DE2819517A1 - Synthetic resin mixture containing a partially hydrogenated block copolymer - Google Patents

Description

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Patent application

Applicant: SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ B.V. Carel van Bylandtlaan 30, Ben Haag The Netherlands

Title: Synthetic resin mixture containing a partially hydrogenated block copolymer

809845/0999

ΙΠί. ING. V. WUKSTIIO KK.

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description

The invention relates to synthetic resin mixtures containing a partially hydrogenated block copolymer which is composed of at least two end blocks A ^

en

a monoalkenyl arene polymer with an average molecular weight from 5,000 to 125,000 and at least one intermediate block B of the polymer of a conjugated diene with a average molecular weight from 10,000 to 300,000; by doing

pn

Block copolymer provide the terminal Polymerblb'cke A 8 to 55 wt .- ^ represents and not more than 25 f <> of the arene double bonds of the polymer blocks A and at least 80% of the aliphatic double bonds of the polymer blocks B have been reduced by hydrogenation.

Thermoplastic resins that can be used in technology and industry, also called "industrial thermoplastics" (Engineering thermoplastic resins) are a group of polymers that have proven themselves as technical building materials, as they have certain Properties such as strength, stiffness, shock and impact resistance and dimensional stability over a long period of time be in a favorable equilibrium. Such "industrial thermoplastics" are particularly suitable as a substitute for metals, because they are much lighter than these, which is often an advantage, especially in automotive engineering.

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A single thermoplastic resin sometimes does not have the combination of properties required for one certain application is desirable and there is interest in compensating for this disadvantage. A special one the obvious way is to use two or more polymers (each of which has the desired properties) to mix together so that a material having 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 methods or additives for this purpose. In general, however, the blending of thermoplastic resins is not a promising route when it is It is all about the desirable properties of two or more polymers in a single material to combine. On the contrary, it has been shown often enough that the mixing leads to the respective weaknesses unite the individual components, so that one obtains a material that is of no interest and worthless in practice. the The reasons for this are well known and are in part that, as thermodynamics teaches, most polymers cannot be mixed with one another, although there are quite a few exceptions to this rule. In addition, there is that most polymers adhere poorly to one another. This leads to the fact that the contact surfaces between the components of the Mixtures (due to their immiscibility) in the mixtures represent areas of particular weakness in which too easily cracks and cracks occur, which affect the mechanical properties of the mixture. It is therefore said of most polymer pairs that they are "incompatible". In some cases compatibility means miscibility, however, the term compatibility is used here in a more general sense, meaning the possibility of To combine polymers with one another in such a way that their properties are improved without necessarily having to do so a real miscibility is meant.

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One method that helps address this problem with polymer blends bypassing consists in making the two polymers compatible by using a third Component, which is often referred to as a compatibilizing agent and opposite the two to be mixed Polymer has a mutual solubility. Examples of such third components are certain Block or graft copolymers. Because of the property mentioned This mediator attaches itself to the interface between the two polymers and improves the mutual Adhesion and thus the stability of the product against a coarse phase separation are extraordinary.

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

As already mentioned, the invention relates to a synthetic resin mixture with a content "of a partially hydrogenated block copolymer, the latter having at least two end blocks A from one Monoalkenyl arene polymer with an average molecular weight of 5,000 to 125,000 and at least one intermediate block B. comprised of a polymer of a conjugated diene having an average molecular weight of 10,000 to 300,000; in the invention Synthetic resin mixtures represent the terminal ones

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The polymer block A 8 to 55 wt .- ^ of Blockeopolymeien represents and 25 of the arene double bonds ° / o in the polymer blocks A and at least 80 "/> of the aliphatic double bonds in the Polymerblöckgn B reduced by hydrogenating no more than; are in the Synthetic resin mixtures according to the invention by the following components:

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

b) a halogenated thermoplastic polymer having a generally crystalline structure and a melting point above 12O ⁰ C;

c) 5 to 48 parts by weight of at least one of different types thermoplastic industrial synthetic resin, which was chosen from the group of polyamides, polyolefins, thermoplastic polyester, poly (aryl ether), poly (aryl sulfone), polycarbonate, acetal resin, thermoplastic Polyurethanes and nitrile resins,

being the weight ratio of the halogenating thermoplastic Polymers to the various thermoplastic industrial synthetic resin is greater than 1: 1, so that a polymer mixture wherein at least two of the polymers are at least partially continuous, interlocking Build networks.

The block copolymer according to the invention in question acts here as a mechanical or structural stabilizer that links the various polymer network structures and the later Prevents 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 interlocking ones linked networks. So there is a polymer mixture which is stable in its dimensions and which is due to its structure does not separate into individual layers either during extrusion or during subsequent use «

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In order for stable mixtures to arise, at least two of the polymers must have an at least partially continuous network have, the two networks interlocking or being linked to one another. Preferably the block copolymer has and at least one of the other polymers has a partially continuous, interlocking network structure Ideally, all of the polymers were considered to be completely continuous There are networks that are interlinked. A partially continuous network means that part of the polymer has a continuous reticulate structure, while the other part as a disperse phase is present. Preferably the major part, i.e. greater than 50% by weight, of the network is continuous, i.e., self-contained. As is readily apparent, the structure of the mixtures can be very different because of the structure of the polymer in the mixture either completely continuously, completely disperse or partially continuous and partially disperse can be. In addition, the disperse phase of one polymer can be in a second polymer and not in a third polymer be distributed. To show some of these structural possibilities, below are the various possible combinations of poly-mer structures listed, whereby all structures are not partial structures, but complete structures. Included three polymers (A, B and C) are involved. The subscript "G" means a continuous structure, while the subscript "djj means a disperse structure. The term "AB" means so that the polymer A continuously decrease polymer B a-bweohsel-t and the designation "B = C" means that that Polymer B is dispersed in polymer C, etc.

^A c ^B A _d B ^A c ^B B _d A

^B c ^G V ^B c ^G B _d G ^A c ° ^B c ° ^A c ^B V ^A c ^{B A} c ^{G A} c ^{B A} c °

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With the aid of the invention, one type of physical property can be improved in the synthetic resin mixture without any other physical property being noticeably impaired. In the past this was not always possible. For example, it has been expected in the past that when an amorphous rubber such as ethylene-propylene rubber is added to a thermoplastic polymer in order to improve its impact resistance, deteriorated heat resistance (HDT) will inevitably be obtained. This was due to the fact that the amorphous rubber formed discrete particles in the mixture and rubber almost by definition has extremely poor dimensional stability around room temperature. With the help of the

However, it is possible in some cases

to improve the impact strength noticeably without the dimensional stability is impaired at the same time. If namely the relative increase in the Izod impact strength is measured against the relative decrease in the dimensional stability, • the numerical value for this ratio is often much higher than one would initially expect. For example, the Numerical value for this ratio Me mixtures containing a halogenated contain thermoplastic polymer, a block copolymer and other industrial resins such as nylon 6 and polycarbonates, much higher than one would normally expect.

What is particularly surprising in the present Pail is that even even a small proportion of block copolymer is sufficient to expand the structure of the polymer mixture within a wide range To stabilize the concentration range. For example, four parts by weight of bio-elco-polymer are sufficient to. a mixture from 5 to 90 parts by weight halogenated - 90 to 5 parts by weight to stabilize a different type of industrial thermoplastic

It is also surprising that the block copolymers are used to stabilize polymers of so diverse chemical Texture can use. As will be explained in more detail, this ability of block copolymers is based on Stabilize a whole range of polymers within one

^ thermoplastic polymers and

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wide concentration range that they are stable to oxidation, with a shear stress of O a practical one have infinite viscosity, and in the melt the maintain the underlying network structure.

Another important aspect of the invention is that the various polymer blends are much easier to process and allowed to deform when the block copolymers according to the invention are used as stabilizers.

Those used in the synthetic resin mixtures according to the invention Block copolymers can have a very different geometric structure, since according to the invention it is not based on any one specific geometric structure, but only on the chemical constitution of each of the polymer blocks arrives. For example, the block copolymers can be linear, radial or branched. Process for the production of such Polymers are known. The structure of the polymers is determined by the particular polymerization process. So get one e.g. linear polymers by successive introduction the corresponding monomers in the reaction vessel, when initiators, such as lithium alkyls or dilithiostilbene, are used, or when a block copolymer of two segments is used couples with a difunctional coupling agent. In contrast, branched structures are obtained by using suitable ones Coupling agents which have a functionality of three or more with respect to the precursor polymers. The coupling can be carried out with multifunctional coupling agents, such as with haloalkanes or alkenes and divinylbenzene) as well with certain polar compounds, such as silicone halides, siloxanes or esters of monohydric alcohols with carboxylic acids. The presence of any residual coupler in the polymer can be considered when describing the polymers, which represent part of the plastics according to the invention, be ignored. Also, in terms of the genre, it does not depend on the respective structure. According to the invention In particular, selectively hydrogenated polymers are used which, prior to hydrogenation, have the following typical configuration in their configuration Types correspond to:

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AO

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Polystyrene-Polybutadiene-Polystyrene (SBS) Polystyrene-Polyisoprene-Polystyrene (SIS)

Poly (iX-methylstyrene) polybutadiene-poly (* -methylstyrene) and Poly (<* - methylstyrene) polyisoprene-poly (<x -methylstyrene).

Both the polymer blocks A and the blocks B can be either homopolymer blocks or random copolymer blocks, as long as each polymer block predominates in at least one class of the monomers characterizing the polymer blocks. Thus, the polymer block A can comprise homopolymers of a monoalkenyl arene and copolymers of a monoalkenyl arene with a conjugated diene, as long as the monoalkenyl arene units only predominate in the individual polymer blocks A. The term “monoalkenyl arene” here means, among other things, especially styrene and its analogs and homologues, including cx-methylstyrene and ring-substituted styrenes, in particular ring-methylated styrenes. In addition to tf-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 monoalkenyl arene, as long as the conjugated diene units only predominate in the polymer blocks B. If butadiene is used as the monomer, the condensed butadiene units in the butadiene polymer block should have the 1,2-configuration to an extent of at least 35 to 55 mol. If such a block is then hydrogenated, the resulting product is a regular copolymer block of ethylene and butene-1 (EB), or at least resembles such a copolymer block. If the conjugated diene used is isoprene, the hydrogenation produces a regular copolymer block of ethylene and propylene (EP) or at least a similar block.

A reaction product of an aluminum alkyl compound with a nickel or cobalt carboxylate or alkoxide under such conditions that at least 80 % of the aliphatic double bonds are practically completely hydrogenated, while the aromatic

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Be at most 25 hydrogenated Alkenylarendoppelbindungen $ »Preferred are block copolymers in which the aliphatic double bonds are hydrogenated at least 99 ° i, whereas only less than 5 ° / ° are hydrogenated of the aromatic double bonds.

The average molecular weight of the individual blocks can fluctuate within certain limits. That in the invention The block copolymer present in synthetic resin compositions 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 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 of 10,000 to 500,000, preferably from 30,000 to 150,000. These molecular weights are numerical mean values that can be most precisely determined by tritium counting methods or by ) Measurement of the osmotic pressure.

The proportion of MonoalkenylarenpolymerblöckenA is 8-55 ° f f preferably between 10 and 30% of the total weight of the block copolymer.

The halogenated thermoplastic polymers are homopolymers and copolymers of tetrafluoroethylene, chlorotrifluoroethylene, Bromotrifluoroethylene, vinylidene fluoride and vinylidene chloride.

Polytetrafluoroethylene (PTEE) are fully fluorinated polymers

the basic chemical formula - {- CPp GFp- ) - , the

76 wt -. ° / o Eluor included. These polymers are highly crystalline and have a KristallGchmelzpunkt of over 300 ⁰ O. (trade name: Teflon ^ ^ and hydrofluoric). High molecular weight polychlorotrifluoroethylene (PCTPE) and polybromotrifluoroethylene (PBl ¹ I ¹ E) are also available and can be used in the compositions of the invention.

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Homopolymers and copolymers of vinylidene fluoride are particularly preferred as halogenated polymers. The homopolymers are the partially fluorinated polymers of

chemical formula - (- CH ₂ ^{σΐ <} 2 "~ ^ ή * ^These polymers are

tough linear polymers with a crystal melting point at 17O ⁰ C (eg Kynar®). The term "polyvinylidene fluoride" refers here not only to the normally solid homopolymers of vinylidene fluoride, but also to its normally solid copolymers which have at least 50, preferably at least 70 and in particular at least 90 mol $ polymerized vinylidene fluoride units. Suitable comonomers are halogenated Olefins with up to 4 carbon atoms, ZeB. Sym. Dichlorodifluoroethylene, vinyl fluoride, vinyl chloride, vinylidene chloride, perfluoropropene, perfluorobutadiene, chlorotrifluoroethylene, triehloroethylene and tetrafluoroethylene.

Another useful group of halogenated thermoplastics are homopolymers and copolymers of vinylidene chloride. Crystalline Vinylidene chloride copolymers are particularly preferred. The normally crystalline ones useful in the context of the invention 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 aralkyl acrylate with alkyl or aralkyl groups With up to about 8 carbon atoms, acrylic acid, acrylamides, vinyl alkyl ethers, vinyl alketones, acrolein, allyl ethers and the like and butadiene and chloropropenes Known ternary mixtures can also be used to advantage. Representative for such polymers are those composed of at least 70% by weight vinylidene chloride, where the rest, for example, 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

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Acetate, vinyl propionate or vinyl chloride and vinyl ethers and vinyl chloride, quaternary polymers of appropriate monomer composition, are also known. Particularly useful for purposes of the invention are copolymers with 70 to 95 wt .- $ vinylidene chloride, Resij vinyl chloride. Such copolymers can contain the usual plasticizers, stabilizers, • nucleators and extrusion auxiliaries in appropriate amounts. Mixtures of two or more such crystalline under normal circumstances, vinylidene chloride polymers may be used as well as mixtures in which such normally crystalline polymers along with other PoIymermodifikatoren, for example _o the copolymers of ethylene Vinylacet'at, styrene-maleic anhydride, styrene-acrylonitrile, and polyethylene, available are.

The term "different thermoplastic industrial resin" refers to thermoplastic engineering or industry resins that differ from the synthetic resin mixtures used in the inventions differentiate the halogenated thermoplastics present.

The term "thermoplastic industrial resin" or "thermoplastic." engineering resin "includes the various polymers listed in Table A below and included here will be described later.

Table A '

1. Polyolefins

2. thermoplastic polyester

3. Polyaryl ethers and polyarylsulfones' 4. Polycarbonates 5 # acetal resins

£>. thermoplastic polyurethanes 7 * polyamides §> .. Mtrilharze

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The thermoplastic engineering or industrial resins preferably have a glass transition temperature or an apparent crystalline melting point (defined as the temperature at which the low strain modulus a very large drop suffers) of more than 120, preferably between 150 and 55O ⁰ G and have the ability, due to to form a continuous network structure of a thermally peversible cross-linking mechanism. Such thermally reversible crosslinking mechanisms include crystallite formation, polar aggregation, ionic aggregation, lamination or hydrogen bonding. In a special embodiment in which the viscosity of the block copolymer or the block copolymer mixture at the processing temperature Tp and a. Shear rate 100s ~ is equal to -η, the ratio of the viscosity of the thermoplastic industrial resin or of its genius with viscosity modifiers to "Tj" can be between 0.2 and 4.0 and preferably between 0.8 and 1.2. As the viscosity of the block copolymer , the halogenjerten and the thermoplastic industrial resin is to be understood here the so-called "melt viscosity", which is obtained by using a piston driven Kapillarschmelzrheometers at constant shear rate, and some constant temperature above the melting point, for example, 26O ⁰ C. the upper limit (35O ⁰ C) for the apparent crystalline melting point or -the glass transition temperature is set so that the resin can be used in a device with low to moderate shear at a temperature conventional in the art • temperature of 35O ⁰ C or less processed.

The thermoplastic industrial resins mentioned 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:

* thermoplastic polymers

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possibly v Kttffj / '

if applicable, the η plastic masses present in the invention.

Polyolefins are crystalline or crystallizable. They can be homopolymers or copolymers and derived from a ^ f-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 with the other polymers in the polymer mixture according to the invention. The number average molecular weight of the polyolefins may be above 10 000, preferably above 50 OOO _f lie <The apparent crystalline melting point is preferably between 100 and 250 ⁰ C, in particular between 140 and 25O ⁰ C. The preparation of these various polyolefins is well known (see "Olefin Polymers "in Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 14, pp. 217-535

If a high density polyethylene is used, it will have an approximate crystallinity of more than $ 75 and a density between 0.94 and 1.0 kg / l, while any low density polyethylene that may be used will have an approximate crystallinity of over 35 f <> and has a density between 0.90 and 0.94 kg / l. 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, it is a so-called isotactic polypropylene in contrast to an atactic one Polypropylene. The number average molecular weight of the

The polypropylene used can be over 100,000. i> as polypropylene can be made in the usual known manner. Depending on the catalyst used and the polymerization conditions

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the polymer produced contains atactic as well as isotactic, syndiotactic or so-called stereo block molecules. These can be separated by selective extraction, so that one obtains products with few atactic constituents that are more complete crystallize. The preferred commercial polypropylenes are usually made using of a solid, crystalline, soluble in hydrocarbons Catalyst made from a mixture of titanium chloride and an aluminum alkyl compound, e.g. triethylaluminum or diethyl aluminum chloride. If necessary, the polypropylene used is a copolymer, the smaller proportions (1 to 20 wt .- $) of ethylene or another ok-olefin as a comonomer contains ^ j ^ The poly-1-butene preferably has one isotactic structure. The catalysts used for its production are preferably organometallic compounds, commonly referred to as Ziegler-Natta catalysts will. A typical catalyst is the product obtained by mutual action when using equimolar Amounts of titanium tetrachloride and triethylaluminum mixed. The production usually takes place in an inert solvent, like hexane. It is important to be careful in all phases of polymer formation to exclude ¥ aster, yourself in traces, took care

A particularly useful polyolefin is PοIy (-4-methyl-1-pentene), which has an apparent crystalline melting point between 240 and 25O ⁰ C and a specific gravity from 0.80 to 0.85. Monomeric 4-methyl-1-pentene is produced industrially by the dimerization of propylene catalyzed with alkali metals. 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 (2 "ed. 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-i-pentene is therefore practically a

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Copolymer with lower proportions of 'other alpha' olef ines, the corresponding oxidation and melt stabilizer systems are also added. Such copolymers are in the above Kirk-Othmer's Encyclopedia, Supplement, pp. 792-907

(2nd ed., 1971): in the trade they are under the

ffi)
Protected designation TPX ^ resins available. Typical

o ^ -olefins are the linear ^ -olefins with 4 to 18 Carbon atoms. Suitable resins are copolymers of methyl-1-pentene with 0.5 to 30% by weight of linear κ? -Olefin

The polyolefin is optionally a mixture of different polyolefins. However, the most preferred polyolefin is isotalctic polypropylene,

The thermoplastic polyesters optionally present in the compositions according to the invention have a generally crystalline structure, a 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 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 that are suitable for producing the polyesters are: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p-carboxyphenylacetic acid, p, p ^! -Dicarboxydiphenyl, ρ, ρ ¹ -Dioarboxydiphenylsulfon, p-carboxyphenoxyacetic acid, p-Carboxyphenoxypropionsäure, p-Carboxyphenoxybuttersäure, p-carboxyphenoxyvaleric acid, p-Carboxyphenoxyhexansäure, ρ, ρ'-Dicarboxydiphenylmethan, ρ, ρ-Dicarboxydiphenylpropan, p, p ^f -Dicarboxydiphenyloctan, 3-alkyl-4- (β-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. '

ORIGINAL INSPECTED

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The glycols suitable for producing the polyesters include straight-chain alkylene glycols having 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. Aromatic glycols can be completely or partially substituted. Suitable aromatic dihydroxy compounds include p-xylylene glycol, pyrocatechol, resorcinol, hydroquinone or alkyl-substituted derivatives of these compounds. Another suitable glycol is 1 ^ cyclohexanedimethanol. ^ ^E straight chain alkylene glycols are particularly preferably having 2 to 4 carbon atoms.

A preferred group of polyesters are: polyethylene terephthalate, Polypropylene terephthalate and especially polybutylene terephthalate; the latter, a crystalline one Copolymer, can be formed by polycondensation of 1,4-butanediol and dimethyl terephthalate or terephthalic acid, and has the general formula:

where η can be 70 to 140. The mean 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 which can be used here Also used in many other ways as an aid in shaping, as coatings and as film-forming substances. Mentioned below among other things the solid thermoplastic forms of cellulose nitrate, gellulose acetate <5. {z, B »gellulssediacetafr, cellulose triacetate),

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Cellulose butyrate, cellulose acetate butyrate, cellulose propionate, Cellulose tridecanoate, carboxymethyl cellulose, ethyl cellulose, Hydroxyethyl cellulose and acetylated hydroxyethyl cellulose (see pp. 25-28 of "Modern Plastics Encyclopedia", 1971-72)

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

ie with units derived from pivalolactone. The polyester is preferably a pivalolactone homopolymer, but copolymers of pivalolactone with no more than 50 mol $, preferably no more than 10 mol $ of another β-propiolacbon are also useful: such as ß-propiolactone, cx _t Λ'-diethyl-ß-propiolatone and iX-metbyl-iX-ethyl-ß-propiolactone. The term "ß-propiolactone" refers to ß ~ propiolactone- (2-oxetanone) _and on derivatives thereof, which are at the ß-C-atom of the La'cton-

rings do not carry any substituents. ß-Propiola.ctones which contain a tertiary or quaternary carbon atom in the alpha position to the carbonyl group, in particular the CK, c < -dialkyl-ß-propiola-ctones, in which each of the alkyl groups is 1 has up to 4 carbon atoms.

Examples of suitable monomers are: x-ethyl--methyl-ß-propiolactone, • X-methyl-Λ -isopropyl-ß-propiolactone, (X-ethyl- <an-butyl-ß-propiolactone , tX-chloromethyl- ίΛ-methyl-ß-propiolactone,. οι) <x-bis (chloromethyl) -ß-propiolactone and, χ, <x-dimethyl-ß-propiolactone (pivalolactone)

This Polypivalola.dtone have an average molecular weight of more than 20, 000 and melt over 120 ⁰ C, Another

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a suitable polyester is a polycaprolactone. Preferred poly- caprolactones are essentially linear polymers, in which the recurring unit can be represented by the following formula:

0 CH ₂ CH

These polymers have practically the same properties as the Polypivalolalctone and can by a corresponding Polymerization mechanism can be produced.

Various polyaryl polyethers are also useful as industrial thermoplastic resins, the polyaryl polyethers, the can be present in the compositions according to the invention are, inter alia, linear thermoplastic polymers made of recurring Units of the formula

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

II

III

where R is a bond between aromatic carbon atoms

0 _f s, S — S—, or a divalent carbon

denotes a hydrogen radical with 1 to 18 carbon atoms and G ^{1 is} the radical of a dibromo or diodobenzene compound selected from the following group:

ORIGINAL

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-ο- ■ -

where R ¹ denotes a bond between aromatic carbon atoms, O, S, S — S or a divalent hydrocarbon radical having 1 to 18 carbon atoms, however

with the following "caveat: if RO means, R is ¹

not equal to O; if R ^{1 is} O, then R is not

equal to O; if G equals II, G ¹ equals V, and

if G »equals IV, G equals ΙΪΙ.

Polyarylenpolyäther of this type have excellent physical properties and are particularly against heat, oxidation and chemical influences · Commercially available Polyarylpolyäther are stable with melting temperatures of 280-310 ⁰ O available under the registered trade name aryl ο η Τ®.

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

-SO ₂ -

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

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wherein Z is oxygen or sulfur or the residue of an aromatic diol such as a 4,4 ^f -bisphenol. An example of such a polysulfone has repeating units of the formula:

another has repeating units of the formula:

-OO-.

and others of the formula:

-O-

or they are copolymerized units in different Share ratios of the formula:

009045/0900

- 21 -

ORIGINAL INSPECTEP

2813517

The thermoplastic polysulfones can also be repeating units of the formula

to have.

Polyether sulfones with repeating units of the Structure:

SO ₂ -

and polyether sulfones with repeating units of the Structure:

IfA-SO ₂ -Q ^

ο-

are also suitable as thermoplastic industrial resins.

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

ti

-kr --Ar-O-C-Ol

r Ar — O — C — 0-

309845/0999

II

ORIGINAL INSPECTED - 22 -

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 η is 2 or more iat ₀

The production of the polycarbonates is known. A preferred one Process is based on the reaction that occurs when the dihydroxycomponent is dissolved in a base such as pyridine and under Introducing phosgene into the solution while stirring at the appropriate speed. As a catalyst for the implementation you can tertiary amines are used, which also act as acid acceptors during the reaction. Because the reaction normally exothermic, the reaction can be controlled by the rate of addition of phosgene. Usually one works with equimolar amounts of phosgene and dihydroxy compound, but the ratio can vary depending on the reaction conditions changed.

In formulas I and II above, Ar and A are preferably p-phenylene and isopropylidene, respectively. This polycarbonate is made by reacting ρ, ρ'-isopropylidenediphenol with

Phosgene and is marketed under the protected names and Merlon ^. It has a molecular weight of around 18,000 and melts above? _30 ° C. Other polycarbonates can be produced by reacting other dihydroxy compounds or mixtures can be made from several dihydroxy compounds with phosgene. Aliphatic dihydroxy compounds can be used as dihydroxy compounds can be used, but aromatic rings are essential for temperature-resistant compounds. The dihydroxy compounds can have diurethane bonds in their structure. Part of the structure can also be replaced through siloxane bonds.

Those optionally present in the compositions according to the invention Acetal resins are among other things the high molecular weight, by

809845/0999 - 23 -

ORIGINAL INSPECTED

1-50 825

Polymerization of formaldehyde or trioxane produced polyacetal homopolymers, which, as commercial products, have the protected designation Delrin. ^. A related polyether type resin (Trade name Penton ^) has the structure:

CH ₉ Cl

-O CH ₂ C CH ₂ -

G ¹ H ₂ Cl

The acetal resin made from formaldehyde h.er _ .. has a high Molecular weight and the following structure:

-H — O-

-H-

in which terminal groups come from controlled proportions of water and χ denotes a larger number (preferably 1500), which denotes the number of formaldehyde units present one behind the other »To the resistance to heat and To improve chemical attack, the terminal groups in typical resins are in ester or ether groups transferred.,

The term "polyacetal resins" also includes the polyacetal copolymers. These copolymers include block copolymers of formaldehyde with monomers or prepolymers of other substances that 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 located below the protected designation Celcon ^ commercially copolymer of formaldehyde and ethylene oxide particularly well suited for the inventive mixtures _e The typical structure of these copolymers comprising repeating units of the formula: _"0RiQ lNAL INSPECTED

809845/0399 ^'24 "

-O-

H / R ₁

I 1 ^Χ

-C Οι

R,

1-50,825

2844517-

η - ¹

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

Formaldehyde and trioxane can be copolymerized with other aldehydes, cyclic ethers, vinyl compounds, Ketenes, cyclic carbonates, epoxides, isocyanates and Ethers, including e.g. ethylene oxide, 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepene, epichlorohydrin, propylene oxide, isobutylene oxide and styrene oxide.

Polyurethanes, also known as isocyanate resins, can also be used as industrial thermoplastic resins insofar as they are actually thermoplastic and not thermosetting. Examples are: Polyurethanes from Toluene diisocyanate (TDI) or diphenylmethane-4,4-diisocyanate (MDI) and numerous polyols, such as polyoxyethylene glycol, Polyoxypropylene glycol, polyester with terminal OH groups, polyoxyethylene-oxypropylene glycols · «-

These thermoplastic polyurethanes are among the ge ^ and Pellethane ^ OPP i

protected names Q-Thane
Trade.

With polyamide is meant a condensation product that is aromatic and recurring as parts of the main polymer chain or or has aliphatic amide groups; such products are commonly known as "nylons". The polyamides can

809845/0939

are held by polymerizing a monoaminocarboxylic acid or an internal lactam of such an 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; are used, or by polymerizing a monoaminocarboxylic acid or its lactam interior has, as above, together with substantially equimolar proportions of a diamine and a dicarboxylic acid The dicarboxylic acid may be in the form of one of its functional derivatives, for _e B "of an ester...

With the expression "practically equimolecular proportions" (of the diamine and the dicarboxylic acid) are next to exactly equimolecular η Proportions also mean slight deviations in the usual stabilization of the viscosity of the resulting polyamides may occur"

Examples of the mentioned monoaminomonocarboxylic acids or their lactams are those compounds which between the amino and the carboxyl group have 2 to 16 carbon atoms, which in the case of a lactam with the -CO.NH-

Group form a ring. As special examples are mentioned: £ -aminocaproic acid, butyrolacbam, caprolactam, Capryllactam, enantholactam, undecanolactam, dodecanolactam and 3- and 4-aminobenzoic acid.

Examples of the diamines mentioned are those of the general formula H ₂ N (CH ₂ ) ^ NH ₂ , where η is an integer from 2 to 16, such as trimethylenediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, decamethylenediamine, dedecamethylenediamine, hexadecamethylenediamine and especially hexamethylenediamine.

Further examples are C-alkylated diamines, e.g. 2,2-dimethyl- pentamethylenediamine and 2,2,4- and 2,4 ^ 4-trimethylhexametbylene-

809845/0999 TO ^ - ^: "^{;;? Γ} '*' - ' ^: ''

-26 -

diamine. Mention should also be made of aromatic diamines, for example p-phenylenediamine, 4 »4 ^! -I) iaminodiphenyl sulfone, 4,4'-ΰϊ3πιιηοαί ~ phenyl ether and 4,4 ^I -diaminodiphenyl sulfone, 4> 4 ^! Diaminodiphenyl ether and 4>4'-diaminodiphenyl methane and cycloaliphatic diamines, for example diaminodicyclohexyl methane.

The dicarboxylic acids mentioned can be aromatic acids such as isophthalic and terephthalic acid. Dicarboxylic acids are preferred of the formula HOOCY.COOH, in which Y stands for a divalent aliphatic radical having at least 2 carbon atoms; Examples are: sebacic acid, octadecanedioic acid, suberic acid, azelaic acid, Undecandi ^^,. Acid, glutaric acid, pimelic acid and especially adipic acid, oxalic acid is also preferred «

In the thermoplastic polymer mixtures according to the invention In particular, the following polyamides can be incorporated:

Polyhexamethylene adipamide (nylon 6: (j) polypyrrolidone (nylon 4) Polycaprolactam (nylon 6) Polyheptolactam (nylon 7)

Polycapryllactam (nylon 8) Polynonanolactam (nylon 9) Polyundecanola.ptam (Nylon 11) Polydodecanolactam (Kylon 12) Polyhexamethylene azelamide (nylon 6: 9) Polyhexamethylene sebacamide (nylon 6: 10) Polyhexamethylene isophthalic acid amide (nylon 6: iP) Polymetaxylylene adipamide (nylon MXD: 6)

Polyamides of hexamethylenediamine and n-dodecanedioic acid

(Nylon 6:12)

Polyamides of dodecamethylenediamine and n-dodecani ^ diacid (nylon 12:12)

Nylon copolymers can also be used, e.g. Copolymers of:

809845/0999 _ _2? _

1A-50 025

Hexamethylene adipamide / caprolactam (nylon 6: 6/6) Hexamethylene adipamide / hexamethylene isophthalic acid

(Nylon 6: 6 / 6ip) hexamethylene adipamide / hexamethylene terephthalic acid amide

(Nylon 6: 6 / 6T) trimethylhexamethylene oxamide / hexamethylene oxamide

(Nylon trimethyl 6: 2/6: 2) Hexamethylene adipamide / hexamethylene azelamide

(Nylon 6: 6/6: 9) hexamethylene adipamide / hexamethylene azelamide /

Caprolacrtam (nylon 6: 6/6: 9/6)

Nylon 6: 3, a product of the dimethyl ester of terephthalic acid and a mixture of isomeric trimethyl / hexamethylenediamine, can also be used.
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 ones that can be used in the present pail as industrial malts Nitrile resins are thermoplastics with a content of s <, ß-olefinically unsaturated mononitrile of 50 wt .- $ or more. These nitrile resins may be homopolymers, copolymers, graft copolymers, or copolymers on a rubbery one Be a substrate or mixtures of homopolymers and / or copolymers.

The ^ X, ß-olefinically unsaturated ones in question here • Mononitriles have the structure:

wherein R is V / a ss he substance, an alkyl group having 1 to 4 carbon atoms or a halogen atom. Be mentioned are: acrylonitrile, <* _T bromoacrylonitrile, ^ -Fluoracrylnitril, methacrylonitrile and ethacrylonitrile. Acrylonitrile and methacrylonitrile and their mixtures are preferred.

809845/09 99 rr ^ Wt

- 28 -

38 ^1A -5 °

Due to their complexity, these nitrile resins can be used in different classes can be divided. The simplest molecular structure is a random copolymer »-t mainly Acrylonitrile or methacrylonitrile. The best-known example is a styrene-acrylonitrile copolymer. Block copolymers of acrylonitrile, in which long sections of polyacrylonitrile with sections of polystyrene or of Alternate 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 aliphatically substituted derivatives such as vinyl chloride and vinylidene chloride, or the monomers of monovinylidene aromatic hydrocarbons the formula

-R ₁

H ₂ C = 0

where R .. represents hydrogen, chlorine or a methyl group and R _{2 is} an aromatic radical with 6 to 10 carbon atoms, which can also contain substituents, e.g. halogen and alkyl groups bonded to the aromatic nucleus, e.g. _e styrene, (X-methylstyrene , Vinyltoluene, C 1-4 chlorostyrene, orthochlorostyrene, parachlorostyrene, methachlorostyrene, orthomethylstyrene, paramethylstyrene, ethylstyrene, isopropylstyrene, dichlorostyrene and vinylnaphthalene, with isobutylene and styrene being particularly preferred.

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

-29-

809845/0999

U-ΠΟ 825

C ι

0 0 = 0

where R ~ hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, Represents aryl groups with 6 to 10 carbon atoms including the carbon atoms in the ring-substituted alkyl substituents; e.g. Vinyl formate, vinyl acetate, vinyl propionate and vinyl benzoate.

Like those mentioned above, the vinyl ether monomers can be used the general formula

HpC = ¹ CH Ό Ri

where R. 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 hydrocarbon or oxygen-containing, such as for example an aliphatic radical with ether bonds and which can 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 have a mono- or dinitrile function contain, e.g. methylenglutaronitrile, (2,4-dicyanobutene-i) n-vinylidenecyanide, Crotonitrile, fumaronitrile and maleodinitrile.

3098A5 / 0999

-30-

¹¹ " ^{50 825}

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

COOR

^R 1

'where R _{1 is} hydrogen, an alkyl group having 1 to 4 carbon atoms or a halogen and R _{2 is} an alkyl group having 1 to 2 carbon atoms. Compounds of this type are, for example, methyl or ethyl acrylate, methyl or ethyl methacrylate and methyl ίΚ-chloroacrylate. Methyl and ethyl acrylate and methyl and ethyl methacrylate are preferred.

Another class of nitrile resins are the graft copolymers, in which side chains of another polymer are grafted onto a polymer main chain. The main chain is in its own Prepared reaction. For example, chains of styrene, vinyl acetate or methyl methacrylate can be grafted onto polyacrylonitrile will. The main chain can consist of one, two, three or more components order and the grafted side chains can also be composed of one, two, three or more comonomers be.

Much is to be expected from nitrile copolymers that are partially grafted onto a preformed rubbery substrate are. You can use a synthetic or natural rubber for this substrate, such as polybutadiene, Isoprene, neoprene, nitrile rubber, natural rubber, acrylonitrile-butadiene copolymers., Ethylene-propylene copolymers ·. and chlorinated rubbers, which are used to make the 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 on the acrylonitrile

-31-

809845/0999

1A-50 825

Monomer mixture on the rubber backbone or by physical Mixing in the rubber component. Particularly preferred are polymer mixtures that arise when one Graft copolymer of acrylonitrile and comonomer with one another copolymer of acrylonitrile and the same comonomer grafted onto the rubber backbone. The thermoplastics on Acrylonitrile-based are generally polymer mixtures of a graft polymer and a homopolymer without a grafted component.

A nitrile resin based on acrylonitrile with over 65 % nitrile (Barex ^ 210) and another with over 70 $ nitrile, three quarters of which come from methacrylonitrile (Lopac®; are commercially available.

In order to better match the viscosity properties of the thermoplastic industrial resin, the halogenated thermoplastic polymer and the block copolymer, it is often advisable to first mix the different thermoplastic industrial resin with a viscosity modifier before adding the halogenated thermoplastic polymer and the block copolymer to the final mixture Viscosity modifiers with a relatively high viscosity and a melting temperature of more than 250 ⁰ O, at which the viscosity is not too sensitive to temperature changes, are suitable. Examples are poly (2,6-dimethyl-1,4-phenylene) oxide and mixtures of poly (2,6-dimethyl-1,4-phenylene) oxide with polystyrene.

Those optionally present as viscosity modifiers Poly (phenylene oxides) can be represented by the formula:

R '

30984 5/0993

-32-

1A-50 825

in desrR ^ is a monovalent substituent selected from the following group: hydrogen, no tertiary hydrocarbon radicals containing X -C atoms, halogenated hydrocarbon radicals with at least 2 carbon atoms between the halogen atom and the phenol ring that do not have a tertiary χ -C atom contain, hydrocarbon oxy radicals which do not contain any aliphatic tertiary <XC atoms and halogenated hydrocarbon radicals with at least 2 carbon atoms between the halogen atom and the phenol ring which do not contain an aliphatic tertiary << -C atom; R '.. has the same meaning as R ^ and can also be a halogen atom; m is a number from at least 50 to 800, preferably from 150 to 300. These preferred polymers include those with a molecular weight of between 6,000 and 100,000, preferably 40,000. 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). Will be 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 viscosity of the block copolymer and the thermoplastic industrial resin at the temperature Tp. The amount used 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 can (apart from the fact that no layer separation occurs) with Using at least two methods can be demonstrated. One of these methods is to solve molded or extruded objects from a mixture according to the invention under reflux in one

809845/0999 -33-

4 * 3 ¹ A- 50 025

Solvent which the block copolymer and others soluble Dissolves components quantitatively; if then the remaining polymer structure (from the thermoplastic industrial resin and HalogenLerten are still related to each other and the shape of the shaped or extruded object and is structurally still intact without wrinkles or delamination, and if If the solvent does not contain any insoluble particles, there is evidence that a network is in front of you in which the non-extracted and extracted phases interlocking and are continuously present. The non-extracted phase must be continuous because it is geometrical and remains mechanically intact. The extracted phase must also have been present continuously before extraction as quantitative extraction of a dispersed phase from an insoluble matrix is highly unlikely is. After all, the networks from both phases must interlock, otherwise both phases could not exist continuously be. In addition, the continuous nature of the non-extracted phase can also be demonstrated microscopically. In the present mixtures of more than two components, the interlocking and the continuity of each individual Phase can be detected by selective extraction.

In the second method, a mechanical property, such as the tensile modulus, is measured and compared with the Value to be expected from a system in which every continuous; isotropically distributed phase contributes to the mechanical Contributes behavior that corresponds to their volume share. If the two values match, this is proof for the presence of an interlocking network, while in the other pail the measured value is different from the theoretical value is.

* thermoplastic polymers -34-

& 09846 / 099Θ

³²⁵

An important aspect of the invention is that the proportion ratio of the various polymers in the mixture can be varied within a wide range. The proportions of the polymers, expressed in wt .- ^ (the total mixture being 100 parts) are the following:

Parts by weight, preferably parts by weight

different
thermoplastic industrial resin 5 - 48 10 - 35

Block copolymer 4-40 8-20

The halogenated © thermoplastic polymer is in a lot present, which is greater than that on different industrial thermoplastics, i.e. the weight ratio of halogenic thermoplastic polymer to the industrial resin is greater than 1: 1, i.e. the amount of halogenated thermoplastic Polymers can vary between 30 and 91 parts by weight, preferably between 48 and 70 parts by weight. Note that the The minimum amount of block copolymer in these mixtures may vary with the thermoplastic industrial resin present can.

The three components, the different thermoplastic industrial resin, the halogenated « * \ mä the block copolymer, can be mixed in any way that ensures that an interlocking network is created. For example. Resin, halogenated and block copolymers are dissolved in a common solvent and precipitated again by adding another solvent in which none of the polymers is soluble. However, it is particularly useful if the polymers in grain and / or

^ • thermoplastic polymer
** thermoplastic polymer -35-

809845/0999

1A-5Ü 825

Powder form intimately mixed in a mixer with high shear speed. "Intimate mixing" means that the mixing occurs at such a high mechanical shear rate and thermal energy that interlocking occurs of the various networks is secured. For this purpose, extrusion devices with a high shear effect 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.

The mixing or processing temperature (Tp) is chosen depending on the polymers to be mixed. If, for example, the polymers are not to be mixed in solution but rather in the melt, 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 chosen so that isoviscous mixing of the polymer is made possible. The mixing or working temperature is between 150 and 400, preferably between 230 and 30O ⁰ O.

Another parameter that is important when considering the formation of interlocking by mixing in the melt Wants to achieve networking, consists in that one the viscosities of the block copolymer, the halogenated and the thermoplastic Industrial resin equalizes in temperature and shear stress during the mixing process (isoviscous mixing). The more uniform the industrial resin and the halide in the network of the block copolymer are distributed, the greater the chance that a three-dimensional network will form during the subsequent cooling, in which the individual networks interlock continuously and simultaneously. Therefore, the block copolymer has a viscosity of oiPoise, a temperature Tp and a shear rate of 100 s, the viscosity of the thermoplastic industrial resin and / or the halogenated resin should preferably be at the Temperature Tp and a shear rate of 100 s

* thermoplastic polymers ** thermoplastic ajtfjff 4 5 / Q 9 9 9

-36-

1A-50 825

kind of set that the ratio of the viscosity of the block copolymer divided by the viscosity of the thermoplastic Industrial resin and / or the halogenated ^ between 0.2 and 4.0, preferably between 0.8 and 1.2. A Thus, "isoviscous mixing" herein 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 ~ between 0.2 and 0.4 lies. It must be taken into account that the shear rate inside an extruder over a wide range can be distributed. Isoviscous mixing can therefore also take place when the viscosity curves of the two polymers differ at some of the shear rates.

In some cases, the order in which the polymers are blended is important. If necessary, you can therefore first the block copolymer with the halved or the other polymer mix and then mix this mixture with the different thermoplastic industrial resin or you can simply mix all polymers at the same time. Due to the multiple constituents of the mixtures according to the invention, various Variants can be chosen in the order of shuffling. Under certain circumstances you can also achieve that the viscosities of the different polymers get along better.

The block copolymer or the block copolymer mixture can be chosen so that it is essentially the industrial resin and / or tolerates the halogenated. If necessary, can the block copolymer can be blended with a rubber extending oil or additional resin, as will be described later, in order to change its viscosity properties.

To create co-continuous, interlocking networks are the special physical properties of the

»Thermoplastic polymer ** thermoplastic polymer

8098A5 / 0999. ~ ³ ! L _r

1A-50 825

-yr-

. -_ _ .2119517. _

Block copolymers important. In particular, the most preferred block copolymers melt in the neat state not in the usual sense with increasing temperature, since the viscosity of these polymers is to a large extent "non-Newtonian" and tends to increase indefinitely towards zero shear. Also is the viscosity these block copolymers are largely independent of temperature. This rheological behavior and the already existing thermal stability the block copolymers increase their ability to work in the Melt their network structure practically to maintain, so that in the most varied of mixtures again and again interlocking and form continuous networks.

The viscosity behavior of the thermoplastic industrial resins and the halogenated thermoplastic depends much more on temperature than that of the block copolymers. One can therefore often choose a working temperature Tp at which the Viscosities of the block polymer and that differentiated from it Industrial resin and / or polyolefin fall into the area in which interlocking networks are formed. Possibly As already mentioned, a viscosity modifier can also be mixed with the industrial resin or the halogenated resin first to match the viscosities to one another.

The mixture of partially hydrogenated block copolymer, halogenated and differentiated thermoplastic industrial resin can be mixed with an extension oil that is customary 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 oil begins preferably above 26O ⁰ C.

The amount of oil used is up to 100 phr (phr = weight, -

* Polymers on the other hand ** thermoplastic polymer

809845/0999 -38-

U-50 825

Parts per 100 parts of block copolymer), preferably 5 to 30 o'clock,

The mixture of partially hydrogenated block copolymers and thermoplastic industrial resin differentiated from these can also be admixed with an additional resin, which can be, for example, a resin that increases the flowability, such as a <X -methylstyrene resin or a plasticizer for the end blocks.

Suitable plasticizer resins for the end blocks include coumarone-indene resins, vinyltoluene-e £ -methylstyrene copolymers, Polyindene resins and low molecular weight polystyrene resins "

The amount of additional resin can be up to 100, preferably 5 to 2.5 phr

In addition, the masses can contain other polymers, fillers, reinforcers, Antioxidants, stabilizers, fire retardant additives, antiblocking agents and other rubber and Contains plastic additives.

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

Enhancers are also suitable for inclusion in the present polymer blends. These are substances

which can be added to a resin matrix to improve the strength of the polymer. Mostly these are inorganic or organic products of high molecular weight, for example 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 which have glass fibers in an amount of 2 to 80 % of their weight are particularly preferred.

Thermo-plastic polymer

-39-809845 / 0999 original inspected

1A-5Ö 325

28-ia £ 17

The inventive polymer mixtures can be used in areas in which high demands are placed on the material, can be used as a metal substitute.

In the following examples according to the invention and for comparison, various polymer mixtures were prepared with the aid of a 3.125 cm Sterling extruder with a Kenics nozzle (length to diameter ratio 24: 1, compression ratio of the fichnocko jü, 0: 1) hur / jüijlolll. The following polymers were used Substances:

1) Block copolymer - a selectively hydrogenated block copolymer according to of the invention with S-EB-S structure .. - - -

2) Oil - TUFFLO 6056 rubber extender oil;

3) nylon 6 - PLASKON® 8207 polyamide;

4) nylon 6-12 - ZYTEL®158 polyamide;

5) polypropylene - a substantially isotactic polypropylene with melt index 5 (230 ° C / 2.16 kg);

6) poly (butylene terephthalate) ("PBT") - VALOX® 310 resin;

7) Polycarbonate - MERLON® M-40 polycarbonate;

8) poly (ether sulfone) - 200 P;

9) polyurethane - PELLETHANE® CPR; 10) polyacetal - DELRIN® 500; 1I) Poly (acrylonitrile-co-styrene) - BAREX®210;

12) Fluoropolymer - TEFZEL® 200 poly (vinylidene fluoride) copolymer.

In all mixtures that contained the exne oil component, the block copolymer and the oil were first mixed before the other polymers were added.

ORIGINAL INSPECTED

809845/0999

example 1

SO ^1A -5 ° 325

Various polymer mixtures according to the invention were prepared. In some of them, a mixture of two higher and lower molecular weight block copolymers was found used to compare the viscosity with the fluoropolymer and / or the other industrial resin different from the remaining components correspond to. For comparison purposes, mixtures or compositions were prepared without a block copolymer. These But masses are not easy to mix. For example, in the case of the mixture 121, which only consists of the fluoropolymer and nylon 6, extremely intermittent throughput and a coarse grain profile were observed. In contrast, each could Slightly mix mass containing a block copolymer according to the invention and the extrudate showed a homogeneous appearance. aside from that each compound containing a block copolymer exhibited the desired continuous intermeshing upon mixing Networks as determined by the criteria described above.

The various weights and test results are summarized in Tables 1 and 2 below. The composition of the various mixtures is given in wt .- ^.

Tables 1 and 2:

309845/0999

1A-5C 825

a b e 1 1 e 1

Mixture Kr. 71 72 85 86 101 102

Block copolymer

gemiscli 15.0 30.0 15.0 30.0 15.0 30.0

Fluoropolymer 21.2 17.5 21.2 17.5 21.2 17.5

Poly (butylene terephthalate) 63.8 52.5

Polycarbonate 63rd, 8 52.5

Nylon 6 63.8 52 ^ 5

Poly (acrylonitrile-styrene)

Tab 1 1 e 1 (cont.) Mixture Ur. 119 120 121 162 166 170

Block copolymer

mixture 15.0 3O ₇ O

Fluoropolymer 25.0 25 < > O 25.0 21.2 25.0 17.5

Polybutylene terephthalate) 75.0

Polycarbonate 75 ^ 0

Nylon 6 75.0

Poly (acrylonitrile-
co-styrene) 63.8 75.0 52.5

8098A5 / 0999

Tabel

mixture
Mr. Polymer art % Block
copolymer 1 2 2 2 3 6th 4th 5 9 6th 300 7th { 2 100 121 0 - 0 - 1 - 5 - - 5 400 2 _; 45 1 50ό 101 Nylon ό 15th 4,800 , 56 4th - 5 2 500 1.65 800 102 30th 2,400 2 , 94 2 _? ° 3 - 1.0 9 '900 0.71 2 100 119 0 - 1 - - - - 6th 300 3.18 1 400 71 PBT 15th 3 700 3 , 50 3 _? 66 - 4th 3 800 2.10 700 72 30th 2,400 2 P5 2 , 44 - 7th 9 800 1.18 5 200 120 0 5,500 1 _; 26th 1 , 04 500 1 7th 600 2 _; 84 4th 300 85 Polycarbonate 15th NB * _; 65 , 65 500 - 4th 900 2.24 3 ooo 86 30th NB , 89 , 89 000 - 1.59

as co ο

Mixture of polymer type, no.

Table 2-CJLocations.)

11 12

$ Block

copolymer 9. 12 13 Ii

121

101 nylon 6 102

119

71
72

PBT

120

85 polycarbonate

0 15 30

15 30

15 30

11 Ik 11

0.40 185.6 5.12 0.74 104 1.66 2.06 0.9 ^ 0.91

O ₇ 3l 101.1 5.51 0.68 90 1.43 1.70 0.77 0.65

0.17 -91.7 5.71 0.63 36 1.96 2.11 O ₉ 7O 0.68

0.41171.6 5.94 0.07 102 0.51 0.52 0.40 0.58

0.26 149 "6.39 0.07 87 0.51 0.48 0 _? 40 0.55

0.14 73.3 6.05 0.07 51 0.76 0.90 0.67 0.50

95.9

1.42137.4 4.32 0.116 114 4.50 4.23 2.19 2.50

1.11142.4 4.44 0.131 92 10.60 9.60 11.4 6.69

0.82 136.9 4.50 0.102 54 11.90 9.70 8.91 7 ^ 66

^K NB means "no break" Headings of columns 1 to 17:

1. Tensile strength, psi

2. Young's modulus, psi χ "\ 0

3. Secant module, psi χ 10

A-. Yield strength, psi

5. elongation, %

6. Maximum, psi

7th module, psi χ 10 ⁵

8. Maximum, psi

9th module, psi χ 10 ⁵

σ> ο co

10, dimensional stability, ⁰ C

11. Linear expansion, χ 10 " ⁵ , inches per inch and ⁰ C 12. Water absorption, %

13.Rockwell hardness, R ^

14. Impact strength at gate, ft-lbs / inch 15. Impact toughness against sprue, ft-lbs / inch 16. Impact strength at the gate, ft-lbs / inch 17. Impact strength opposite the gate, ft-lbs / inch

The comparison of the results shows the unexpected properties achieved with the mixtures according to the invention. If one compares, for example, the ratio of the relative increase in Izod impact strength (at 23 ° C) to the relative decrease in the dimensional stability (temperature) of the various polymer blends with an increasing percentage of block copolymers from 0 to 15 % and a constant ratio of fluoropolymer to different industrial synthetic resin from 1: 3 »you can see that much higher values than expected are achieved. Usually the person skilled in the art would expect this numerical value to be positive and less than 1. For mixtures containing nylon 6 and polycarbonate, however, the numerical values for this ratio are 3.8 and -23. The minus value is particularly surprising because this increases the dimensional stability together with an increase in impact strength with an increasing percentage of block copolymer indicates; this was completely unexpected.

3098A5 / 0999

Claims (1)

Claims 1. Synthetic resin mixture containing a partially hydrogenated block copolymer, the at least two end blocks A of a monoalkenyl arene polymer with an average molecular weight of 5,000 to 125,000 and at least one intermediate block B of a polymer of a conjugated diene with an average molecular weight of 10,000 comprises up to 30 000, and wherein the terminal polymer blocks A 8 to 55 wt .- ^ represent the block copolymer and not more than 25 of the arene double bond fo in the polymer blocks A and at least 80 <$> of the aliphatic double bonds in the polymer blocks B by Hydrogenation are reduced, characterized by the following composition: a) 4 to 40 parts by weight of partially hydrogenated block copolymers; b) a halogenated thermoplastic polymer with a generally crystalline structure and a melting point above 20 ^° C c) 5 to 48 parts by weight of at least one thermoplastic industrial synthetic resin different from the other components from the group of polyamides, polyolefins, thermoplastic polyesters, poly (aryl ethers), poly (aryl sulfones), Polycarbonates, acetal resins, thermoplastic polyurethanes and nitrile resins, where the weight ratio of halogenated thermoplastic Polymers to thermoplastic industrial synthetic resin different therefrom is greater than 1: 1, so that in the polymer mixture at least two of the polymers with one another form wholly or partly continuous, interlocking networks. 809845/0999 ORIGINAL INSPECTED 1A-50 '825 2. Synthetic resin mixture according to claim 1, characterized in that the polymer blocks A are numerical average molecular weight of 7000 to 60,000 and the polymer blocks B a number average molecular weight of 30,000 to 150,000. 3. synthetic resin mixture according to claim 1 or 2, characterized ge kenntzeich.net that the terminal polymer blocks A 10 / make up to 30 ° o of the total weight of the block copolymer. 4. Synthetic resin mixture according to one of the preceding claims, characterized in that at least 5 i ° of the arene double bond in the polymer blocks A and at least 99 ° of the aliphatic double bonds in the polymer blocks B are reduced by hydrogenation. 5. Synthetic resin mixture according to one of claims 1 to 4, characterized in that the halogenated thermoplastic A homopolymer or copolymer of tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, vinylidene fluoride or polymers Is vinylidene chloride. 6. resin mixture according to claims 1 to 5, characterized in that da.ß various of the other ingredients thermoplastic resin industry has an apparent crystalline melting point of more than 120 ⁰ C which is preferably between 150 and 35O ⁰ C. 7. Synthetic resin mixture naoh one of claims 1 to 6, characterized in that the thermoplastic industrial synthetic resin different from the other components is a polyolefin with an average molecular weight (number average) of more than 10,000 and an apparent crystal melting point above 100 ^° C. 809845/0999 "3- 1 £ -5σ 825 δ "resin mixture according to claim 7, characterized, geke η η is characterized in that the polyolefin is a homopolymer or a copolymer of an <£ olefin or 1-olefin having 2 to 5 carbon atoms. 9. Synthetic resin mixture according to Claim 7 or 8, characterized in that the number average molecular weight of the polyolefin is more than 50,000. 10. resin mixture according to one of claims 7 to 9, characterized gekennz et eichn that the apparent crystalline melting point of the polyolefin between HO and 25O ⁰ C. 11. Synthetic resin mixture according to one of claims 7 to 10, characterized in that it contains a polyethylene of high density with an approximate Kr is ta lim it ät of more than 75 % and a density of 0.94 to 1.0 kg / l . 12. Synthetic resin mixture according to one of claims 7 Ms 10, characterized in that it contains a low density polyethylene which has an approximate crystallinity of more than 35 % and a density of 0.90 to 0.94 kg / l. 13o synthetic resin mixture according to one of claims 7 to 12, characterized marked that it contains a polyethylene with a numerical molecular weight of 50,000 to 500,000. 14. Synthetic resin mixture according to one of claims 7 "to 10, characterized marked that it is an isotical polypropylene contains. 15. Synthetic resin mixture according to claim 14, characterized in that g e k e η η, that the polypropylene has a number average molecular weight of more than 100,000. 16. Synthetic resin mixture according to one of claims 7 "to 10, characterized characterized in that it contains a propylene copolymer, which ethylene or another «^ -olefin as a comonomer in SQ9845 / 0999 . 1A-50 825 contains in an amount of 1 Ms 20 wt .- ^, 17. Synthetic resin mixture according to one of claims 7 to 10, characterized in that it contains poly (I-butene) as the polyolefin. 18, synthetic resin mixture according to one of claims 7 to 10, characterized in that it contains as polyolefin is a homopolymer of 4-methyl-1-pentene with an apparent crystalline melting point of 240 to 25O ⁰ G and a relative density from 0.80 to 0.85 contains. 19 · Synthetic resin mixture according to one of Claims 7 to 10, characterized in that it contains a copolymer of 4-methyl-1-pentene and a tC -olefin as the polyolefin 20. Resin composition according to claim 19, characterized in that it contains as polyolefin is a copolymer of 4-methyl 1-pentene and 0.5 to 30 wt. -Fo a linearenoC ~ 01efins with Contains 4 to 18 carbon atoms. 21, synthetic resin mixture according to one of claims 1 to 6, characterized in that that is on the other ingredients, various thermoplastic resin industry a thermoplastic polyester having a melting point of more than 120 ⁰ C. 22. Synthetic resin mixture according to one of claims 1 to 6 and 21, characterized in that the thermoplastic industrial resin different from the other components is polyethylene t er ephtha.la t, polypropylene terephthalate. or polybutylene terephthalate is. 23. Synthetic resin mixture according to claim 22, characterized in that daa industrial resin polybutylene terephthalate having an average molecular weight of 20,000 to 25,000. 309845/0999 1A-50 24. Synthetic resin mixture according to one of claims 1 to 6 and 21, characterized in that the thermoplastic industrial resin is a cellulose ester. 25. Synthetic resin mixture according to one of claims 1 to 6 and 21, characterized in that the thermoplastic industrial resin is a homopolymer of pivalolactone. 26. Synthetic resin mixture according to one of claims 1 to 6 and 21, characterized in that the thermoplastic Industrial resin is a copolymer of pivalolactone and no more than 50 M0I.-7 & another ß-propiolactone. 27. Synthetic resin mixture according to claim 26, characterized in that the thermoplastic industrial resin is a Copolymer a.us pivalolactone and not more than 10 mol .- $ of another ß-propiolactone. 28, synthetic resin mixture according to one of claims 25 to 27, characterized in that the thermoplastic industry ha da.ß. Rz a Polypivalola.cton having an average molecular weight of over 20 000 and a melting point above 120 ⁰ C. 29. Synthetic resin mixture according to one of claims 1 to 6 and 21, characterized in that the thermoplastic Industrial resin is polycaprolactone. 30. Synthetic resin mixture according to one of claims 1 to 6, characterized in that the thermoplastic industrial resin a polycarbonate of the general formula: Il - (- Ar -A-Ar-O-O -O ^ or Il : Ar-0-C-i 809845/0999 ΤΑ-5Ό825 in which Ar is an optionally alkyl, alkoxy, halogen or nitro-substituted phenylene group and A is a carbon-carbon bond or an alkylidene _r , cycloalklylidene, alkylene, cycloalkylene, azo, imino, sulfur, oxygen, sulfoxide - or sulphone group and n is at least 2. 31. Synthetic resin mixture according to one of claims 1 to 6, characterized eichn et et that the thermoplastic industrial resin is a homopolymer of JOrmaldeyd or trioxane. 32. Synthetic resin mixture according to one of claims 1 to 6, characterized in that the thermoplastic industrial resin is eichn et is a polyacetal copolymer. 33. Synthetic resin mixture according to one of claims 1 to 6, characterized in that the other components various thermoplastic industrial synthetic resin a polyamide with a number average molecular weight is more than 10,000. 34. Synthetic resin mixture according to one of claims 1 to 6, characterized in that the thermoplastic industrial resin is a nitrile resin with a content of more than 50 wt .- $ amount of a J ^, ß-olefinically unsaturated mononitrile. 35 · Synthetic resin mixture according to claim 34, characterized in that the mononitrile of the general formula CH ₉ = C-CK ^c ι corresponds, in which R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom. 36. synthetic resin mixture according to claim 34 or 35, characterized in that the nitrile resin is a homopolymer _f 303845/0999 a copolymer, one grafted onto a rubbery substrate Is a copolymer or a mixture of homopolymers and copolymers. 37. Synthetic resin mixture according to one of claims 1 to 36, characterized in that it is the block copolymer in an amount of 8 to 20 parts by weight and that of the others Components of various thermoplastic industrial resin contains in an amount of 10 to 35 parts by weight. 38. synthetic resin mixture according to one of the preceding claims, characterized in that there is 0 to 100, preferably 5 to 30 parts by weight of extending oil per 100 parts by weight contains. 39. Synthetic resin mixture according to one of the preceding claims, characterized in that, per 100 parts by weight, it additionally contains up to 100, preferably 5 to 25 parts by weight of a resin which improves the flowability. 40. synthetic resin mixture according to claim 39, characterized in that there is a <> £ -Methylstyrene resin as an additional resin, a coumarone-indene resin, a yinyltoluene-oC-methylstyrene copolymer, a polyindene resin or a low molecular weight polystyrene resin. 41. Process for the preparation of the synthetic resin mixtures according to one of claims 1 to 40, characterized in that 4 to 40 parts by weight of the partially hydrogenated block copolymers at a working temperature Tp of 150 to 400 ⁰ C, preferably 230 to 30O ⁰ C in such a way as in claim 1 under b) and c) marked other resins mixed that in the Ö-emisch the weight ratio of ha.logenosed thermoplastic polymer to thermoplastic industrial resin is more than 1: 1. 809845/0999 42. Procedure after. Claim. 41, characterized in, that one dissolves the polymers in a common solvent and they by mixing in a solvent in which none is soluble of them, which precipitates again. 43. Procedure after. Claim 41, characterized in that that the polymers in the form of granules or powder are mixed in a device with shear action. 44. The method according to any one of claims 41 "to 43j, characterized in that that one adjusts the viscosity so that at a working temperature Tp and a shear rate from 100 s ~ the viscosity of the block copolymer divided by the viscosities of the halogenated thermoplastic polymer, of the thermoplastic industrial resin or the mixture of these two is 0.2 to 4.0, preferably 0.8 to 1.2. 45. The method according to any one of claims 41 to 44, characterized in that the thermoplastic industrial resin prior to blending with the halogenated thermoplastic polymer and the block copolymer with a viscosity modifier mixed. 46. The method according to claim 45, characterized in that that ma.n as a viscosity modifier poly (2,6-dimethyl-1,4-phenylene) oxide or a mixture of poly (2,6-dimethyl-1,4-phenylene) oxide and polystyrene are used. 47. The method according to claim 45 or 46, characterized in that the viscosity modifier in one Amount of up to 100, preferably 10 to 50 parts by weight each 100 parts by weight of thermoplastic industrial resin used. 48. The method according to any one of claims 41 to 47, characterized in that the block copolymer is in 8Q9845 / 0999 -9- U-50 "825 an amount of 8 "to 20 weight and that of the others Components of various thermoplastic industrial resin used in an amount of 10 to 35 parts by weight η. 509845/0999