CH637665A5 - Synthetic resin mixture containing a partially hydrogenated block copolymer and thermoplastic engineering resins, and process for its preparation - Google Patents

Description

The invention relates to synthetic resin mixtures containing a partially hydrogenated block copolymer which is composed of at least two end blocks A made of a monoalkenylarene polymer with a number average molecular weight of 5,000 to 125,000 and at least one 60 intermediate block B made of the conjugated polymer Diene with a number average molecular weight of 10,000 to 300,000; in the block copolymer, the terminal polymer blocks A represent 8 to 55% by weight and not more than 25% of the arene double bonds of polymer blocks A and at least 65 80% of the aliphatic double bonds of polymer blocks B are hydrogenated.

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The thermoplastic effect that can be used in technology and industry does not correspond to that of the usual method

Resins, also known as “industrial thermoplastics” (engineering ther- to improve compatibility, and this is called moplastic resins), are a group of polymers, which is demonstrated by the very general ability of these materials.

which have proven their worth as technical building materials, since they have even, uniformity for a wide range of mixtures.

to present certain properties, such as strength, stiffness, impact and components, which meet the requirements

Impact resistance and dimensional stability over a long period of time do not meet solubility requirements.

to have a favorable balance. Such «Industrie-Ther- As already mentioned, the invention relates to a synthetic resin plastic» are particularly suitable as a replacement for metals, since mixtures containing a partially hydrogenated block are much lighter than these, which is often the case, especially in the automobile copolymer the latter at least two end blocks A from bilbau, is an advantage. 10 a monoalkenylarene polymer with a number average of

A single thermoplastic resin sometimes does not have a molecular weight of 5,000 to 125,000 and at least one has the combination of properties which is desirable for a particular intermediate block B made of a polymer of a conjugated diene and it has a number average molecular weight of 10 000 to be interested in compensating for this disadvantage. One particularly includes 300,000; In the synthetic resin mixture according to the invention, two or more polymers 15 represent the terminal polymer blocks A 8 to 55% by weight (each of which represents the desired properties on% of the block copolymer and it is not more than 25% of the points) to mix together, so that a material with the arene double bonds in the polymer blocks A and the desired combination of properties is obtained. This can be successful in at least 80% of the aliphatic double bonds in the polymers in certain cases, e.g. when improving blocks B hydrated; the impact and impact resistance of thermoplastic resin 2Q synthetic resin mixtures according to the invention are characterized by a content of the following constituents, such as polystyrene, polypropylene and polyvinyl chloride, the following parts:

special mixing processes or additives a) 4 to 40 parts by weight of partially hydrogenated block copolymer

used. In general, however, is the mixing of ether;

Moplastic resins are not a promising way, if it is b) a polycarbonate with a melting point above, in a single material, the respective 25120 ° C and desirable properties of two or more polymers c) 5 to 48 parts by weight on at least one different

to combine. On the contrary, it has been shown often enough that the gene thermoplastic industrial resin that was chosen

Mixing causes the respective weaknesses of those from the group of polyamides, polyolefins, thermoplastic

Combine individual components so that a polyester, poly (aryl ether), poly (aryl sulfone), acetal resin, ether

uninteresting and worthless material. The reasons for this - 30 moplastic polyurethanes, halogenated thermoplastics and for are well known and partly consist in the fact that, nitrile resins,

As thermodynamics teaches, most polymers cannot be mixed with one another in which the weight ratio of the polycarbonate to that can be mixed, although some exceptional thermoplastic industrial synthetic resins are well known from this rule. In addition, it is 1: 1, so that a polymer mixture is formed in which most polymers adhere poorly to one another. This leads to at least partially continuous at least two of the polymers, so that the contact surfaces between the components of the general form interlocking networks.

mix (due to their immiscibility) in the mixture. The block copolymer in question acts as mechanical districts of particular weakness, in which shear or structural stabilizers, which all too easily develop cracks and cracks, which link the mechanical polymer network structures and which subsequent separation of the properties of the mixture impair. For this reason, 40 polymers are said to be “incompatible” during processing and the actual use of most polymer pairs. need prevented. The resulting structure of the polymer mixture- In some cases, compatibility means as much as mixing is more precisely defined so that it is at least availability, but the expression compatibility is used here in a two part continuous, interlocking or more general sense, and means the ability to trade other linked networks. It is therefore a matter of combining its two polymers with one another in such a way that their inherently stable polymer mixture 45 is present, which is improved on the basis of properties without necessarily referring to one of its structure neither in the extrusion nor in the subsequent real miscibility . send use separated into individual layers.

One method by which this problem can be solved with poly- In order that stable mixtures have to be avoided, at least two mer mixtures have to be avoided, is that the two polymers are made compatible with an at least partially continuous network by adding a third 50 work, with the two networks intermeshing component, which are often linked as a means of compatibility or with each other. The block has preferably been designated and has a mutual solubility with respect to the two copolymer to be mixed and at least one of the other polymers. Sometimes continuous, interlocking network structure. In the case of such third components, certain block ideal cases would be all polymers as completely continuous or graft copolymers. Because of the property mentioned, there are 55 networks that are linked to one another, this mediator is located at the interface between a partially continuous network means that the two polymers are firm and the mutual ad- part of the polymer improves a continuous network-like structure and thus the stability of the product against a coarse one, while the other part is in the form of a disperse phase. Phase separation extraordinary. Preferably the main part, i.e. more than 50 wt .-%, des

In contrast, the invention opens up the possibility of continuously 60 networks, i.e. coherent. How to stabilize mixtures of several polymers, which can be easily understood, the structure of the mixtures can be very different depending on the above-mentioned means of increasing them, since the structure of the polymer in the mixture is compatible and not dictated by the need is either completely continuous, fully dispersed or partially restricted, substances with bilateral solubility properties can be continuous and partially disperse. It can also be used. The inventively disperse phase of the one polymer in a second polymer to be used for this purpose are special block copolymers with and not distributed in a third polymer. In order to show some of them the possibility of a reversible in the heat (these structural possibilities), there is the variously reversible self-crosslinking. Your possible combinations of polymer structures according to the invention

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leads, whereby all structures are not partial structures, but complete structures. Three polymers (A, B and C) are involved. The index «c» means a continuous structure, while the index «d» means a disperse structure. The designation “ACB” means that polymer A continuously alternates with polymer B and the designation “BdC” means that polymer B in polymer C

is dispersed etc.

ACB AcC

BcC

AdB AcC

BcC

ACB AcC

BdC

BdA AcC

BcC

BdC ACB

AcC

CdA ACB

AcC

QB ACB

AcC

According to the invention, it is in hand to improve one or the other physical property of the mixtures without adversely affecting another physical property. So far, this has not always been possible. So you were e.g. Hitherto believed that to add an amorphous rubber, such as an ethylene-propylene rubber, to a thermoplastic polymer to improve its impact resistance, it would be necessary to obtain a mixture in which the heat distortion temperature (HDT) * is significantly reduced. This view is based on the fact that the amorphous rubber forms discrete particles in the mass and the rubber, almost by definition, has an extraordinarily low HDT value, which is around room temperature. According to the invention, however, it is possible to significantly improve the impact resistance or impact resistance without the dimensional stability temperature being reduced thereby. It is even more surprising that, as can be seen from the examples, the heat distortion temperature increases in some cases if the proportion of block copolymers is increased. This is a completely surprising phenomenon for a person skilled in the art.

This possibility of producing “tailor-made” polymer mixtures and thereby achieving a significantly improved balance of properties cannot be found in the prior art.

*) «Dimensional stability (limit) temperature» (heat distortion temperature) HDT is the temperature in ° C at which a test rod suffers a certain deflection under a given load.

It is particularly surprising in the present case that even a small proportion of block copolymer is sufficient to stabilize the structure of the polymer mixture within a wide concentration range. For example, already four parts by weight of block copolymer in order to stabilize a mixture of 5 to 90 parts by weight of polycarbonate with 90 to 5 parts by weight of a different type of industrial thermoplastic.

It is also surprising that the block copolymers can be used to stabilize polymers of such diverse chemical properties. As will be explained in more detail below, this ability of the block copolymers to stabilize a large number of polymers within a wide concentration range is based on the fact that they are stable against oxidation, have a practically infinite viscosity at a shear stress of 0 and in the melt they underlie them maintain lying network structure.

Another important aspect of the invention is that the different polymer mixtures can be processed and shaped much more easily if the above-mentioned block copolymers are used as stabilizers.

The block copolymers contained in the synthetic resin mixtures according to the invention can have a very different geometric structure, since according to the invention it is not a question of any specific geometric structure, but only the chemical constitution of each of the polymer blocks. The block copolymers can e.g. be linear, radial or branched. Methods for producing such polymers are known. The structure of the polymers is determined by the respective polymerization process. So you get e.g. linear polymers by successively introducing the corresponding monomers into the reaction vessel when using initiators such as lithium alkyls or dilithiostilbene or when coupling a block copolymer from two segments with a difunctional coupling agent. On the other hand, branched structures are obtained by using suitable coupling agents which have a functionality of three or more with regard to the precursor polymers. The coupling can be carried out with multifunctional coupling agents, such as with haloalkanes or alkenes and divinylbenzene, and with certain polar compounds, such as silicone halides, siloxanes or esters of monohydric alcohols with carboxylic acids. The presence of any coupler residues in the polymer can be neglected in describing the polymers that form part of the plastics used. Also, in the sense of the genre, it does not depend on the respective structure. According to the invention, selectively hydrogenated polymers are used in particular, which correspond to the following typical types in their configuration before the hydrogenation:

Polystyrene-polybutadiene-polystyrene (SBS)

Polystyrene-polyisoprene polystyrene (SIS)

Poly (a-methylstyrene) polybutadiene-poly (a-methylstyrene)

and

Poly (a-methylstyrene) polyisoprene-poly (a-methylstyrene).

Both polymer blocks A and blocks B can be either homopolymer blocks or random copolymer blocks, as long as only each polymer block predominates in at least one class of the monomers characterizing the polymer blocks. Thus, the polymer block A can comprise homopolymers from a monoalkenylarene and copolymers from a monoalkenylarene with a conjugated diene, as long as the monoalkenylarene units predominate only in the individual polymer blocks A. The term “monoalkenyl arene” here means, inter alia, particularly styrene and its analogs and homologues including a-methylstyrene and ring-substituted styrenes, in particular ring-methylated styrenes. In addition to a-methylstyrene, unsubstituted styrene is particularly preferred. The polymer blocks B can be homopolymers of a conjugated diene, such as butadiene or isoprene or copolymers of a conjugated diene with a monoalkenylarene, as long as the conjugated diene units predominate only in the polymer blocks B. If butadiene is used as the monomer, the condensed butadiene units in the butadiene polymer block should have at least 35 to 55 mol% of the 1,2 configuration. Then, when such a block is hydrogenated, the resulting product is a regular copolymer block of ethylene and butene-1 (EB) or is similar to such a copolymer block. If the conjugated diene is isoprene, a regular copolymer block of ethylene and propylene (EP) or in any case a similar block is formed during the hydrogenation.

For the hydrogenation of the block copolymers representing the precursors, a reaction product of an aluminum alkyl compound with a nickel or cobalt carboxylate or alkoxide is preferably used as the catalyst under conditions such that at least 80% of the aliphatic double bonds are virtually completely hydrogenated, while at most 25% of the aromatic alkenyl arene double bonds hy5

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be third Block copolymers are preferred in which at least 99 q- of the aliphatic double bonds are hydrogenated, while only less than 5 c'c of the aromatic double bonds are hydrogenated.

The average molecular weight of the individual blocks can fluctuate within certain limits. The block copolymer present in the synthetic resin compositions according to the invention has at least two end blocks A made of a monoalkenyl arene polymer with an average molecular weight of 5,000 to 125,000, preferably from 7,000 to 60,000, and at least one intermediate block B which is a polymer of a conjugated diene with an average molecular weight from 10,000 to 300,000, preferably from 30,000 to 150,000. These molecular weights are numerical mean values which can be determined most precisely by tritium counting methods or by measuring the osmotic pressure.

The proportion of monoalkenyl arene polymer blocks A is between 8 and 55%, preferably between 10 and 30% of the total weight of the block copolymer.

The polycarbonates present in the compositions according to the invention can have the following general formulas:

O

II

- (Ar-A-Ar-O-C-O) ^ - I

or

- (Ar-0-C-0) -n— II

wherein Ar represents a phenylene group or an alkyl, alkoxy, halogen or nitro substituted phenylene group; A represents a carbon-carbon bond or an alkylidene, cyclo-alkylidene, alkylene, cycloalkylene, azo, imino, sulfoxide or sulfone group or a sulfur or oxygen atom and n is 2 or more. The production of the polycarbonate is known. A preferred method is based on the reaction which takes place when the dihydroxy component is dissolved in a base such as pyridine and phosgene is introduced into the solution with stirring at an appropriate rate. Tertiary amines can be used as a catalyst for the reaction, which also act as acid acceptors during the reaction. Since the reaction is normally exothermic, the rate of phosgene addition can control the reaction. Usually you work with equimolar amounts of phosgene and dihydroxy compound, but the ratio can be changed depending on the reaction conditions.

In formulas I and II above, Ar and A are preferably p-phenylene and isopropylidene, respectively. This polycarbonate is produced by reacting p, p'-isopropylidene diphenol with phosgene and is marketed under the protected names Lexan® and Merlon®. It has a molecular weight of around 18,000 and melts above 230 ° C. Other polycarbonates can be produced by reacting other dihydroxy compounds or mixtures of several dihydroxy compounds with phosgene. Aliphatic dihydroxy compounds can be used as dihydroxy compounds, but aromatic rings are essential for temperature-resistant compounds. The structure of the dihydroxy compounds can have diurethane bonds. Part of the structure can also be replaced by siloxane bonds.

The term “various types of thermoplastic industrial resin” refers to technical or industrial thermoplastic resins which differ from the thermoplastic polyesters present in the synthetic resin mixtures according to the invention.

The term “thermoplastic industrial resin” (“thermoplastic technical resin”) encompasses the various polymers which are listed in Table A below and are described in more detail below.

Table A

1. Polyolefins

2. thermoplastic polyester

3. Polyaryl ether and polyaryl sulfone

4. Polyamides

5. Acetal resins

6. Thermoplastic polyurethanes

7. halogenated thermoplastics

8. Nitrile resins

The thermoplastic engineering or industrial resins preferably have a glass transition temperature or an apparent crystal melting point (defined as the temperature at which the module suffers a catastrophic drop under low load) of more than 120, preferably between 150 and 350 ° C, and have the ability, due to a thermal reversible cross-linking mechanism to form a continuous network structure. Such thermally reversible crosslinking mechanisms include crystallite formation, polar aggregation, ionic aggregation, lamination or hydrogen bonding. In a particular embodiment, in which the viscosity of the block copolymer or the block copolymer mixture at the processing temperature Tp and a shear rate 100 s_1 equal to r | , the ratio of the viscosity of the thermoplastic industrial resin or of its mixture with viscosity modifiers to r) can be between 0.2 and 4.0 and is preferably 0.8 to 1.2. The viscosity of the block copolymer, the polycarbonate and the thermoplastic industrial resin is to be understood here as the so-called "melt viscosity", which is obtained by using a piston-driven capillary melt rheometer at constant shear rate and any constant temperature above the melting point, e.g. 260 ° C. The upper limit (350 ° C) for the apparent crystal melting point or the glass transition temperature is set so that the resin can be processed in a device with low to medium shear temperature at a temperature of 350 ° C or less which is customary in the art.

The aforementioned thermoplastic industrial resins can also be mixtures of such resins with one another or mixtures with additional, viscosity-modifying resins.

The different classes of industrial thermoplastics are described in more detail below.

The polyolefins which may be present in the plastic compositions according to the invention can be crystalline or crystallizable. They can be homopolymers or copolymers and can be derived from an α-olefin or a 1-olefin having 2 to 5 carbon atoms. Examples of particularly useful polyolefins are low or high density polyethylene, isotactic polypropylene, poly (l-butene), poly (4-methyl-1-pentene) and copolymers of 4-methyl-1-pentene with linear or branched Alpha olefins. A crystalline or crystallizable structure is important so that the polymer is able to form a continuous structure in the polymer mixture according to the invention with the other polymers. The number average molecular weight of the polyolefins can be above 10,000, preferably above 50,000. The apparent crystal melting point, i.e. the transition point at which the crystalline regions of the polymer change into the amorphous state can be above 100 ° C., preferably between 100 and 250 ° C. and in particular between 140 and 250 ° C. The production of these different polyolefins

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is known (see "Olefin Polymers" in Kirk-Othmer, Encyclopaediof Chemical Technology, Volume 14, pp. 217-335 [1967]).

If a high density polyethylene is used, this has approximately a crystallinity of more than 75% and a density between 0.94 and 1.0 kg / 1, while an optionally used low density polyethylene has an approximate crystallinity of over 35% and has a density between 0.90 and 0.94 kg / 1. The compositions according to the invention can contain a polyethylene with a number average molecular weight of 50,000 to 500,000.

If a polypropylene is used, this is a so-called isotactic polypropylene in contrast to an atactic polypropylene. The number average molecular weight of the polypropylene used can be over 100,000. The polypropylene can be manufactured in the usual known manner. Depending on the catalyst used and the polymerization conditions, the polymer produced contains atactic and isotactic, syndiotactic or so-called stereo block molecules. These can be separated by selective extraction, so that products with few atactic components are obtained, which crystallize more completely. The preferred commercially available polypropylenes are usually made using a solid, crystalline, hydrocarbon-insoluble catalyst made from a mixture of titanium chloride and an aluminum alkyl compound, e.g. Triethylaluminium or diethylaluminium chloride. Optionally, the polypropylene used is a copolymer containing minor proportions (1 to 20% by weight) of ethylene or another alpha olefin as a comonomer. The poly-1-butene preferably has an isotactic structure. The catalysts used in its manufacture are preferably organometallic compounds, commonly referred to as Ziegler-Natta catalysts. A typical catalyst is the product that is obtained by interacting by mixing equimolar amounts of titanium tetrachloride and triethyl aluminum. It is normally made in an inert solvent such as hexane. It is important that care is taken in all phases of polymer formation to exclude water, even in traces.

A particularly useful polyolefin is poly (4-methyl-1-pentene), which has an apparent crystal melting point between 240 and 250 ° C and a relative density between 0.80 and 0.85. Monomeric 4-methyl-1-pentene is produced industrially by alkali metal-catalyzed dimerization of propylene. The homopolymerization of 4-methyl-1-pentene with Ziegler-Natta catalysts is described in Encyclopedia of Chemical Technology by Kirk-Othmer, Supplementary Volume, pp. 789-792 (2nd edition, 1971). However, the isotactic homopolymer of 4-methyl-1-pentene has certain technical disadvantages, such as brittleness and insufficient transparency. The commercially available poly-4-methyl-1-pentene is therefore practically a copolymer with lower proportions of other alpha-olefins, to which appropriate oxidation and melt stabilizer systems have also been added. Such copolymers are described in the above Encyclopédie by Kirk-Othmer, Supplement, p. 792-s 907 (2nd edition, 1971); they are commercially available under the protected name TPX® resins. Typical alpha-olefins are the linear alpha-olefins with 4 to 18 carbon atoms. Suitable resins are copolymers of methyl 1-pentene with 0.5 to 30% by weight of linear alpha olefin. ■ »The polyolefin may be a mixture of different polyolefins. However, the most preferred polyolefin is isotactic polypropylene.

The thermoplastic polyesters which may be present in the compositions according to the invention can have a generally crystalline structure; they have an apparent crystal melting point above 120 ° C and are thermoplastic (as opposed to thermosetting).

A particularly useful group of polyesters are those thermoplastic polyesters which are prepared 2 (1 by condensing a dicarboxylic acid or its lower alkyl ester, its acid halide or anhydride with a glycol in a manner known per se. Among the aromatic and aliphatic dicarboxylic acids which are suitable for the preparation suitable for the polyester are: oxalic acid, malonic acid, Bern-2: 1 rock acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p-carboxyphenyl acetic acid, p, p'-dicarboxydiphenyl, p, p'- Dicarboxydiphe-nylsulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxy-propionic acid, p-carboxyphenoxybutyric acid, p-carboxyphe-30 noxyvaleric acid, p-carboxyphenoxyhexanoic acid, p, p'-dicar-boxydiphenylmethane, p, p-picodiphenylmethane, p, p-picodiphenylphenane -carboxydiphenyloctane, 3-alkyl-4- (ß-carboxyethoxy) -benzoic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid, mixtures of dicarboxylic acids can also be used. Terephthalic acid is particularly preferred.

The glycols suitable for the production of the polyester include straight-chain alkylene glycols with 2 to 12 carbon atoms, such as ethylene glycol, 1,3-propylene glycol, 1,6-hexylene glycol, 1,10-decamethylene glycol and 1,12-dodecamethylene glycol. 40 col. Aromatic glycols can be substituted in whole or in part. Suitable aromatic dihydroxy compounds include p-xylylene glycol, pyrocatechol, resorcinol, hydroquinone or alkyl-substituted derivatives of these compounds. Another suitable glycol is 1,4-cyclohexanedimethanol. The straight-chain alkylene glycols having 2 to 4 carbon atoms are particularly preferred.

A preferred group of polyesters are: polyethylene terephthalate, polypropylene terephthalate and in particular poly-butylene terephthalate; the latter, a crystalline copolymer, 50 can be formed by polycondensation of 1,4-butanediol and dimethyl terephthalate or terephthalic acid and has the general formula:

0

"\

M

\\ W

) '

) —C —- 0 1 — C-

-0-

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where n can be 70 to 140. The average molecular weight of the polybutylene terephthalate is preferably between 20,000 and 25,000 (commercial products: VALOX®, CELA-NEX®, TENITE®, VITUF®).

Other suitable polyesters are the cellulose esters; the thermoplastic cellulose esters that can be used here are also widely used as auxiliaries for shaping, as coatings and as film-forming substances. The solid thermoplastic forms of cellulose nitrate, cellulose acetates (for example cellulose diacetate, cellulose triacetate), cellulose losebutyrate, cellulose acetate butyrate, cellulose propionate, cellulose losetriadecanoate, carboxymethyl cellulose, ethyl cellulose and methyl cellulose, methyl cellulose, methyl cellulose, methyl cellulose, methyl cellulose, hydroxyethyl cellulose, methyl cellulose, hydroxyethyl cellulose, methyl cellulose, hydroxyethyl cellulose, methyl cellulose, hydroxyethyl cellulose, methyl cellulose, hydroxyethyl cellulose, methyl cellulose, hydroxyethyl cellulose, cellulose hydroxylate, cellulose cellulose Encyclopedia », 1971-72).

Another useful polyester is a polypivalolactone, i.e. a linear polymer with recurring ester units, mainly according to the formula:

-CH2-C (CH3> 2 — C (0) 0-

i.e. with units derived from pivalolactone. The polyester is preferably a pivalolactone homopolymer. However, the copolymers of pivalolactone with not more than 50 mol%, preferably not more than 10 mol%, of another β-propiolactone, such as β-propiolactone, a, a-di-ethyl-β-propiolactone and a-Methyl-a-ethyl-ß-propiolactone - The term "ß-propiolactone" refers to ß-propio-lactone (2-oxetanone) and to derivatives thereof which have no substituents on the ß-C atom of the lactone ring wear. Preference is given to β-propiolactones which contain a tertiary or quaternary carbon atom in the alpha position relative to the carbonyl group, in particular the a, a-dialkyl-β-propiolactones, in which each of the alkyl groups in each case has 1 to 4 carbon atoms.

Examples of suitable monomers are: α-ethyl-α-methyl-β-propiolactone, α-methyl-α-isopropyl-β-propiolactone, α-ethyl-an-butyl-β-propiolactone, α-chloromethyl-α-methyl ß-propiolactone, a, a-bis (chloromethyl) -ß-propiolactone and a, a-dimethyl-ß-propiolactone (pivalolactone)

These polypivalolactones have an average molecular weight of more than 20,000 and melt above 120 ° C. Another suitable polyester is a polycaprolactone. Preferred poly-E-caprolactones are essentially linear polymers in which the repeating unit can be represented by the following formula:

II

w and

O

—O-ch2-ch2-ch2-ch2-ch2-c-

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15

m wherein R is a bond between aromatic carbon atoms -O-, —S—, -SS-, or a divalent hydrocarbon radical having 1 to 18 carbon atoms and G 'is the residue of a dibromo or diiodobenzene compound which follow-20 from the group is selected:

iv and

V

35

where R 'is a bond between aromatic carbon atoms, -O—, -S-, —SS- or a divalent hydrocarbon radical having 1 to 18 carbon atoms, but with the following proviso: if R is -O-, R' is not the same 40 -O-; if R 'is -O-, R is not equal to -O-; if G is II, G 'is V, and if g' is IV, G is III.

Polyarylene polyethers of this type have excellent physical properties and are particularly stable against heat, oxidafion and chemical influences. Commercial poly-aryl polyethers with melting temperatures between 280 and 310 ° C are available under the protected trade name Arylon T®.

50 Another group of usable thermoplastic industrial resins are the aromatic polysulfones with repeating units of the formula:

These polymers have practically the same properties as the polypivalol lactones and can be prepared by an appropriate polymerization mechanism.

Various polyaryl polyethers are also useful as industrial thermoplastic resins. The polyaryl polyethers which may be present in the compositions according to the invention include linear thermoplastic polymers from recurring units of the formula

—FO-G-O-G ') -

55

—Ar-SO, -

wherein Ar is a divalent aromatic radical, which can optionally change from unit to unit in the polymer chain, so that copolymers of different types are formed. Thermoplastic polysulfones generally have at least a few units of the following structure:

where G is the residue of a dihydric phenol selected from s ~ a group consisting of: '

~ ^ S0,

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wherein Z is oxygen or sulfur or the remainder of an aromatic diol such as a 4,4'-bisphenol. An example of such a polysulfone has recurring units of the formula:

-0-

/

-SO,

another has recurring units of the formula:

//

y so2 ~

and others of the formula:

r, -

y-so2

-0-

\? H3 /

//

/ '-> CH,

, J

-0-

or they are copolymerized units in different proportions of the formula:

\\

-30.

or

T

r

-O-

10th

The thermoplastic polysulfones can also have repeating units of the formula

/ r

> —O-

-50,

to have.

Polyether sulfones with repeating units of the structure:

r

// w

r * -

-so2-

and polyether sulfones with repeating units of the structure:

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-SO"

> - 0

are also suitable as thermoplastic industrial resins. By polyamide is meant a product that is commonly known as “nylons”. The polyamides can be obtained by polymerizing a monoaminocarboxylic acid or an internal lactam of such an acid with at least two carbon atoms between the amino and the carboxyl group. They are also obtainable by polymerizing practically equimolar parts of a diamine containing at least two carbon atoms between the amino groups and a dicarboxylic acid; or by polymerizing a monoaminocarboxylic acid or its internal lactam, as above, together with practically equimolar proportions of a diamine and a dicarboxylic acid. The dicarboxylic acid can be in the form of one of its functional derivatives, e.g. of an ester.

The expression “practically equimolecular fractions” (of the diamine and the dicarboxylic acid) means, in addition to precisely equimolecular fractions, also slight deviations which can occur during the usual stabilization of the viscosity of the resulting polyamides.

Examples of the monoaminomonocarboxylic acids or their lactams mentioned are those compounds which have 2 to 16 carbon atoms between the amino and carboxyl groups and which form a ring in the case of a lactam with the —CO • NH group. The following may be mentioned as special examples: e-aminocaproic acid, butyrolactam, calcium prolactam, pivalo and caprylic lactam, enantholactam, undecanolactam, dodecanolactam and 3- and 4-aminobenzoic acid.

Examples of the diamines mentioned are those of the general formula H2N (CH2) nNH2, where n is an integer from 2 to 16, such as trimethylene diamine, tetramethylene diamine, pentamethylene diamine, octamethylene diamine, decamethylene diamine, dedecamethylene diamine, hexadecamethylene diamine and in particular hexamethylene diamine.

Other examples are C-alkylated diamines, e.g. 2,2-dimethylpentamethylenediamine and 2,2,4- and 2,4,4-trimethylhexamethylene diamine. Aromatic diamines, e.g. p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylmethane as well as cycloaliphatic diamines, e.g. Diaminodicyclohexyl methane.

The dicarboxylic acids mentioned can be aromatic acids, e.g. Isophthalic and terephthalic acid. Preferred are dicarboxylic acids of the formula HOOC • Y • COOH, in which Y represents a divalent aliphatic radical with at least 2 C atoms; Examples are: sebacic acid, octadecanedioic acid, suberic acid, azelaic acid, undecanedioic acid, glutaric acid, pimelic acid and in particular adipic acid, oxalic acid is also preferred.

The following polyamides can in particular be incorporated into the thermoplastic polymer mixtures according to the invention:

Polyhexamethylene adipinamide (nylon 6: 6)

Polypyrrolidone (nylon 4)

Polycaprolactam (nylon 6)

Polyheptolactam (nylon 7)

Polycapryllactam (nylon 8)

Polynonanolactam (nylon 9)

10 polyundecanolactam (nylon 11)

Polydodecanolactam (nylon 12)

Polyhexamethylene azelaine amide (nylon 6: 9) polyhexamethylene sebacinamide (nylon 6:10) polyhexamethylene isophthalamide (nylon 6: iP) 15 polymetaxylylene adipinamide (nylon MXD: 6)

Polyamides of hexamethylenediamine and n-dodecanedioic acid (nylon 6:12)

Polyamides of dodecamethylene diamine and n-dodecanedioic acid (nylon 12:12)

20 nylon copolymers can also be used, e.g. copolymers of:

Hexamethylene adipinamide / caprolactam (nylon 6: 6/6) Hexamethylene adipinamide / hexamethylene isophthalic acid (nylon 6: 6 / 6ip)

25 hexamethylene adipamide / hexamethylene terephthalic acid amide (nylon 6: 6 / 6T)

Trimethylhexamethylene oxamide / hexamethylene oxamide (nylon trimethyl 6: 2/6: 2)

Hexamethylenadipinamid / Hexamethylenazelainamid (Nylon so 6: 6/6: 9)

Hexamethylene adipinamide / hexamethylene azelaine amide / capro-lactam (nylon 6: 6/6: 9/6)

Also usable is nylon 6: 3, a product of the dimethyl ester of terephthalic acid and a mixture 35 of isomeric trimethylhexamethylene diamine.

Preferred types of nylon are nylon 6,6 / 6,11,12 6/3 and 6/12.

The number average molecular weight of the polyamides can be above 10,000.

40 The acetal resins optionally present in the compositions according to the invention include the high molecular weight polyacetal homopolymers produced by polymerizing formaldehyde or trioxane, which have the protected name Delrin® as commercial products. A related 45 resin of the polyether type (trade name Penton®) has the structure:

50

ch2c1 I

—O-ch2-c-ch2 I

ch, c1

55 The acetal resin made from formaldehyde has a high molecular weight and the following structure:

-h-0 - (ch2-0-ch2-0) -x — h-

in which terminal groups come from controlled proportions of water and x denotes a larger number (preferably 1500), which denotes the number of formal-65 dehydrogen units present in succession. In order to improve the resistance to heat and chemical attacks, the terminal groups in the typical resins are converted into ester or ether groups.

11 637 665

The term “polyacetal resins” also encompasses those that contain fluoride units. Suitable comonomers are polyacetal copolymers. These copolymers are among others halogenated olefins with up to 4 carbon atoms, e.g. sym. dichloro-rem block copolymers of foramaldehyde with monomers or difluoroethylene, vinyl fluoride, vinyl chloride, vinylidene chloride, prepolymers of other substances which have the ability to provide perfluoropropene, perfluorobutadiene, chlorotrifluoroethylene, tri-active hydrogen, such as alkylene glycols, 5 chloroethylene and tetrafluoroethylene.

Polythiols, copolymers of vinyl acetate and acrylic acid or another useful group of halogenated thermo-

reduced butadiene / acrylonitrile polymers. thermoplastics are homopolymers and copolymers of vinyl

A denchloride commercially available under the protected name Celcon®. Crystalline vinylidene chloride copolymers are particularly preferred copolymer of formaldehyde and ethylene oxide. The usable within the scope of the invention

1 (1 normally crystalline vinylidene chloride copolymers contain at least 70% by weight vinylidene chloride, along with 30% or less of a copolymerizable monoethylene monomer. Examples of such monomers are vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, alkyl and 15 aralkyl acrylate with alkyl or aralkyl groups with up to about 8 carbon atoms, acrylic acid, acrylamides, vinyl alkyl ethers, vinyl alkyl ketones, acrolein, allyl ethers and the like and butadiene and chloropropene, known ternary mixtures can also be used with advantage those which are composed of at least 70% by weight of vinylidene chloride, the rest consisting, for example, of: acrolein and vinyl chloride, acrylic acid and acrylonitrile, alkyl acrylates and alkyl methacrylates, acrylonitrile and butadiene, acrylonitrile and itaconic acid, acrylonitrile and vinyl acetate, vinyl-25 propionate or vinyl chloride, allyl esters or ethers and vinyl chloride, butadiene and Vinyl acetate, vinyl propionate or vinyl chloride and vinyl ether and vinyl chloride. Quaternary poly with other aldehydes, cyclic ethers, vinyl compounds, mers of a corresponding monomer composition are ketene, cyclic carbonates, epoxides, isocyanates and are also known. Particularly useful for the purposes of the Erfin ether, including e.g. Ethylene oxide, 1,3-dioxolane, 1,3-30 dung are copolymers with 70 to 95 wt .-% vinylidene chloride, dioxane, 1,3-dioxepene, epichlorohydrin, propylene oxide, isobuty rest vinyl chloride. Such copolymers can use the usual lenoxide and styrene oxide. Plasticizers, stabilizers, nucleators and extrusion aids

Polyurethanes, which are also known as isocyanate resins, contain medium in an appropriate amount. Mixtures of two or more of these can also be used as industrial thermoplastic resins under normal circumstances, provided that they are actually thermoplastic and non-thermoplastic. Vinylidene chloride polymers can be used and are curing. Examples are: polyurethanes from toluene diisocyanates in which such normally crystalline polymers nat (TDI) or diphenylmethane-4,4-diisocyanate (MDI) and together with other polymer modifiers, e.g. the copo-numerous polyols, such as polyoxyethylene glycol, polyoxypropyl- mers of ethylene-vinyl acetate, styrene-maleic anhydride, lenglycol, polyesters with terminal OH groups, polyoxy-styrene-acrylonitrile and polyethylene are present. ethylene oxypropylene glycols. 40

These thermoplastic polyurethanes are among the proprietary names Q-Thane® and Pellethane® CPR in nitrile resins, which are usable as industrial resins in the present case, are plastics containing a, ß-olefi trade. niche unsaturated mononitrile of 50% by weight or more.

Another group of usable industrial thermopla- These nitrile resins can be homopolymers, copolymers, graft-es are the halogenated thermoplastics with essentially 45 copolymers or copolymers on a rubber-like subcrystalline structure and an apparent crystal melt strat or also mixtures of homopolymers and / or copopoints above 120 ° C. These are especially lymeric.

Homopolymers and copolymers of tetrafluoroethylene, chloro- The a, ß-olefinically unsaturated trifluoroethylene, bromotrifluoroethylene, vinylidene fluoride and vi-mononitrile in question have the structure:

nylidene chloride. 50

Polytetrafluoroethylene (PTFE) are fully fluorinated polymers CH2 = C -CN

the basic chemical formula -fCF2-CF2) -n, which I

Contain 76% by weight fluorine. These polymers are highly crystalline R

and have a crystal melting point of over 300 ° C (trade name: Teflon® and Fluon®.) High molecular weight Po- 55 where R is hydrogen, an alkyl group with 1 to 4 C-atychlorochififluoroethylene (PCTFE) and polybromotrifluoroethylene or a halogen atom. The following may be mentioned: acrylonitrile (PBTFE) are also available and can be used in the inventions a-bromoacrylonitrile, a-fluoroacrylonitrile, methacrylonitrile and compositions according to the invention. Ethacrylonitrile. Acrylonitrile and methacrylonitrile and their mixtures

Particularly preferred halogenated polymers are preferred.

polymers and copolymers of vinylidene fluoride. The homopo 60 These nitrile resins can be divided into different classes due to their complexity in the polymeric and partially fluorinated polymers. The simplest molecule formula - (CH2-CF2) -n. These polymers are tough linear lar structure is a statistical copolymer mainly composed of polymers with a crystal melting point at 170 ° C (e.g. Ky-acrylonitrile or methacrylonitrile. The best-known example is a nar®). The term “polyvinylidene fluoride” here refers to styrene-acrylonitrile copolymer. Block copolymers of Acrylni not only on the normally solid homopolymers of 65 tril, in which long sections of polyacrylonitrile alternate with section vinylidene fluoride, but also on its normally solid sections of polystyrene or of polymethyl methacrylate, copolymers which are at least 50, preferably at least 70 also known.

and in particular at least 90 mol% of polymerized vinyl

is particularly good for the mixtures according to the invention. The typical structure of these copolymers includes repeating units of the formula:

wherein Rt and R2 each represent hydrogen, a lower alkyl radical or a halogen-substituted lower alkyl radical and n is a number from 0 to 3, where n in 85 to 99.9% of the repeating units is zero.

Formaldehyde and trioxane can be copolymerized

637 665

12

Simultaneous polymerization of more than two comonomers leads to an interpolymer or, in the case of three components, a terpolymer. A large number of comonomers are known, including alpha olefins with 2 to 8 carbon atoms, e.g. Ethylene, propylene, isobutylene, butene-1 and pentene-1 and their halogenated and aliphatically substituted derivatives, such as vinyl chloride and vinylidene chloride, or the monomers of aromatic monovinylidene hydrocarbons of the formula

H, C = C

-R,

'R?

wherein Rj represents hydrogen, chlorine or a methyl group and R2 is an aromatic radical with 6 to 10 C atoms, which may also contain substituents, e.g. Halogen and alkyl groups attached to the aromatic nucleus, e.g. Styrene, a-methylstyrene, vinyltoluene, a-chlorostyrene, orthochlorstyrene, parachlorstyrene, methachlorstyrene, orthomethylstyrene, paramethylstyrene, ethylstyrene, isopropylstyrene, dichlorostyrene and vinyl naphthalene. Particularly preferred comonomers are isobutylene and styrene.

Another group of comonomers are vinyl ester monomers of the general formula:

H

I.

R3C = C

I.

0

1

c = o

I.

r3

wherein R3 represents hydrogen atoms, alkyl groups with 1 to 10 C atoms, aryl groups with 6 to 10 C atoms including the C atoms in the ring-substituted alkyl substituents; e.g. Vinyl formate, vinyl acetate, vinyl propionate and vinyl benzoate.

Like the abovementioned, the vinyl ether monomers of the general formula can be used

H2C = CH-0-R4

wherein R4 can have the following meaning: an alkyl group with 1 to 8 carbon atoms, an aryl group with 6 to 10 carbon atoms or a monovalent aliphatic radical with 2 to 10 carbon atoms, which can be a hydrocarbon or oxygen-containing, such as a aliphatic radical with ether bonds, and which may also contain other substituents, such as halogen or carbonyl. Examples of such monomeric vinyl ethers are: vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl 2-chloroethyl ether, vinyl phenyl ether, vinyl isobutyl ether, vinyl cyclohexyl ether, p-butylcyclohexyl ether, vinyl ether and p-chlorophenyl glycol.

Other comonomers are those that contain a mono- or dinitrile function, e.g. Methylene glutaronitrile, (2,4-dicy-anobutene-1), vinylidene cyanide, crotonitrile, fumarodinitrile and maleodinitrile.

Other comonomers are the esters of olefinically unsaturated carboxylic acids, preferably the lower alkyl esters of α, β-olefinically unsaturated carboxylic acids and in particular the esters of the structure:

ch2 = c-coor2 I.

Ri

5 wherein Rj stands for hydrogen, an alkyl group with 1 to 4 carbon atoms or a halogen and R2 for an alkyl group with 1 to 2 carbon atoms. Connections of this type are e.g. Methyl or ethyl acrylate, methyl or ethyl methacrylate and methyl a-chloroacrylate. Methyl and ethyl acrylate and io methyl and ethyl methacrylate are preferred.

Another class of nitrile resins are the graft copolymers, in which side branches of another polymer chain are attached or grafted onto a polymer backbone. The "backbone", i.e. the main chain is preformed in a separate reaction. On polyacrylonitrile e.g. Chains of styrene, vinyl acetate or methyl methacrylate can be grafted on. The backbone can consist of one, two, three or more components and the grafted-on side branches can also be composed of one, two, three or more comonomers.

A lot can be expected from nitrile copolymers, some of which are grafted onto a preformed rubber-like substrate. For this substrate, use of a synthetic or natural rubber such as Polybu-25 tadiene, isoprene, neoprene, nitrile rubber, natural rubber, acrylonitrile-butadiene copolymers, ethylene-propylene copolymers and chlorinated rubbers are used to achieve this To make polymer stronger or tougher. The rubber component can be incorporated into the nitrile-containing polymer in any manner known to those skilled in the art, e.g. by direct polymerization of the monomers, by grafting the acrylonitrile-monomer mixture onto the rubber backbone or by physically mixing in the rubber component. Polymer mixtures are particularly preferred which are formed when a graft copolymer of acrylonitrile and the comonomer is grafted onto the rubber backbone with another copolymer of acrylonitrile and the same comonomer. The acrylonitrile-based thermoplastics are generally polymer mixtures of a graft polymer and a homopolymer without a grafted-on component.

One acrylonitrile-based nitrile resin with over 65% Nitrii (Ba-rex® 210) and another with over 70% Nitrii, three quarters of which are from methacrylonitrile (Lopac®), are commercially available.

45 To determine the viscosity properties of the thermoplastic industrial resin, polycarbonate and the like. to bring the block copolymer into better agreement, it is often advisable to first mix the different thermoplastic industrial resin with a viscosity modifier before adding u. of the block copolymer prepares the final mixture. Viscosity modifiers with a relatively high viscosity and a melting temperature of more than 230 ° C are suitable, at which the viscosity is not too sensitive to temperature changes. Examples are poly (2,6-55 dimethyl-1,4-phenylene) oxide and mixtures of poly (2,6-dimethyl-1,4-phenylene) oxide with polystyrene.

The poly (phenylene oxides) which are optionally present as viscosity modifiers can be represented by the formula:

65

n l

-O-

i

N '

m

13

637 665

where Rj is a monovalent substituent selected from the following group: hydrogen, no hydrocarbon radicals containing no tertiary aC atom, halogenated hydrocarbon radicals with at least 2 carbon atoms between the halogen atom and the phenol ring, which contain no tertiary aC atom, hydrocarbonoxy radicals which do not contain aliphatic tertiary aC atoms and halogenated hydrocarbon residues with at least 2 C atoms between the halogen atom and the phenol ring, which contain no aliphatic tertiary aC atom; Rt 'has the same meaning as Rx and can also be a halogen atom; m is a number from at least 50 to 800, preferably from 150 to 300. Among these preferred polymers, those with a molecular weight between 6000 and 100,000, preferably from 40,000 may be mentioned. The polyphenylene oxide is preferably poly (2,6-dimethyl) -1,4-phenylene) oxide.

The polyphenylene oxide is commercially available as a mixture with styrene resin; such mixtures usually contain between 25 and 50 wt .-% polystyrene units (trade name thermoplastic Noryl® resin). If a mixture of polyphenylene oxide and polystyrene is used, the preferred molecular weight is between 10,000 and 50,000 and is preferably around 30,000.

The amount in which the viscosity modifier is used depends primarily on the difference in the viscosity of the block copolymer and the thermoplastic industrial resin at temperature Tp. The proportion is from 0 to 100, preferably from 10 to 50 parts by weight of viscosity modifier per 100 parts by weight of thermoplastic industrial resin.

The presence of an interlocking network (apart from the fact that there is no layer separation) can be shown using at least two methods. According to one of these methods, molded or extruded objects are dissolved from a mixture according to the invention under reflux in a solvent which quantitatively dissolves the block copolymer and other soluble components;

if the remaining polymer structure (made of the thermoplastic industrial resin and polycarbonate) is still connected and has the shape of the molded or extruded object and is structurally intact without wrinkles or decoating, and if the solvent does not contain any insoluble particles , there is proof that you have a network in front of you, in which the non-extracted and the extracted phase are interlocking and continuous. The non-extracted phase has to be continuous simply because it remains geometrically and mechanically intact. The extracted phase must also have been present continuously before the extraction, since quantitative extraction of a dispersed phase from an insoluble matrix is highly unlikely. Finally, the networks from both phases must interlock, otherwise the two phases could not be continuously present. The continuous nature of the non-extracted phase can also be verified microscopically. In the present mixtures of more than two components, the intermeshing and the continuity of each individual phase can be demonstrated by selective extraction.

In the second method, a mechanical property, such as the tensile modulus, is measured and compared to the value that can be expected from a system in which each continuous, isotropically distributed phase contributes a proportion to the mechanical behavior that corresponds to its volume fraction. If the two values match, this is evidence of the presence of an interlocking network, while in the other case the measured value is different from the theoretical value.

An important aspect of the invention is that the proportion ratio of the different polymers in the mixture can be varied within a wide range. The proportions of the polymers, expressed in% by weight 5 (the total mixture comprising 100 parts) are as follows:

Parts by weight preferably

Parts by weight

10th

different types of thermoplastic

Industrial resin 5-48 10-35

Block copolymer 4-40 8-20

15

The polycarbonate is present in an amount larger than that of industrial thermoplastics, i.e. the weight ratio of polycarbonate to industrial resin is greater than 1: 1; the amount of polycarbonate can vary between 30 and 91 20 parts by weight, preferably between 48 and 70 parts by weight. Note that the minimum amount of block copolymer can vary with these blends with the particular thermoplastic industrial resin present.

25 The three components, the thermoplastic industrial resin, the polycarbonate and the block copolymer, can be mixed in any way that ensures that an interlocking network is created. For example, resin, polycarbonate and block copolymer can be dissolved in a common solvent and precipitated again by adding another solvent in which none of the polymers is soluble. However, it is particularly expedient if the polymers in the form of granules and / or powder are intimately mixed in a mixer at a high shear rate. 35 “Intimate mixing” means that the mixing takes place with such a high mechanical shear rate and thermal energy that an interlocking of the various networks is ensured. For this purpose, extrusion devices with high shear, such as extruders with twin screws and thermoplastic extruders with an L / D ratio of at least 20: 1 and a compression ratio of 3 or 4: 1, are preferably used.

The mixing or processing temperature (Tp) is selected depending on the polymers to be mixed. For example, if the polymers are to be mixed in the melt rather than in solution, the working temperature must of course be above the melting point of the highest melting polymer. In addition, as will be explained in more detail below, the working temperature is also selected so that isovis-50-free mixing of the polymers is made possible. The mixing or working temperature is between 150 and 400, preferably between 230 and 300 ° C.

Another parameter that is important if you want to achieve intermeshing networks by mixing in the melt, is that the viscosities of the block copolymer, the polycarbonate and. of the thermoplastic industrial resin at the temperature and the shear stress during the mixing process aligns (isoviscous mixing). The more uniform the Indu-60 resin, the polycarbonate is distributed in the network of the block copolymer, the greater the chance that a three-dimensional network is formed during the subsequent cooling, in which the individual networks intermesh continuously and in unison. Therefore, if the block copolymer has a viscosity of T] poise, a temperature Tp and a shear rate of 100 s_1, the viscosity of the thermoplastic industrial resin and / or the polycarbonate should preferably be at the temperature Tp and a shear rate of 100

637 665

14

s-1 can be set such that the ratio of the viscosity of the oil used is up to 100 phr

Block copolymer divided by the viscosity of the thermoplastic (phr = parts by weight per 100 parts block copolymer), preferably see industrial resin and / or the polycarbonate between 0.2 5 to 30 phr.

and 4.0, preferably between 0.8 and 1.2. An «isovis-mixture of partially hydrogenated block copolymer, po-kosischen mixing» means here that the viscosity of the 5 lycarbonate and the thermoplastic block copolymer different from them, divided by the viscosity of the other poly-industrial resin, can also be mixed with an additional resin or of the polymer mixture at the temperature Tp and, for example a flowability-increasing resin, such as a shear rate of 100 s "" 1 between 0.2 and 0.4 an a-methylstyrene resin or a plasticizer for the final. It must be taken into account that there can be a block inside.

Extruders the gravitational speed over a wide range 10 can be distributed among plasticizers as resins for the end blocks. Isoviscous mixing can therefore also be used for other coumarone indene resins, vinyltoluene-alphamethylsty-

take place when the viscosity curves of the two polymers rol copolymers, polyinden resins and low molecular weight poly

differ at some of the shear rates. styrene resins.

In some cases, the order of mixing the amount of additional resin can be up to 100, preferably

Polymers important. If necessary, one can therefore be 15 to 25 phr.

next the block copolymer with the polycarbonate or the masses can be other polymers, fillers,

mix other polymer and then mix this mixture with the booster, antioxidants, stabilizers, fire-proof

different thermoplastic industrial resin mix de additives, anti-blocking agents and other rubber and or you can simply contain all polymers at the same time vermi- plastic additives.

see. Due to the multiple components of the examples of suitable fillers according to the invention,

According to mixtures, different variants can be found in the travel guide Modern Plastics Encyclopedia, pp. 240-247 (1971-

sequence of mixing can be selected. Under certain circumstances 72).

you can also achieve that the viscosities of the different polymers are better tolerated. Amplifiers are also for use in the existing

The block copolymer can be chosen so that it is suitable for the appropriate polymer mixtures. These are essentially compatible with the industrial resin and / or the polycar substances which can be added to a resin matrix. If necessary, the block copolymer can improve the strength of the polymer. Mostly these are mixed with a rubber expanding oil or additional inorganic or organic products of high molecular weight

Resin, as will be described, for its viscosity weight, e.g. Glass fibers, asbestos, boron fibers, carbon and graphite

properties to change. 30 phite fibers, quartz and silica fibers, ceramic or me-

To form the co-continuous, interlocking tall fibers and natural and synthetic organic fiber networks, the special physical properties are fe. Reinforced polymer mixtures that are important for the block copolymers are particularly preferred. In particular, the block copolymers, most preferred in an amount of 2 to 80% of their weight, melt in the unmixed manner.

Condition not in the usual sense with increasing temperature, 35 The polymer mixtures according to the invention can be

because the viscosity of these polymers does not offer a high degree, in which high demands are placed on the material

Is Newtonian »and tends to be used against shear stress as a metal substitute.

increase from zero to unlimited. In addition, according to the following examples (including the viscosity of these block copolymers largely independent of the same examples), different polymer blends were obtained based on the temperature. This rheological behavior and the thermal stability of the block copolymers, which is provided by mixing the polymers in a 3.125 cm high, increases the sterling extruder with a Kenics nozzle. The extruder has its ability to practically maintain its network structure in the melt - length to diameter ratio of 24: 1, while maintaining it so that the compression ratio of 3.8: 1 can be found in a wide variety of mixtures.

interlocking and continuous mesh. The following substances were used for the mixtures:

form works. 45 1) Block copolymer: a hydrogenated block copolymer of the structural

The viscosity behavior of the S-EB-S thermoplastic industry.

resins and on the other hand the polycarbonate depends essentially 2) Oil: a rubber-extending oil (TUFFLO 6056)

more from the temperature than that of the block copoly- 3) nylon 6: PLASKON® 8207 polyamide.

You can therefore often choose a working temperature Tp for 4) nylon 6-12: ZYTEL® 158 polyamide.

which is the viscosities of the block copolymer and of which 50 5) polypropylene: an essentially isotactic polypropylene

differentiated industrial resin and / or polycarbonate in oils with a melt index of 5 (230 ° C / 2.16 kg)

the area in which interlocking network 6) poly (butylene terephthalate) («PBT»): VALOX® 310 resin plants are formed. Optionally, as already mentioned, 7) polycarbonate: MERLON® M-40 polycarbonate first a viscosity modifier with the industrial resin or 8) poly (ether sulfone): 200 P.

be mixed with the polycarbonate to reduce the viscosities. 55 9) Polyurethane: PELLETHANE® CPR.

to coordinate each other. 10) Polyacetate - DELRIN® 500

The mixture of partially hydrogenated block copolymer, Po- 11) polyacrylonitrile-co-styrene) B AREX® 210

lycarbonate and differentiated thermoplastic 12) fluoropolymer TEFZEL® 200 poly (vinylidene fluoride) -

Industrial resin can be mixed with a standard oil used for processing chew-copolymer chuk and plastics. 60 For all mixtures that contained an oil

The types of oil which are premixed with the elastomer block copolymer and oil before the other poly-

polymer blocks of the block copolymer are compatible. In addition to mers were added.

The usable oils with a higher aromatic content are the petroleum-based white oils, which have a low volatility, example 1

and have an aromatic content of less than 50% (65 different polymer mixtures according to the invention

agrees with the clay-gel method, ASTM method D 2007), whereby in some cases a mixture of two is particularly preferred. The boiling range of the oils begins with block copolymers of higher and lower molecular weight.

preferably above 260 ° C. was used to determine the viscosity with the polycarbo-

15

637 665

nat and / or the other industrial thermoplastics better- In contrast, Hessen from all approaches that agree. In some blends, the block copolymer, block copolymer contained, without further polymer blends also for the purpose of better matching the viscosities, an oil was prepared and the extrudate always had a homogeneous appearance. In addition, in all of these batches containing a block copolymer comparative blends that did not contain a block copolymer, the resulting copolymer was also made as above, but in these cases the desired structure, i.e. they made a run-on ingredient not readily miscible with each other. So the interlocking network suffered.

for example the mixture 110, which is not a block copolymer, but in Tables I and II the composition of the mixture

which contained only polycarbonate and nylon 6, given in percentages by weight.

break, swelling after exit and intermittent throughput, ok

Table I

Mixture No. 110 81 82 111 83 84 120 85 86

Block copolymer blend 15.0 30.0 15.0 30.0 15.0 30.0

oiled

Block copolymers

Poly (butylene terephthalate)

Polypropylene

Nylon 6 25 21.3 17.5

Polycarbonate 75 63.7 52.5 75 63.7 52.5 75 63.7 52.5

Poly (ether sulfone) 25 21.3 17.5

Polyurethane

Polyacetal

Poly (acrylonitrile-co-styrene)

Fluoropolymer 25 21.3 17.5

Mix number

Block copolymer mixture with oil added

Block polymer blends

Poly (butylene terephthalate)

Polypropylene

Nylon 6

Polycarbonate

Poly (ether sulfone)

Polyurethane

Polyacetal

Poly (acrylonitrile-co-styrene) fluoropolymer

109 91 92 108 93 94 107 95 96

15.0 30.0 15.0 30.0 15.0 30.0

25 21.3 17.5

75 63.7 52.5 75 63.7 52.5 75 63.7 52.5

25 21.3 17.5

25 21.3 17.5

Tables

Mixture polymer type

% Block

No.

copolymer

2 **

2nd

3rd

4th

5

6

7

8th

9

110

0

NB *

3.20

3.09

7,700

6

10,100

3.19

3,100

1.70

81

Nylon 6

15

NB

2.50

2.41

6,200

-

9,400

2.51

3,500

1.40

82

30th

NB

1.80

1.76

4,400

-

6,200

1.70

2,300

0.95

111

0

NB

4.02

3.70

9,500

-

13,500

3.59

8,200

2.81

83

Poly

15

NB

2.70

2.71

6,500

6

9,800

2.77

5,400

1.73

(ether sulfone)

84

30th

NB

1.72

1.71

4,100

8th

5,500

1.60

3,100

1.27

120

0

5,500

3.26

3.04

6,500

1

9,800

2.84

5,200

1.42

85

Fluoropolymer

15

NB

2.65

2.48

5,500

-

7,600

2.24

4,300

1.11

86

30th

NB

1.89

1.76

4,400

-

4,900

1.59

3,000

0.82

109

0

8,900

3.55

3.48

9,100

6

13,700

3.45

3,000

1.17

91

PBT

15

NB

-

2.98

7,200

6

10,400

2.77

2,900

1.08

92

30th

NB

-

2.19

5,000

5

6,800

2.1

1,800

0.81

* NB

means «no break»

637 665

16

Table II continued

mixture

Polymer type

% Block

No.

copolymer

2nd

3 4

5

6

7

8th

9

108

0

9.150

4.11

3.88 -

4th

14,300

3.97

6,900

2.37

93

Polyacetal

15

6,500

2.97

2.86 6,600

5

10,100

2.94

4,810

1.79

94

30th

4,800

2.20

2.07 4.800

6

6,800

2.13

3,030

1.25

107

0

NB *

2.56

2.41 6.200

NB

9,200

2.36

7,600

1.04

95

Polyurethane

15

NB

2.07

2.03 4,900

NB

7,500

8.03

1,800

1.11

96

30th

NB

1.40

1.33 3,500

NB

5,000

1.45

1,100

0.72

* NB

15

means «no break»

mixture

Polymer type

% Block

Izod at

Impact at

No.

copolymer

23 ° C

-20 °

10 **

11

12

13

14

15

16

17th

110

0

271

4.54

0.37

117

0.30

0.42

0.14

0.18

81

Nylon 6

15

274

4.82

0.33

99

2.48

1.86

0.74

0.50

82

30th

270

4.41

0.79

73

19.0

2.75

1.40

1.16

111

0

5.17

0.23

122

0.57

0.75

0.72

0.67

83

Poly

15

4.33

0.19

106

3.54

7.72

1.44

1.42

(ether sulfone)

84

30th

4.24

0.20

68

10.8

8.74

2.94

2.71

120

0

279

4.72

0.116

114

4.50

4.23

2.19

2.50

85

Fluoropolymer

15

289

4.44

0.131

92

10.6

9.60

11.4

6.69

86

30th

277

4.50

0.107

54

11.9

9.70

8.91

7.66

109

0

234

4.38

0.12

122

1.47

1.95

1.37

1.02

91

PBT

15

244

3.35

0.12

105

12.2

12.0

3.03

2.77

92

30th

239

3.15

0.11

78

15.6

19.1

9.0

4.83

mixture

Polymer type

% Block

Izod at

Impact at

No.

copolymer

23 ° C

- 20 ° F

10 **

11

12

13

14

15

16

17th

108

0

286

4.74

0.14

120

1.45

1.81

1.26

1.41

93

Polyacetal

15

278

5.09

0.13

100

2.23

4.34

1.33

1.98

94

30th

277

4.90

0.09

77

4.82

5.31

2.51

1.84

107

0

255

4.79

0.19

167

15.2

15.5

4.9

15.4

95

Polyurethane

15

250

4.85

0.16

88

19.5

14.8

5.7

6.3

96

30th

248

4.48

0.15

59

14.6

18.6

11.5

15.4

Values given in columns 1-17 of Table II:

1. tensile tensile strength in psi (psi = pounds per inch2)

2. Young's module in psi X 105

3. Secant module in psi X 105

4. Yield strength in psi

5. Elongation in%

6. Maximum in psi

7. Module in psi X 105

8. Maximum in psi

9. Module in psi X 105

10. Dimensional stability limit temperature (HDT) in ° F

11. Linear expansion X 10 ~ 5 in inches per inch per ° C

12. Water absorption in%

13. Rockwell hardness, R

14. at the gate

15. opposite the sprue - | Notched impact strength

16. at the gate | nachlzod

17. versus sprue J in ft-lbs / inch

17th

637 665

Table 111 Mixture No.

50 51 73 74 97 98

Block copolymer blend

Poly (butylene terephthalate)

Polypropylene

15.0 30.0 15.0 30.0 15.0 30.0 42.5 35.0 63.7 52.5

Nylon 6

Polycarbonate

Poly (acrylonitrile-co-styrene)

63.7 52.5

42.5 35.0 21.3 17.5 21.3 17.5

Mix number

164 190 204 209 88 117 163

Block copolymer blend

Poly (butylene terephthalate)

Polypropylene

Nylon 6

Polycarbonate

Poly (acrylonitrile-co-styrene)

15.0 15.0 15.0 30.0

75.0

51.0 42.5

17.5

21.2 34.0 42.5 52.5 25.0

75.0

25.0 25.0 75.0

63.8

The surprising properties of the relative increase in notched impact strength according to Izod in the mixtures according to the invention are clearly evident from the tables. Ver 23 ° relative to the relative drop in shape retention

If, for example, the mixture 109 is compared with the mixture temperatures for polymer mixtures, if the percentage of gen 91 and 92, it is found that with a ratio of block copolymer with a fixed ratio of 3: 1 of poly-

Polycarbonate to PBT of 3: 1 an increase in the proportion of carbonate to industrial thermoplastics from 0 to 15% of block copolymer increases from 0 to 15-30% the dimensional stability - so you can see that the values achieved are significant

Limit temperature (HDT) does not drop as you should expect; are higher than expected. On the contrary, those skilled in the art would, without the HDT being in the blends with a content of 30, doubt that this value would be positive and less than in block copolymer higher than in blend 109, which would not be 1. Mixtures containing nylon 6, a fluorine

Contains block copolymer. When adding an amorphous rubber copolymer, a polyacetal and poly (butylene terephthalate)

Tschuks to a thermoplastic should actually contain one, the ratio is minus 142 or minus 23.28

expect a significant decrease in the HDT value because the mold and 37. The minus values are particularly surprising because they show very low resistance limit temperature of the rubber 35 an increase in the deformation limit temperature,

is. if the block copolymer content is increased.

It is also noteworthy that with increasing proportions of block copolymer, the notched impact strength according to Izod is clearly Example 2

increases, while the dimensional stability limit temperature as in Example 1, various other mixtures were not significantly affected. This shows up dramatically, which are listed in Table III.

see way of the ratio of the percentage increase. With a content of block copolymer, the polymer showed

Notched impact strength divided by the percentage change mixtures in all cases the desired interlocking of the HDT value. For example, examine the relationship between network structure.

C.

Claims (45)

637 665 2nd PATENT CLAIMS 1. Synthetic resin mixture containing a partially hydrogenated block copolymer which contains at least two terminal polymer blocks A from a monoalkenylarene with a number average molecular weight of 5,000 to 125,000 and at least one intermediate polymer block B from a conjugated diene with a number average molecular weight of 10,000 to 300,000 contains, wherein the terminal polymer blocks A make up 8 to 55 wt .-% of the block copolymer and no more than 25% of the arene double bonds in the polymer blocks A and at least 80% of the aliphatic double bonds in the polymer blocks B are hydrogenated, characterized by a Content of the following components: a) 4 to 40 parts by weight of partially hydrogenated block copolymer; b) a polycarbonate with a melting point of over 120 ° C. and c) 5 to 48 parts by weight of at least one thermoplastic industrial synthetic resin from the group of polyamides, polyolefins, thermoplastic polyester, poly (aryl ether), poly ( arylsulfones), acetal resins, thermoplastic polyurethanes, halogenated thermoplastics and nitrile resins, wherein the weight ratio of polycarbonate (b) to thermoplastic industrial resin (c) is greater than 1: 1 and in the polymer mixture at least two of the polymers are present with one another as completely or partially continuous, interlocking networks. 2. A synthetic resin mixture according to claim 1, characterized in that the polymer block A has a number average molecular weight of 7,000 to 60,000 and the polymer blocks B have a number average molecular weight of 30,000 to 150,000. 3. Resin mixture according to claim 1 or 2, characterized in that the terminal polymer blocks A10 represent 30 to 30% of the total weight of the block copolymer. 4. Synthetic resin mixture according to one of claims 1 to 3, characterized in that less than 5% of the arene double bonds in the polymer blocks A and at least 99% of the aliphatic double bonds in the polymer blocks B are hydrogenated. 5. Synthetic resin mixture according to one of claims 1 to 4, characterized in that the polycarbonates can have the following general formulas O II fAr-A-Ar-O-C-O ^ -n I or O II fAr-O-C-O ^ II, wherein Ar represents a phenylene or an alkyl, alkoxy, halogen or nitro substituted phenylene group, A represents a carbon-carbon bond or an alkylidene, cycloalkylidene, alkylene, cycloalkylene, azo, imino, sulfoxide or Means sulfone group or a sulfur or oxygen atom and n is at least equal to two. 6. Synthetic resin mixture according to one of claims 1 to 5, characterized in that the thermoplastic industrial resin different from the other constituents has an apparent crystal melting point of more than 120 ° C. 7. A synthetic resin mixture according to claim 6, characterized in that the thermoplastic industrial resin has an apparent crystal melting point between 150 and 350 ° C. 8. Synthetic resin mixture according to one of claims 1 to 5, characterized in that the thermoplastic industrial resin is a polyolefin which has a number average molecular weight of more than 10,000 and an apparent crystal 5 has a melting point of more than 100 ° C. 9. A synthetic resin mixture according to claim 8, characterized in that the polyolefin is a homopolymer or copolymer derived from an α-olefin or a 1-olefin having 2 to 5 carbon atoms. 10th 10. A synthetic resin mixture according to claim 8 or 9, characterized in that the number average molecular weight of the polyolefin is over 50,000. 11. synthetic resin mixture according to one of claims 8 to 10, 15 characterized in that the apparent crystal melting point of the polyolefin is between 140 and 250 ° C. 12. Synthetic resin mixture according to one of claims 8 to 11, characterized in that it contains a high-density polyethylene which has a crystallinity of more than 75% and 20 has a density of 0.94 to 1.0 kg / 1. 13. Resin mixture according to one of claims 8 to 11, characterized in that it contains a low-density polyethylene which has a crystallinity of more than 35% and a density of 0.90 to 0.94 kg / 1. 25 14. Resin mixture according to one of claims 8 to 13, characterized in that it contains a polyethylene with a number average molecular weight of 50,000 to 500,000. 15. synthetic resin mixture according to one of claims 8 to 11, 30 characterized in that it contains an isotactic polypropylene. 16. A synthetic resin mixture according to claim 15, characterized in that the polypropylene has a number average molecular weight of more than 100,000. 35 17. Synthetic resin mixture according to one of claims 8 to 11, characterized in that it contains, as polyolefin, a polypropylene copolymer which contains ethylene or another α-olefin as comonomer in an amount of 1 to 20% by weight. 40 18. Synthetic resin mixture according to one of claims 8 to 11, characterized in that it contains poly-l-butene as the polyolefin. 19. Synthetic resin mixture according to one of claims 8 to 11, characterized in that it is a copolymer as a polyolefin Contains 45 of 4-methyl-1-pentene and an α-olefin. 20. A synthetic resin mixture according to claim 19, characterized in that it is a polyolefin, a copolymer of 4-methyl-1-pentene and a linear α-olefin with 4 to 18 carbon atoms. 50 atoms, which is present in an amount of 0.5 to 30 wt .-% based on the weight of the copolymer. 21. A synthetic resin mixture according to one of claims 1 to 7, characterized in that the other constituent 55 len various thermoplastic industrial resin is a polyamide with a number average molecular weight of more than 10,000. 22. Synthetic resin mixture according to claim 21, characterized in that the thermoplastic industrial resin 60 is polyethylene terephthalate, a polypropylene terephthalate or a polybutylene terephthalate. 23. A synthetic resin mixture according to claim 22, characterized in that the thermoplastic industrial resin is a polybutylene terephthalate with a number average molecular weight 65 is from 20,000 to 25,000. 24. A synthetic resin mixture according to claim 21, characterized in that the thermoplastic industrial resin is a cellulose ester. --rr 637 665 25. A synthetic resin mixture according to claim 21, characterized in that the thermoplastic industrial resin is a homopolymer of pivalolactone. 26. The synthetic resin mixture according to claim 21, characterized in that the thermoplastic industrial resin is a copolymer of pivalolactone with not more than 50 mol% of another β-propiolactone. 27. A synthetic resin mixture according to claim 26, characterized in that the thermoplastic industrial resin is a copolymer of pivalolactone with not more than 10 mol% of another β-propiolactone. 28. Synthetic resin mixture according to one of claims 26 and 27, characterized in that the thermoplastic industrial resin is a pivalolactone copolymer which melts above 120 ° C and has a number average molecular weight of more than 20,000. 29. A synthetic resin mixture according to claim 21, characterized in that the thermoplastic industrial resin is a polyca prolactone. 30. Synthetic resin mixture according to one of claims 1 to 7, characterized in that the thermoplastic industrial resin is a homopolymer of formaldehyde or trioxane. 31. A synthetic resin mixture according to one of claims 1 to 7, characterized in that the thermoplastic industrial resin is a polyacetal copolymer. 32. Synthetic resin mixture according to one of claims 1 to 7, characterized in that the thermoplastic industrial synthetic resin is a homo- or copolymer of tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, vinylidene fluoride or vinylidene chloride. 33. Synthetic resin mixture according to one of claims 1 to 7, characterized in that the thermoplastic industrial resin is a nitrile resin with an α, β-olefinically unsaturated mononitrile content of more than 50% by weight. 34. Resin mixture according to claim 33, characterized in that the a, ß-olefinically unsaturated mononitrile has the general formula CH-> = C -CN I R in which R represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a halogen atom. 35. Synthetic resin mixture according to claim 33, or 34, characterized in that the nitrile resin is a homopolymer, a copolymer, a copolymer grafted onto a rubber-like substrate or a mixture of homopolymers and / or copolymers. 36. Synthetic resin mixture according to one of claims 1 to 35, characterized in that it contains 100 parts by weight of 8 to 20 parts by weight of block copolymer and 10 to 35 parts by weight of thermoplastic industrial resin. 37. Synthetic resin mixture according to one of claims 1 to 36, characterized in that it contains 0 to 100 parts of an expanding oil per 100 parts by weight. 38. Synthetic resin mixture according to claim 37, characterized in that it contains the stretching oil in an amount of 5 to 30 parts by weight per 100 parts by weight. 39. Synthetic resin mixture according to one of claims 1 to 38, characterized in that it contains as an additional resin a flow-promoting resin in an amount of 0 to 100 parts by weight per 100 parts. 40. synthetic resin mixture according to claim 39, characterized in that it contains the additional resin favoring the flow in an amount of 5 to 25 parts by weight per 100 parts. 41. A synthetic resin mixture according to claim 39 or 40, characterized in that it contains an a-methylstyrene resin, a coumaroneind resin, a vinyltoluene-a-methylstyrene copolymer, a polyinden resin or a polystyrene resin as additional resin 5 contains low molecular weight. 42. A process for the preparation of the synthetic resin mixture as claimed in one of claims 1 to 41, characterized in that 4 to 40 parts by weight of the partially hydrogenated block copolymer (a) are characterized by those in claim 1 under (b) and (c). 1 (1 neten other resins mixed in the specified ratio, the weight ratio of the polycarbonate (b) to the different thermoplastic industrial resin (c) is greater than 1: 1, so that a polymer mixture is formed in which at least two of the polymers 15 form an at least partially continuously interlocking network with one another. 43. The method according to claim 42, characterized in that the polymers are mixed with one another at an operating temperature Tp of 230 to 300 ° C. 44. The method according to claim 42 or 43, characterized in that the polymers are dissolved in a common solvent and coagulated by mixing in a solvent in which none of them is soluble. 45. The method according to claim 42 or 43, characterized in 25 shows that the polymers are mixed as granules and / or powder by shear. 46. The method according to any one of claims 42 to 45, characterized in that the ratio of the viscosity of the block copolymer divided by the viscosity of the polyester, or 30 from the other constituents different thermoplastic industrial resin or the mixture of the latter two at the relevant working temperature Tp and a shear rate of 100 s_1 between 0.2 and 4.0, in particular between 0.8 and 1.2. 47. The method according to any one of claims 42 to 46, characterized in that the thermoplastic industrial resin different from the other constituents is mixed with at least one viscosity modifier before mixing with the polycarbonate and the block copolymer. 48. The method according to any one of claims 42 to 47, characterized in that the viscosity modifier is poly (2,6-dimethyl-1,4-phenylene) oxide or a mixture of poly (2,6-dimethyl-l, 4-phenylene) oxide and polystyrene. 49. The method according to claim 47 or 48, characterized in 45 shows that the viscosity modifier is used in an amount of up to 100, preferably from 10 to 50 parts by weight per 100 parts of industrial thermoplastic resin. 50. The method according to any one of claims 42 to 49, characterized in that the block copolymer in an amount 50 from 8 to 20 parts by weight and the thermoplastic industrial resin in an amount of 10 to 35 parts by weight. 35