei'b (SeI :.) L.1
i αχ s) ; Charpy
(ir ρ he / he " ¹ ^ ' ; by-
jschrr-.tt-
: 1 I he Katbsdiü: -
[' ellohen-
!diameter ; 5 1 40 ■ 77 (0.77) 7.3 ί
j O 5 510 ! 96 (0.96) ; 10.3 t 0
I. • 5 525 : 93 (0.93) ^; 10.0 ! 2 Ul 755 Π 00 (1.00) 9.7 '. 2; 10 ■ 79 (0.79) 9.5 5 10 210 . 62 (0.32) 10.2 ^: 3: 10 550 52 (0.02) 10.7 3 10 525 ο 5 (0.53) 10.5 • 3 Ί 0 700 70 (0.70) 9.2 : 3 ^; 15th 105 ; 55 (0.55) 13.5 • V 210 : 67 (0.67) 15, p 4; : 15 . 35Ü '' -. 60 • (0.60) 15.3 .4: ^r 15 ! 525 -.55 ) O, 55) 15.4 L "\ ^; 15th
? I 700 52 (0.52) 11.6

909830 / U3X

Claims (1)

(2) A rubber-like material made of at least one amorphous or slightly crystalline high molecular weight synthetic polymer or high-molecular-weight polymer, which is insoluble in polyethylene terephthalate, so that it forms a separate disperse phase therein and which forms a glass / chewing material -'JOergangstenperatur below before. O ⁰ C and a dynamic schema module of not greater than 5 x "0 ^J dyn / ciu possesses, and (3) at least one ροIyfunctional connection the group of (a). VerlDinaungen, v / elche with min- ™ at least 2 GHr and / or COOH groups among the 3e to react to din3urj.gen des Klimelzformverfalirens ability, and ("b) connections, v / ei before under the Conditions of the Schmelafom process for connections of type (a) are dissociable, and the rubbery material is 1 to 50% of the total weight of (1), (2) and (3) and the polyfunctional 909830 / U3 3 Γ7 - * ^T 18U073 bond 0.05 to ΊΟ '/ * of the total weight of (1), (2) and (;>) form. 2) I-Iasse after. Claim 1, characterized in that the rubber-like material contained therein with the polyfunctional Connection under the conditions of the rapid curing process au is able to react. 'j) Composition according to one of the preceding claims, characterized in that the rubber-like material contained therein contains hydroxyl groups. 4) Hasse according to one of the preceding claims, characterized in that the rubber-like material contained therein is a Hischpolyr.ieres aus- Ethylen rat Ilischiiiononerennaterial, which includes at least one hyarozyl alkyl ester of an ethylenically unsaturated carboxylic acid. 5) mass according to any one of the preceding claims, characterized in that the rubber-like contained therein Material is selected from the group of rubbery Ilischpolymeren from ethylene nit at least one 2-hydroxy-n-propyl methacrylate and hydroxyisopropyl methacrylate, rubber-like copolymers of ethylene and 2-hydrocyan 909830/1 433 18U073 ethyl methacrylate and rubbery Hisehpolyrieren auo Ethylene nit I'ethylnethacrylat and at least one of the Yar connections 2-Hydro :: y-n-propyli: .ethacrylate and Hydroxyisopropylnethacrylat. 5-) Hasse according to one of the preceding claims, characterized in that the polyfunctional contained therein Compound is selected from the group of polyisocyanates, uretidione diners of polyisocyanates and higher molecular uretide ionomers of polyisocyanates. 7) Hasse according to claim 6, characterized in that the polyisocyanate is 4.4 ^f -Diisocyanatdipheny! Methane. 3)! Let according to one of the preceding claims, characterized in that. that they also have a ktir. o-forming Contains agent for the polyethylene terephthalate. 9)! 'Let according to one of the preceding claims, characterized in that it also contains glass fibers. 10) Hasse according to one of the preceding claims, characterized in that the rubber-like contained therein Material 5 "" to 35 $ of the total weight of (1), (2) and (5) forms. ■. .... 909830/1433 18U073 1 ',) cash register according to one of the preceding claims, characterized in that the rubber-like material contained therein forms 5 to 1 pji of the total weight of (1), (2) and ( ' ■)) . 12) Cash register according to one of the preceding claims, characterized in that the polyfunctional compound contained therein forms 0.5 to 5i * of the total weight of (1), (2) M and (5). 13) cash register according to one of the preceding claims, characterized in that the possibly contained therein Glass fibers 20 to 40? S by weight of the crowd. 14) Method of making a hat according to one of the preceding claims, characterized in that; 3 ii3.li a mixture of polyethylene terephthalate in one stage Liit the rubbery 'material shear conditions at a Temperature above the melting point of the polyethylene terephthalate subject. 15) Method according to claim 14-j, characterized in that Ώ.0Λ1 adds the polyfunctional compound to the polyethylene terephthalate after the latter is mixed with the rubber: -artigen material and optionally nit glass fibers has been. 909830 / H33 To]. Method according to one of the preceding. At characterized in that the polyethylene terephthalate, with the chewy cheeky. I-Iaterial and. possibly the. · Galsfibres e'extrudiert and then the: Extrudat η-it of the paly— funlctione.ilen YerOinding extruded « 17) A process for the production of a shaped object from Ätb.ylentereph.th.alatpolyaeren uit verdesserter impact strength, characterized in that nan. a liasce gen: ä; 3 J. Samples 1 "to Yo for the production of a shaped object from a base material of an ethylene terephthalate polymer and a disperse phase of finely dispersed" special ^j cen "particles, the" oschuk-like material in the ial " forms and melts. 18) Procedure according to. Claim 17, characterized in that " that includes a step "wherein the ethylene terephthalate polymer base material crystallized or allowed to crystallize in the molded article., 19) Method according to one of claims 17 or 13, characterized in that the mass is injection molded forms. 909830/1433 18U073 20) Consume after one of the previous-erL claims, characterized in that the polyethylene terephthalate is used a temperature in the range of 255 to 29C C during a duration of one T / 2 liinute to 15 minutes in the presence subject to the polyfunctional connection. 21) Shaped object characterized by a Material made of an ethylene terephthalate polymer basic matorial μ - ~ s \ ■ J ^ -ι y> i ~ ^ ι- « * 'Q O ζ \ V ^ Γ' Γ \ V> * ~ Λ>" * V ^ i ¹ "Γ ¹ O Π11 ^^ Ό * ι *>"^""1-" ■ * η V ^ disperse phase, the base material containing macromolecular units, each of which is formed from at least 2 polymeric chains, in which at least 90% of the units have the structure -OCH ₉ CH ₉ OCOArCO-, where Ar 'forms a para-phenylene group and where each Chain is bound to another chain by a chemically different unit, which is the polyvalent residue of a • polyfunctional compound, which is able to react with at least sw ei u.er groups -OH and / or -COQH, whereby 'the disperse phase is finely dispersed ropes a rubber-like material made of at least one amorphous or scawachcrictalline high molecular weight synthetic polymer or IlicchpolymerGn, which has a glass / rubber transition temperature below O ⁰ C and a dynamic shear modulus of less than 5 x 10 ^ dyn / cm ^, and which has: the polyfunctional compound is reactive, 9098 30/143 3 18U073 and ν / ob ei the rubber-like material on the ethy.lentorph-. thalatpoly.;.: er-Grund: .iaterial medium., polyvalent hectare of -.olyfunctional compound is graft polymerized and 1 Mg-5Cyj of the total weight of the. Gruno / r.aterzalD and the aisperse phase forms. 22) Shaped object according to claim 21, characterized in that the kau-ischük-like material is 5 to 55 / j. the total weight of the base material and the dispersed W " phase, ■ 2''j) Shaped object according to claim 22, characterized in that the rubber-like material is 5 to 15> * • ".es total weight of the base material and the disperse phase - - ;. icLet. 24) Shaped article according to one of the preceding claims, characterized in that it additionally ^ Contains glass fibers. 25) Shaped object according to one of the preceding- the claims, characterized in that the glass fibers. 20 to vOfa, based on the weight of the object. 25) Formed object according to one of the preceding Claims, characterized in that the ethylene terephthalate 909 830 / U33 BATH ORIGINAL indesterus partially crystallized. 27) The article of -GrojiTorrrter, any one of the preceding claims, - in that, in the average DA3 * grotto of ^f _} eilche: i of the disperse phase is not greater than 7 I; II: is ron. 2c.) C-shaped object according to one of the preceding claims, daiurcVi ^ elcennesc that the basic material a ~ round polar viscosity, measured as a solution of the poly-Lieren in c-chlorophenoi at 25 ⁰ G, by ninuestenc 0.5 deciliters 2S) Geometric object according to one of the preceding claims, characterized in that the fundamental molar Yiskositllt of the grand material O, op "to 0.55 deciliter g"" ¹ oe- 909830/1433