CH635601A5 - Mixture containing synthetic resins and containing a partially hydrogenated block copolymer and a synthetic thermoplastic engineering resin - Google Patents

Description

The invention relates to a mixture containing synthetic resins containing a partially hydrogenated block copolymer, the latter comprising at least two end blocks A of a monoalkenylarene homo- or copolymer with a number average molecular weight of 5,000 to 125,000 and at least one intermediate block B of one Homo- or copolymer of a conjugated diene with a number average molecular weight of 10,000 to 300,000, and wherein the terminal polymer blocks A 8 to 55 wt .-% of the block

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represent copolymers 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 reduced.

Thermoplastic resins that can be used in technology and industry, also referred to as “engineering thermoplastic resins”, are a group of polymers that have proven themselves as technical building materials because they have certain properties such as strength, rigidity, impact and Impact resistance and dimensional stability are in a favorable balance for a long time. Such “industrial thermoplastics” are particularly suitable as a replacement for metals, since they are much lighter than these, which is often an advantage, especially in automotive engineering.

A single thermoplastic resin sometimes does not have the combination of properties that is desirable for a particular application and there is interest in overcoming this disadvantage. A particularly obvious way is to mix two or more polymers (each of which has the desired properties) so that a material with the desired combination of properties is obtained. This can be successful in certain cases, e.g. in improving the impact and shock resistance of thermoplastic resins such as polystyrene, polypropylene and polyvinyl chloride, using special mixing processes or additives for this purpose. In general, however, the blending of thermoplastic resins is not a promising way to combine the desirable properties of two or more polymers in a single material. On the contrary, it has often been shown that mixing leads to the fact that the respective weaknesses of the individual components unite, so that one obtains a material that is uninteresting and worthless in practice. The reasons for this are well known and partly consist in the fact that, as thermodynamics teaches, most polymers cannot be mixed together, although some exceptions to this rule are well known. In addition, most of the polymers adhere poorly to one another. As a result, the contact surfaces between the constituents of the mixture (due to their immiscibility) represent areas of particular weakness in the mixtures, in which cracks and cracks occur all too easily and impair the mechanical properties of the mixture. Most polymer pairs are therefore said to be "incompatible". In some cases, compatibility means something like miscibility, but the term compatibility is used here in a more general sense and means the possibility of combining two polymers in such a way that their properties are improved, without necessarily meaning real miscibility.

One method of avoiding this problem with polymer blends is to make the two polymers compatible by adding a third component, often referred to as a compatibilizer, and a reciprocal one compared to the two polymers being blended Has solubility. Examples of such third components are certain block or graft copolymers. Because of the property mentioned, this mediator attaches itself to the contact surface between the two polymers and greatly improves the mutual adhesion and thus the stability of the product against rough phase separation.

In contrast, the invention opens up a possibility of stabilizing mixtures of several polymers, which is independent of the above-mentioned agents for increasing the compatibility and is not restricted by the need to use substances with bilateral solubility properties. The substances provided according to the invention to be used for this purpose are special block copolymers in which there is the possibility of a heat-reversible (thermally reversible) self-crosslinking. Its effect according to the invention does not correspond to that sought in the customary method for improving the compatibility, and this is demonstrated by the very general ability of these substances to uniformly represent components for a wide range of mixtures, which are those which have hitherto been provided in the past Solubility requirements do not meet.

As already mentioned, the invention relates to a synthetic resin mixture containing a partially hydrogenated block copolymer, the latter comprising at least two end blocks A made of 15 a monoalkenylarene polymer with an average molecular weight of 5,000 to 125,000 and at least one intermediate block B made of a polymer of a conjugated diene with an average molecular weight of 10,000 to 300,000; In the synthetic resin mixtures according to the invention, 20 the terminal polymer blocks A represent 8 to 55% by weight 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. Reduced hydrogenation; the synthetic resin mixtures according to the invention are characterized by a content of the following components:

a) 4 to 40 parts by weight of partially hydrogenated block copolymer;

b) a polyolefin with a numerical mean for 30 the molecular weight of more than 10,000 and an apparent crystal melting point between 100 and 250 ° C;

c) 5 to 48 parts by weight of at least one different. gene thermoplastic industrial resin, which was selected from the group of polyamides, thermoplastic polyesters, 35 poly (aryl ethers), poly (aryl sulfones), polycarbonates, acetal resins, polyamide imides, thermoplastic polyurethanes, halogenated thermoplastics and nitrile resins, wherein the weight ratio of the polyolefin to the various thermoplastic Industrial synthetic resin is at least 1: 1, so that a poly-40 mer mixture is present, in which at least two of the polymers form at least partially continuous, interlocking networks.

The relevant block copolymer according to the invention acts as a mechanical or structural stabilizer, 45 which links the various polymer network structures and prevents the later separation of the polymers during processing and actual use. The resulting structure of the polymer mixture is to be defined more precisely in such a way that there are at least two partially continuous, interlocking or interlinked networks. A dimensionally stable polymer mixture is therefore present which, due to its structure, does not separate into individual layers either during extrusion or during subsequent use.

55 In order to produce stable mixtures, at least two of the polymers must have an at least partially continuous network, the two networks intermeshing or being linked to one another. Preferably, the block copolymer and at least one of the other polymers have a partially continuous, interlocking network structure. Ideally, all polymers would exist as completely continuous networks that are linked together. By a partially continuous network it is meant that part of the polymer has a continuous network structure 65, while the other part is in the form of a disperse phase. Preferably the main part, i.e. more than 50% by weight of the network continuously, i.e. coherent. As can be easily seen, the structure of the mixtures

5

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be very different since the structure of the polymer couples in a mixture with a difunctional coupling agent,

on the other hand, either completely continuous, completely disperse or partially con-branched structures can be obtained by using them continuously and partially disperse. In addition, the use of suitable coupling agents, which with regard to the preliminary

disperse phase of one polymer in a second polymer ferpolymer have a functionality of three or more,

and not be distributed in a third polymer. To show some 5 The coupling can be carried out with multifunctional of these structural possibilities, below are the various coupling agents, such as with haloalkanes or alkenes and the possible combinations of polymer structures, divinylbenzene, as well as with certain polar compounds, with all structures leading no substructures, but silicone halides, siloxanes or esters of monovalent AI

are complete structures. Three polymers (A, B alcohols with carboxylic acids. The presence of any and C) are involved. The index «c» means a continuous io chen coupler residues in the polymer can

Structure, while the index “d” means a disperse structure of the polymers that form part of the inventive

tet. The term “ACB” means that the polymer A is a mixture containing plastics, is neglected continuously alternating with the polymer B and the beings. Also, in the sense of the genre, it does not come down to that

Drawing «BdC» means that the polymer B in polymer C has the respective structure. According to the invention, selectively

is dispersed etc.

15 third polymers used before the hydrogenation in their

Configuration in particular the following typical types

ACB

AcC

BcC

speak:

AdB

AcC

BcC

Polystyrene-polybutadiene-polystyrene (SBS)

ACB

AcC

BdC

Polystyrene-polyisoprene polystyrene (SIS)

BdA

AcC

BcC

20 poly (a-methylstyrene) polybutadiene-poly (a-methylstyrene) and

BjC

ACB

AcC

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

CdA

ACB

AcC

Both the polymer blocks A and the blocks B can ent

QB

ACB

AcC

neither be homopolymer blocks or statistical copolymer blocks, as long as only each polymer block in at least one class. According to the invention, polymer mixtures can be produced which contain the monomers characterizing the polymer blocks, over which the properties are particularly useful. Thus, the polymer block A homopolymers can be in egg equilibrium, so that the respective properties of a monoalkenylarene and copolymers of a monoalkene of the individual polymers mutually support and reinforce one another. So include nylarene with a conjugated diene, as long as only in accordance with the invention, for example, a mixture of individual polymer blocks A can predominate the monoalkenylarene units in a large proportion of a relatively inexpensive polyolefin 30. The term “monoalkenyl arene” means here and a smaller proportion of a more complex thermoplastic, among other things especially styrene and its analogs and hoplastic industrial synthetic resin, such as polybutylene terephthalate mologists including a-methylstyrene and ring-substituted, which produce at much lower production costs. Styrenes, especially ring-methylated styrenes. Preferred is a large part of the desirable properties of the above a-methylstyrene, in particular unsubstituted styrene. has more agile industrial resin. 35 Polymer blocks B can contain homopolymers of a conjugated

It is particularly surprising in the present case that even ten diene, such as butadiene or isoprene or copolymers made from a small proportion of block copolymer, is sufficient to be a conjugated diene with a monoalkenylarene, so that the structure of the polymer mixture is only within a wide range the polymer blocks B to stabilize the conjugated diene unit concentration region. For example, already prevail. If butadiene is used as the monomer, then four parts by weight of block copolymer, in order to obtain a mixture of 5 to 40, the condensed butadiene units in the butadiene-90 parts by weight of polyolefin with 90 to 5 parts by weight of a polymerizer block of at least 35 to 55 mol -% stabilize the 1,2-configura-like industrial thermoplastics. tion. Then when such a block is hydrogenated,

It is also surprising that the block copolyme- the resulting product is a regular copolymer block of ren for stabilizing polymers of so diverse chemical ethylene and butene-1 (EB) or similar in any case can be used with such a shear nature. How to explain 45 copolymer block. If the conjugated diene is isoprene, which will be, this ability of the block copolymers is based on hydrogenation, so a regular copolymer block is formed from the hydrogenation to stabilize a whole range of polymers within ethylene and propylene (EP) or in any case a similar block, a broad concentration range, based on that against the hydrogenation of the precursor block copo-

Oxidation are stable, at a shear stress of 0 a lymer one is preferably used as the catalyst and has a practically infinite viscosity, and in the melt 50 product of an aluminum alkyl compound with a network structure on which it is based is maintained. Nickel or cobalt carboxylate or alkoxide under such conditions

A further important aspect of the invention consists in conditions that at least 80% of the aliphatic double binders — that the different polymer mixtures are much easier to process — are practically completely hydrogenated, while the aro-work and deform them if the alkenylarene double bonds according to the invention are mat a maximum of 25% hy-intended block copolymers are used as stabilizers. 55 be third. Preference is given to block copolymers in which at least 99% of the aliphatic double bonds in the synthetic resin mixtures according to the invention are hydrogenated, and block copolymers can have a very different geometric structure from the aromatic double bonds since they are not hydrogenated as 5% according to the invention .

to any specific geometric structure, but only The average molecular weight of the individual blocks can vary within certain limits depending on the chemical constitution of each of the polymers. That arrives in the invention blocks. The block copolymers can e.g. linear block copolymer present in accordance with synthetic resin compositions has to be radial or branched. Processes for producing such at least two end blocks A from a monoalkenyl arene poly polymer are known. The structure of the polymers is particularly good with an average molecular weight of 5000 to depending on the respective polymerization process. Thus 125,000, preferably from 7,000 to 60,000, and at least one e.g. linear polymers by successive introduction of an intermediate block B, which is a polymer of a conjugation of the corresponding monomers into the reaction vessel, diene with an average molecular weight of 10,000 to 300,000, preferably from 30,000 to, if initiators, such as lithium alkyls or dilithioostilbene 150,000. These are used or if you have a block copolymer of two Seg molecular weights are numerical mean values that change on

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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 polyolefins present in the plastic compositions according to the invention are 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 (1-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 is 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 is between 100 and 250 °, preferably between 140 and 250 ° C. The production of these various polyolefins is known (see “Olefin Polymers” in Kirk-Othmer, Encyclopedia of 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 / l, 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 is over 100,000. The polypropylene can be produced 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 commercial polypropylenes are usually made using a solid, crystalline, hydrocarbon soluble catalyst made from a mixture of titanium chloride and an aluminum alkyl compound, e.g. Triethyl aluminum or diethyl aluminum 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 obi-io gene encyclopedia by Kirk-Othmer, Supplementary Volume, pp. 792-907 (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 151-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 expression “different thermoplastic industrial

20th

strieharz »refers to thermoplastic technical or industrial resins which differ from the polyolefins present in the synthetic resin mixtures according to the invention.

The term “thermoplastic industrial resin” or 25 “thermoplastic technical resin” encompasses the various polymers which are listed in Table A below and are described in more detail below.

Table A

30th

1. Polyamides

2. thermoplastic polyester

3. Poly aryl ether and polyarylsulfones

4. Polycarbonates 35 5. Acetal resins

6. Polyamide imides

7. Thermoplastic polyurethanes

8. halogenated thermoplastics

9. Nitrile resins

40

The thermoplastic engineering or industrial resins preferably have an oil transition temperature or an apparent crystal melting point (defined as the temperature at which the module suffers a catastrophic drop under light load) of more than 120, preferably between 150 and 350 ° C., and have the ability to a thermal reversible cross-linking mechanism to form a continuous network structure. Such thermally reversible crosslinking mechanisms include crystallite formation, 50 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 ratio of 1005-1 is equal to i], the ratio of the viscosity of the thermoplastic industrial resin or of its mixture can also Viscosity modifiers to r | are between 0.2 and 4.0 and are preferably 0.8 to 1.2. The viscosity of the block copolymer, the polyolefin and the thermoplastic industrial resin is to be understood here as the so-called 60 “melt viscosity” which is obtained by use 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 in such a way that the resin can be processed in a device with low to medium shear temperature at a temperature of 350 ° C or less customary in the art .

7

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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 as follows:

Polyamide means a condensation product which has recurring aromatic and / or aliphatic amide groups as parts of the main polymer chain; such products are commonly known as "nylons". The polyamides can be obtained by polymerizing a monoaminocarboxylic acid or an internal lactam of such acid with at least two carbon atoms between the amino and carboxyl groups. They are also obtainable by polymerizing practically equimolar parts of a diamine which contains 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. 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 mentioned or their lactams 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, Ca. prolactam, 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'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylsulfone, 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. Dicarboxylic acids of the formula HOOC.Y.COOH are preferred, in which Y represents a divalent aliphatic radical having at least 2 carbon atoms: Examples are: sebacic acid, octadecanedioic acid, suberic acid, azelaic acid, undecanedioic acid, glutaric acid, pimelic acid and in particular adipic acid, oxalic acid also preferred.

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

Polyhexamethylene adipinamide (nylon 6 :()

Polypyrrolidone (nylon 4)

Polycaprolactam (nylon 6)

Polyheptolactam (nylon 7)

Polycaprylic lactam (nylon 8)

Polynonanolactam (nylon 9)

Polyundecanolactam (nylon 11)

Polydodecanolactam (nylon 12)

Polyhexamethylene azelaine amide (Nylon 6: 9) Polyhexamethylene sebacinamide (Nylon 6:10) Polyhexamethylene isophthalamide (Nylon 6: iP) s 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)

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)

i5 hexamethylene adipamide / hexamethylene terephthalic acid amide (nylon 6: 6 / 6T)

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

Hexamethylene Adipinamide / Hexamethylene Azelaine Amide (Nylon 20 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 25 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.

The thermoplastic polyesters which may be present in the compositions according to the invention have a generally crystalline structure, a melting point preferably above 120 ° C. and are thermoplastic (in contrast to thermosetting).

A particularly useful group of polyesters are those thermoplastic polyesters which are produced by condensing a dicarboxylic acid or its lower alkyl ester, its acid halide or anhydride with a glycol in a manner known per se. Aromatic 40 and aliphatic dicarboxylic acids which are suitable for the production of the polyesters include: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p-carboxyphenolacetic acid, p, p'-dicarboxiphenyl, p, p'-di-45 carboxydiphenyl sulfone, p-carboxyphenoxyacetic acid,

p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, p-carboxyphenoxyhexanoic acid, p, p'-dicarboxydiphenylmethane, p, p-dicarboxydiphenyl-propane, p, p'-dicarboxydiphenyloctane, 3 -carboxy-50 ethoxy) -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 55 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 col. Aromatic glycols can be substituted in whole or in part. Suitable aromatic dihydroxy compounds include 60 and others. 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.

65 A preferred group of polyesters are: polyethylene terephthalate, polypropylene terephthalate and in particular polybutylene terephthalate; the latter, a crystalline copolymer, can be formed by polycondensation of 1,4-

635 601

8th

Butanediol and dimethyl terephthalate or terephthalic acid, and has the general formula:

i.a. linear thermoplastic polymers from recurring units of the formula

-fO-G-O-G '}

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

10th

II

and o

where n can be 70 to 140. The average molecular weight of the polybutylene terephthalate is preferably between 20,000 and 25,000.

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, Celiu - should be mentioned. D.,. , _ .., ", cc

, ",,. . , '' 20 wherein Pure bond between aromatic carbon -

loseacetate (e.g. cellulose diacetate, cellulose tnacetate), cellulose

losebutyrate, cellulose acetate butyrate, cellulose propionate, ceflu-

losetridecanoate, carboxymethyl cellulose, ethyl cellulose, hydr

oxyethyl cellulose and acetylated hydroxyethyl cellulose (see

Pp. 25-28 from «Modern Plastics Encyclopedia», 1971-72)

Another useful polyester is a polypivalol lactone,

i.e. a linear polymer with recurring ester units,

mainly according to the formula:

III

atoms -O-, -S-, -S-S—, or a divalent hydrocarbon radical having 1 to 18 carbon atoms and G 'is the remainder of a dibromo or diiodobenzene compound selected from the following group:

25th

IV

-CH2-C (CH3> 2-C (0) 0-

i.e. with units derived from pivalolactone. Preferably the polyester is a pivalolactone homopolymer. However, the copolymers of pivalolactone with not more than 50 mol%, preferably not more than 10 mol%, can also be used.

another ß-propiolactone, such as ß-propiolactone, a, a-diethyl-ß-propiolactone and a-methyl-a-ethyl-ß-propiolak-ton. The term "ß-propiolactone" refers to ß-propiolactone (2-oxetanone) and to derivatives thereof which have no substituents on the ß-C atom of the lactone ring. Preference is given to β-propiolactones which contain a tertiary or quaternary carbon atom in the alpha position 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 C atoms.

Examples of suitable monomers are: a-ethyl-a-methyl-β-propiolactone, a-methyl-a-isopropyl-β-propiolactone, a-ethyl-butyl-β-propiolactone, a-chloromethyl-a-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-s-caprolactones are essentially linear polymers in which the repeating unit can be represented by the following formula:

O

II «

4o-ch2-ch2-ch2-ch2-ch2-c] -

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 can be present in the compositions according to the invention are and

35

V

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 RO- means R' is not equal to -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, oxidation and chemical influences. Commercial polyaryl polyethers with melting temperatures between 280 and 310 ° C are available under the protected trade name Arylon T®.

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

-Ar-SO, -

where Ar is a divalent aromatic radical that may optionally change from unit to unit in the polymer chain, so that copolymers of various types are formed. Thermoplastic polysulfones generally have at least some units of the following structure:

50

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:

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another has recurring units of the formula:

-so.

5 and others of the formula:

£ / Vo-

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

-SO,

or

-T \.

-so.

15

to have.

Polyether sulfones with repeating units of the structure:

The thermoplastic polysulfones can also contain recurring and polyether sulfones with repeating units of the end units of the formula Structure:

-SO.

are also suitable as thermoplastic industrial resins.

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

O

40

-f A r-A - Ar-O-C -Of "

or

O

4Ar-0-C-0> n

II

wherein Ar is a phenylene group 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 sulfone group or a sulfur or oxygen atom and n is 2 or more.

The production of the polycarbonates 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 50

made by reacting p, p'-isopropylidenediphenol with phosgene and is sold under the protected names Le-xan® 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 compounds. Part of the structure can also be replaced by siloxane bonds.

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 resin of the polyether type (trade name Penton®) has the • structure:

55

60

CH2C1 I

0-CH2-C -CH24tt I

CH2C1

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

-H-O- -fCH2-0-CH2-0) -x-H

in which terminal groups come from controlled proportions of water and x denotes a larger number (preferably 1500), which is the number of formals present in succession

635 601

10th

called dehydrogen units. 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.

The term “polyacetal resins” also includes the polyacetal copolymers. These copolymers include block copolymers of formaldehyde with monomers or prepolymers of other substances which have the ability to provide active hydrogen, such as alkylene glycols, polythiols, copolymers of vinyl acetate and acrylic acid or reduced butadiene / acrylonitrile polymers.

A copolymer of formaldehyde and ethylene oxide which is commercially available under the protected name Celcon® is particularly suitable for the mixtures according to the invention. The typical structure of these copolymers includes repeating units of the formula:

-0-

H / FL t -1-

V

R,

n - '

wherein R 1 and R 2 each represent hydrogen, a lower alkyl radical or a halogen-substituted lower alkyl radical and n is a number from 0 to 3, n in 85 to 99.9% of the repeating units being zero.

Formaldehyde and trioxane can be copolymerized with other aldehydes, cyclic ethers, vinyl compounds, ketenes, cyclic carbonates, epoxies, isocyanates and ethers, including e.g. Ethylene oxide, 1,3-dioxolane, 1,3-5 dioxane, 1,3-dioxepene, epichlorohydrin, propylene oxide, isobutylene oxide and styrene oxide.

The polyamideimides which can be used in the compositions according to the invention as thermoplastic industrial resins generally have a crystalline structure and melt above 340 ° C. io These copolymers can be prepared by reacting dianhydrides with diamines containing amide groups pre-formed in an amide imide structure:

30 Other copolymers can be made by reacting the acid chloride of anhydride of a tri-acid with diamine as follows:

(1)

12T

2HN-Ar-NH2

-h2o

-NH-Ar

The bracket in the above equation means that the ent and have a crystal melting point of over 300 ° C. (The corresponding part of the molecule as shown or on the reverse 45 designation: Teflon® and Fluon®). High molecular Po way can be present. lychlorotrilfluoroethylene (PCTFE) and polybromotrifluoroethylene

Polyamide imides are also available under the Protected Trade Name (PBTFE) and can be found in the invented

Torion® in retail. appropriate masses are used.

Polyurethanes, which are also known as isocyanate resins, are particularly preferred as halogenated polymers. Homo-can also be used as thermoplastic industrial resins. 50 polymers and copolymers of vinylidene fluoride. The homopo

insofar as they are actually thermoplastic and not thermoplastic, the partially fluorinated polymers of chemical

are curing. Examples are: Polyurethanes from Toluoldiisocya- see formula 4CH2-CF2) -n. These polymers are tough linear nat (TDI) or diphenylmethane-4,4'-diisocyanate (MDI) and polymers with a crystal melting point at 170 ° C (e.g. Ky-

numerous polyols, such as polyoxyethylene glycol, Polyoxypropylnar®). The term "polyvinylidene fluoride" here refers to englycol, polyester with terminal OH groups, polyoxy- 55 not only to the normally solid homopolymers of

ethylene oxypropylene glycols. Vinylidene fluoride, but also on its normally solid

These thermoplastic polyurethanes are among the copolymers which have at least 50, preferably at least 70

protected designations Q-Thane® and Pellethane® CPR in and in particular at least 90 mol% of polymerized vinyl

Trade. have the fluoride units. Suitable comonomers are

Another group of useful industrial thermoplastic 60 halogenated olefins with up to 4 carbon atoms, e.g. sym. dichlor-

Most are the halogenated thermoplastics with essentially difluoroethylene, vinyl fluoride, vinyl chloride, vinylidene chloride,

crystalline structure and a melting point above 120 ° C. Perfluoropropene, perfluorobutadiene, chlorotrifluoroethylene, tri-

These are homopolymers and copolymers in chloroethylene and tetrafluoroethylene.

for example of tetrafluoroethylene, chlorotrifluoroethylene, bromine. Another useful group of halogenated thermo-

trifluoroethylene, vinylidene fluoride and vinylidene chloride. 65 thermoplastics are homopolymers and copolymers of vinyl

Polytetrafluoroethylene (PTFE) are fully fluorinated polymers denchloride. Crystalline vinylidene chloride copolymers are particularly basic chemical formula -fCF2-CF2) -n, which 76 preferred. The wt .-% fluorine contained in the invention contain. These polymers are highly crystalline, normally crystalline, vinylidene chloride copolymers.

11

635 601

hold 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 aralkyl acrylate with alkyl or aralkyl groups with up to about 8 carbon atoms, acrylic acid, acrylamides, vinyl alkyl ethers, vinyl alkyketones, acrolein, allyl ethers and the like and the like Butadiene and chloropropene. Known ternary mixtures can also be used to advantage. Representative of such polymers are those which are composed of at least 70% by weight of vinylidene chloride, the rest e.g. consists 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 propionate or vinyl chloride, allyl esters or ethers and vinyl chloride, butadiene and vinyl acetate, vinyl propionate and vinyl chloride and vinyl chloride Vinyl chloride. Quaternary polymers of appropriate monomer composition are also known. Copolymers with 70 to 95% by weight of vinylidene chloride and residues of vinyl chloride are particularly useful for the purposes of the invention. Such copolymers can contain the usual plasticizers, stabilizers, nucleators and extrusion aids in an appropriate amount. Mixtures of two or more such normally crystalline vinylidene chloride polymers can also be used, as well as mixtures in which such normally crystalline polymers together with other polymer modifiers, e.g. the copolymers of ethylene-vinyl acetate, styrene-maleic anhydride, styrene-acrylonitrile and polyethylene are present.

The nitrile resins which can be used as industrial resins in the present case are thermoplastic materials with a .beta.-olefinically unsaturated mononitrile content of 50% by weight.

or more. These nitrile resins can be homopolymers, copolymers, graft copolymers or copolymers on a rubber-like substrate or else mixtures of homopolymers and / or copolymers.

The a, ß-olefinically unsaturated mononitriles that come into question here have the structure:

wherein R represents hydrogen, chlorine or a methyl group and R2 is an aromatic radical with 6 to 10 carbon atoms, which may also contain substituents, e.g. Halogen and alkyl groups attached to the aromatic nucleus, e.g. Styrene, 5 a-methyl styrene, vinyl toluene, a-chlorostyrene, orthochlorostyrene, parachlorostyrene, methachlorstyrene, orthomethylstyrene, paramethylstyrene, ethylstyrene, isopropyl styrene, dichlorostyrene and vinyl naphthalene. Particularly preferred comonomers are isobutylene and styrene.

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

15

r, c =

H

I.

= c I

O

CH,

-CN

R

wherein R represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a halogen atom. The following may be mentioned: acrylonitrile, a-bromoacrylonitrile, a-fluoroacrylonitrile, methacrylonitrile and ethacrylonitrile. Acrylonitrile and methacrylonitrile and their mixtures are preferred.

Due to their complexity, these nitrile resins can be divided into different classes. The simplest molecular structure is a statistical copolymer with mainly acrylonitrile or methacrylonitrile. The best known example is a styrene-acrylonitrile copolymer. Block copolymers of acrylonitrile in which long sections of polyacrylonitrile alternate with sections of polystyrene or of polymethyl methacrylate are also known.

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 halogen and aliphatic substituted derivatives, such as vinyl chloride and vinylidene chloride, or the monomers of aromatic monovinylidene hydrocarbons of the formula c = 0

20 '

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;

25 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

30 h2c = ch-o-r4

wherein R4 can have the following meaning: an alkyl group with 1 to 8 C atoms, an aryl group with 6 to 10 C atoms or a monovalent aliphatic radical with 2 to 10 C atoms,

35 which may contain hydrocarbons or oxygen, such as an aliphatic radical with ether bonds, and which may also contain other substituents, such as halogens 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-

45 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:

40

CH,

-COOR,

55

Ri

H.C:

/ Ri

-R-

wherein R [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 60 or ethyl acrylate, methyl or ethyl methacrylate and methyl a-chloroacrylate. Methyl and ethyl acrylate and 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 grafted on

12

635 601

will. 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, the use of a synthetic or natural rubber such as polybu-tadiene, isoprene, neoprene, nitrile rubber, natural rubber, acrylonitrile-butadiene copolymers, ethylene-propylene copolymers and chlorinated rubbers are used to make the polymer to make it firmer 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. Particularly preferred are polymer mixtures 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 (Bar-ex®210) and another with over 70% Nitrii, three quarters of which are from methacrylonitrile (Lopac®) are commercially available.

In order to better match the viscosity properties of the thermoplastic industrial resin, the polyolefin and the block copolymer, it is often expedient to first mix the different thermoplastic industrial resin with a viscosity modifier before preparing the final mixture by adding the polyolefin and the block copolymer. 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-dimethyl-1,4-phenylene) oxide and mixtures of poly (2,6-dimethyl-1,4-phenylene) oxide with polystyrene.

The polyphenyl oxides which may be present as viscosity modifiers can be represented by the formula:

m in which Rj is a monovalent substituent which is 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 contain no aliphatic tertiary aC atoms and halogenated hydrocarbon residues with at least 2 C atoms between the halogen atom and the phenol ring which do not contain an aliphatic tertiary aC atom; R '! has the same meaning as Rj 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. Preferably the polyphenylene oxide is 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 5 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.

10 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 0 to 100, preferably 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 thermoplastic industrial resin and polyolefin) is still connected and has the shape of the molded or extruded object and is still structurally intact without wrinkles or decoating, and if the solvent does not contain any insoluble particles contains, there is proof that you have a "" network in front of you, in which the non-extracted and the

30th

extracted phase are interlocking and continuously present. The non-extracted phase has to be continuous simply because it remains geometrically and mechanically intact. The extracted phase must also have been continuously present before 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. Furthermore, 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. For example, in the case of a mixture of block copolymers, polypropylene and nylon 6, the block copolymers can first be extracted under reflux with toluene, so that the polypropylene and nylon phases remain. Then the nylon can be extracted with hydrochloric acid so that the polypropylene phase remains. Alternatively, one can extract the nylon first and then the block copolymer. The continuous nature of the phases and the interlocking of the cavities can be examined microscopically after each 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 of the various polymers in the mixture can be varied within a wide range. The proportions of the polymers, expressed in% by weight (the total mixture comprising 100 parts) are as follows:

13

635 601

different thermoplastic industrial resin block copolymer

Parts by weight

5-48

4-40

preferably parts by weight

10-35

8-20

The polyolefin is present in an amount equal to or larger than that on different industrial thermoplastic, i.e. the weight ratio of polyolefin to industrial resin may be 1: 1 or greater, i.e. the amount of polyolefin can vary between 30 and 91 parts by weight, preferably between 48 and 70 parts by weight. Note that the minimum amount of block copolymer in these blends can vary with the particular thermoplastic industrial resin present.

The three components, the different industrial thermoplastic resin, the polyolefin and the block copolymer, can be mixed in any way which ensures that an interlocking network is formed. For example, resin, polyolefin 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 grain and / or powder form are intimately mixed in a mixer at high shear rate.

“Intimate mixing” is understood to mean 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 are preferably used, 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. 35

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, the working temperature is also selected so that the polymers can be mixed in an isoviscous manner. The mixing or working temperature is between 150 and 400, preferably between 230 and 300 ° C. 45

Another parameter that is important if one wants to achieve intermeshing networks by mixing in the melt is that the viscosities of the block copolymer, the polyolefin and the thermoplastic industrial resin at the temperature and thus the shear stress during the mixing process aligns with each other (isoviscous mixing). The more uniformly the industrial resin and the polyolefin are distributed in the network of the block copolymer, the greater the chance that a three-dimensional network will form during the subsequent cooling, 55 in which the individual networks intermesh continuously and in unison. Therefore, if the block copolymer has a viscosity of r | Poise, a temperature Tp and a shear rate of 100 s ~, the viscosity of the thermoplastic industrial resin and / or the polyolefin should preferably be set at m the temperature Tp and a shear rate of 100 s ~ 1 that the ratio of the viscosity of the block copolymer divided by the viscosity of the thermoplastic industrial resin and / or the polyolefin is between 0.2 and 4.0, preferably between 0.8 and 1.2. 65 “Isoviscous mixing” here means that the viscosity of the block copolymer, divided by the viscosity of the other polymer or the polymer mixture at the temperature Tp and a shear rate of 100 s-1, is between 0.2 and 0.4. It must be taken into account that the shear rate inside an extruder can be distributed over a wide range. Isoviscous mixing i can therefore also take place if the viscosity curves of the two polymers differ at some of the shear rates.

In some cases the order in which the polymers are mixed is important. If necessary, one can therefore first mix the block copolymer with the polyolefin or the other polymer and then mix this mixture with the different thermoplastic industrial resin or one can simply mix all the polymers at the same time. Because of the multiple constituents of the mixtures according to the invention, different variants can be selected in the order in which they are mixed. Under certain circumstances it can also be achieved that the viscosities of the different polymers are better tolerated.

The block copolymer or the block copolymer mixture can be selected so that it is essentially compatible with the industrial resin and / or the polyolefin. Optionally, the block copolymer can be blended with a rubber extension oil or additional resin, as will be described, to change its viscosity properties.

The special physical properties of the block copolymers are important for the formation of the co-continuous, interlocking networks. In particular, the most preferred block copolymers do not melt in the unmixed state in the usual sense as the temperature rises, since the viscosity of these polymers is to a large extent “non-Newtonian” and tends to increase indefinitely against zero shear stress. In addition, the viscosity of these block copolymers is largely independent of the temperature. This rheological behavior and the already existing thermal stability of the block copolymers increases their ability to practically maintain their network structure in the melt, so that intermeshing and continuous networks form again and again in the most diverse mixtures.

The viscosity behavior of the thermoplastic industrial resins and on the other hand of the polyolefins depends much more on the temperature than that of the block copolymers. It is therefore often possible to choose a working temperature Tp at which the viscosities of the block copolymer and the industrial resin and / or the polyolefin different from it fall within the area in which interlocking networks form. Optionally, as already mentioned, a viscosity modifier can first be mixed with the industrial resin or the polyolefin in order to match the viscosities to one another.

The mixture of partially hydrogenated block copolymer, polyolefin and differentiated thermoplastic industrial resin can be mixed with a standard oil used for processing rubber and plastics. The types of oil which are compatible with the elastomer polymer blocks of the block copolymer are particularly preferred. In addition to the usable oils with a higher aromatic content, the white oils based on petroleum, which have a low volatility and an aromatic content of less than 50% (determined by the clay-gel method, ASTM method D 2007) are particularly preferred. The boiling range of the oils preferably begins above 260 ° C.

The amount of oil used is up to 100 phr (phr = parts by weight per 100 parts of block copolymer), preferably 5 to 30 phr.

The mixture of partially hydrogenated block copolymer, polyolefin and different thermoplastic industrial resin can also be mixed with an additional resin

635 601

14

the one that e.g. a flowability-increasing resin, such as an a-methylstyrene resin or a plasticizer for the end blocks.

Suitable plasticizer resins for the end blocks include coumarone indene resins, vinyltoluene-alphamethylstyrene copolymers, polyinden resins and low molecular weight polystyrene resins.

The amount of additional resin can be up to 100, preferably 5 to 500 phr.

In addition, the compositions may contain other polymers, fillers, reinforcers, antioxidants, stabilizers, fire-retardant additives, antiblocking agents and other rubber and plastic additives.

Examples of suitable fillers can be found in the reference book Modern Plastics Encyclopedia, pp. 240-247 (1971-72).

Amplifiers are also suitable for use in the present polymer mixtures. These are substances that can be added to a resin matrix to improve the strength of the polymer. Most often these are inorganic or organic products of high molecular weight, e.g. Glass fibers, asbestos, boron fibers, carbon and graphite fibers, quartz and silica fibers, ceramic or metal fibers and natural and synthetic organic fibers. Reinforced polymer mixtures containing glass fibers in an amount of 2 to 80% of their weight are particularly preferred.

Table I

The polymer mixtures according to the invention can be used as metal substitutes in areas in which high demands are placed on the material.

The examples serve to explain the invention in more detail.

Example I

Various polymer-io mixtures were prepared on a 3.125 cm sterling extruder with a Kenics die (ratio of length to diameter 24: 1, compression ratio of the screw 3.8: 1).

The block copolymer used in the present example I and in examples II to VI was a selectively hydrogenated block copolymer of the structure S-EB-S with block molecular weights of 7500-38000-7500. The oil was a commercial rubber extension oil, the polybutylene terephthalate "PBT" was a commercially available resin and the polypropylene was an essentially isotactic polypropylene with a melt flow index of 5 (230 ° C! 2.16 kg). The nylons were standard grades of nylon 6 and nylon 6 to 12.

In Example I, the block copolymer and oil were mixed before adding the polyolefin, PBT, or nylon.

The composition of the resin mixtures, the working conditions and the test results are shown in Table I-25. In all cases, the resulting polymer blends had the desired interlocking network according to the criteria set out above.

Trial No.

1

2nd

3rd

4th

5

Components,

Parts by weight

Block copolymer

6.1

5.8

12.2

12.2

11.2

oil

0.9

1.2

1.8

1.8

2.8

PBT

24.3

-

43.0

21.5

-

Nylon 6

-

25.2

-

-

-

Nylon 6-12

-

-

-

-

43.0

Polypropylene

68.7

67.8

43.0

64.5

43.0

Extrusion

temperature ° C

230

230

230

230

230

Properties Young's module x 103, kPa

1372

1544

1393

1186

1296

Yield, kPa

30265

28334

29987

27230

27576

Tensile strength, kPa

29506

26611

29987

27230

27438

Elongation at break,%

12.0

8.74

11.7

12.4

8.0

Flexural modulus x 103, kPa

1248

1200

1151

1117

1034

Impact strength after

Izod (notched),

J / cm

0.22

0.33

0.34

0.43

0.43

Example II

The polymer mixtures according to Example I, experiments 1 and 2, were reinforced with PPG 114 "glass fiber strands by first mixing the mixtures dry and then melt-mixing them with the glass fibers in the extruder. The composition, the working conditions and the test results are all good Table II before.

Tables attempt no.

Components, wt .-% polymer mixture of

100.0

100.0

Experiment No. 55 thermoplastic industrial resin glass fibers

Extrusion temperature, ° C

60 properties Young's modulus x 103, kPa yield, kPa tensile strength, kPa elongation at break,% 65 flexural modulus x 103, kPa impact strength according to Izod (notched),

J / cm

1

PBT 64.2 240

7204

48258

48258

1.06

6308

0.47

Nylon 6

65.6

240

7431

50188

50188

1.58

6081

0.69

15 635 601

Example III Composition, Working Conditions and Test Regulations

Mixtures reinforced with glass fiber were obtained in accordance with the results in Table III. All polymer mixtures

Example II produced, but all four main components had the desired interlocking network plus the glass fiber in the dry state at the same time.

were mixed instead of adding the glass fiber to the prepared 5 mixture as above.

Table III

Experiment No. 8 9 10 11 12

Components,% by weight

Block copolymer

3.7

3.5

7.7

7.7

6.8

oil

0.6

0.7

1.1

1.1

1.7

PBT

14.9

-

26.9

13.5

-

Nylon 6

-

15.0

-

-

-

Nylon 6-12

-

-

-

-

26.1

Polypropylene

41.8

41.0

26.9

40.3

26.1

glass fiber

39.8

39.8

37.4

37.4

39.2

Extrusion

temperature ° C

240

240

240

240

240

properties

Young's module x 103,

kPa

7446

7487

6673

6067

5522

Yield, kPa

47431

51498

56462

45225

52877

Tensile strength, kPa

47431

51498

56462

45225

52877

Elongation at break,%

0.97

1.21

1.61

1.11

1.78

Flexural modulus x 103, kPa

5839

5943

5495

5495

4957

Impact strength after

Izod (notched),

J / cm

0.43

0.72

0.59

0.54

0.63

35

Example IV

In this case, the block copolymer and the oil were premixed, after which the PBT was added to the mixture with thorough mixing. After the polypropylene had also been mixed in, the resulting polymer mixture had at least two polymers with at least partially continuous, intermeshing network structure, which corresponded to the plastic compositions according to the invention. Composition and working temperature are shown in Table IV.

PBT

Polypropylene 40 extrusion temperature, ° C

Table IV Experiment No.

Components,% by weight

Block copolymer

oil

13

6.1 0.9

14

12.2 1.8

45

23.2 69.8 230

21.5 64.5 230

Example V

Various polymer blends were prepared which contained nylon 6 as a different thermoplastic industrial resin from the other resins. For all blends containing the block copolymer, the oil and block copolymer were premixed and the nylon and polypropylene were blended into the melt. All mixtures were prepared at 230 ° C via the extruder. Their composition is shown in Table V 50.

Experiments 15, 16 and 21 are comparative experiments, while experiments 17 to 20 and 22 gave mixtures according to the invention with at least two continuous, interlocking networks.

55

Table V

Trial No.

15 *)

16 *)

17th

18th

19th

20th

21 *)

22

Components

% By weight

Block copolymer

-

-

4th

8th

12

24th

-

25.5

oil

-

-

1

2nd

3rd

6

-

4.5

Nylon 6

100

50

47.5

45

42.5

35

50

35

PBT

-

-

-

-

. -

-

50

35

Polypropylene

-

50

47.5

45

42.5

35

-

-

635 601

16

Table V

Trial No.

Components weight%

soluble in toluene:

expected

(% By weight)

found

(% By weight)

soluble in HCl:

expected

(% By weight)

found

(% By weight)

*) Comparison test

15 *) 16 *) 17 18 19 20 21 *) 22

0 0 5 10 15 30 0 30

1.2 3.1 4.9 10.7 14.0 28.3 0.4 29.2

100 50 47.5 45.0 42.5 35 50 35

98.8 17.8 45.0 42.9 47.6 28.6 2.3 35.3

35

40

45

A selective extraction technique was used to investigate whether there was a continuous, interlocking network. For this purpose, the polymer mixture 25 is subjected to a 16-hour Soxhlet extraction with hot toluene under reflux. Ideally, the hot toluene should extract the block copolymer and the oil, but should not dissolve the PBT or the nylon. The non-extracted portion of the mixture is then introduced into a vessel with 6 molar hydrochloric acid (HCl) 30 and shaken at room temperature for 20 hours.

The HCl should dissolve the nylon 6, but not the polypropylene or PBT. After the extraction with HCl, the undissolved portion is weighed out and the weight loss is compared with the expected values.

In experiment 15, 1.2% of the nylon 6 was soluble in hot toluene compared to an expected solubility of 0% (this value remained within the error limit). The residue of the polymer dissolved completely in the HCl.

Comparative experiments 16 and 21, in which none of the block copolymers provided according to the invention were present, missed any continuous, interlocking crosslinking. In experiment 16, 3.1% of the mixture was soluble in hot toluene, which is also within the error limit. On the other hand, however, only 17.8% of the extracted mixture was soluble in HCl, compared to an expected solubility of 50%. This shows that a large proportion of nylon was encapsulated in the polypropylene so that it could not be reached by the HCl, i.e. there was no continuous nylon network that could have been reached by the HCl. In comparative experiment 21, 0.4% of the mixture of PBT and nylon 6 was soluble in hot toluene, which almost corresponded to the theoretical value. On the other hand, however, only 2.3% of the extracted mixture was soluble in HCl (expected solubility 50%), which showed that there was no continuous, interlocking network, because obviously only a small part of the nylon was accessible to the HCl.

In contrast to the results of experiments 16 and 21, experiments 17 to 20 and 22, in which the block copolymers according to the invention were used, show the presence of continuous, interlocking networks. For example, 4 parts by weight of block copolymer are used in experiment 17. 4.9% was extracted by toluene (theoretical value 5%) and, most clearly, the HCl extracted 47.5% (compared to a theoretical value of 45.0%); all of these values are within the error limits. The experiment showed, like the other experiments in which the block copolymers according to the invention were used,

55

60

65

that the nylon existed as a continuous network accessible to the HCl.

Example VI

Microphotos of four polymer mixtures which contained the block copolymers provided according to the invention and had at least two interlocking continuous crosslinks were produced. For this purpose, the sample to be examined was freeze-fractionated in both cases by first introducing it into liquid nitrogen, from which it was then removed and broken up into two parts. The sample was then placed in an electron microscope (AMR Model 1200 Scanning Electron Microscope) and the fracture surface was photographed.

For the first uptake, the polymer blend from Run 14 was subjected to hot toluene extraction for 16 hours so that the block copolymer and oil were removed therefrom. As can be seen from Fig. 1, the polypropylene portion is continuous and honey-like, which means that the block copolymer and the polypropylene were continuously and intermeshing. The small beads that appear in the picture are made of PBT and indicate that the PBT is at least partially dispersed. The enlargement was 2,000.

For the second uptake, the polymer mixture from experiment 4 was also subjected to extraction with hot toluene. The microphotograph (enlargement 2000) shows that the polypropylene and the block copolymer were continuous and interlocking and the PBT was at least partially dispersed. Comparing FIG. 1 with FIG. 2, it can be seen that the PBT beads in FIG. 2 are larger than in FIG. 1. This can be partly explained by the fact that in experiment 4 a different order of mixing was followed than in test 14. In test 4, the PBT, the block copolymer and the polypropylene were mixed together, while in test 14 the PBT and the block copolymer were first mixed and only then was the polypropylene incorporated.

3, a polymer mixture was prepared from a selectively hydrogenated styrene-butadiene copolymer, into which nylon 6 was then mixed in a weight ratio of 1: 1. The block copolymer was extracted again with hot toluene and the remaining structure of the nylon 6 was examined at a thousandfold magnification. 3 clearly shows the continuous and interlocking network structure of the nylon 6.

17th

635 601

For the recording corresponding to FIG. 4, a polymer mixture of an essentially isotactic polypropylene with a melt flow index of 5 (230 ° C./2.16 kg) and a selectively hydrogenated styrene-butadiene block copolymer was used. After extracting the block copolymer with hot

The residual structure of polypropylene (magnification 5,000 times) was examined in toluene; As can be seen from FIG. 4, this is also a continuous, interlocking networking in this case.

5

Claims (44)

635 601 2nd PATENT CLAIMS 1. A mixture containing synthetic resins containing a partially hydrogenated block copolymer, the latter having at least two end blocks A made of a monoalkenylarene ho-mo or copolymer with a number average molecular weight of 5,000 to 125,000 and at least one intermediate block B made of a homo- or Copolymer of a conjugated diene with a number average molecular weight of 10,000 to 300,000, and wherein the terminal polymer blocks A represent 8 to 55% by weight of the block copolymer and no more than 25% of the arene double bonds in polymer blocks A and at least 80% of the aliphatic double bonds in polymer blocks B are reduced , characterized by a content of the following mixture components: a) 4 to 40 parts by weight of partially hydrogenated block copolymer; b) at least one polyolefin homo- or copolymer with a number average molecular weight of more than 10,000 and an apparent crystal melting point between 100 and 250 ° C; c) 5 to 48 parts by weight of at least one thermoplastic industrial synthetic resin which differs from the other constituents and is selected from the group of the homo- or copolyamides, thermoplastic homo- or copolyesters, homo- or copoly (aryl ether), homo- or copoly (aryl sulfones), homo- or copolycarbonates, homo- or copolyacetal resins, polyamideimides, thermoplastic polyurethanes, homo- or copolymers of halogenated thermoplastics and homo- or copolyitrile resins, the weight ratio of polyolefin to thermoplastic industrial resin being at least 1: 1, so that in the polymer mixture at least two of the polymers intermesh completely or partially continuously with one another. de form networks. 2. Mixture according to claim 1, characterized in that the polymer blocks A have 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. 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. Mixture according to one of claims 1 to 3, characterized in that at least 5% of the arene double bonds in the polymer blocks A and at least 99% of the aliphatic double bonds of the polymer blocks B are reduced. 5. Mixture according to one of claims 1 to 4, characterized in that the polyolefin is a homopolymer or a copolymer of an alpha olefin or 1-olefin having 2 to 5 carbon atoms. 6. Mixture according to one of claims 1 to 4, characterized in that the number average molecular weight of the polyolefin is more than 50,000. 7. Mixture according to one of claims 1 to. 6, characterized in that the apparent crystal melting point of the polyolefin is between 140 and 250 ° C. 8. Mixture according to one of claims 1 to 7, characterized in that it contains a polyethylene with a crystallinity of more than 75% and a density of 0.94 to 1.0 kg / 1. 9. Mixture according to one of claims 1 to 7, characterized in that it contains a polyethylene which has a crystallinity of more than 35% and a density of 0.90 to 0.94 kg / 1. 10. Mixture according to one of claims 1 to 9, characterized in that it contains a polyethylene with a number average molecular weight of 50,000 to 500,000. 11. Mixture according to one of claims 1 to 7, characterized in that it contains an isotactic polypropylene. 12. Mixture according to claim 11, characterized in that the polypropylene has a number average molecular weight of more than 100,000. 13. Mixture according to one of claims 1 to 7, characterized 5 characterized in that it contains a polypropylene which is a copolymer which contains ethylene or another alpha olefin as a comonomer in an amount of 1 to 20 wt .-%. 14. Mixture according to one of claims 1 to 7, characterized in that it contains poly (l-butene) as the polyolefin. 15. Mixture according to one of claims 1 to 7, characterized in that it contains as the polyolefin a homopolymer of 4-methyl-1-pentene with an apparent crystal melting point of 240 ° C and a relative density of 0.80 to 0.85 . 15 16. Mixture according to one of claims 1 to 7, characterized in that it contains as a polyolefin a copolymer of 4-methyl-1-pentene and an alpha olefin. 17. Mixture according to claim 16, characterized in that it is a polyolefin, a copolymer of 4-methyl-1-pentene 20 and a linear alpha olefin having 4 to 18 carbon atoms, the linear alpha olefin being present in an amount of 0.5 to 30% by weight based on the weight of the copolymer. 18. Mixture according to one of claims 1 to 17, characterized 25 characterized in that the thermoplastic industrial resin different from the other components has an apparent crystal melting point of more than 120 ° C. 19. Mixture according to one of claims 1 to 18, characterized in that the different components 30 different industrial thermoplastic resin is a polyamide with a number average molecular weight of more than 10,000. 20. Mixture according to one of claims 1 to 18, characterized in that the mixed from the other components 35 different thermoplastic industrial resin is a thermoplastic polyester with a melting point of more than 120 ° C. 21. Mixture according to one of claims 1 to 18 or 20, characterized in that the thermoplastic industrial resin different from the other constituents polyethylene 40 is rephthalate, polypropylene terephthalate or polybutylene terephthalate. 22. Mixture according to one of claims 1 to 18 or 20, characterized in that the thermoplastic industrial resin is a cellulose ester. 45 23. Mixture according to one of claims 1 to 18 or 20, characterized in that the thermoplastic industrial resin is a homopolymer of pivalolactone. 24. Mixture according to one of claims 1 to 18 or 20, characterized in that the thermoplastic industrial 50 resin is a copolymer of pivalolactone with not more than 50 mol% based on the weight of the copolymer of another beta propiolactone. 25. Mixture according to claim 24, characterized in that the thermoplastic industrial resin is a copolymer of Pi 55 valolactone with not more than 10 mol% based on the weight of the copolymer of another beta propiolactone. 26. Mixture according to one of claims 1 to 18, characterized in that the thermoplastic industrial resin is poly-caprolactone. 27. Mixture according to one of claims 1 to 18, characterized in that the thermoplastic industrial resin is a polycarbonate of the general formula: O II -f AR-A-Ar-O-C -0) -n I 3rd 635 601 or O f Ar-0-C-04-n II wherein Ar is a phenylene or an alkyl, alkoxy, halogen or nitro substituted phenylene group and A is a carbon-carbon bond or an alkylidene, cycloalkylidene, alkylene, cycloalkylene, azo, imino, sulfur -, Oxygen, Sufoxid- or sulfone group represented and n is at least equal to 2. io 28. Mixture according to one of claims 1 to 18, characterized in that the thermoplastic industrial resin is a homopolymer of formaldehyde or trioxane. 29. Mixture according to one of claims 1 to 18, characterized in that the thermoplastic industrial resin is a poly 15 acetal copolymer. 30. Mixture according to one of claims 1 to 18, characterized in that the thermoplastic industrial resin is a polyamideimide with a melting point of more than 340 ° C. 31. Mixture according to one of claims 1 to 18, characterized in that the thermoplastic industrial resin is a homopolymer or copolymer of tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, vinylidene fluoride or vinylidene chloride. 32. Mixture according to one of claims 1 to 18, characterized in that the thermoplastic industrial resin is a Ni-tril resin with a content of more than 50% by weight, based on the weight of the nitrile resin, of an a, ß-ole- finically unsaturated mononitrile. 33. Mixture according to claim 32, characterized in that the mononitrile has the formula CH, = C-CN R wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or halogen. 34. Mixture according to claim 32 or 33, characterized in that the nitrile resin is a homopolymer, a copolymer, 40 a copolymer grafted onto a rubber-like substrate or a mixture of homopolymers and copolymers. 35. Mixture according to one of claims 1 to 34, characterized in that it contains the block copolymer in an amount of 8 to 20 parts by weight and the different thermoplastic industrial resin from the other components in an amount of 10 to 35 parts by weight. 36. Mixture according to one of claims 1 to 35, characterized in that it contains 100 parts by weight of 0 to 100, preferably 5 to 30 parts by weight of oil. 50 37. Mixture according to one of claims 1 to 36, characterized in that it additionally contains up to 100, preferably 5 to 25 parts by weight of a flow-improving resin per 100 parts by weight. 38. Mixture according to one of claims 36 or 37, 55 characterized in that it contains an Al-phamethylstyrene resin, a coumarone-indene resin, a vinyltoluene-alphamethylstyrene copolymer, a polyinden resin or a low-molecular polystyrene resin as additional resin. 39. A process for the preparation of a synthetic resin-containing mixture as claimed in claim 1, containing a partially hydrogenated block copolymer, the latter comprising at least two end blocks A made from a monoalkenylarene-horn copolymer or copolymer having a number average molecular weight of 5,000 to 125,000 and at least one Intermediate block B 65 from a homo- or copolymer of a conjugated diene with a number average molecular weight of 10,000 to Comprises 300,000, and wherein the terminal; :; n polymer blocks A Represent 8 to 55 wt .-% of the block copolymer and not 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 reduced, characterized in that a) 4 to 40 wt. Parts of partially hydrogenated block copolymer at 150 to 400 ° C with b) at least one polyolefin homo- or copolymer with a number average molecular weight of more than 10,000 and an apparent crystal melting point between 100 and 250 ° C; c) 5 to 48 parts by weight of at least one thermoplastic industrial resin different from the other constituents, which is selected from the group of homo- or co-polyamides, thermoplastic homo- or copolyesters, homo- or copoly (aryl ether), homo - Or copoly (aryl sulfones), homo- or copolycarbonates, homo- or copolyacetal resins, polyamide-imides, thermoplastic polyurethanes, homo- or copolymers of halogenated thermoplastics and homo- or copoly-nitrile resins, mixed in such a way that the weight ratio of polyolefin to thermoplastic industrial resin is at least mixed Is 1: 1. 40. The method according to claim 39, characterized in that the polymers are mixed at 230 to 300 ° C. 41. The method according to claim 39, characterized in that the polymers are dissolved in a common solvent and they precipitate out again by admixing a solvent in which none of them is soluble. 42. The method according to claim 39, characterized in that the polymers are mixed in the form of granules or powder in a device with a shear effect. 43. The method according to any one of claims 39 to 42, characterized in that the viscosity is adjusted such that at a working temperature Tp and a shear rate of 100 s "" 1 the viscosity of the block copolymer divided by the viscosity of the polyolefin, the thermoplastic industrial resin or the mixture of these two is 0.2 to 4.0, preferably 0.8 to 1.2. 44. The method according to any one of claims 39 to 43, characterized in that the thermoplastic industrial resin is mixed with a viscosity modifier before mixing with the polyolefin and the block copolymer. 45. The method according to claim 44, characterized in that the viscosity modifier is poly (2,6-dimethyl-1,4-phenylene) oxide or a mixture of poly (2,6-dimethyl-1,4-phenylene) oxide with polystyrene used. 46. The method according to claim 44 or 45, characterized in that the viscosity modifier is used in an amount of up to 100, preferably 10 to 50 parts by weight per 100 parts by weight of thermoplastic industrial resin. 47. The method according to any one of claims 39 to 46, characterized in that the block copolymer is used in an amount of 8 to 20 parts by weight and the thermoplastic industrial resin different from the other components in an amount of 10 to 35 parts by weight.